WO2013111814A1 - 塗料組成物、これを含有する缶用塗料、及び該缶用塗料を塗装した缶内面被覆用塗装金属材料 - Google Patents
塗料組成物、これを含有する缶用塗料、及び該缶用塗料を塗装した缶内面被覆用塗装金属材料 Download PDFInfo
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- WO2013111814A1 WO2013111814A1 PCT/JP2013/051440 JP2013051440W WO2013111814A1 WO 2013111814 A1 WO2013111814 A1 WO 2013111814A1 JP 2013051440 W JP2013051440 W JP 2013051440W WO 2013111814 A1 WO2013111814 A1 WO 2013111814A1
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- WIPO (PCT)
- Prior art keywords
- coating
- polyester resin
- coating film
- parts
- resin
- Prior art date
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Classifications
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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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Definitions
- the present invention relates to a resin composition for paints used for interior paints such as beverage cans and food cans.
- beverage cans, food cans, and lids are coated with an organic film to prevent the corrosion of metals caused by food (corrosion resistance and sulfur resistance) and to preserve the taste and flavor of the contents.
- organic solvent-type paints such as paints using bisphenol A type epoxy resin as a main resin and phenol resin as a curing agent and vinyl organosol type paints have been generally used as inner surface paints.
- the polymer linear polyester resin-based paint has the characteristics that it is excellent in adhesion to the metal material as the base, the flavor retention of the coating film, and the coating film hardness.
- an invention has been made to contain a certain amount of a specific monomer (1,4-butanediol, 1,4-cyclohexanedimethanol) in order to avoid a decrease in processability during storage, but it was insufficient. (For example, patent document 2).
- the subject of the present invention is used notably for inner coatings of beverage cans, food cans and the like, and not only suppresses crystallization of the coating film, which is a cause of processability deterioration, but also imparts suppression of internal stress and elongation of the coating film.
- An object of the present invention is to provide a coating composition having excellent coating film processability.
- the present inventors can increase the molecular weight of the main polyester resin by adding a polyester resin having a low glass transition temperature (Tg) without defining the composition of the main polyester resin.
- Tg glass transition temperature
- the present invention has found a coating composition that can impart elongation to the coating film and can impart higher workability.
- the ratio [(A) / (B)] (weight ratio) of the polyester resin (A) having a Tg of 0 ° C. or more and the polyester resin (B) having a Tg of less than 0 ° C. is 95/5 to 60 / 40 to 100 parts by weight of a polyester resin composition, 1 to 100 parts by weight of a resol type phenol resin (C), a paint for cans containing the paint composition, and for cans Provided is a coated metal material for coating the inner surface of a can having a cured coating film obtained by curing a coating film of a paint.
- the low Tg polyester resin as an essential component according to the present invention, the deterioration of workability over time, which has been a problem with polyester resin / phenolic resin-based coatings from the prior art, without impairing the properties as a coating film for beverage can inner surfaces. It is possible to obtain a coating composition that overcomes the above.
- the polyester resin (A) used in the coating composition of the present invention preferably has a number average molecular weight of 1,000 or more from the viewpoint of good processability, and can be appropriately coated without excessively increasing the viscosity during coating. Therefore, the number average molecular weight is preferably 100,000, and more preferably 6,000 to 30,000.
- the glass transition temperature is preferably 0 ° C. to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 30 to 90 ° C.
- the barrier properties such as water vapor and oxygen are inferior, so that the corrosion resistance of the coating film is inferior and the blocking property is also inferior.
- the glass transition temperature is higher than 100 ° C., the coating film becomes hard and workability deteriorates.
- the polyester resin (A) may be any resin obtained by esterifying a polybasic acid component and a polyhydric alcohol component.
- the polybasic acid component include one or more dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dimer acid, and the like.
- the lower alkyl esterified products are mainly used, and if necessary, monobasic acids such as benzoic acid, crotonic acid, pt-butylbenzoic acid, trimellitic anhydride, methylcyclohexeric tricarboxylic acid, pyromellitic anhydride, etc.
- a tribasic or higher polybasic acid is used in combination.
- polyhydric alcohol component examples include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, cyclohexanedi
- a dihydric alcohol such as methanol is mainly used, and a trihydric or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol can be used in combination as necessary.
- These polyhydric alcohols can be used alone or in admixture of two or more.
