TWI338707B - - Google Patents

Description

IX. INSTRUCTIONS: I: TECHNICAL FIELD OF THE INVENTION The present invention relates to a coating composition for cans. I: Prior Art 3 A coating film is usually formed on the inner surface and the outer surface of a can body such as a canned food or beverage. Heretofore, the can coating composition has an epoxy resin/phenol resin paint, an epoxy resin/amine resin paint, and the like. Although the epoxy resin coatings have excellent properties such as corrosion resistance and adhesion of the coating film, they are worried that bisphenol A having environmental hormones is dissolved therein. In recent years, in order to shorten the manufacturing process to reduce the manufacturing cost and solve the environmental problems that accompany the oil processing after the forming process, the metal sheet is formed into a can and then coated, and then the coating method is replaced with a pre-existing application. A coated metal sheet is formed into a can-like precoating method. When the precoating method is used, the coating film formed on the can, especially in the inner surface of the can, needs to have excellent draw smoothing property (hereinafter also referred to as D & I (Draw and Ironing) processability) and high temperature resistance (vapor). The film properties of bactericidal, scented, and hygienic properties are not simple enough to fully satisfy all of their properties.

For the same purpose as the precoating method, a lamination method has been disclosed, that is, a piece of polyethylene terephthalate (PET) film is adhered to a metal plate, and the obtained resin film metal plate is formed, that is, A can body (refer to Japanese Patent Application Laid-Open No. 05-147647). However, when a lamination method is used, new equipment is required and it is difficult to control the thickness of the film to be thinned, so the lamination method is applied to the thickness. The use of the film formation is more expensive than the precoating method of forming a coating film by coating. Further, in the production of the PET film, in addition to the acetaldehyde which produces the decomposition product, the remaining monomer is included. And low-molecular components such as cyclic oligomers, which need to be further improved in terms of hygienic properties. Here, a composition of a polystyrene resin, in particular, a polyethylene terephthalate (PET) can be used. The object is attracting attention, but since PET has high crystallinity and is difficult to dissolve in an organic solvent which is generally used, it is not simple to exhibit characteristics when used as a precoating coating. A resin composition for a can coating film, which can be used as a coating composition for a precoating method, in which a non-crystalline pear polyester resin and a crystalline polyester resin are dissolved in a solvent and gradually cooled. A resin containing a crystalline polycondensate which is present in a dispersed state is obtained (refer to Japanese Laid-Open Patent Publication No. 2001-234115). However, the resin composition for coating the can coating film is applied to a resin coated metal of a metal plate. The plate has a D&I processability which is insufficient. Further, there is known a can coating composition which heats and dissolves a crystalline polyester resin and a non-crystalline polyester resin in an organic solvent, and then the resin The polyester resin dispersion obtained by quenching the solution from the temperature above the temperature rising crystallization starting temperature of the crystalline polyester resin to the glass transition temperature of the crystalline polyester resin is used as a user of the can coating composition (refer to the present invention) Application Publication No. 2004-2671 and No. 2004-292467. However, when such a can coating composition is used in a precoating method, coating smoothness and D&I processability are insufficient. An object of the present invention is to provide a coating composition for a can, which is advantageous for use in a precoating method, and which has excellent coating film properties such as appearance of the coating film, smooth processability, high temperature sterilization resistance, flavor maintenance, and hygiene. [The content of the item] The inventors of the present invention have carefully studied and found that the crystal-type polyester resin fine particles (A) mainly containing ethylene glycol diester units are used. a crystalline poly(tetra) lyoparticle (B) having a unit of butyl dibenzoate; and a specific ratio of the organic solvent (C) having a solubility in the specific range of the microparticle (A) and the microparticle (8) The coating composition can obtain a coating film which is excellent in coating film appearance, D&I processability, high temperature sterilization resistance, flavor retention property, and hygienic property, can be used for the precoating method, and the like; The present invention provides the following coating compositions for cans. 1. - Coating composition for cans 'includes: crystalline polyurethane particles (A)' is based on ethylene terephthalate units; crystalline polyester resin particles (B) are The butyl phthalate unit is the main component; and the organic solvent (C) is used for the solubility of the fine particles (A) and the solubility with respect to the fine particles (B). When the amount is less than 5% by mass and the mass is 99% by mass or more, the ratio of the fine particles (A) to the fine particles (b) is 95% by mass to 30% by weight. The mass%, the latter is 5% by mass to 7% by mass, and the organic solvent (C) content is 40 parts by mass to 8 parts by mass based on the total amount of the fine particles (A) and the fine particles (B). 〇〇 mass parts. 2. The can coating composition according to the above item 1, wherein the crystalline polyester resin microparticle (A) has a resin intrinsic viscosity of 〇4cn/g to 4dl/g and a ruthenium transformation temperature (Tg) of 55°. C~130. (:, the melting point (Tm) is 160. 〇 260. (: 3. The can coating composition according to item 1 above, wherein the crystalline polyester resin fine particles (A) are composed of bismuth diacetate A polyester resin composition having an ester unit content of 8 〇 mol% or more. 4. The can coating composition according to the above item 1, wherein the crystalline polyester resin microparticle (B) has a resin inherent viscosity of 〇4di. /g~丨4di/g, glass transition temperature (Tg) is 0 to 40 ° C, melting point (Tm #130 °c~25 (TC. 5. The can coating composition according to item 1 above, wherein the crystal The polyester resin fine particles (B) are composed of a polyester resin having a unit content of not less than 9% by mole of butyl succinate. 