JP5586362B2 - Resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin composition used for film adhesives or film coatings on the inner and outer surfaces of trunks and lids of laminate-type beverage cans, food cans and the like.

  Conventionally, film adhesives using bisphenol A type epoxy resin have been widely used for laminated beverage cans and food cans, but bisphenol A can affect estrogen action and the brain of fetuses and infants. It has been reported that there is sex.

  The resin composition using the above-described bisphenol A type epoxy resin is widely used because it has excellent processability, retort resistance, corrosion resistance, and the like. Although an adhesive for a film having a resin composition that does not use bisphenol A as a raw material is demanded from the market, the actual situation is that satisfactory performance as a can application cannot be obtained. Furthermore, the laminated cans that bond the current film to the metal are subjected to post-heat treatment at 200 ° C for several seconds to several minutes after the film lamination, so that the adhesive coating cures in this process and the necessary performance such as retort resistance Is obtained. However, there are problems such as an increase in energy cost and an increase in carbon dioxide emission due to the subsequent heat treatment.

  Examples of thermosetting adhesives for bonding a plastic film to a metal material include polyester / amino adhesives (for example, see Patent Documents 1, 2, and 3) and polyester / block isocyanate adhesives (for example, Patent Documents 2, 3). 4, 5, 6, 9), epoxy / block isocyanate-based adhesive (see, for example, Patent Documents 7 and 8), epoxy / phenol-based adhesive (see, for example, Patent Documents 9 and 10), epoxy / acid-based adhesive Agents (see, for example, Patent Documents 11 and 12) have been reported.

JP 2005-162960 A JP 2000-319363 A JP 2000-328033 A JP-A-11-199851 JP 2004-107409 A JP 2001-123142 A JP 2001-107015 A JP-A-9-279117 JP 2002-206079 A Japanese Patent No. 4006609 Japanese Patent No. 3407551 Japanese Patent No. 3521929

The object of the present invention is particularly used for film adhesives or film coatings on the inner and outer surfaces of trunks and lids of laminate-type beverage cans, food cans, etc., and is particularly excellent in curability and cures the film with very little heat energy. Another object of the present invention is to provide a resin composition that has excellent adhesion, workability, retort resistance, and corrosion resistance and does not contain bisphenol A as a raw material.

  The present inventors have very little reaction by reacting the polyester resin (A), the phenol resin (B), the metal alkoxide compound and / or the metal chelate compound (C) and the epoxy resin (D) not containing bisphenol A. The film is cured by thermal energy, and has excellent adhesion, workability, retort resistance, corrosion resistance, and does not contain bisphenol A, and is used for film adhesives or film coatings for food cans and beverage cans. The present inventors have found a resin composition that can be obtained and completed the present invention.

That is, the present invention is a resin composition containing a polyester resin (A), a phenol resin (B), a metal alkoxide compound and / or a metal chelate compound (C) and an epoxy resin (D) not containing bisphenol A. The polyester resin (A) has a glass transition temperature of 0 to less than 35 ° C, a polyester resin (A-1), a polyester resin (A-2) of less than 35 to 65 ° C, and a polyester resin of 65 to 100 ° C. A polyester resin comprising (A-3),
The ratio of the polyester resin (A-1) / the polyester resin (A-2) / the polyester resin (A-3) is 30 to 70/10 to 35/10 to 35, and
The ratio in the total resin solid content is 50 to 80% by mass for the polyester resin (A), 10 to 50% by mass for the phenol resin (B), 0.01 for the metal alkoxide compound and / or the metal chelate compound (C). It is in providing the resin composition characterized by 0.5-10 mass% of epoxy resin (D) which does not contain -10 mass% and bisphenol A.

  The resin composition of the present invention is used as a film adhesive or film coating for beverage cans, food cans, etc., does not contain bisphenol A, and the coating curing reaction proceeds with very little heat energy, adhesion, processing Film having excellent heat resistance, retort resistance, and corrosion resistance can be formed.

  The resin composition of the present invention contains a polyester resin (A), a phenol resin (B), a metal alkoxide compound and / or a metal chelate compound (C), and an epoxy resin (D) not containing bisphenol A. It relates to a resin composition. Hereinafter, the resin composition of the present invention will be described in more detail.

