JPS5984742A - Vessel made of metal with circumferential side-surface joint - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal container having a circumferential side seam, and more particularly to a bottle-shaped container having significantly improved seam adhesion, sealing properties, and corrosion resistance. Regarding.

An upper body and a lower body, which are made of a cup-shaped molded body formed by drawing or drawing-shidoki processing of a metal material, are lapped (overlapping) and joined at the circumferential open end, and a circumferential side seam is formed. A bottle-shaped metal container formed with a metal container has many advantages over a can-shaped metal container.

Among conventional metal containers for packaging, what is called a three-piece can has two ta-lids vertically wrapped around the top and bottom of a stone plate with side seams to form a sealed part. In this method, a sealed portion is formed by double seaming between the open end of a cup-shaped can body formed by drawing or drawing-sealing a metal material and the can lid.

However, the whole story of such a double seaming structure? V-containers are subject to major restrictions in terms of pressure resistance of the sealed portion and in terms of material savings in the metal shell. That is, in a double-sealed joint, the load applied to the joint deforms the joint constituting the joint first, and this deformation causes joint leakage and joint failure with a relatively small load. In order to prevent this, the thickness of the moon itself must be made considerably large. In addition, in packaging containers, it is always required to make the metal materials used thinner, both from the standpoint of cost efficiency and from the standpoint of container quantification.
When thinning the container body wall, use the Nikyo winding process or 7
There is a problem in that buckling is likely to occur due to loads applied in the axial direction of the container during preparatory steps such as lunging.

A metal bottle made by lap-joining an upper body and a lower body, each of which is a cup-shaped molded body, at their open ends, has a seam of 1/C, regardless of the thickness of the material, if the material forming the seam is extremely thin. It is possible to withstand seams σ) and has the advantage that the side wall of the container can be made thinner without fear of buckling, since a seaming process is not required.

However, when forming a circumferential side seam by lap-joining the lower body and the upper body at their circumferential open ends, there are many restrictions regarding the adhesive to be used and the adhesive primer/hφ coating film. do.

In other words, in the case of a straight lap joint, both ends of this joint are mechanically fixed by seaming with the end cover, but in the case of the circumferential side joint described above, mechanical fixation is applied over the entire circumference. There is no fixed fixation, and the dimensional deformation of the joint itself is likely to occur easily. Since the diameter of the open end portion still tends to change due to temperature changes, stress is likely to occur in the adhesive layer. Furthermore, the open ends forming the joints are often thinned, and the joints tend to be easily deformed by external forces. For these reasons, the adhesive used must be one that exhibits strong adhesion to the coating film on the surface of the metal moon (although the mechanical strength and dimensions of this adhesive layer itself It must have great stability, and its physical properties must be stable both thermally and over time.Furthermore, the brimer coating film used must be resistant to both the metal material and the adhesive layer even under the harsh conditions mentioned above. The material must exhibit strong adhesion or adhesion to the surface.

Furthermore, since the lower body and upper body are formed by advanced drawing or drawing-shidoki processing, it is possible to use adhesive primer and adhesive I! The coating film as a layer must also withstand these molding processes and must have excellent R4 corrosion resistance.

According to the present invention, each of the lower body and the upper body is made of a painted metal tab-shaped molded body, and the open ends of the lower body and the upper body are overlapped and joined via an adhesive, and the circumferential periphery is bonded. A container made of gold JP%, forming a 9111-plane seam, wherein the coated metal cup-shaped molded product has a total vinyl chloride unit content of 30 to 97% by weight, and contains carboxyl groups and/or carboxyl groups. or rich in hydroxyl groups at 10 to 500 mmIJmol/100F resin with a glass transition temperature of 40
It is formed of a metal material with a vinyl chloride resin coating film at a temperature of 5°C or higher, and the adhesive contains a terephthalic acid component as an acid component.
0 mol% or more, 50 mol% or more of 1,4-butanediol component as alcohol component, and 1 mol% or more of at least one of acid components and alcohol components other than the above in the main chain. A metal container is characterized in that the lower body and the upper body are bonded via the vinyl chloride resin coating and the copolyester adhesive. be done.

The invention will be explained in detail below.

In FIGS. 1 to 6 showing an example of a bottle-shaped metal container, this bottle includes a lower body 1 consisting of a seamless cup-shaped molded body made of painted gold, and a seamless cup-shaped molded body made of painted metal. These cup-shaped molded bodies are formed by joining the open ends 6 and 4 to form a circumferential side seam 5, thereby forming a container. integrated into the shape.

In this specific example, the lower body 1 is a cup consisting of a side wall portion 6 and a bottom portion 7 formed by drawing a painted metal material, and the lower body 2 also has a side wall portion 8 formed by drawing a painted metal material. It is a cup consisting of an upper wall 9. The side wall 6 of the lower body 1 and the side wall 8 of the lower body 2 have approximately the same diameter, and in this specific example, their heights are also approximately the same,
Seam 5 is located approximately at the mid-height of the container. The upper wall 9 of the upper body 2 has an upwardly convex tapered surface, and a spout 10 for filling or taking out the contents is formed at the center &'L. It will thus be clear that the lower body 2 is joined onto the lower body in the form of the shoulders, neck and half of the torso of an open bottle.