6. The can coating composition according to the above item 1, When the amorphous polyester resin (D) is further contained, and the total amount of the crystalline polyester resin fine particles (A) and the crystalline polyester fine particles (B) is 1 part by weight, the amorphous polyester resin (D) The amount of the glass transition temperature (Tg) of the non-crystalline polyester resin (D) is 5, in the range of 0.1 to 100 parts by mass. 5t~15(TC. 8. The can coating composition according to the above item 1, which further contains a dispersing agent (E). 9. The can coating composition according to item 8 above, wherein the dispersing agent is A phosphoric acid compound represented by the formula (1), wherein the formula (1) is: Ο r1〇~-P-OR3 (l) [Structure] 〇R2 (wherein R1, R2 and R3 are the same or different, It is represented by an aliphatic group having 6 to 18 carbon atoms, or an aromatic hydrocarbon, or a CmH2inOCnH2n+1; here, m and η are integers of 1 or more, and 111+11 is an integer of 6 or more. The can coating composition according to the above item 1, which further contains a phenolic phenol phenol, and is combined with the crystalline poly arylene resin fine particles (A) and the crystalline pear vinegar resin micro (four) (B) The secret type benzene-lipid is 0.1 parts by mass to 10 parts by mass. 11. The can coating composition according to the above item 1 which further contains an epoxy resin and is relatively fine with respect to the crystalline polyester resin fine particles and crystal form. When the total amount of the polyester resin fine particles (B) is 丨〇〇 by mass, the epoxy resin accounts for 5 parts by mass to 20 parts by mass. 12· A coated metal plate is attached to a metal plate to The same is applied to the can coating composition of the above item 1 and baked together. 13_ - The can body is subjected to the extension processing in a state in which the coated surface of the coated metal plate of the above item 12 is the inner surface of the can. In the present specification, the resin intrinsic viscosity, glass transition temperature, melting point, and average particle diameter of the polyester resin are measured as follows: (1) Resin inherent viscosity: according to the method specified in JIS Z 8803 The mixture was measured at 25 ° C using a mixed solution of phenol/tetra-ethane ethane = (mass ratio). (2) Glass transition temperature: It is determined by the method specified in JIS K 7121 9.3 (1987). (3) Melting point: measured by a differential scanning pyrolyzer. The differential scanning pyrolyzer is exemplified by a commercially available product. For example, "DSC-60A" (trade name, manufactured by Hiroshima Shimadzu Corporation) can be used. (4) Volume average particle diameter: those measured by a laser scattering type particle size distribution analyzer. Such a particle size distribution measuring instrument is exemplified by a commercially available product, and can be used, for example, "MICROTRAC HRA model 9320-X100" (trade name, manufactured by Nisshin Instruments Co., Ltd.). Hereinafter, the composition for a can coating of the present invention will be described in detail. Crystalline Poly S-Resin Fine Particles The crystalline polyester resin fine particles (A) of the present invention are fine particles of a polyester resin mainly composed of a terephthalic acid ethylene glycol unit. Crystalline type means: According to the measurement of the differential scanning calorimeter, it shows clear demon point. The polyester resin mainly composed of ethylene glycol diacetate unit can be obtained by polycondensation reaction of terephthalic acid or its lower alkyl ester with ethylene glycol, but it can also be used for p-dicarboxylic acid or its lower alkane. A part of the portion of the ester is replaced with other polybasic acid such as meta-benzoic acid, adipic acid or a lower alkyl ester thereof, or a part of ethylene glycol is replaced with propylene glycol or 1,4-cyclohexanedimethanol. Other polyols are also used in the case of polyg-resin, which is mainly composed of the unit of the present dicarboxylic acid, and is based on the possession of aroma, or a lower alkyl group. A polyester resin having a content of an ester of ethylene terephthalate and an ethylene glycol content of 80 mol% or more is preferred. As long as the content of the ethylene terephthalate unit is more than 80 mol%, for example, even polyethylene terephthalate having a unit content of 100 mol% of ethylene terephthalate (PET) Or a copolymer of other units such as polyethylene terephthalate unit and ethylene phthalate unit. Further, it also includes a rubber-like polyester structure (for example, a chain segment composed of a polyether having a low glass transition temperature). 1338707 In order to obtain the microparticulation method of the crystalline polyester resin of the fine particles (A), there are a pulverization method, a dissolution cooling method, a spray drying method, and the like, and from the viewpoint of coating appearance, heating by an organic solvent is used. It is preferred that the crystalline polyester resin fine particles obtained by the dissolution cooling method after being dissolved are cooled. The characteristics of the crystalline polyester resin fine particles (a) which can be used in the present invention are preferably in the range of 〇4 dl/g to 1.4 dl/g, particularly 0.7 dl/g. The 1.2dl/g level is preferred. Also, the glass transition temperature is preferably hunger to 13 〇C, and the melting point is 160. (:~260. (: The degree is better. Also, the volume average particle size of the 10 crystal polyester resin fine particles (A) is usually 〇1"m~25 //m degree, 0.1//m~ΙΟ" It is also preferable to use a range of the m degree. A commercially available product may be used as the crystalline polyester resin fine particles (A). Commercial products such as PA-200" (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), " 】125" (trade name, manufactured by Mitsui Chemicals Co., Ltd.), rj丨35" (trade name, manufactured by Mitsui Chemicals Co., Ltd.), "TN8756" (trade name, Japanese business Teijin Chemicals Co., Ltd.) Product: Crystalline Resin Tweezers The crystalline polyester resin microparticles (B) in the present invention are fine particles of a polyester resin mainly composed of a butylene terephthalate unit. The crystalline type means: 20 The measurement of the melting point by the differential scanning pyrolyzer shows a clear melting point. The polyester resin based on the unit of butyl phthalate is based on terephthalic acid or its lower alkyl vinegar and hydrazine, 4 - obtained by a polycondensation reaction between butanediol, also <one of p-phenylenecarboxylic acid or