  The polyester resin (A) used in the resin composition of the present invention preferably has a number average molecular weight of 3,000 to 100,000, more preferably 5,000 to 30,000, still more preferably 10,000. Within the range of ~ 25,000. The number average molecular weight is a number average molecular weight in terms of polystyrene of GPC. The glass transition temperature of the polyester resin (A) is preferably in the range of 0 to 100 ° C., but it may be difficult to satisfy many required performances with one kind of polyester resin. When used alone, for example, when the glass transition temperature of the polyester resin (A) is 0 ° C. to less than 35 ° C., the coating film is given flexibility and processability is excellent. The film will block in the wound state. When the glass transition temperature is 35 ° C. to less than 65 ° C., the film is not blocked, and the workability is improved without impairing the aesthetic appearance of the film. When the glass transition temperature is 65 ° C. to less than 100 ° C., the blocking property is excellent, but the workability is somewhat inferior because the film becomes hard. Accordingly, the polyester resin (A) can be used in combination with a plurality of resins having different glass transition temperatures, and by drawing out the good performance of each polyester resin, a balanced and more excellent resin composition can be obtained. That is, polyester resin (A-1) having a glass transition temperature of 0 to less than 35 ° C./polyester resin (A-2) having a temperature of 35 to less than 65 ° C./polyester resin (A-3) having a temperature of 65 to 100 ° C. = 30 When the ratio is in the range of ˜80 / 10 to 35/10 to 35, the balance between workability and blocking property is remarkably improved.

  When the polyester resin (A) contains diphenolic acid as an essential component, the reactivity with the phenol resin increases and the curing rate increases, resulting in improved retort whitening resistance. Moreover, even if it uses polyester (A-1) which made diphenol acid an essential monomer and whose glass transition temperature is 0-35 degreeC in a high ratio, since sclerosis | hardenability improves, a glass transition temperature is low. Both have the feature that the blocking property of the coated film is excellent.

The polyester resin (A) may be any one obtained by esterifying a polybasic acid component and a polyhydric alcohol component.
Examples of 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. Lower alkyl esterified acid is mainly used, if necessary, monobasic acid such as benzoic acid, crotonic acid, pt-butylbenzoic acid, trimellitic anhydride, methylcyclohexericarboxylic acid, pyromellitic anhydride, etc. A tribasic or higher polybasic acid is used in combination.

  Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and 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 the commercially available polyester resin (A) used in the resin composition of the present invention include Byron 300, 500, 560, 600, 630, 650, 670, and 670 manufactured by Toyobo Co., Ltd. Byron GK130, 140, 150, 190, 330, 590, 680, 780, 810, 890, 200, 226, 240, 245, 270, 280, 290 296, 660, 885, Byron GK250, 360, 640, 880, Eritel UE-3220 manufactured by Unitika Ltd., 3500, 3210, 3215, 3216, 3620, 3240 3250, 3300, UE-3200, 9200, 3201, 3203, 3203, 3350, 3370, 3380, 36 0, the 3980, the 3660, the 3690, the 9600, the 9800, manufactured by Toagosei Co., Ltd. Aron Melt PES-310, the 318, the 334, the 316, such as the 360 and the like.

  If only typical examples of the phenol resin (B) used in the resin composition of the present invention are exemplified, carboxylic acid, m-cresol, m-ethylphenol, 3,5-xylenol, m-methoxyphenol, etc. Trifunctional phenolic compounds or various bifunctional compounds such as p-cresol, o-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol, m-methoxyphenol Phenol and formaldehyde are synthesized in the presence of an alkali catalyst. These phenol compounds can be used alone or in admixture of two or more. Moreover, the thing of the form which etherified one part or all part of the methylol group contained in a phenol resin by alcohol with 1-12 carbon atoms can also be used.