In the specific example shown in FIG. 1, the open end 6 of the lower body 1 is narrowed to a smaller diameter than the rest of the body wall by neck-in processing in the vicinity of the open end 6. It is fitted into the open end 4 of the large diameter upper body. As shown in an enlarged view in FIG. 6, the coated metal material constituting the lower body and the upper body consists of a surface-treated aluminum substrate 11 such as a metal scrap substrate 11 such as aluminum + ram, etc., and an adhesive primer/retaining layer applied to the surface of the metal substrate 11. Paint film 12
a112h. An adhesive layer 16 is provided between the outer surface of the lower body open end 6 and the inner surface of the upper body open end 4 to join and fix the lower body and the upper body. It is desirable from the viewpoint of corrosion resistance that a portion of the adhesive 16 protrudes from the seam 5 to form a coating layer 15 on the cut edge 14 of the metal element located inside the seam.

In the present invention, the coating films 12a and 12b have a vinyl chloride unit content of 60 to 97%, particularly preferably 50 to 95J (% by weight), and carboxyl groups and/or hydroxyl groups of 10 to 97%. 500 mmol/100r#4
fat, particularly preferably 20 to 400 mmIJmol/100
The glass transition temperature contained in the concentration of F resin is 40°C or higher,
Particularly preferably, as the vinyl chloride resin of 60"C or more and the adhesive layer 16, 5% of the terephthalic acid component is used as the acid component.
50 mol% or more of 1,4-butanediol as the alcohol component, particularly preferably 70 mol% or more.
In an amount of mol % or more, 1rfK preferably 60 mol % or more,
In addition, an adhesive mainly composed of a copolyester containing at least one of acid components and alcohol components other than those mentioned above in an amount of 1 mol % or more, particularly preferably 3 mol % or more in the main chain is used in combination, and The body 1 and the lower body 2 are made of metal if;
, material 11, coating film 124, adhesive 16, coating film 126, metal base 5' (having important features for joining with the body of 11).

First, the present invention utilizes the phenomenon that a specific vinyl chloride resin coating film and a specific copolyester adhesive described above form a strong adhesive bond when heated. That is, according to the research conducted by the present inventors, when a copolyester adhesive is heat-sealed to a vinyl chloride resin coating, the two resins are mixed extremely well at the bonding interface between the two. This is thought to be the reason why strong adhesion is possible. Despite the fact that these two resins have completely different chemical structures, their good mixing under heated conditions is related to the fact that the solubility indices of both resins are quite close. It is recognized that

Solubility parameter
er+ Sp value) means, for example, It-X, J, ERAND
Edited by RUP et al. - Pal yrn, e rHandboo
Chapter 4 (John Wt l my & So o
ns, Inc.

Published in 1967) and is defined as the % power of the cohesive energy density (cal/'cc). This solubility index is closely related to the strength of hydrogen bonds in thermoplastic resins. It is related to hydroxyl group, amide group, varnish.
Thermoplastic polymers containing polar groups such as alkyl groups, nitrile groups, or chlorine atoms in the polymer main chain or side chain generally have a high molecular weight of 9 or higher, depending on the content and distribution of these polar groups. −・Indicates solubility index.

Table 4 below shows the sp values of polyvinyl chloride, polyethylene terephthalate, and polybutine terephthalate.

Table 4 Polyvinyl chloride 9.55 Polyethylene terephthalate) 10.7 Polybutylene terephthalate
It can also be determined approximately from the values as an arithmetic mean value.

For example, polybutylene/ethylene terephrate s
The p value is calculated using the following formula: , EM can be approximately determined by the molar fraction of ethylene terephthalate units in the copolyester. This also applies to co-op type vinyl chloride resins.

Even when ordinary polyethylene terephthalate is fused to a vinyl chloride resin coating, almost no adhesion is observed. On the other hand, the fact that by introducing butylene terephthalate units into the ester chain, in addition to the general increase in thermal adhesive properties due to copolyester, 7JI+
The closeness of the solubility indices of both resin layers suggests that the improvement in compatibility with resin A at the adhesive interface is an important factor. It is preferable that the difference in sp value between the coating resin and the copolyester adhesive used in the present invention is within 1.0 ((Cal/偲)/l, particularly within 0.8 ((Car/偲)%).ゝO Furthermore, the use of vinyl chloride resin coatings not only enables strong adhesion with copolyester adhesives, but also has remarkable advantages in processability of the coating and corrosion resistance as a protective coating. As will be explained in detail later, vinyl chloride resin is a thermoplastic resin with excellent mechanical properties and processability, and metal materials with this coating can be used in advanced drawing processes, such as the drawing process Even when subjected to drawing processing, etc., coating film defects such as cracks, pinholes, and wrinkles do not occur.

Furthermore, although vinyl chloride resin is a resin with relatively strong polarity, it is water resistant and also exhibits excellent barrier properties against metal corrosive components contained in the contents of the container.