its lower alkyl ester Substituting for other polybasic acids such as isophthalic acid, caproic acid, sebacic acid or lower alkyl esters thereof, or 11 1338707 replacing a part of 1,4-butanediol with 1,6-hexane Other polyols such as alcohol, 1,4, cyclohexanedialdehyde, etc. may also be used. The polyester resin based on the butyl dibenzoate is mainly based on the benzoic acid or its lower alkyl hydrazine and 1,4 — Butylene glycol terephthalic acid 5 is preferably a polyester resin having a diester unit content of 9 〇 mol% or more. As long as the content of the benzene diacetate unit is 9 〇 mol% or more When, even the unit of butyl dibenzoate is 1 〇〇 mol% of polybutylene dicarboxylate (PBT), or to the dibutyl succinate unit and dibutyl phthalate A copolymer of other units such as a diester unit may also include a structure having a rubbery structure of 10 (for example, a chain segment composed of a polyether having a low glass transition temperature). To obtain the fine particles (B) The method for atomizing the crystalline polyester resin may be a pulverization method, a dissolution cooling method, a spray drying method, or the like. From the viewpoint of the appearance of the coating film, it is preferred to use a crystalline polyester resin fine particle obtained by a solution cooling method in which the organic solvent is heated and dissolved and then cooled by 15 to be cooled. The crystalline polyester resin usable in the present invention can be used. In terms of the characteristics of the fine particles (B), the intrinsic viscosity of the resin is preferably from 4 dl/g to 1.4 dl/g, and particularly preferably from 0.7 dl/g to 1, 2 dl/g. 〇~4〇〇c is preferably 20 degrees, and the melting point is 13〇°C~25 (the degree of TC is better. Further, the volume average particle diameter of the crystalline polyester resin fine particles (B) is usually 〇丨" The degree of m~25ym is particularly good in the range of 〇.1μη1~7#ηι. Commercially available products can also be used for the crucible polyester resin fine particles (Β). For example, rN_1000" (trade name, Nissho Mitsubishi Rennes Co., Ltd.) can be used as an example of a commercially available product. The ratio of the use ratio of the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B) in the can coating composition of the present invention to the polyester resin fine particles (Al and the crystalline polyester resin fine particles) is based on The total of the fine particles is 95% by mass to 30% by mass, and the latter is 5% by mass to 70% by volume. When the fine particles are dispersed in an organic solvent, fine particles (A) and fine particles (B) are formed. When the proportion of the crystalline polyester resin fine particles (A) exceeds 95% by mass, the draw smoothing property (D&I processability) of the coated ruthenium is lowered. When the ratio of the crystalline polyester resin fine particles (A) is less than 5% by mass, the flavor retention of the coating film is lowered, which is not preferable. The use ratio of the (B) is that the former is 90 based on the total of the fine particles. Mass. / 〇 ~ 40% by mass, the latter is 10% by mass to 6% by mass. The former is 80% by mass to 50% by mass, and the latter is 2% by mass to 5% by mass. Ester resin microparticles (A) and crystallization Linear polyester resin microparticles solvent (X :) with respect to the crystalline "and the solubility of the resin particles with respect ⑷

π / sub-materials are also! That is, the solution is in a state of dispersion with good fluidity, and the coating composition of the present invention is in a normal temperature state, and when heated for the formation of the coating film 13, the fine particles (A) and the fine particles (B) - It melts to form a uniform coating film. The organic solvent (C) may specifically be a mixed solvent in which a mixture of dimethyl adipate glutaric acid glutaric acid and y-white vinegar and vinegar is mixed (,; the range of the point is He 205. (: degree), N -Methyl-2-indole B each, _, isophorone, etc. As an example, the mixed solvent of the mixed adipic acid dimethyl sulphate glutaric acid and glycerol can be used commercially. For example, the product of the "face" (product name "American company DuPont") can be used as a commercial product. From the viewpoint of the dispersibility of the fine particles and the coating workability, it is relative to the crystalline polyester resin fine particles. And the crystalline polyester resin fine particles (8) in the case of a combined amount of 'organic solvent (the content of t contains about 800 parts per square centimeter. Further, relative to the fine particles (A) and the fine particles (B) When the total amount of the organic solvent (c) is from 1 part by mass to 500 parts by mass, the non-crystalline polyester blush non-crystalline polyester resin (D) means: differential scanning The melting point of the spectrometer does not show a clear melting point, for example, it is like: at room temperature, it is easily dissolved in the organic solvent. a resin having a high affinity or compatibility with the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B), or a crystalline polyester resin fine particles (A) and crystals in a molten state. The polyester resin microparticles (B) phase react to form a continuous layer of resin. By virtue of this property, the polyester resin (D) can contribute to the improvement of the appearance of the coating. Non-.° SB type brewing resin (D The glass transition temperature (Tg) is preferably from 55 ° C to 15 ° C and is preferably from about 12 Gt, especially from 1338707 to 65 ° C to 11 ° C. The poly(10) resin (9) can be obtained by reacting a polyacid component and a polyol component. The polyacid component can be used, for example, from o-benzoic acid needle, isophthalic acid 5-dicarboxylic acid, terephthalic acid. Four recorded phthalic acid phthalate, hexacosyl phthalate needle, _ acid, fumaric acid, adipic acid, azelaic acid, maleic acid needle, 2,6-naphthalene dibasic acid, 1,6-hexyl Burning two New Zealand, ring-burning and second-removing acid, etc.! The second test acid and its lower acid base are the compounds; trimellitic acid An acid anhydride, methylcyclohexane triterpenic acid, or a tetrabasic acid or the like having a ternary or higher ternary acid such as benzoic acid, crotonic acid or p-tert-butylbenzoic acid may be used in combination. The polyol component is, for example, ethylene glycol, diethylene glycol 'propylene glycol, 14-butyl difer acid, neopentyl glycol, 3-mercapto pentanediol, i, 4-hexanediol, hydrazine, 6_ a glycol such as butyl ethyl propylene glycol or cyclohexane dimethanol; a polyhydric alcohol such as glycerol (propane 15 triol), trihydroxymethyl