- Examples of commercially available products include Byron 300, 500, 560, 600, 630, 650, 670, Byron GK130, 140, 150, 190, 330 manufactured by Toyobo Co., Ltd. 590, 680, 780, 810, 890, 200, 226, 240, 245, 270, 280, 290, 296, 660, 885, Byron GK250, 360, 640, 880, Elitel UE-3220 manufactured by Unitika Ltd., 3500, 3210, 3215, 3216, 3620, 3240, 3250, 3300, UE-3200, 9200 3201, 3203, 3350, 3370, 3380, 3600, 3600, 3980, 3660, 3690, 96 0, the same 9800, Toagosei Co., Ltd. Aron Melt PES-310, the 318, the 334, the 316, such as the 360, and the like.
- the content of the polyester resin (B) having a Tg of less than 0 ° C. used in the coating composition of the present invention is 5 to 40 parts by weight, preferably 10 to 30 parts by weight.
- the glass transition temperature is preferably ⁇ 5 to ⁇ 40 ° C., more preferably ⁇ 10 to ⁇ 30 ° C. When the glass transition temperature is close to 0 ° C., the effect of the invention tends to be small. When the glass transition temperature is lower than ⁇ 30 ° C., the handling property is deteriorated and the blocking property is also adversely affected.
- polyester resin (B) having a Tg of 0 ° C. or less used in the coating composition of the present invention commercially available products are Byron 516, 550, BX-1001, GM900, and GM920 manufactured by Toyobo Co., Ltd. GM913, GM420, GA1300, GA3200, GA5300, GA5410, GA6300, GA6400, Aronmelt PES-110H, 120H, 140F, 340 manufactured by Toa Gosei Co., Ltd., and the like.
- the content of the resol-type phenol resin crosslinking agent (C) is 1 to 100% by weight, preferably 20 to 80 parts by weight.
- Examples of the resol type phenol resin cross-linking agent (C) used in the coating composition of the present invention include trifunctional phenolic compounds such as carboxylic acid, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol. Or various bifunctional phenols such as p-cresol, o-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol, m-methoxyphenol, and formaldehyde Is synthesized in the presence of an alkali catalyst. These phenol compounds can be used alone or in admixture of two or more. Further, it is also possible to use a form in which some or all of the methylol groups contained in the phenol resin are etherified with alcohols having 1 to 12 carbon atoms.
- the coating composition of the present invention can further contain an acid catalyst (D) that accelerates the curing reaction.
- an acid catalyst (D) for example, inorganic acids such as phosphoric acid, organic acids such as dodecylbenzenesulfonic acid and toluenesulfonic acid, and those blocked with an amine or the like can be used.
- the content of the acid catalyst (D) is 0.1 to 5 parts by weight, preferably 0.2 to 3.0 parts by weight.
- the coating composition of the present invention can be preferably used particularly for can coatings. Furthermore, it can be used as a coating agent for various metal materials such as aluminum and tin-plated steel sheets or pretreated metals and steel, and other materials and processed products such as wood and films. Good. Hereinafter, the use as a paint for cans will be described.
- the solvent that can be used in the paint using the paint composition of the present invention is not particularly limited.
- aromatic hydrocarbons such as toluene, xylene, Solvesso # 100, Solvesso # 150, hexane, heptane, octane
- Examples include aliphatic hydrocarbons such as 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, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, and ethylene Glycol monopropyl 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 monobutyl ether, dipropylene glycol (mono, di) include various organic
- lubricants Various kinds of lubricants, antifoaming agents, leveling agents, lubricants, pigments and the like can be added to the can coating materials using the coating composition of the present invention.
- other curing agents such as melamine resin, benzoguanamine resin, and isocyanate resin may be used in combination as curing aids, and these can be used in combination with paint drying conditions, baking conditions, and curing conditions. It is.
- the paint for cans using the coating composition of the present invention is a spray coating, immersion coating, roll coater coating, gravure coater and electrodeposition coating, such as air spray, airless spray or electrostatic spray, It can be applied as a metal substrate such as a steel plate or an aluminum plate for cans or a paint such as a PET pet film.
- the coating amount is preferably about 0.1 to 20 ⁇ m in terms of dry film thickness.
- the resin composition of the present invention when used as a can coating, it is preferably baked within a range of 100 to 280 ° C. for 1 second to 30 minutes.
- a coated metal material for coating the inner surface of the can By forming a coating film, a coated metal material for coating the inner surface of the can can be obtained.
- Example Synthesis Example 1 As an acid component, 106 parts of terephthalic acid, 225 parts of isophthalic acid, 4 parts of trimellitic anhydride, 143 parts of 2-methyl-1,3-butanediol, 86 parts of 1,4-butanediol, 1, The flask was charged with 92 parts of 4-cyclohexanedimethanol and 0.13 part of titanium tetrabutoxide, and the temperature was gradually raised to 220 ° C. over 4 hours to distill water and perform esterification.