  The metal alkoxide compound and / or metal chelate compound (C) that can be used in the resin composition of the present invention includes a polyester resin (A), a phenol resin (B), and an epoxy resin (D) that does not contain bisphenol A. Cause a reaction. A crosslinking reaction proceeds between the functional group of each resin and the metal alkoxide compound and / or metal chelate compound (C). Compared to the case where there is no metal alkoxide-based compound and / or metal chelate-based compound (C), this crosslinking reaction has a significantly faster curing rate, resulting in excellent adhesion and processing with very little heat energy. , Retort resistance and corrosion resistance can be exhibited. For example, existing laminate cans are baked at 180 ° C. or higher for several seconds to several minutes after laminating films, and then the post-heating is used to harden the adhesive coating to bring out the above-mentioned performance. In the adhesive using the resin composition, the adhesive film is sufficiently cured only by momentary heating at the time of laminating, and performance equivalent to or higher than that obtained after post-heating is obtained. Therefore, a post-heating step in the manufacturing process is not required, and the manufacturing efficiency is remarkably improved. In addition, the emission of carbon dioxide can be reduced, which can be a practically extremely useful adhesive. Furthermore, by incorporating a metal in the coating, the strength of the coating is improved, and as a result, the function of dramatically improving impact resistance and corrosion resistance is imparted.

  Examples of the metal alkoxide compound and / or metal chelate compound (C) include alkoxide metal compounds such as aluminum, titanium, tin, and zirconium, and metal chelate compounds in which acetoacetic acid is coordinated to the metal.

  Further, in the resin composition of the present invention, a titanium alkoxide compound and / or a titanium chelate compound (C-1) in which the metal alkoxide compound and / or metal chelate compound (C) is particularly titanium is used. In this case, the film is colored yellow by the interaction with the phenol resin (B).

  For cans and lids of beverage cans and food cans, gold-colored ones are preferred from the viewpoint of design. As a general production example of a laminated can having a gold color, a yellow colored film is bonded to a metal directly or using an adhesive. In this case, the yellow colored film is considerably more expensive than the generally used colorless film, which results in a direct increase in can price.

  In the resin composition of the present invention, when an adhesive using a titanium alkoxide compound and / or a titanium chelate compound (C-1) is used, an inexpensive colorless film is used because the adhesive layer is colored. Even in this case, it is possible to impart the same designability as that when an expensive colored film is used to a beverage can and a food can. As a result, the can price can be reduced, which is extremely useful in practice.

  The epoxy resin (D) containing no bisphenol A used in the resin composition of the present invention mainly improves the adhesion of the coating film, and is particularly preferably a novolac type epoxy resin. As a commercial product of the novolak type epoxy resin, Epicron N-665, 670, 673, 680, 690, 695, 730, 740, 770, 870, 865, manufactured by DIC Corporation 870, ECN-1273 manufactured by Asahi Kasei Epoxy Co., Ltd., ECN-1299 and the like.

  Polyester resin (A) is 50 to 90% by mass, phenol resin (B) is 10 to 50% by mass, metal alkoxide compound and / or metal chelate compound (C) is 0.01 in the ratio in the total resin solid content. It is preferable that the epoxy resin (D) which does not contain -10 mass% and bisphenol A is 0.5-20 mass%. The ratio of the polyester resin (A) is preferably in the range of 55 to 85% by mass. When the ratio of the polyester resin A is lower than 50% by mass, the workability deteriorates, and when it exceeds 85% by mass, the curability is insufficient and the retort resistance is lowered. The ratio of the phenol resin (B) is preferably 20 to 40% by mass, and if it is lower than 10% by mass, the curability is insufficient and the retort resistance is inferior, and if it exceeds 50% by mass, the workability is deteriorated. The ratio of the metal alkoxide compound and / or the metal chelate compound (C) is preferably 0.1 to 7% by mass. If the content is lower than 0.01% by mass, the effect of fast curability expected cannot be obtained, and if it exceeds 10% by mass, the film becomes hard and the workability becomes inferior. The ratio of the epoxy resin (D) not containing bisphenol A is preferably 2 to 7% by mass, and if it is lower than 0.5% by mass, the adhesion is lowered, resulting in poor corrosion resistance and the like, and 20% by mass. If it exceeds 1, retort whitening resistance will be inferior.

  The resin composition of the present invention can further contain a curing catalyst (E). Examples of the curing catalyst (E) include, in particular, typical ones, inorganic acids such as phosphoric acid, organic acids such as dodecylbenzenesulfonic acid and toluenesulfonic acid, and those blocked with amines or the like. Can be used. The mixing ratio of the curing catalyst (E) is preferably 0.01 to 5% in the total solid content.