ethane, trimethylolpropane or pentaerythritol; Commercially available products can be used for the type of polyester resin (D). Commercial products such as "UE-3201", "UE-3203", and "XA-0653" (product names, the above are the traders of the company) ) company system), "GK-640 j, "(JK-880) (product 20 name 'above is the company's Toyo Textile Co., Ltd. system). In the can coating composition of the present invention, 0.1 parts by mass of the amorphous polyester resin (D) is blended with respect to 100 parts by mass of the total of the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B). When the amount is 100 parts by mass, the appearance of the coating film can be improved. The total amount of the resin (D) is preferably 5 parts by mass to 1 part by mass based on 1 〇〇 15 1338707 parts by mass of the fine particles (A) and the fine particles (B). Dispersant (E) The dispersant (E) is used to increase the dispersibility of the crystalline polyester resin fine particles (4) and the 5 crystalline polyester resin fine particles (B) dispersed in the organic solvent (C). As the dispersing agent (8), for example, a linear polymeric dispersing agent having a group having affinity with the fine particles (A) and (B) at one end or both ends of the main chain can be used. The affinity group may be exemplified by a 3-stage amine group, a 4-stage ammonium group, a nitrogen atom heterocyclic group, etc., and a linear polymer such as 10 polyacrylic acid, Stuffed, vinegar, etc. Further, examples of the above-mentioned complex ring group include a pyrrolyl group, an imidazolyl group, a pyridyl group, and a pyrimidinyl group. A commercially available product can be used as the polymer-based dispersant. Commercial products such as "ΒΥΚ-160", "ΒΥΚ·161", "ΒΥΚ-162", "ΒΥΚ-180", "BYK-181", "BYK-182" (trade names, above are German businessmen) Bi Kehua 15 (BYKChemie), "Surbas 20000" (trade name "British company") and other products. The following compounds can also be used as the dispersant (E), namely: General formula (1): Ο (1) R1〇—p—〇R3 【Structure】 OR2 0 (In the formula, R1, r2 and R3 are the same or different, and are aliphatic or aromatic with 6 to 18 carbon atoms. The hydrocarbon is represented by the formula (1), which is represented by the formula (1), wherein the hydrocarbon is represented by CmH2rn〇CnH2n+1; and the work is 11 and the integer is 1 and the integer is m+η is an integer of 6 or more. Phosphonium compound, specifically, 2-ethylhexyl monophenyl phosphate, ginxyl (2-ethylhexyl) phosphate, cis (butoxyethyl) phosphate, triphenyl phosphate, tricresol Phosphate esters and the like are exemplified. 5 The dispersing agent (6) can be used alone or in combination with two or more types of users. The amount of dispersing agent (E) is used to From the viewpoint of dispersibility of the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B), when the total mass of the resin fine particles (A) and the resin fine particles (b) is 1 part by weight, the dispersing agent (E) It is preferably 1 part by mass to 1 part by mass, and more preferably 5 parts by mass to 5 parts by mass. Other ingredients For the can coating composition of the present invention, as needed, It is a resin other than a resole resin such as a resol type phenol resin, an epoxy resin or an amine resin. It is used to enhance the adhesion between the metal sheets and the resin. A resol type phenol resin or epoxy resin is preferred. The resol type phenol resin is particularly preferably one of the following: a part of the methylol group of the methylated benzene resin is subjected to an alkyl alcohol. 20% of the hydroxymethylated phenol resin is obtained by heating a phenol component and a formaldehyde in the presence of a reaction catalyst to carry out a condensation reaction, and introducing a hydroxy thiol group. Phenol compound used in the manufacture of phenol resin For example: phenol, o-cresol, p-cresol, p-tert-butyl phenol, p-ethyl 17 phenol, 2,3-xylenol, 2,5-dialdehyde, m-diphenol, m-B a phenol, a phenol, a bisphenol, a bisphenol phenol, a bisphenol F, a bisphenol F, a phenol, or a bisphenol F. The formaldehyde to be used is, for example, formaldehyde, paraformaldehyde, trioxane, etc. The components may be used singly or in combination of two or more. A part of the alkyl etherification of the methylol group of the methylolated phenol resin. The alcohols may be used in an amount of from 1 to 8 carbon atoms, particularly preferably from 1 to 4 unit alcohols. Examples of suitable unit alcohols include methanol, ethyl yeast, n-propanol, n-butanol, and isobutanol. The blending amount of the phenolic phenol resin is 100 parts by mass based on the balance between the appearance of the coating film and the D&I processability with respect to the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B). In the case of 1 part by mass to 1 part of the enamel, it is preferable, and it is preferably 5 parts by mass to 5 parts by mass. When the epoxy resin of the crystalline polyester fine particle (A) and/or the crystalline polyester resin fine particle (B) has a carboxylic acid group, the epoxy resin can be effectively used as a crosslinking agent, but the polyester resin is used. When the carboxylic acid group is not contained, it is also possible to effectively use the reinforcing material of the polystyrene resin or the film-forming component used for crosslinking with the above-mentioned A-step benzene-based resin. When epoxy resin is added, it can improve hardness, adhesion, steam resistance (high temperature) bactericidal properties, etc., and the towel is also secreted with varnish, which does not contain suspected bismuth & hormone bisbenzene. Look forward to varnish-type epoxy tree moon 曰 曰 彳胄 彳胄 彳胄 彳胄 酿 清 环氧树脂 环氧树脂 环氧树脂 环氧树脂 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 1338707 Resin and other kinds of Linqing _ epoxy tree material as an example. The film coating performance depends on the material paint lacquer resin, the type A epoxy resin is more appropriate. The amount of the epoxy resin is from the viewpoint of the balance between the appearance of the coating film and the D&I processability, and is equivalent to 1 part by mass of the crystalline polyester resin micropolyacetate fine particles (9), epoxy resin ( The proportion of 〇5 = parts to 2 parts by mass is preferably in the range of 2 parts by mass to 1 part by mass.

For the can coating composition of the present invention, it may be further added as needed, and other organic resins, residues, defoamers, coating agents, coagulant-preventing agents, coloring pigments, light-free pigments, body pigments, and rust-proofing agents may be used. The pigment, the remaining organic solvent other than the organic solvent (C), and the like.