It is also extremely important that the vinyl chloride resin paint used in the present invention has vinyl chloride units within the range described above. The amount of vinyl chloride units in the coating is related to both the adhesion with the copolyester and the corrosion resistance of the metal substrate. In other words, the total vinyl chloride unit element contained in the coating film is 30% valuable.
If the content of agglomerated vinyl units exceeds 97%, the adhesive strength to the copolyester will decrease, and the barrier properties against edible components will not deteriorate.On the other hand, if the content of agglomerated vinyl units exceeds 97%, the coating film becomes hard and difficult to process. The problem is that the adhesiveness and adhesion with metal materials decrease.

Furthermore, from the viewpoint of adhesion to the metal substrate, the vinyl chloride resin coating film used in the present invention contains at least 1 m of polar groups selected from the group consisting of carboxyl groups and hydroxyl groups in a concentration within the above-mentioned range. It is also important that if this concentration is 10 mmol/100 lower than that of the resin, there is a tendency for peeling between the metal substrate and the coating film.
On the other hand, if this concentration is higher than that of the 500 mm, ol/100 f resin, the water resistance of the coating film will decrease and the corrosion resistance will also be lost.

Furthermore, this vinyl chloride resin coating film has a glass transition temperature (ff'g) of 40°C or higher, especially 60°C or higher.
□It is also necessary to have salt. That is, in a metal container having a circumferential side seam, which is the object of the present invention,
In most cases, the load applied to the container during oral heat sterilization, storage, transportation, etc. acts as a shearing force on the adhesive and coating film. Plasticizer f? In ordinary vinyl chloride-based resin coating films that have a relatively large amount of stagnation, on the order of 20 to 30%, the glass transition temperature is around room temperature, and such coating films cannot withstand the above-mentioned shearing force. Although peeling easily occurs between the coating film and the metal or adhesive layer, since the coating film of the present invention has the above-mentioned glass transition temperature, it can withstand shearing force applied to the joint and can prevent adhesive deterioration and airtightness.

In the present invention, it is important to use the above-mentioned copolyester adhesive among various heat-sealable thermoplastic adhesives. First, this copolyester adhesive is
As already pointed out, it not only shows excellent adhesion to vinyl chloride resin coatings, but also has higher mechanical strength such as tensile strength and bending strength than adhesives made of other resins. It can withstand the shearing force applied to the adhesive layer at the seam, and can prevent adhesive deterioration, airtightness, etc. even under severe conditions. Moreover, this copolyester has strong toughness,
Since it also has properties such as flexibility, even in the 411% case where the adhesive layer is strained due to stress and the joint is deformed, it prevents fil, m and leakage at the joint. Furthermore, this copolyester adhesive has excellent heat resistance, has a thermal bonding temperature within a convenient range, has a lower water absorption rate than polyamide thermal adhesives, and has excellent water resistance, hot water resistance, etc. It is also excellent.

It is also important that this copolyester adhesive contains a terephthalic acid component, a 1,4-butanediol component, and other acid components and/or diol components in the above-mentioned quantitative ratios. The terephthalic acid component is mainly related to the mechanical properties such as creep resistance and heat resistance of the copolyester, and if this amount is lower than the above range, these properties will deteriorate.

The 1.4-butanediol component is mainly related to the improvement of adhesive workability by lowering the melting point of the copolyester and the flexibility of the copolyester, and if this amount is less than the above range, these properties will be impaired. descend. In addition, acid and/or alcohol components other than these are also associated with improved adhesion and adhesive workability by lowering the melting point, and if the content is lower than the above range, satisfactory results regarding the above properties cannot be obtained.

The metal plates that make up the seamless cup include untreated steel plates (black plates), various surface-treated steel plates, such as tin-plated steel plates (tinplate), galvanized steel plates, aluminized steel plates, Niracle-plated steel plates, chrome-plated steel plates, etc. Metsugi steel plate: Electrolytically treated steel plate such as electrolytic chromic acid treated steel plate, chemically treated steel plate such as diphosphoric acid and/or chromic acid treated steel plate, light metal plate such as aluminum, or a composite material thereof.

The vinyl chloride resin used for coating metal materials may be used without any particular restrictions as long as it satisfies the above-mentioned requirements. First, this paint contains vinyl chloride units in an amount of 30 to φ7%, and these vinyl chloride units are in the form of a copolymer with other monomers, which will be described later, or partially in the form of vinyl chloride units. In the form of a copolymer, the remaining part is present in the form of a straight resin, ie a homopolymer. On the other hand, the carboxyl group and/or hydroxyl group in the paint may exist in the paint film in the form of a co-composite of an ethylenically unsaturated eleventh-membered unit having such a polar group and a vinyl chloride unit. Alternatively, it may exist in the form of a blend of the above-mentioned polar group-containing resin and vinyl chloride resin. In short, in the present invention, vinyl chloride units and carboxyl groups and/or hydroxyl groups may be present in the coating film in the above-mentioned member and concentration, whether in the form of a copolymer or a blend. Furthermore, from the viewpoint of processability and adhesion of the coating film, it is desirable for the cyclized vinyl resin to contain vinyl acetate units in its main chain, and the amount of vinyl acetate units is 30% or less per coating. can exist.