- the polymerization was carried out under reduced pressure to 10 mmHg over 30 minutes, the temperature was raised to 250 ° C., and the latter polymerization was carried out at 1 mmHg or less for 50 minutes.
- polyester resin GK-880 (A2, Tg: 84 ° C., Mn: 18000) manufactured by Toyobo Co., Ltd.
- 150 parts of Solvesso-150 and 150 parts of cyclohexanone are placed in a four-necked flask and heated to 80 ° C. After warming, the temperature was kept for 2 hours, and after confirming that the resin was completely dissolved, the resin was cooled to room temperature to obtain a solution having a GK-880 solid content of 40%.
- Resin Solution-A2 Similarly, a 40% solid solution (resin solution-A3) of GK-360 (A3, Tg: 56 ° C., Mn: 16000) manufactured by Toyobo Co., Ltd. was obtained.
- test coating plate was cut into 40 mm x 50 mm, and a test coating plate was formed by folding it in a V-shape with a bending tester so that the coating surface was on the outside, and the thickness between the test pieces was 0.26 mm
- Two aluminum plates were placed on a testing machine, and a weight of 3 kg was dropped from a height of 50 cm to obtain a test piece.
- the outer side of the bent part of this test piece was pressed against a sponge soaked with 1% saline, and the test piece was energized for 6 V ⁇ 3 seconds, and the current value was measured using a SONCON enamelator (electricity tester). Evaluation was made according to the following four stages.
- the coated plate was placed in a constant temperature storage at 40 ° C. and stored for 15 days and 30 days, and then evaluated by the same test method as the initial workability.
- the test solution is filled into a 350 ml can at low temperature, and then the above lid-processed lid is wrapped, heated once to 60 ° C., and stored at 37 ° C. for one month. Thereafter, 20 cans were opened, and the inner surface side of the lid was observed to evaluate the presence or absence of corrosion according to the following four steps.
- the DSC of the coating film was measured with a DSC measuring instrument (Differential Scanning Calorimetry) manufactured by Mac Science Co., Ltd.
- Tables 1-1 and 1-2 show the paint compositions and evaluation results described in Examples 1 to 8.
- Table 2 shows the paint compositions and evaluation results described in Comparative Examples 1 to 4.
- the resin composition of the present invention does not contain bisphenol A, which may adversely affect the human body in terms of estrogen action, etc., and has good workability, coating film hardness, curability, and retort resistance and corrosion resistance. And can be widely used as a paint for various cans having excellent content retention.
