JPH0345116B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to sealant compositions, and more particularly to:
The present invention relates to a sealant composition that is advantageously used in the production of canned, bottled, and other packages that have excellent storage stability. In the production of canning and bottling, there is always a space called a head space in the upper part of the can body or bottle, and the oxygen remaining in this head space oxidizes and deteriorates the contents, and can also cause mold and yeast. The problem is that it causes the proliferation of bacteria, etc. To remove oxygen from this headspace,
It is common practice to spray water vapor or nitrogen gas onto a can or bottle filled with contents to replace the air in the head space with these gases, and then double-seal the can with the can lid or cap the lid. However, even with these methods, it is difficult to remove dissolved oxygen from the contents, and when canning or bottling fruits, fruit juices, vegetables, etc.
It is known that dissolved oxygen causes deterioration of the contents. The most commonly used method to prevent the effects of dissolved oxygen is to construct at least a portion of the container surface with metallic tin, and use the reducing action of the metallic tin layer to prevent the effects of residual oxygen. It is. However, if the container surface is made of tin, tin ions will inevitably be leached into the contents, and from a hygienic standpoint, alternative methods and means are highly desired. The present inventor has discovered that when a water-insoluble oxygen absorber made of a specific phenol-aldehyde resin is blended with an elastomeric polymer and applied to a can lid or an ordinary bottle lid in the form of a sealing gasket, this Under normal storage conditions, things can be stored stably for a relatively long period of time without losing their oxygen absorption ability, but under high humidity conditions such as when packed in cans or bottles, they have excellent It has been found that oxygen absorbability is developed and the influence of residual oxygen in the container is effectively prevented. According to the present invention, an oxygen absorber made of a phenolic aldehyde resin having a plurality of phenolic hydroxyl groups per ring in the phenol skeleton is added to an elastomeric polymer at a rate of 100% by weight of the solid content of the elastomeric polymer. A sealant composition is provided, characterized in that it is formulated in an amount of 0.1 to 50 parts by weight. An important feature of the present invention is that, as mentioned above, when an elastomer polymer containing a water-insoluble oxygen absorber made of a specific phenol aldehyde resin is used as a sealant for a can lid or a bottle lid, Under normal storage conditions, this sealant has a
The sealant remains stable for a relatively long period of time, such as months or more, with virtually no loss of oxygen absorbency; It is based on the finding that, in connection with exposure to a humid atmosphere, residual oxygen in the packaging container is almost completely absorbed within a very short time, such as within 4 days. According to the present invention, residual oxygen in the packaging container is absorbed into the sealant within a relatively short period of time, thereby preventing oxidative deterioration of the contents and preventing the growth of mold, yeast, bacteria, etc. becomes possible. In addition, since the oxygen absorbent in the sealant exhibits a higher oxygen absorption rate as the temperature increases, the content is filled hot,
Or when performing hot water sterilization, retort sterilization, etc.
The advantage is also achieved that residual oxygen can be removed very quickly. In the present invention, the phenol aldehyde resin used as an oxygen scavenger is insoluble in water and has a large molecular weight, so it has the characteristics of retaining the flavor of the contents and preventing migration and elution into the contents. It also has The oxygen absorption effect of the phenol aldehyde resin used in the present invention can be expressed by the following chemical formula: It is expressed as Polyhydric phenols such as hydroquinone themselves have oxygen absorbing properties, but when such polyhydric phenols are used as they are, they pose problems such as elution and migration into the contents. On the other hand, when this polyhydric phenol is incorporated into the phenol aldehyde resin as a phenol skeleton, its alkyl substitution effect significantly promotes oxygen absorption. Not only that, by polymerizing polyhydric phenol as a resin, its elution and migration into the contents is completely suppressed, and as is clear from the chemical formula (1) above, the absorbed oxygen is harmless in the form of water. It is something that can be converted into A further supplementary explanation will be given regarding this point. The reaction in which a polyvalent phenol skeleton such as hydroquinone absorbs oxygen is expressed by the following formula: It is expressed as This reaction is an equilibrium reaction, and its equilibrium constant (k) is expressed by the following formula: 1nK=(4F/RT)E0 ₀₂ −E0 _R ) ...(1″) where E0 ₀₂ : Redox potential of oxygen E0 _R : Oxidation-reduction potential of the compound F: Hairradday's constant R: Gas constant T: Temperature. From the above formula (1''), the smaller E0 _R is, the larger K is, and the equilibrium shifts to the right, that is, deoxidation It is determined that progress will be made quickly. In fact, the redox potential of hydroquinone monomer and the phenolaldehyde resin obtained by polycondensing hydroquinone with formaldehyde (resin of Example 1 alone) was measured by cerium ammonium nitrate titration, and the amount of dissolved oxygen was measured. The measured results are shown in Table A. The amount of dissolved oxygen was measured by mixing an amount of the oxygen absorbent with the same amount of effective functional groups in 250 ml of water, and measuring the amount of dissolved oxygen 3 days later. Note that the initial dissolved oxygen amount was 8.2 ppm.