  Examples of the organic pigment and / or inorganic pigment (F) that can be used in the resin composition of the present invention include chromate (yellow lead, chromium vermillion) ferrocyanide (bitumen), sulfide (cadmium yellow, cadmium). Red), oxide (titanium oxide, bengara, iron black, zinc oxide) sulfate (barium sulfate, lead sulfate), silicate (ultraviolet, calcium silicate), carbonate (calcium carbonate, magnesium carbonate) phosphate (cobalt violet) ) Metallic powder (aluminum powder, bronze) Inorganic pigments such as carbon (carbon black), azo type (benzidine yellow, Hansa Yellow, Vulcan Orange, Permanent Red F5R, Carmine 6B, Lake Red C, Chromothal Red, Chromoval Yellow ), Phthalocyanineline (phthalocyanine blue, lid) Sianiline Green), vat dyes (Induslen Blue, Thioindigo Bordeaux) dyed rakes (Eosin Lake, Quinoline Yellow, Rhodamine Lake, Methyl Violet Lake), quinacrines (Sincacia Red, Shinkasia Violet) Organic pigments such as (PV Fast Violet BL) can be mentioned, and these may be used alone or in combination. These pigments make it possible to color the coating film and impart design properties, and arbitrary organic pigments and inorganic pigments can be added to the required design.

  The blending ratio of the organic pigment and / or inorganic pigment (F) is preferably 0.1 to 70 parts by mass in the total solid content.

  The resin composition of the present invention can be preferably used for an adhesive for laminated cans such as a PET film. Furthermore, it can be used as a coating agent for various materials such as aluminum and tin-plated steel sheets, or pre-treated metals, and other metal materials such as steel, and other materials and processed products such as wood and films. Good. Hereinafter, the use as an adhesive for laminate cans will be described.

  The solvent that can be used for the adhesive for a film using the resin composition of the present invention is not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene, Solvesso # 100, Solvesso # 150, hexane, heptane, etc. And aliphatic organic solvents such as octane and decane, and various 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 cyclohexanone, ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, 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 solvents glycol ether such as methyl ether.

  Conventionally known lubricants, antifoaming agents, leveling agents, pigments, anti-blocking agents such as silica, and the like can be added to the film adhesive using the resin composition of the present invention. In addition, other curing agents such as a melamine resin, a benzoguanamine resin, and an isocyanate resin may be used in combination as a curing auxiliary agent, and these can be used in combination with an appropriate one depending on the drying conditions and lamination conditions of the film.

  The adhesive for film using the resin composition of the present invention can be applied by various means such as air spray, airless spray or electrostatic spray, such as various spray coating, dip coating, roll coater coating, gravure coater and electrodeposition coating. It can be applied as an adhesive to metal substrates such as steel plates and aluminum plates for cans and PET films.

  The dry coating amount of the adhesive for film using the resin composition of the present invention is preferably in the range of 0.1 to 20 μm. If it exists in the range of 0.1-20 micrometers, it is excellent in continuous uniform application | coating property, there is no problem of design property, retort resistance and adhesiveness can be hold | maintained, and the blocking property at the time of film winding is also eliminated. When the thickness is less than 0.1 μm, it is easy to cause difficulty in continuous uniform coating properties, and it is somewhat difficult to develop physical properties and design properties. In addition, the barrier property of water vapor in the pressurized hot water treatment is slightly inferior, moisture tends to stay at the adhesive / plastic film interface, and retort whitening may occur. On the other hand, if it exceeds 20 μm, the solvent detachability after coating is lowered, the workability is remarkably lowered, and the problem of residual solvent is likely to occur, whereby the blocking property at the time of winding the film may be significantly lowered.

  Although it does not specifically limit as a plastic film, It can use with respect to a pet film, a polyethylene-type film, a polypropylene film, a polyvinyl chloride-type film, and an acrylic film. Examples of the steel plate to be laminated include a sheet-shaped or coil-shaped steel plate, steel foil, iron foil, and a steel plate that has been surface-treated. An aluminum plate can be used in addition to the steel plate. In particular, an electrolytic chromic acid-treated steel sheet having an upper layer of chromium hydrated oxide and a lower layer of metallic chromium, ultrathin tin plating, nickel plated steel sheet, galvanized steel sheet, chromium hydrated oxide coated steel sheet or phosphate Examples thereof include steel plates treated with chromate.