Suitable examples of ethylenically unsaturated monomers providing carboxyl groups include acrylic acid, methacrylic acid, Tuma l'rWl,
Maleic anhydride, Croton Rs '1 taconic acid, citraconic acid, tetrahydrophthalic anhydride, etc., and suitable examples of monomers providing hydroxyl groups include vinyl alcohol (i.e. vinyl thiacetate saponified product), hydroxyethyl acrylate,
These include hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

Suitable examples of vinyl chloride resins include polycyclized vinyl, vinyl chloride-vinyl acetate copolymer, partially saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic acid copolymer, and vinyl chloride. - Vinyl acetate coelectrolyte partially saponified/partially butyralized product, vinyl chloride-vinyl acetate-methacrylic acid copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate-hydroxyethyl acrylate copolymer vinyl chloride-vinyl acetate-hydroxyethyl methacrylate copolymer, etc. Generally, resins that do not have carboxyl groups and/or hydroxyl groups, such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers, are used in the form of a blend with vinyl chloride copolymers that have carboxyl groups and/or hydroxyl groups. It is desirable to do so.

In addition to these vinyl chloride resins, thermosetting resins, especially thermosetting resins having hydroxyl groups, such as resol type and/or novolac type phenol aldehyde resins, urea-
It can be used alone or in combination with two or more of aldehyde resins, melamine-aldehyde resins, epoxy resins, alkyd resins, and the like.

These vinyl chloride resin paints are compatible with aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as ethanol, propatool, and butanol; ethyl 1f of cellosolve solvents such as cellonlube and butyl cellosolve; ester solvents such as ethyl acetate and butyl acetate! It can be used in the form of an organic solvent solution paint in which li or two or more are dissolved, and furthermore, it can be used in the form of a so-called organosol paint in which vinyl chloride polymer particles are suspended in these organic solvent solution paints. . This paint has a concentration of 10 to 50% by weight.
It is used for coating metal materials with a viscosity suitable for painting within the range of . Coating can be performed by any means such as roller coating, brush coating, doctor coater, spray coating, electrostatic coating, and dip coating. The amount of coating on metal materials is 0.5 to 50 f/TIL” 14 f on a dry basis.
K 1 to 20 t/m” CD range,
Advantageous for the purposes of the invention.

The coated metal material is baked at 150 to 350° C. for 5 seconds to 30 minutes in a hot air oven, infrared heating furnace, etc. to form a desired coating film.

As already detailed, in the present invention, it is important that the vinyl chloride resin coating film has a glass transition temperature of 40° C. or higher. In this regard, the vinyl chloride resin coating of the present invention should contain no plasticizer at all, or if it does contain it, it should be contained in a relatively small amount such that the glass transition temperature does not fall below 40°C. . In addition, vinyl acetate units incorporated into vinyl chloride-based resins also tend to lower the glass transition temperature), so vinyl acetate units should be incorporated within the range where the glass transition temperature is within the above range. The vinyl resin may be blended with known compounding agents. For example, plasticizers such as dioctyl phthalate and epoxidized soybean oil can be used within the above flG limits, as well as heat stabilizers such as calcium stearate, zinc stearate, organotin compounds, organophosphate esters, microcrystalline waxes, and A lubricant such as fatty acid amide or a filler such as calcium carbonate or calcined clay may be blended in a known formulation.

In order to obtain a seamless cup, the above-mentioned painted metal material is punched into a shape such as a disk, subjected to a one-stage or multi-stage drawing process between a drawing punch and a drawing tie, and if desired, the drawing cup is ironed and punched. Add it to the multi-tiered roe between the sieve and the sieve dice. The operations and conditions for these drawing and ironing processes are known per se, and can be performed under conditions known per se.

The thickness of the painted metal material to be processed varies depending on the final dimensions of the container and the class XIa material, but is generally 0.1
It is preferable that the thickness of the side wall is between 0.0 and 0.5 mm, especially between 0.2 and 0.65 mm, and when ironing is performed, the thickness of the side wall is between 0.05 mm and 0-20 mm, especially between 0.2 mm and 0.65 mm. In the present invention, the coated metal material is subjected to drawing forming or -1 drawing (deep drawing) forming to form a cup-shaped formed object. Although it is desirable to produce a cup-shaped molded body by drawing and tightening an unpainted metal material, it is of course also possible to coat this cup-shaped molded body with the vinyl chloride resin paint. be.

The copolyester adhesive used in the present invention also has
50 mol% or more of terephthalic acid component as an acid component; 1.
Copolyester alone, copolyester containing 50 mol% or more of a 4-butanediol component as an alcohol component, and 1 mol% or more of at least 111 of an acid component other than the above and an alcohol component. It may be a blend of polyesters or a copolyester and a homopolyester, or a blend of a polyester or a blend of the above and another thermoplastic resin.

Acid components other than terephthalic acid include inphthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylmethanedicarboxylic acid, adipic acid, sepatic acid,
Maleic acid, 1-fluoric acid, succinic acid, hexyhydroterephthalic acid, etc. can be mentioned, and alcohol components other than 1,4-butanediol include ethylene glycol, propylene glycol, neopentyl glycol, etc. , diethylene glycol, triethylene glycol, cyclohexanediol, xylene glycol, and the like.