[Table] From the above results, it can be seen that by incorporating polyhydric phenol into the resin, the redox potential of the compound itself can be reduced to a small value, and the deoxidation reaction actually progresses rapidly. The oxygen absorbent used in the present invention is designed to be used in high humidity conditions or for liquid contents, and for hygienic reasons, it needs to be water-insoluble. The compound having multiple phenolic hydroxyl groups per ring, which is the raw material for this oxygen absorbent, is water-soluble, but by polymerizing it, it becomes water-insoluble, making it suitable for liquid contents. It has been made available for use. That is, the solubility of hydroquinone in water at 20° C. is about 6% by weight, whereas the solubility of the resin of Example 1 in water is 0.0003% by weight or less. The phenol skeleton that forms this phenol aldehyde resin has the following formula: In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an amino group, or a halogen atom, and is derived from a phenol containing a polyhydric phenol represented by the following formula. In the above general formula (2), it is particularly desirable for the two phenolic hydroxyl groups to be in the rose position for the production of a phenolic aldehyde resin. Suitable examples of the phenols of the above general formula (2) are:
Examples include hydroquinone, catechol, methylhydroquinone, pyrogallol, and hydroquinone is particularly preferred. In addition, the polyhydric phenol used is
It is preferable that the aldehyde has a polyfunctionality of difunctionality or higher, but even a monofunctional one can be incorporated into the phenol skeleton in the form of a polymer chain terminal. When manufacturing phenol aldehyde resin,
The polyhydric phenol of general formula (2) above can be used alone or in combination with other phenols. Phenols that can be used in combination include monocyclic monovalent phenols and polynuclear phenols in which one phenolic hydroxyl group is bonded to one ring. As monocyclic monovalent phenols, trifunctional phenols, such as those of the formula In the formula, R ₁ is a hydrogen atom, a monovalent hydrocarbon group, or an alkoxy group. Phenols represented by the following, especially carbolic acid, m-cresol, m-methylphenol, 3,5-xylenol, m-methoxyphenol, etc. ; difunctional phenols, e.g. In the formula, R ₁ has the above-mentioned meaning, R ₂ is a hydrogen atom, a monovalent hydrocarbon group, or an alkoxy group, and two of the three groups R ₂ are hydrogen atoms,
One of which is a hydrocarbon or alkoxy group, difunctional phenols represented by, in particular ₀ -cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol, p-tert-amylphenol, p-cyclohexylphenol, p-phenylphenol, etc.; monofunctional phenols, for example, in the general formula (4), three groups
Phenols in which one R ₂ is a hydrogen atom and two are hydrocarbon groups or alkoxy, particularly 2,4-xylenol, 2,6-xylenol, etc. can be mentioned. On the other hand, polycyclic phenols include tetrafunctional phenols, such as In the formula, R ₃ is a direct bond or a divalent bridging group, especially an alkylidene group having 10 or less carbon atoms, -O-, -S
phenols represented by -, -SO-, especially 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)butane [bisphenol A], -, -SO-, Phenol B], 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane [bisphenol F], 4,4'-dihydroxydiphenyl, 4,4-dihydroxydiphenyl ether can be mentioned. In the above-described condensation reaction between phenols and aldehydes, it is important to ensure that the polyhydric phenol component of formula (2) is introduced into the phenol aldehyde resin without being oxidized. The oxidation reaction of polyhydric phenols is significantly promoted on the alkaline side. From this point of view, in one embodiment, a phenol component and formaldehyde are condensed and polymerized in the presence of an acidic catalyst, such as oxalic acid, hydrochloric acid, phosphoric acid, etc., and used in the form of a novolac type phenol aldehyde resin. When producing a novolak type phenol-aldehyde resin, the condensation polymerization reaction is carried out in a non-oxidizing atmosphere, for example in a nitrogen stream or under vacuum, in order to prevent oxidation of the phenol component as much as possible. The degree of oxidation of the phenol component that occurs during seed polymerization is influenced to some extent by the type of polyhydric phenol used. For example, hydroquinone is relatively stable to oxidation during condensation, while pyrogallol is relatively unstable to oxidation during condensation. In the production of novolak resin, the formaldehyde component is preferably used in an amount of 0.7 to 3.0 mol per ring of the phenol component, and the molecular weight of the resin is within the same range as that of ordinary novolac resins, e.g.