The above-mentioned stone butterfly is added to the dynamic friction coefficient temple of the coating film for adjusting the coating composition of the can, and can be used for the transportation of the metal plate coated with the composition and the occurrence of scratches during the processing of the metal sheet. Paraffin wax has a softening point of 3 〇. . The above is better for Jiayou to be 33~150C, such as fatty acid brewing fiber of polyalcohol compound and fatty acid, scorpion scorpion, gas moth, polysmoke, animal wax, vegetable wax and many more. The polyalcohol compound as a raw material of the above fatty acid ester paraffin is, for example, a drunken, triethylene glycol, tetraethylene glycol, 1,3-butanediol, J-butanol, neopentyl glycol, 1, 6-hexanediol, glycerol (glycerol), polyglycerol on two trr, trimethoprim, pentaerythritol, dicetotetraol, and the like. Among them, a polyhydric alcohol compound having three or more hydroxyl groups in the i molecule is preferred, and polyglycerol, trimethylmethanone, and pentaerythritol are preferred. The fatty acid constituting the other raw material of the above fatty acid ester wax may be exemplified by a saturated or unsaturated fatty acid, and a fatty acid having 6 to 32 carbon atoms is preferred. Particularly suitable fatty acid systems are, for example, caprylic acid, capric acid, capric acid, lauric acid, tetradecyl carbonate, hexadecanoic acid, stearic acid, eicos carbonic acid, behenic acid, '26 carbonic acid, octadecanoic acid , thirty carbonic acid and other saturated fatty acids; bismuth acid, eleven carbon dioxide, hexadecetic acid, oleic acid, linoleic acid, linolenic acid, oleic acid, decenoic acid, tea acid, licic acid, An unsaturated acid such as linoleic acid or arachidonic acid. The fatty acid ester paraffin has at least the number of hydroxyl groups of the above polyalcohol compound "3 is preferably a fatty acid esterified. Commercially available products can be used as the paraffin wax. In terms of commercial products, "8-foot-300", "BYK-320", and "BYK-330" (product names, all of which are manufactured by BYK Chemie), "Silver" Special L-77", "Hilwitt L-720", "Hilwitt L-76〇2" (trade name, all of which are manufactured by Konica Konica Co., Ltd.) 29", "Tian Ta Duo 32", "Tian Ta Duo M" (commodity name, all of which are made by the Foreign Business University Coney Company), "Shin-Eye Poly Oxygen KF-96" (trade name, Nissho Shin-Etsu Chemical Co., Ltd. ))), etc., and fluorine-based paraffin such as "SHAMROCK WAX SST-1 MG", "SHAMROCK WAX SST-3", "SHAMROCK WAX Flus 231" (trade name, the above is American Shamrock Chemistry) Made by the company), "POLYFLUO (polyfluoro) 120", "POLYFLUO150", "POLYFLUO 400" (trade name, the above is a foreign micro-powder company) and so on. Commercially available products can be used as the polyolefin paraffin. Commercial products such as "SHAMROCK WAX S-394", "SHAMROCK WAX S-395" 1338707 (trade name, the above is manufactured by American shamr〇ck Chemical Co., Ltd.), "HOECHST WAX PE-520", "HOECHST WAX PE" -521" (trade name, the above is manufactured by Texaco HOECHST Co., Ltd.), "Mitsui High Wax" (trade name, manufactured by Mitsui Chemicals Co., Ltd.), etc. Further, the animal paraffin wax may be exemplified by water-containing lanolin wax, honey wax, and the like, and the plant wax may be exemplified by carnauba wax or water wax. The above-mentioned stone can be used alone or in combination of two or more. The addition amount of the stone weave is a resin fine particle (A) and a crystalline polyester resin which are excellent in the stability of the coating and can be processed by the smoothing process of the anti-resistance film. When the total amount of the fine particles (B) is 1 part by mass, it is preferably 5 parts by mass or less, and more preferably 5 parts by mass to 25 parts by mass. 15 20 % of the organic solvents such as: propionyl, decyl ethyl fluorenone, methyl butyl ketone, decyl isobutyl hydrazine, cyclohexanone, methyl amyl guanidine and other ketones Class; alcohols such as methanol, ethanol, 2-propanol, n-propanol, isopropanol, 2-methyl-propanol, butanol, 2~methoxyethanol; tetrahydro-t-South, (4) diterpene乙乙乙氡乙烧土 and other ethers; acetic acid methyl vinegar, acetic acid B, acetic acid butyl vinegar, etc.; dimethylformamide, dimethylacetamide and other amines; toluene, xylene, Cyclohexene, positive: gas; fluorenyl phthalate, diethyl phthalic acid di: phthalic acid _, ethylene glycol monobutyl (tetra), and the like. One or more of them may be used. Early detection of the above-mentioned curing catalyst system may be an acid such as p-benzoic acid, dinonylnaphthalene, octagonal basic naphthalene-sulfonic acid, phosphoric acid or the like or 21 1338707 Neutral substances and the like are specific examples. Coating composition 〇 Preparation method The can coating composition of the present invention mixes the essential components of the crystalline polyester resin fine particles (A), the crystalline polyester resin fine particles (B), and the organic solvent 5 (C) according to a known method. Further, if necessary, the optional components of the amorphous polyester resin (d) and the dispersant (E) and the other components described above are added. The obtained coating composition of the present invention is usually an organic solvent-based coating composition. The solid content of the coating composition is usually set to be in the range of 5 mass% to 5050% by mass. When the total amount of the solid content of the crystalline polyester resin fine particles (A) and the crystalline polyester resin fine particles (B) is adjusted to 5% by mass or more based on the total amount of the solid content of the coating composition of the present invention It is preferable from the viewpoint of improving the processability of D&I of the coating film. The coating composition of the present invention can be applied to a coating composition for a can according to the present invention. After the coating of the food and beverage can be processed into a can shape, the coating can be applied, and the coating can be applied to the coating. The coated metal sheet obtained from the metal sheet is formed into a can-like precoat type. The can coating composition of the present invention is excellent in the appearance of the coating film and the D&I processability 20, and is therefore particularly suitable for the precoating type. In addition, it has excellent relationships such as hygiene and scent retention, so it is suitable as a coating for inner surfaces of cans. When the can coating composition of the present invention is used for precoating, it is first coated on at least one side of the metal plate, heated to a temperature above the bright point of the crystalline polyester resin microparticles (A) and (B), and then grilled. That is, a coated metal 22 1338707 plate is obtained. When the coated metal sheet after baking is quenched to decrystallize