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Abstract
Description
また、ガラス転移温度は、0℃~100℃であることが好ましく、より好ましくは、10~90℃であり、更に好ましくは30~90℃である。ガラス転移温度が0℃より低いポリエステル樹脂を主樹脂として使用すると水蒸気、酸素等のバリアー性が劣るために塗膜の耐食性が劣り、またブロッキング性も劣るようになる。一方、ガラス転移温度が100℃より高いと、塗膜が硬くなり加工性が悪くなる。
酸成分として、テレフタル酸106部、イソフタル酸225部、無水トリメリット酸4部、多価アルコール成分として2-メチル-1,3-ブタンジオール143部、1,4-ブタンジオール86部、1,4-シクロヘキサンジメタノール92部、チタンテトラブトキシド0.13部をフラスコに仕込み、4時間かけて220℃まで徐々に昇温し、水を留出させエステル化を行った。所定量の水を留出させた後、30分かけて10mmHgまで減圧重合行うとともに温度を250℃まで昇温し、更にこのまま1mmHg以下で50分間後期重合を行った。減圧重合を終了させたのち、樹脂を取り出し数平均分子量20,000、酸価19(mgKOH/g)、ガラス転移温度30℃のポリエステル樹脂(A1)を得た。この後、100℃以下まで冷却し、シクロヘキサノン/ソルベッソ150=50/50の混合溶液で希釈し、不揮発分40%のポリエステル樹脂溶液(樹脂溶液-A1)を得た。
東洋紡績(株)社製ポリエステル樹脂GK-880(A2、Tg:84℃、Mn:18000)を200部、ソルベッソ-150を150部、シクロヘキサノン150部を4つ口フラスコに入れ、80℃に加温後2時間保温し樹脂が完全に溶解したのを確認した後室温まで冷却し、GK-880固形分40%の溶液を得た。(樹脂溶液-A2)同様に東洋紡績(株)社製GK-360(A3、Tg:56℃、Mn:16000)の固形分40%の溶液(樹脂溶液-A3)を得た。
東洋紡績(株)社製ポリエステル樹脂GA6400(B1、Tg:-20℃)を200部、ソルベッソ-150を150部、シクロヘキサノン150部を4つ口フラスコに入れ、80℃に加温後2時間保温し樹脂が完全に溶解したのを確認した後室温まで冷却し、GA6400固形分40%の溶液を得た。(樹脂溶液-B1)
同様にGA5410(B2、Tg:-3℃)の固形分40%の溶液(樹脂溶液-B2)、BX-1001(B3、Tg:-18℃)の固形分40%の溶液(樹脂溶液-B3)を得た。
樹脂溶液-A1(固形分 40%) 55.0部
樹脂溶液-B1(固形分 40%) 6.0部
フェノール樹脂(C)DIC製TD-2495 (固形分 50%)9.6部
シクロヘキサノン 15.0部
MIBK(メチルイソブチルケトン) 14.3部
酸触媒(D)ドデシルベンゼンスルホン酸 0.1部
合計 100.0部
上記比率にて樹脂溶液ならびに溶剤、酸触媒を混合し実施例-1溶液を得た。
厚さが0.26mmである5182材のアルミニウム板上に、乾燥塗膜の重量が70mg/dm2となるように、バーコーターを用いて、各実施例で得られた、それぞれの塗料を塗布し、オーブン通過時間が23秒でPMTが250℃となるオーブン条件にて焼き付けたのち、室温まで冷却して、試験用塗装板とした。
試験用塗装板を40mm×50mmに切断し、塗膜面が外側になるように折り曲げ試験機にてV字に2つ折りにした試験塗板を作成し、この試験片の間に厚さ0.26mmのアルミニウム板を2枚挟んで試験機に設置し、重さ3kgの錘を高さ50cmから落下させ試験片を得た。
この試験片の折り曲げ部の外側を、1%食塩水をしみ込ませたスポンジに押し当て試験片に6V×3秒間通電させSENCON製エナメルレーター(通電試験機)を用い電流値を測定した。次に示すような4段階によって評価した。
◎………電流値が1mA未満である
○………電流値が1mA以上~5mA未満である
△………電流値が5mA以上~10mA未満である
×………電流値が10mA以上である。
試験用塗装板作成後、直ちに塗装板を40℃恒温庫に入れ15日間ならびに30日間貯蔵経時させた後、初期加工性と同一の試験方法にて評価を実施した。
試験用塗装板に形成された塗膜に、カッターで1×1mmの碁盤目を100個作成し、この試料片を125℃で30分間熱水処理した。その後碁盤目部分に、粘着テープを貼ったのち、粘着テープを急速に剥離し、塗膜の剥離状態を観察し、次に示すような4段階によって評価した。
◎………剥離が全くない
○………全体の1~2%が剥離した
△………全体の3~10%が剥離した
×………全体の11~100%が剥離した。
100ミリリットルの精製水中に、160cm2なる上記試験用塗装版を浸漬し、125℃で0.5時間の熱水処理を行ったのちの、過マンガン酸カリウム消費量を測定し、次に示すような4段階によって評価した。
◎………消費量が3ppm未満である
○………消費量が3ppm以上~5ppm未満である
△………消費量が5ppm以上~10ppm未満である
×………消費量が10ppm以上である。
製蓋加工せしめた蓋を100℃で10分間熱水処理した後、蓋のタブを引き上げ、開口した際の開口部内面塗膜の膜残り幅を、次に示すような4段階によって評価した。
◎………膜残り幅が0.2mm未満である
○………膜残り幅が0.2mm以上~0.4mm未満である
△………膜残り幅が0.4mm以上~0.6mm未満である
×………膜残り幅が0.6mm以上である
試験用塗装板を立ててビーカーに入れ、これにイオン交換水を試験片の半分の高さまで入れる。これを圧力釜に入れ、125℃×30分間のレトルト処理を行い、目視にて評価を行う。
◎………良好
○………わずかに白化はあるがブリスターはない
△………若干の白化または若干のブリスターあり
×………白化またはブリスターあり
試験液を低温で350mlの缶に充填後、上記製蓋加工した蓋を巻き締め、60℃に一度加温した後一ヶ月間37℃で保存する。その後20缶を開缶して蓋の内面側を観察して腐食の有無を、次に示すような4段階によって評価した。試験液は0.5%クエン酸+0.5%食塩水溶液を用いた。
◎………全ての蓋に腐食が全く見られない
○………一部の蓋に小さな腐食が見られる場合がある