  An example of a method of laminating a film coated with an adhesive composition for a plastic film laminated steel plate on a steel plate will be given. An adhesive is uniformly applied to the plastic film so as to have a dry film thickness of about 2 μm, and the solvent is evaporated. The plastic film to be used may be a pre-printed film. A plastic film and a steel plate are thermocompression-bonded by setting the plate temperature or heating roll to an arbitrary temperature of 180 to 250 ° C. via an adhesive. The adhesive using the resin composition of the present invention is instantly cured by heat only at the time of laminating, and exhibits adhesiveness and the like. The plastic film laminated steel sheet thus obtained is excellent in design properties, corrosion resistance, work adhesion and retort resistance, and can be used for various applications.

  Hereinafter, the present invention will be specifically described with reference to Examples. In the examples, “part” and “%” represent “part by mass” and “% by mass”, respectively.

Example of Synthesis 1 (Synthesis of polyester resin (A-1-1) containing diphenolic acid as an essential component)
As an acid component, 50 parts by mass of terephthalic acid, 112 parts by mass of isophthalic acid, 4.9 parts by mass of diphenolic acid, and 50 parts by mass of 2-ethyl-2-butyl-1,3-butanediol as a polyhydric alcohol component, , 4-butanediol 99 parts by mass, 1,4-cyclohexanedimethanol 48 parts by mass, titanium tetrabutoxide 0.07 parts by mass are charged into a 2 L flask, gradually heated to 220 ° C. over 4 hours, water is retained. Esterification was carried out. After distilling a predetermined amount of water, 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. Next, the polymerization under reduced pressure was stopped, the mixture was cooled to 220 ° C. under a nitrogen stream, 1.9 parts by mass of trimellitic anhydride was added, and the mixture was stirred at 220 ° C. for 30 minutes to perform carboxy group modification (post-addition), and then resin The polyester resin (A-1-1) having a number average molecular weight of 22,000, an acid value of 5 (mgKOH / g), and a glass transition temperature of 30 ° C. was obtained. Then, it cooled to 60 degrees C or less, and diluted with the mixed solution of methyl ethyl ketone / toluene = 50/50, and obtained the polyester resin (A-1-1) solution of 40% of non volatile matters.

The following raw materials were blended and stirred at the ratios shown in Tables 1 and 2 (numbers in the table indicate solid mass ratios), and the film adhesives of Example 1-8 and Comparative Example 1-5 were prepared. .
(1) Polyester resin (A-1-1)
Number average molecular weight 22,000, acid value 5 (mg KOH / g), glass transition temperature 30 ° C., 40% solution (dissolved in a mixed solution of methyl ethyl ketone / toluene = 50/50)
(2) Polyester resin (A-1-2) = Byron GK-140, Toyobo Co., Ltd. number average molecular weight 13,000, acid value <2 (mgKOH / g), glass transition temperature 20 ° C., 40% solution (Dissolved in a mixed solution of methyl ethyl ketone / toluene = 50/50)
(3) Polyester resin (A-2-1) = Byron GK-250, manufactured by Toyobo Co., Ltd., number average molecular weight 10,000, acid value <2 (mgKOH / g), glass transition temperature 60 ° C., 40% solution (Dissolved in a mixed solution of methyl ethyl ketone / toluene = 50/50)
(4) Polyester resin (A-3-1) = Byron GK-640, Toyobo Co., Ltd. number average molecular weight 18,000, acid value <4 (mgKOH / g), glass transition temperature 79 ° C., 40% solution (Dissolved in a mixed solution of methyl ethyl ketone / toluene = 50/50)
(5) Phenol resin (B-1) = TD2495, DIC Corporation paracresol type phenol resin, 50% normal butanol solution (6) Metal chelate compound (C-1-1) = TC-200, Matsumoto Fine Chemical ( Titanium octylene glycol chelate (7) Metal alkoxide compound (C-2-1) = ZA-65, Zirconium butoxide (8) Metal chelate compound (C-2-2) = ZC- 150, zirconium acetylacetone chelate manufactured by Matsumoto Fine Chemical Co., Ltd. (9) epoxy resin (D) = Epiclon N-660, cresol novolak epoxy resin manufactured by DIC Co., Ltd., 50% methyl ethyl ketone solution (10) curing catalyst (E) NACURE 5925 Kasei Co., Ltd. dodecylbe Zensuruhon acid (catalyst), 25% solution