This copolyester should have a sufficiently high molecular weight from a mechanical/IV property point of view, generally 6.000
As mentioned above, it is particularly desirable to have a number average molecular weight of 9,000 to 500,000. Furthermore, from the viewpoint of creep resistance mentioned above, this copolyester has a density of 111
It is preferable to have a crystallinity of 3 to 45% and 5 to 40%. Furthermore, from the viewpoint of thermal bonding workability, this copolyester desirably has a melting point of 80 to 280°C, particularly 90 to 240°C.

The above-mentioned copolyesters can be used alone or in a blend of two or more, and can also be used with other thermoplastic resins, such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ionic crosslinking. It can also be used in the form of a blend of olefin resins such as olefin copolymers (ionomers), ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, acid-modified polyethylene, and acid-modified polypropylene. Of course, these olefin resins are used in an amount not exceeding 50% by weight of the entire adhesive, particularly 30% by weight or less.

In the present invention, the adhesive is applied to the open end edges of the cups to be joined prior to fitting the cups together. This adhesive layer has a resin layer with a thickness of 10 to 2005fns, especially 2005fns.
It is preferable to apply the coating so that the thickness is 0 to 150 μm, and the width of the overlapping joint, that is, the inside of the lap, is 1 to 30 μm, particularly 2 to 20 μm.

The adhesive resin can be applied to the desired part of the cup in various forms, for example in the form of a film, powder, slurry, solution, plastisol or emulsion; in particular, the adhesive can be easily handled and applied. It is also an advantage that it can be applied in the form of a film that is easy to handle and can be easily manipulated such as drying.

Depending on the application of the adhesive and the form of the adhesive, lamination,
Application methods such as extrusion, electrostatic powder coating, electrodeposition coating, spray coating, nozzle discharge, dip coating, roll coating, and brushing can be used.

Since the paint is applied to the parts of the gold IIs material to be joined, the paint acts as a primer for the adhesive and provides the desired adhesion.

When overlapping and joining the circumferential open ends of the cups,
The cut edge of the metal material is inevitably exposed at the seam 11. The cut edge is protected by wrapping it with adhesive tape or applying adhesive powder, slurry, or solution to the cut edge prior to fitting the cup. 11 can also be performed.

The adhesive can be applied to the outside or inside surface of the open edge of the cup on the inside or outside of the seam, or can be applied to both sides.

The other cup is fitted onto the cup coated with adhesive, and then the adhesive present in the overlapping portion is melted, and if necessary, the joint is cooled to form a joint.

This can be done by heating wires at the overlapping part, ^frequency induction heating, infrared heating, hot air heating, heat conduction heating from a heating body, etc.
Further, the joint can be cooled by any operation such as natural cooling, air cooling, water cooling, etc.

At this time, it is important to melt the adhesive while the adhesive layer is pressed and clamped between the open end on the outside of the seam and the open end on the inside of the seam to ensure airtightness and adhesive strength. Generally speaking, the outer diameter of the inner open end of the circumferential overlapping joint is DI, and the inner diameter of the outer fill is 7J.
When the thickness of the adhesive layer interposed between the two is dA, these dimensions are selected so that the following inequality % formula % holds true, and the thickness of the adhesive after bonding is 10 to 150 μm, especially 10 to 150 μm. 100μ
It is desirable to set the value to m.

Further, when fitting the cup, it is easier to fit the cup if the open end located on the outside is expanded by heating V.

The bottle-shaped metal container having a circumferential metering joint according to the present invention can be used as a container for contents having autogenous pressure such as carbonated drinks, beer, low-malt beer, etc., and can be filled with nitrogen gas, liquid nitrogen, etc. together with the contents. It is particularly useful as an internal pressure vessel.

The invention is illustrated by the following example.

(Reference) [N'i adjustment of paint] The paint used in the following examples was made by mixing the following components (1) to G) in the proportions shown in Table 1, and the non-volatile content was 2.
It is dissolved and/or dispersed in a solvent to a concentration of 5% by weight.

(1) Vinyl chloride resin: QYNV-2 (U, C
(Vinyl resin manufactured by Co., Ltd., trade name) ■ Vinyl chloride-based co-combined resin: In an autoclave, 0.6f of polyvinyl alcohol with a hydrolysis rate of 80% is dissolved in water 3UOIle1 azobisisobutyronitrile 0.159 and vinyl acetate monomer 1 (l) in a dry ice-methanol bath.
Cooled to 0°C. Then liquid vinyl chloride monomer 9O
Added f quickly. The temperature was raised to 58° C., and polymerization was carried out for 6 hours while stirring. The obtained polymer had a polymerization degree of 525, vinyl chloride/vinyl acetate = 91/9 (JIU
(Ji%) (this is designated as V-1).

Similarly, polymerization degree 310, vinyl chloride/vinyl acetate =
87/13 (ffi amount%) (V-2); 1 degree 290
, Vinyl chloride/Vinyl vinegar = 80/20 (, Retention%) (
Vl), a vinyl chloride-vinyl acetate copolymer was synthesized.