the polyester resin, it is preferable from the viewpoint of improving the workability of D&I. The metal plate of the above-mentioned article to be coated is not particularly limited as long as it can be used for various cans such as food and drink cans, for example, a cold-rolled steel plate, a tin-plated steel plate, a galvanized steel plate, a 5 chrome-plated steel plate, an aluminum plate or the like. The untreated raw sheets may also be used for the metal sheets, but metal sheets which have been subjected to surface treatment such as phosphate treatment, zirconium salt treatment, and chromium salt treatment may also be used. Further, the shape of the metal plate may be a plate shape or a metal tape wound in a spiral shape. The thickness of the metal plate is usually about 15 mm to 0.4 mm, and the longitudinal and lateral lengths are optional. Further, the metal strip 10 is usually a strip-shaped metal plate having a thickness of 0.15 to 0.4 mm and a width of im before and after. The coating method of the coating composition coated on the metal plate is not particularly limited 'may be carried out by, for example, spray coating, roll coating, curtain coating, bar coating, etc., coating the metal plate The highly efficient coating method is more suitable for roll coat 15 coaters. When the coating composition for a can of the present invention is used as a coating film for a can body, the coating amount may be 10 mg to 300 mg/l 〇〇 cm 2 in the inner surface and/or the outer surface of the can body in terms of dry coating amount before processing. Especially, the degree of 50mg~200mg/100cm2 is better. The dry film thickness can be Ι/zm~3〇em, especially the range of 5#m~2〇20 A111. The coating amount in the case of the film for a can lid may be in the range of from 10 mg to 200 mg/100 cm 2 in terms of dry coating amount, and particularly preferably in the range of from 5 mg to 150 mg / 100 cm 2 . The baking temperature of the film may be a temperature higher than the melting point of the crystalline polyester resin particles (A) and (B), and it is 3 〜1 〇〇 above the melting point. The temperature of the temperature is 23 1338707. The specific grilling temperature can usually be 18 〇. 〇~3〇〇°c degree, and to 200. (: ~ 280 ° C is better. In addition, the barbecue time is usually the leap second ~ rib rib second degree, and preferably 5 seconds ~ 60 seconds, the surface temperature of the metal plate of the coated object is expected to remain above Temperature. Secondly, the film after grilling is expected to be blown with 5 cold air or a large amount of cooling water, soaked in cooled water, etc., and the cooling rate is cooled to about the following level within 5 seconds. It is preferable to obtain a coating film having excellent D&I workability. Next, in the state where the coated surface of the coated metal sheet obtained by the above method is made into the inner surface of the can, the stretching process or the drawing is performed smoothly. After processing, the can body is obtained. When the coated metal plate is coated on both sides, it is of course also possible to use any surface to become the inner surface of the can. The above-mentioned extension processing or drawing smoothing process is used for: coating the metal plate Appropriate cutting, stretching or drawing to make the can body or can lid. The can body and the lid of the can body also have excellent hygienic properties and fragrance, and the appearance and closeness of the coating film. Sexuality, anti-narrative In addition, the coating composition for a can of the present invention may be applied to the surface side of the can body, and a known coating composition for a can is applied to the outer surface of the can body. [Effect of the Invention] In the can coating composition of the present invention, when the specific crystal type 20 polyester resin fine particles (A), the crystalline polyester resin fine particles (B), and the organic solvent (C) of the present invention each contain a specific ratio, the following can be exhibited. (1) The coating composition for a can of the present invention has excellent coating film appearance, smooth processing property, steam sterilization resistance, flavor retention, hygiene, adhesion, corrosion resistance, and the like. Membrane performance. Therefore, it is very suitable for use in food and beverages 24 1338707. It can be used on the inside and outside of cans, etc. (2) In addition, the composition of the can coating of the present invention is based on the appearance of the coating film, the smooth processing property of the coating film, and the like. It is excellent, and is particularly suitable for pre-coating a coated metal sheet obtained by previously coating a metal sheet into a can-like shape. (3) Further, the can coating composition of the present invention is applied to a coating material. Stability is also good. (3) The present invention will be described in further detail below with reference to the production examples, examples, and comparative examples. However, the present invention is not limited to the above-described embodiments. In each of the examples, "parts" and "%" are set in accordance with the quality standard. Production of crystalline polyester resin fine particles (A) and ruthenium) Production Example 1 A composition of a basic acid component, terephthalic acid/isophthalic acid = 85 mol 15% / 15 mol%, and A polyethylene terephthalate (PET) resin obtained by adding a polyol component and ethylene glycol as a raw material of 100 mol% is cooled and pulverized by a jet mill in a general manner, and after being classified, Crystalline poly(p-ethylene dicarboxylate) resin microparticles (referred to as PET-No. 1) were obtained. 20 Production Example 2 Polyethylene terephthalate resin composed of the raw materials shown in Table 1 was used, and the resin was "DBE" (trade name, manufactured by DuPont, Dimethyl adipate, glutaric acid). Mixing dimethyl diester and dimethyl succinate in a mixed solvent, boiling point 205 ° C) 400 parts, and heating to dissolve, then put 500 25 之 ring _ (4 points 丨 55 ° c), which After cooling and precipitating the crystal fine particles, #过; considering the reduction >1 drying', the crystallized polyethylene terephthalate resin fine particles (referred to as PET_Nc) 2). The reconstituted example 3 is shown in Table 1. The polyethylene terephthalate was used as the raw material, and the solvent was changed to N-methyl 2 - ketone ketone (boiling point 2 hunger), and the rest was carried out in the same manner as in Production Example 2 to obtain Crystalline poly(ethylene terephthalate) resin fine particles (referred to as PET-No. 3). I. Example 4 聚 Polybutylene terephthalate resin using the raw material composition shown in Table 1, the resin Mixed with "Caf" (commodity name, manufactured by American DuPont, mixed with monomethyl monomethyl methacrylate, dimethyl glutarate and dimethyl succinate; The boiling point of 205. 〇 400 parts together with the mixing, and heated to dissolve, and then put into the 5 〇〇 之 环 环 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Crystalline polybutylene terephthalate fine particles (referred to as PBt_n〇.i) were obtained. Production Example 5 Using the poly(p-butylene dicarboxylate) resin having the composition shown in Table 1, the rest and the production examples 4 was carried out in the same manner to obtain a crystalline poly(terephthalic acid) 20-butyl diester resin fine particle (referred to as ΡΒΤ-Νο. 2). Table 1 shows each of the crystalline polyethylene terephthalate obtained in Production Example 1.5. The raw material composition of the diester resin microparticles and the crystalline polybutylene terephthalate resin microparticles, as well as the resin intrinsic viscosity, the glass transition temperature, the melting point and the volume average particle diameter. 26 __Production Example Resin Microparticle Name [Form Π PET -No. 1 2 PET-