It can range from 300 to 1500. In another embodiment of producing an oxygen absorbent, a resol type phenol aldehyde resin is produced by polycondensing a phenol component and formaldehyde in the presence of an alkali catalyst such as ammonia, caustic soda, magnesium hydroxide, etc. A phenol aldehyde resin is reduced to obtain a reduced resol type phenol aldehyde resin containing a polyhydric phenol component in a non-oxidized state. The reduction of the resol resin can be easily carried out by a method known per se, for example, a hydrogenation method using a hydrogenation catalyst such as a palladium catalyst, or a method of bringing it into contact with a reducing agent such as hydrosulfite. When producing a resol resin, the formaldehyde component is preferably used in an amount of 1.0 to 1.5 mol per ring of the phenol component, and the molecular weight of the resin is within the same range as that of ordinary resol resins, for example,
It can range from 300 to 700. The polyhydric phenol-containing phenolaldehyde resin used in the present invention may be modified with a known modifier such as a fatty acid, a polymerized fatty acid, a fatty acid (or rosin), a drying oil, an alkyd resin, etc., as long as its essence is not lost. After modification with a species or two or more species, combination with epoxy resin, or both resins,
If desired, vinyl acetal (butyral) resin, amino resin, xylene resin, acrylic resin,
Of course, it is also possible to modify with a modifying agent such as silicone resin, wax, phosphoric acid, or amino. These modifiers may be added in an amount of 0.01 to 5.0 per the total amount of both resins.
%, especially from 0.1 to 2.0%. These phenolic aldehyde resins used in the present invention are used alone or in combination with other resins as oxygen absorbers. At this time, the phenol skeleton having a plurality of phenolic hydroxyl groups per ring is contained in an amount of 50 mmol or more, especially 100 mmol or more per 100 g of solid resin content. In other words, if the content of the polyvalent phenol skeleton is less than the above range, sufficient oxygen absorption may not be obtained to effectively prevent oxidative deterioration of the food contents when used as an oxygen absorber. be.
On the other hand, there is no particular disadvantage if the amount of polyvalent phenol skeleton is large, but the resin yield may decrease and the amount of soluble components may increase, so the concentration of polyvalent phenol skeleton should be 850 mmol/100 g or less. ,especially
The amount is preferably 800 mmol/100 g or less. In the present invention, all elastomer polymers conventionally used as sealants can be used. Suitable examples of elastomeric polymers include, but are not limited to, flexible vinyl chloride resins, low density polyethylene, ethylene-vinyl acetate copolymers, and low-density polyethylene/ethylene-vinyl alcohol copolymer blends. , ethylene-propylene copolymer, thermoplastic styrene-butadiene-styrene block copolymer, thermoplastic styrene-isobrene-styrene copolymer, ethylene-propylene rubber, ethylene-propylene-nonconjugated diene rubber, styrene-butadiene - Rubber, nitrile-butadiene rubber, butyl rubber, natural rubber, polyptadiene, chloroprene rubber, polyurethane, acrylic rubber, silicone rubber, etc. These elastomeric polymers are available in the form of coating solutions, such as solutions, organosols, plastisols, suspensions, emulsions, etc., or in the form of powders, preforms, packings or melts, for easy application to the lid. It is applied to the lid. Particularly suitable elastomeric polymers are vinyl chloride resins, especially in the form of plastisols, styrene-butadiene rubber (SBR), especially solvent-type SBR, and low density polyethylene. According to the present invention, for the above-mentioned elastomeric polymer, per 100 parts by weight of the elastomeric polymer,
0.1 to 50 parts by weight of the aforementioned water-insoluble oxygen absorber;
In particular, it is blended in an amount of 5 to 20 parts by weight. That is, when the amount of the oxygen absorbent is less than the above range, the residual oxygen absorption effect is unsatisfactory, while when it is more than the above range, the cushioning properties, elasticity, sealing action, etc. inherent to the sealant are impaired. become. Various means can be employed to incorporate the oxygen absorber into the elastomeric polymer. For example, to incorporate the oxygen absorber into a coating solution, the oxygen absorber may be incorporated in the form of a powder filler or in the form of a solution, and to incorporate into the elastomeric polymer itself, the oxygen absorber powder may be incorporated. They may be blended in the form of a dry blend or during kneading. In addition to the above-mentioned essential components, the sealant composition of the present invention can contain various components known per se. For example, calcium carbonate, silica, various clays, magnesium hydroxide, magnesium carbonate, aluminum silicate,