In addition, the degree of polymerization is 295, vinyl chloride/vinyl acetate/maleic anhydride = 86/1015 (wt%) (V-4) 6
The original copolymer was also synthesized by the same method.
By partially saponifying -3 with an alkali, a vinyl chloride-vinyl acetate-vinyl alcohol copolymer was obtained. Polymerization degree 625, vinyl chloride/vinyl acetate/vinyl alcohol = 91/3/6 (wt%) (F-5);
The degree of polymerization was 290, and the composition was vinyl chloride/vinyl acetate/vinyl alcohol=8015/15 (% by weight) (V-6).

(6) Epoxy resin: Epon 828 (product of Shell Chemical Co., Ltd., trade name, bisphenol A type epoxy resin, average molecular weight 380, epoxy equivalent 184-194)
(4) Amino resin: Beckamine 7'-138 (product of Dainippon Ink Co., Ltd., trade name, butyl etherified area resin) (5) Phenol resin: 0.5 mol of carbolic acid and 0.5 mol of p-cresol at 37%
It was dissolved in 1.5 mol of formaldehyde aqueous solution, 0.15 mol of ammonia was added as a catalyst, and the mixture was reacted at 95°C for 3 hours. The reaction product is extracted with a mixed solvent consisting of ketones, alcohols, hydrocarbons, etc., washed with water, the aqueous layer is removed, a small amount of remaining water is removed using an azeotropic method, and the product is cooled to produce a resol type phenolic resin. A 30% solution of was obtained.

(6) Plasticizer: Epoxidized soybean oil Also, the final vinyl chloride unit content of each paint and the content of carboxyl groups and/or hydroxyl groups determined using the calibration curve method from the infrared spectral characteristic absorption of carboxyl groups and hydroxyl groups. The concentrations and glass transition temperatures measured using TMA at a heating rate of 5° C./min are shown in Table 3.

[Creation of copolyester adhesive]

The copolyester used in the following examples or adhesive samples mainly composed of the copolyester were prepared according to the method described below. First, predetermined corresponding acid components and alcohol components were charged in advance into a glass reactor together with a catalyst such as tetra-n-butyl titanate corresponding to about Of14 wt%, and the mixture was heated at 200° C. with stirring.
The reaction was continued for about 1.00 minutes while removing the generated methanol, and then the temperature was raised to about 260°C and O-1~0.
Polymerization was carried out for about 2 hours under a reduced pressure of 5wt1lf. The obtained polymer was pelletized and then placed on two Teflon sheets.
Masami, melting point or softening point of each resin 20-3
Molded by hot press at a temperature of 0℃ to a thickness of approximately 80mm
A μm film-like sheet was created. The final composition of each sample was analyzed by proton NIIIR and gas chromatography. Table 2 shows the composition ratios in mol% according to the analysis results. According to these polymerization conditions, a number average molecular weight in the range of about 15,000 to 35,000 was obtained, although the degree of polymerization varied depending on the composition.

In addition, for blend samples B-1 and B-2, Surlyn 1706 was used as the ionomer, and 9 polyethylene terephthalate (number average molecule about 1 iaoυ) was separately polymerized.
0) Polyethylene terephthalate/isophthalate
'(composition ratio 70/, riO) (approximately 16,000
) and a high-temperature kneader at approximately 240°C.
, 270°C in a nitrogen atmosphere and then pelletized.

(Composition abbreviations) I-isophthalic acid, A-adipic acid, S-sepathic acid, O-orthophthalic acid, Ag-azelaic acid, E-ethylene glycol, P-propylene glycol, N-neopentyl glycol, TE-)lyethylene Glycol, PEC) - Polyethylene glycol [number average molecular weight] The number in parentheses indicates the mole percent of that component in both components.

Tatami This copolyester 80 wt% and ionomer 2
Blend with 0 wt%.

■ 50wt% of this copolyester and polyethylene terephthalate/isophthalate (70/30) 30wt%
, a blend with 20 wt% polyethylene terephthalate.

Furthermore, in the following examples, metal containers were evaluated according to the method described below.

[Evaluation of metal containers]

0) Measurement of joint shear strength After joining, the 41 metal container was filled with water and 7
After waiting at 0°C for 10 hours, sample pieces were cut out including a joint part of 7 rxt in the height direction and 2 crrt in the circumferential direction, and tensile speed was 10 using Tensilon.
A shear fracture S test was conducted at room temperature at 0 tsm/trLin, and the shear strength was expressed in consideration of the adhesive area of the lap joint. Measurements were made for each of six containers, and the arithmetic mean value was taken as the measured value. In addition, here 54
~57 kl? /ca” or more is indicated as
This indicates that the plate has broken, and the actual strength is greater than this value.

(b) For the metal container after bonding with a peel strength of 6111 at the joint, and for the container filled with water and left at 70°C for 10 hours, the joint was cut out in a circumferential shape, and tensilon was applied. using a tensile speed of 200 mu/
A T-peel fracture test was conducted at room temperature. After considering the width of the lap joint, the average peeling strength was determined for each of the three containers, and the main types of failure were determined by 1. Between the coating film and the plate,
■.