[Production of test panel]
(1) The film adhesives of Examples 1 to 8 and Comparative Examples 1 to 5 were applied to a PET film having a thickness of 12 μm with a bar coater so as to have a dry film thickness of 2 μm, and dried at 115 ° C. for 8 seconds.
(2) This film was laminated on a metal plate (tin-free steel) at 225 ° C.-3.6 m / min to obtain a test piece. Subsequently, it measured according to the evaluation test method shown below.

[Evaluation test method]
1. The appearance of the laminated steel sheet, such as the appearance of laminate appearance bubbles and film wrinkles, was visually evaluated in four stages.
Very good (◎), good (○), slightly bad (△), bad (×)

2. The b value measured with a spectrophotometer SE2000 manufactured by Nippon Denshoku was used. JIS Z8722

3. Adhesiveness: Cross-cut cellophane adhesive tape peeling test A cross-cut was put on a laminated steel sheet film, and the area peeled when forcedly peeled with a cellophane adhesive tape after high-temperature hot water treatment at 125 ° C for 30 minutes was expressed in%. JIS G3312

4). Workability: Cap adhesion test Diameter of φ26mm, height 17mm, formed into a cap of 17mm, and after hot water treatment at 125 ° C for 30 minutes, the side of the cap was forcibly peeled off with cellophane adhesive tape. Evaluation was made in 4 stages.

5. The whitening state of the adhesive layer of the laminated steel sheet after the retortability at 125 ° C. for 30 minutes and the high temperature hot water treatment was visually observed and evaluated in the same four steps as described above.

6). The adhesive coated surfaces of the sample film cut to a blocking property of 8 cm × 8 cm are bonded together, held in a 40 ° C. atmosphere at a pressure of 0.3 MPa for 72 hours, and then the bonded films are peeled at an angle of 180 ° at a peeling rate of 1000 mm / min. The peel strength when peeled with was measured.
Peel strength values: less than 20 g / cm (◎), 20-40 g / cm (◯), 41-60 g / cm (Δ), 61 g / cm or more (x).

7). The corrosion resistance test sample was subjected to a retort treatment at 120 ° C. for 90 minutes with a 3% sodium chloride and 3% citric acid aqueous solution, and the state of the sample was visually judged.
Δ: There is little peeling.
X: There is much peeling.

The evaluation results are shown in Tables 1 and 2. The numbers in the table indicate the solid content weight ratio.

  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 is cured with very little heat energy, and has processability, coating film hardness, water resistance and curability. It can be widely used as an adhesive for laminated can film and paint for film.

Claims (5)

A polyester resin (A), a phenol resin (B), a metal alkoxide compound and / or a metal chelate compound (C), and a resin composition containing an epoxy resin (D) not containing bisphenol A , the polyester resin ( A) from a polyester resin (A-1) having a glass transition temperature of less than 0 to 35 ° C., a polyester resin (A-2) of less than 35 to 65 ° C., and a polyester resin (A-3) of 65 to 100 ° C. A polyester resin,
The ratio of the polyester resin (A-1) / the polyester resin (A-2) / the polyester resin (A-3) is 30 to 70/10 to 35/10 to 35, and
The ratio in the total resin solid content is 50 to 80% by mass for the polyester resin (A), 10 to 50% by mass for the phenol resin (B), 0.01 for the metal alkoxide compound and / or the metal chelate compound (C). 10 to 10% by mass of epoxy resin (D) not containing bisphenol A is 0.5 to 20% by mass . The resin composition according to claim 1 , wherein the polyester resin (A) contains diphenolic acid as an essential component. The resin composition according to claim 1 or 2 , wherein the metal alkoxide compound and / or metal chelate compound (C) is a titanium alkoxide compound and / or a titanium chelate compound (C-1). The resin composition in any one of Claims 1-3 containing a curing catalyst (E). The resin composition according to any one of claims 1 to 4 , comprising an organic pigment and / or an inorganic pigment (F).