No.2 3 PET-

No.3 4 PBT-

No.l 5 PBT-

No.2 Ethanol 00 00 00 4- bismuth alkanoate to acid dimethyl benzoic acid 00 5 8 o lx 00 0, 1«* Resin characteristics Sebacic acid conversion temperature (°c) Melting point (°c) Volume Average particle size (Mm) 0.8 0.9 0.9 1.1 71 223 8.6 60 209 3.4 74 35 25 255 223 217 5.6 6.6 5.5 iMMl__Manufacture of can coating composition No.l PET-No. 1 shown in Table 1 : 50 parts , PBT-No. 1 : 50 copies, "DBE" (trade name, manufactured by DuPont): 5 copies, "BYK-161" (Note 1): 5 copies (solid part) and "School" CKS394" (Note 2): 2 parts (solid part), mixed with a paint shaker for 60 minutes to disperse, by cyclohexanone / mercaptoethyl ketone (50/50 mass ratio), after adjusting the solid part That is, 12% of the solid portion was obtained as the can coating composition No. 1 of the present invention. (Note 1) and (Note 2) are as follows. (Note 1) "BYK-161": a product name, a dispersant of a polyurethane resin manufactured by BYK Chemie Co., Ltd., and an amine price of llmgK〇H/g. (Note 2) "Choltor CKS394": The product name, the Japanese company Showa Polymer Co., Ltd., and the phenolic phenol resin. Examples 2 to 8 Manufactured coating composition No. 2 to No. 8 In the same manner as in Example 1, except that the contents of the formulation of Table 2 were used, the coating composition for cans of the present invention of 27% to 12% of the solid portion was obtained. N〇.2~No.8. [Table 2] - Example 1 2 3 4 5 6 7 8 Coating composition No. 1 2 3 4 5 6 7 8 Resin microPET-No. 1 50 30 10 95 PET-No. 2 80 30 30 50 PET-No.3 40 10 20 Rouge micro^J(B) PBT-No. 1 50 60 30 70 40 50 PBT-No.2 20 10 20 5 Organic soluble jyc) N-mercapto-2-pyrrolidone 200 100 100 50 100 40 TDBEJ 500 300 200 100 200 100 300 10 Tree Moon "GK-640" (Note 3) 60 10 100 Dispersion ΓΒΥΚ-161" (Note 1) 5 5 3 5 2 Agent (E) 2- Ethylhexyldiphenyl phosphate 3 3 Joel CKS394" (Note 2) 2 5 3 5 Dilution solvent 3 hexanone / decylethyl hydrazine) Appropriate amount of 'Resin (D) and dispersant (E) The blending ratio indicates the solid portion (parts). Also, the following is "GK-640" (Note 3). (Note 3) "GK-640": A non-crystalline polyester resin of the product name, manufactured by Toyobo Co., Ltd., and a glass transition temperature of 79 °C. In the same manner as in the first embodiment, the coating material composition No. 9 to Nn 11 was prepared in the same manner as in the first embodiment. .9~No. 11. 28 1338707 [Table 3] Comparative Example 1 2 3 Can coating composition No. 9 10 11 Resin fine particles (A) PET-No. 1 50 PET-No. 2 100 PET-No. 3 20 Resin fine particles (B) PBT -No.l 50 PBT-No.2 80 Organic solvent (C) N-mercapto-2-»pyrrolidone 200 50 fDBEj 20 200 Resin (D) "GK-640" (Note 3) Dispersant (E) ) "BYK-161" (Note 1) 5 2-Ethylhexyl diphenyl phosphate 5 "Herore CKS394" (Note 2) 3 2 Dilution solvent (cyclohexanone / methyl ethyl ketone) Appropriate amount Membrane Performance Test The coating performance tests were carried out on the can coating compositions 5 No. 1 to No. 11 obtained in Examples 1 to 8 and Comparative Examples 1 to 3. The test was carried out in such a manner that the coating composition for the can was coated by a bar coating method on a surface treated with zinc phosphate and having a thickness of 0.32 mm (200 mm x 300 mm) to form a dry thickness to form 100 mg/lOOcm2. The test was carried out at 280 ° C for 17 seconds, and the test plate was used, and the film appearance, D&I processability, steam sterilization resistance, flavor adsorption and hygienic coating were carried out according to the following 10 methods. Performance Testing. Appearance of coating film: The appearance of the coating film of each of the coated aluminum sheets obtained above was evaluated by visual observation and using the following criteria. ◎: Coating film 15 which is transparent, uniform, and smooth. 〇: Transparent and uniform, but the smoothness of the coating film is slightly poor △: The coating film is opaque, and the smoothness of the coating film is poor. 29 1338707 χ: The embossing is clearly visible Or crack, the appearance of the coating film is broken and not consistent D&I processability: the resin coating surface of each film is made into the inner surface of the can after processing, and the metal sheet deep drawing tester type 142 manufactured by Foreign Inkerson Co., Ltd. is used. From the original plate diameter of 82 mm, the five-stage process of 5 shown in the following Table 4 was sequentially performed, and finally, the "extraction smooth tank" having an elongation ratio of about 37% and an extraction smoothness ratio of about 60% was produced. [Table 4] Thin layer holder pressure die clearance processing speed (Kg) (mm) (mm) (mm/sec) Phase 1 500 50 0.2 800 Phase 2 500 40 0.2 800 Phase 3 200 30 0.2 800 Stage 4 200 30 0.15 800 Stage 5 200 30 0.1 800 The resulting drawn smooth can was cut open and the machined surface evaluated on the following basis. 10 ◎: There are no defects such as cracks on the film, and a smooth surface is processed. There is no smooth surface of the film without cracks. △: Defects such as cracks can be seen on the film. X: Peeling of the film during processing and Shedding, failure to process, steam sterilization resistance: The whitening state of the film which was immersed in water in a high-pressure 15 kettle at 125 ° C for 30 minutes was evaluated by the following criteria. ◎: There is no albino cockroach: only a little whitening △: a little whitening 30 1338707 χ: There is a whitening phenomenon Aroma retention: Add d-limonene (fragrance) 30mg/l "S in non-ionized water (pure water) Φ W -1170" (trade name, 曰 曰 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二The M35 C was immersed in the test plate for one month and stored. After storage, * τ was measured by adsorption of d-limonene (perfume) in the Dian group in diethyl ether, and measured by gas chromatography. d. The following criteria were evaluated.