It was classified into coating film-adhesive, II pre-adhesive ■, and coating film, and the results are shown in the table above based on visual observation.

(c) Tenting test After filling each metal container with the specified contents, a weight (A) of 4 kg in weight is placed at a constant height 6 as shown in Figure 4.
Is the gold tilted at an angle of 22.5° to the horizontal? 4 Container CB> Let it fall naturally vertically to a position 0.6 mm from the edge of the outer body of the joint.

In this test, the internal pressure was measured immediately after the upper body and the bottom body were separated for 48 hours, and the internal pressure was determined to be 5% or more lower than immediately after filling. It was considered that leakage was observed when leakage was observed, and when content oozed out near the joint. The net breakage rate (%) is shown in the box.

Incidentally, 0° C. and 25° C. were selected as the test conditions, and after confirming that the entire test specimen had sufficiently reached that temperature, 50 tests were conducted for each.

2) Drop test After filling a metal container with the specified contents, it was tested at room temperature from a height of 90 cIrt in two directions: (1) with the bottom facing downwards, and (II) with the joint facing downwards. 2 each
Five nets were dropped at a time, and the presence or absence of broken nets was examined, and after 48 hours, the presence or absence of leakage was examined. In the table, for each case, the sum of the leakage and network breakage is shown as a leakage rate (%), and the network breakage rate (%) is shown in parentheses.

0 Chronic 3 month aging test at 50°C 0 Volume change The total volume of the container before filling was measured in advance, and the contents were filled with the contents, and after a period of time, the total volume was measured again for containers with no leakage. The difference was defined as the volume change ΔV. Ten pieces of each were measured, and their arithmetic mean value was used as the result.

O Leakage and Broken Network A broken mesh was defined as a mesh where the top and bottom bodies were separated or one of them was deformed and a gap was observed at the joint. Furthermore, cases in which the internal pressure at 25° C. had decreased by 5% or more compared to immediately after filling, and cases in which some kind of contents were observed to ooze out near the joints were considered to be leaks. in some cases,
The sum of the number of leaks and the number of broken nets out of 50 is shown as the leakage rate (%), and the broken net rate (%) is shown in parentheses.

O metal elution □ Metal! A container was filled with a synthetic carbonated beverage, and after aging at a predetermined temperature and time, the amount of eluted metals was measured by atomic absorption spectrometry. Ten pieces of each sample were measured, and the arithmetic average of the measurements was taken as the result and rejected.

Examples, 1-8. Comparative Examples 1 to 5゜Material thickness 0.23mm aluminum plate <3004ql119, chromate treatment) 0? Table 1 inside and outside the circle. The total coating volume of each paint consisting of each composition shown in the figure is 180m9/dm"
801n9/dm", and then punched into a disc with a diameter of 250 baskets and formed by normal press processing, so that the inner diameter of the joint edge was 110.6s.
+w, an upper body having a spout with a diameter of 30tstQ in the middle and 6th part was fabricated.

On the other hand, a disk with a diameter of 2.505 m0 was punched out from the same painted plate and formed by press processing, so that the outer diameter of the edge of the joint was 1.
A 10.6 m lower body was produced.

Over the entire circumference of the edge of this lower body, its outer surface 5-5
mwri]s Adhesive was applied to a width of about 1.5 mm on the inside surface as follows. That is, the copolyesters shown in Table 2 (
C1, terephthalic acid content in the acid component: 80 mol%, 1.4-7" tanediol in the glycol component: 90 mol%)
A film of 80 μm in thickness and 1 width of 7 silk is pasted over the entire circumference of the outer edge of the lower body, which has been preheated with high frequency, so that it protrudes by about 1.5 mm, and then the edge is heated with high frequency again. The protruding portion was folded back with a four-way lever and adhered to the inner surface to produce a lower body whose edges were coated with adhesive.

The capacity obtained by fitting the upper body and the lower body coated with adhesive, then heating the fitted part with high frequency to melt the adhesive, and then cooling and solidifying it to join the upper body and the lower body. A metal container of target 21 was produced.

While evaluating the joint strength of these metal containers, after filling with beer, the spout was vE-oranged, sterilized at 65℃ for 60 minutes, and then aged at 50℃. ,
The presence or absence of broken nets was observed. In addition, the amount of aluminum eluted was measured for those filled with carbonated drinks. Furthermore, a denting test and a drop test were conducted to observe the presence or absence of leakage and broken nets. Table 6 shows these results.

Examples 9-18. Comparative Examples 6 to 10 A modified vinyl paint E1 (containing vinyl chloride units: 170.8 wt%, hydroxyl group concentration 197.
1 mmol/100F resin, 7'g 8B℃; see Table 1) was applied to give a total coating weight of 180g/dm" and 8Qda/d-, and after baking, It is punched out into a disc with a diameter of 110.6 m and is formed by normal press processing, with an inner diameter of 110.6 m at the edge of the joint and a diameter of 60 m at the center.
An upper body with a dragon spout was made.

On the other hand, a disk with a diameter of 250 mm was punched out from the same painted plate and formed by press processing, so that the outer diameter of the edge of the joint was 110 mm.
．． A lower body of 6tnttt was produced.