△………全ての蓋に小さな腐食が必ず見られる
×………全ての蓋に多くの腐食が見られ
上記アルミ板に、乾燥塗膜の重量が70mg/dm2となるように、内外面共バーコーターを用いて塗料を塗布し、同条件で焼き付けし、試験用塗装板とした。500mlのガラスビンに表面積が500cm2の試験用塗装板とスポーツドリンクを低温で充填後、75℃に一度加温し、遮光して一ヶ月間37℃で保存した。比較対照用に塗装板を入れないブランクも用意した。スポーツドリンクのフレーバー保持性を次に示すような4段階によって評価した。
◎………比較対照と比べて差が見られない
○………比較対照と比べて僅かにフレーバーの劣化が見られる
△………比較対照と比べてフレーバーの劣化が見られる
×………比較対照と比べて著しくフレーバーの劣化が見られる。
(株)マック・サイエンス社製DSC測定器(示差走査熱量測定:Differential Scanning Calorimetry)にて塗膜のDSCを測定。乾燥塗膜を40℃にて30日間貯蔵経時させた後に2度続けて測定し、両者のチャートが同じか否かの評価を行う。これは塗膜の結晶化が進行した場合、加熱により結晶構造が崩れ1回目の測定で発現したピークが2回目には発現しなくなるためである。
○・・・・・1回目と2回目のピークが同じ
×・・・・・1回目と2回目のピークが異なる
FSB法(参考文献:色材協会誌、70〔10〕、650-655(1997))にて内部応力を測定。これは、塗膜の結晶化が進行した場合に内部応力が発生するためである。なお、乾燥後の塗膜重量は200mg/dm2にて試験を実施した。
○・・・・・乾燥塗膜を30日間貯蔵経時後に内部応力が発生しない
×・・・・・乾燥塗膜を30日間貯蔵経時後に内部応力が発生
Claims (5)
- ガラス転移温度(以下Tg)が0℃以上のポリエステル樹脂(A)とTgが0℃未満のポリエステル樹脂(B)の重量比〔(A)/(B)〕が95/5~60/40であるポリエステル樹脂組成物100重量部に対し、レゾール型フェノール樹脂(C)が1~100重量部含有することを特徴とする塗料組成物。
- さらに、酸性硬化触媒を請求項1の樹脂組成物に対し、0.1~5.0重量部の範囲で含有する塗料組成物。
- DSC(示差走査熱量測定:Differential Scanning Calorimetry)測定にて20℃~80℃の範囲に塗膜の経時による結晶化由来の吸熱ピークが発現しない請求項1または2に記載の塗料組成物。
- 請求項1~3の何れか1つに記載の塗料組成物を含有する缶用塗料。
- 金属材料表面に請求項4記載の缶用塗料の塗膜を硬化させた硬化塗膜を有する缶内面被覆用塗装金属材料。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13740640.1A EP2808367A4 (en) | 2012-01-27 | 2013-01-24 | COATING COMPOSITION, COATING FOR CANNING BOX CONTAINER AND METALLIC COATING MATERIAL FOR INTERNAL SURFACE COATED THEREWITH |
CN201380006829.6A CN104080867A (zh) | 2012-01-27 | 2013-01-24 | 涂料组合物、含有其的罐用涂料、及涂装有该罐用涂料的罐内面被覆用涂装金属材料 |
US14/374,684 US20150034522A1 (en) | 2012-01-27 | 2013-01-24 | Coating material composition, can coating material containing the same, and metal material with coating formed by the can coating material for can interior surfaces |
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JP2012015226 | 2012-01-27 | ||
JP2012-015226 | 2012-01-27 |
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WO2013111814A1 true WO2013111814A1 (ja) | 2013-08-01 |
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PCT/JP2013/051440 WO2013111814A1 (ja) | 2012-01-27 | 2013-01-24 | 塗料組成物、これを含有する缶用塗料、及び該缶用塗料を塗装した缶内面被覆用塗装金属材料 |
Country Status (5)
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US (1) | US20150034522A1 (ja) |
EP (1) | EP2808367A4 (ja) |
JP (1) | JPWO2013111814A1 (ja) |
CN (1) | CN104080867A (ja) |
WO (1) | WO2013111814A1 (ja) |
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Also Published As
Publication number | Publication date |
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EP2808367A4 (en) | 2015-08-19 |
US20150034522A1 (en) | 2015-02-05 |
CN104080867A (zh) | 2014-10-01 |
JPWO2013111814A1 (ja) | 2015-05-11 |
EP2808367A1 (en) | 2014-12-03 |
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