After 1 week, the limonene (fragrance) is taken, and the weight of the coating film per 120 mg of the weight of the coating is as follows: 10 △: The weight of the coating film is 12 〇mg, and the d-limonene is extracted. 6. 6mg or more and 1.6mg or less; X: coating film weight per 120mg, d-limonene is 1611^ or more. Hygiene: soak the test plate in a hot glass plate-making can with a tap water that is filled with activated carbon and is subjected to activated carbon treatment per 1 cm 2 of the coated area of the test plate to become a 15 ml tap water. The lid was placed in a steam kettle at 125 ° C for 30 minutes. The hygienicity was evaluated against the treated internal solution according to the test method contained in the Japanese Food Sanitation Law and based on the consumption of potassium permanate (ppm). ◎: consumption is 2 ppm or less; 2〇 〇: consumption is 2 ppm or more and 5 ppm or less; Δ: consumption is 5 ppm or more and 10 ppm or less; χ: consumption is 10 ppm or more. The film performance test results are shown in Table 5. 31 [Table 5] Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 Can coating composition No. 1 2 3 4 5 6 7 8 9 10 11 Appearance of coating film function 〇 ◎ 〇 ◎ ◎ ◎ ◎ 〇 XX ◎ D&I processability ◎ 〇 ◎ ◎ ◎ ◎ ◎ 〇 XX 〇 蒸气 蒸气 杀菌 ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 X 〇 保 保 保 卫生 X Hygienic ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇〇〇 Δ 1338707 I: Simple description of the figure 3 No [Main component symbol description] Benefit * *»>

32

Claims (1)

1338707 X. Patent application scope: 1. Paint composition for cans, including: • Crystalline polyester resin microparticles (A), which are mainly composed of ethylene terephthalate units; 5 Crystalline polyester Resin microparticles (B), which are mainly composed of butylene terephthalate; and organic solvent (C), are used for solubility with respect to the microparticles (A) and relative to the microparticles (B) The solubility of any of the solubility is less than 5% by mass in the case of rc or less, and is greater than or equal to 5% by mass in the case of 17 〇〇c or more, and the ratio of the fine particles (A) to the fine particles (B) is The former accounts for 95% by mass to 30% by mass, and the latter accounts for 5% by mass to 7% by mass, and the total amount of the fine particles (A) and the fine particles (B) is 1 〇〇. The organic solvent (C) content is 4 parts by mass to 8 parts by mass. 15 2. The can coating composition of the first aspect of the patent, wherein the crystalline type: polyester resin fine particles (A) The resin has an intrinsic viscosity of 0.4 dl/g to l_4dl/g and a glass transition temperature (Tg) of 55 to 13 Art, melting point (Ding is 160C ~ 260〇C 〇3. The can coating composition of the scope of the patent application, wherein the crystalline 20 polyester resin microparticles (A) are made of ethylene terephthalate The composition of the polyester resin having a unit content of 80 mol% or more. 4. The can coating composition according to claim 1, wherein the crystalline polyester resin microparticle (B) has a resin inherent viscosity of 〇4. Di/g~1.4dl/g, glass transition temperature (Tg) is 〇~4〇r, melting point (1^) is 13〇, it is 33~25 (TC. 5. Can coating as described in claim 1 In the composition, the crystalline polyester resin fine particles (8) are composed of a polyester resin having a unit content of 90 mol% or more of terephthalic acid terephthalate. a coating composition further comprising a non-crystalline polystyrene resin (D), and the amorphous polyester resin is added to the total amount by weight of the crystalline polyacetal resin microparticles (4) and the crystalline polystyrene microparticles (B). (D) 0.1 parts by mass to 100 parts by mass. 7 _ Can coating group according to item 6 of the patent application scope The glass transition temperature (Tg) of the amorphous polyester resin (D) is 55 to 15 Å. 8. The can coating composition according to claim 1, further comprising a dispersing agent (6). 9. The can coating composition according to claim 8, wherein the dispersing agent (E) is a phosphoric acid compound represented by the general formula (1), and the general formula (1) is: Ο r1〇_P_〇 R3 (1) [Structure 1] OR2 (wherein R1, R2 and R3 are the same or different, aliphatic or carbonized with 6 to 18 carbon atoms or an aromatic hydrocarbon); here, m and η It is an integer of 1 or more, and the claw +11 is an integer of 6 or more). 10. The can coating composition according to the ninth aspect of the invention, further comprising a phenolic road type phenol resin, and the fine particles of the above-mentioned crystalline polyester resin (Α) and the aforementioned crystalline polyester resin fine particles (Β) In total of 100 parts by mass, the phenolic acid type phenol resin accounts for 0.1 to 1 part by mass. 34 1338707 11. The can coating composition according to claim 1, further comprising an epoxy resin and having a total mass of 100% with respect to the crystalline polyester resin microparticles (A) and the crystalline polyester resin microparticles (B) The epoxy resin accounts for 0.5 parts by mass to 20 parts by mass. Zero J 5 12. A coated metal sheet is baked on at least one side of a metal sheet and coated with a can coating composition of the first application of the scope of the invention. 13. The can body is obtained by subjecting the coated surface of the coated metal sheet of claim 12 to the inner surface of the can, and performing the drawing processing or drawing and smoothing. 10 35