Over the entire circumference of the edge of this lower body, its outer surface dimension is 5.5
The adhesive was applied as follows with gm width and 1.5 internal width. That is, a film having the composition shown in Table 2IIC, with a thickness of 80 μm and a width of 7 mm, was coated with about 1.5 μm over the entire circumference of the outer edge of the lower body, which had been previously high-frequency heated.
After that, the protruding part was folded back with a roll and the edge was heated with high frequency and attached to the inner side again to produce a lower body with the edge sweat covered with adhesive. The upper body and the lower body coated with adhesive, which were obtained in the same manner, are fitted together, and the fitted part is heated with high frequency to melt the adhesive, and then cooled and solidified to join the upper body and the lower body.The capacity of the upper body and lower body is approximately Twenty-one metal containers were produced.

While evaluating the joint strength of these metal containers, after filling with beer, the spout was sealed, sterilized at 65°C for 30 minutes, and aged at 50°C on a round surface to detect changes in internal volume, leakage, and breakage. The presence or absence of a net was observed. In addition, denting tests and drop tests were conducted to observe the presence or absence of leaks and broken nets. Table 4 shows these results as the composition of each adhesive, including terephthalic acid in the acid component and 1 and 4- in the glycol component.
It is shown along with each content of butanediol.

Example 19゜“Bright tin-plated steel plate CT-1 with a material thickness of 0.23 mm”
Paint E5 (see Table 1 for composition) was applied to the inner and outer surfaces of each material (plating amount ÷ 50150), with a total coating amount of 150 m9/
dm”, 60119/d-, then punched into a 94mm disc, and formed using a regular press (Roe). An upper body having a spout with a diameter of 25 mm was prepared.

On the other hand, a tin plated steel plate with a material thickness of 0.30 yen is approximately 142 ++
It is punched out to a diameter of Ua and formed into a tap shape with an inner diameter of about 85 mm between a drawing punch and a drawing die. Next, this pot-shaped molded product was subjected to a re-drawing process, and then ironed using an ironing punch with a diameter of approximately 66.1 mm and a die. The same paint E3 as the upper body is applied to this outer surface with a coating amount of 601R9.
/ dm” after coating with a mandrel coater and baking, and then apply 1 coat of epoxy paint on the inner surface.
After spray coating to give a coating thickness of 50 m9/dm'' and baking, neck-in processing was performed to produce a lower square body having an outer diameter of 64.40 mm at its inner peripheral edge.

Next, an adhesive was applied around the entire edge of the lower body, approximately 4 times (11 times) on the outer surface and approximately 2 times (11 times) on the inner surface, as follows. That is, copolyester adhesive C4 (composition is shown in Table 2)
A film of 80〃m width and 6mm thick) was pasted on the edge of the outer surface of the lower body, which had been previously heated with high frequency, so that it protruded for about 2 minutes all around the circumference, and then the edge was heated with high frequency. At the same time, this protruding portion was folded back with a roll and attached to the inner surface f11 to produce a lower body whose edges were covered with an adhesive.

The upper body thus obtained and the lower body coated with adhesive are fitted together, the fitted part is heated with high frequency to melt the adhesive, and then cooled and solidified to join the upper body and lower body. 500
A bottle-shaped metal container was prepared.

After filling these metal containers with synthetic carbonated beverages, the spouts were sealed and sterilized using a can warmer at 42°C, followed by an aging test at 50°C, as well as a drop test and 0°C.
When the strength of the container was evaluated by performing dentching test at 25°C, it was found that the performance was sufficiently satisfactory for practical use.

[Brief explanation of the drawings] 1st. , the figure shows gold lA! of the present invention! FIG. 2 is a cross-sectional view showing the upper body and lower body of the M container separately; FIG. is an enlarged view of the cross-section of the attachment part in FIG. 2, and FIG. 4 is a diagram schematically showing the denting fist, where 1 is the lower body, 2 is the upper body, ' 6
and 4 is an open end, 5 is a side seam, 6 is a thin side wall, and 7
is the bottom, 9 is the earthen wall, 10 is the spout, 11 is the metal substrate, 1
2a and 2b are both films, 13 is an adhesive, 14 is a cut edge of a metal material, and 15t is a coating layer. Patent applicant Akira Kishimoto

Claims (1)

[Claims] (1) Each of the lower body and the upper body is made of a painted metal cup-shaped molded body, and the open ends of the armpit body and the upper body are overlapped and joined together with an adhesive to form a circumferential side seam. The coated metal cup-shaped molded body has a vinyl chloride unit content of 30 to 97% by weight, and a carboxyl group and/or hydroxyl group content of 10 to 500 mmol per unit. 10
The adhesive is made of a metal material with a vinyl chloride resin coating film having a glass transition temperature of 40'C or more at a concentration of 0F resin, and the adhesive contains 50 mol% or more of a terephthalic acid component as an acid component and an alcohol component as an alcohol component. 1. It is an adhesive mainly composed of copolyester with a 4-butanediol component, and the lower body and the upper body are bonded via the vinyl chloride resin coating and the copolyester adhesive. Container made of gold R.