Fillers such as barium magnesium silicate, barium sulfate, diatomaceous earth, mica, aspest, etc. can be used, and in order to adjust the hue, white pigments such as titanium dioxide, carbon black, phthalocyanine blue, phthalocyanine green, Bengara,
Coloring pigments such as titanium yellow can be added. Further, for the purpose of increasing the adhesion to can lids and bottle lids, a tackifying agent such as coumaron resin, petroleum resin, rosin, modified rosin, etc. can be added. Furthermore, for use as packing or liner for bottle lids, treatments such as foaming or cross-linking foaming may be performed to increase cushioning properties, and in this case, 2,2'- Azobisisobutyronitrile, azodicarbonamide,
Or blowing agents such as 4,4-oxybisbenzenesulfonyl hydrazide, sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, dicumyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide, benzoyl peroxide, etc. , 4-dichlorobenzoyl peroxide,
Crosslinking agents such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3, poly-p-dinitrosobenzene, and triallyl cyanurate can be used. Furthermore, a stabilizer can be added when mixing an oxygen absorber to the elastomer polymer or for the purpose of protecting the elastomer polymer from heat history during embossing. In this case, commonly used stabilizers for elastomers can be used, but from a sanitary standpoint, metal salts of stearic acid or lauric acid such as zinc, calcium, lithium, magnesium, aluminum, etc. Preferred are organic tin compounds represented by octyltin dilaurate, di-n-octyltin-s,s'-bis(isooctylmercabutoacetate), and the like. Furthermore, when vinyl chloride resin is used in the form of plastisol, commonly used di-2-ethylhexyl phthalate, di-n
- Phthalic acid derivatives such as octyl phthalate, diisobutyl phthalate, diphenyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, ethyl phthalylethyl glycolate, butylphthalyl butyl glycolate, di-2-ethylhexyl adipate, diisodecyl adipate, diisononyl adipate , di-(butoxyethoxyethyl)adipate, adipic acid derivatives such as di-2-ethylhexyl azelate, di-n
- azelaic acid derivatives such as hexyl azelate,
Sebacic acid derivatives such as di-2-ethylhexyl sebacate and di-n-butyl sebacate, di-n-
Maleic acid derivatives such as butyl maleate, epoxidized soybean oil, epoxidized linseed oil, epoxidized butyl linseed oil fatty acid, epoxy derivatives such as epoxidized castor oil, paraffin chloride, glyceroyl triacetate, polyethylene glycol, and 2- Phosphoric acid derivatives such as ethylhexyl diphenyl phosphate, citric acid derivatives such as acetyl tri-2-ethylhexyl citrate, oleic acid derivatives such as butyl oleate, ricinoleic acid derivatives such as butylacetyl ricinoleate, n- Stearic acid derivatives such as butyl stearate, sulfonic acid derivatives, etc. can be used. In addition, when lowering the viscosity of plastisol for processing reasons, linear paraffin solvents such as diisobutyl ketone, methyl isobutyl ketone, butyl acetate, ethyl acetate, glycol ether, n-hexane, n-heptane, benzene, Aromatic hydrocarbons such as toluene and xylene, alcohols such as ethanol and methanol, naphthenic solvents such as cyclopentane, cyclohexane and methylcyclohexane, or terpene compounds such as myrcene and linalool can also be added as main components. In the present invention, the oxygen absorption reaction of the phenol aldehyde resin having the polyhydric phenol skeleton described above is significantly accelerated on the alkaline side. From this point of view, in the present invention, 1 to 1000 parts by weight per 100 parts by weight of resin for the phenol aldehyde resin,
In particular, it is desirable to use 10 to 200 parts by weight of a solid base in combination. As a solid base, in terms of flavor retention and hygienic properties of the contents,
Water-insoluble materials are desirable, such as anion exchange resins, zinc oxide, magnesium carbonate, silicates,
Any electron-donating material such as zeolite, melamine resin, urea resin, ammonia resol resin, etc. can be used. Furthermore, in order to further satisfy the purpose of promoting the oxygen absorption reaction, gelatin, modified casein,
Modified starch, sodium alginate, tracanth gum, polyvinyl alcohol, methyl cellulose,
Cellulose derivatives such as methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, partially saponified polyvinyl acetate, polyvinyl methyl ether, polyacrylic acid, polymethacrylic acid, vinyl methyl ether/maleic anhydride copolymer,
Polyvinylpyrrolidone, acrylamide/acrylate copolymer, acrylamide/methylenebisacrylamide copolymer partial silicide, vinyl acetate/methyl acrylate copolymer silicide, polyoxyethylene compound, polystyrene sulfonic acid,
Hydrophilic compounds such as poly-2-acrylamido-2-methylpropanesulfonic acid can also be included. In the present invention, the above-mentioned sealant composition can be applied to the can lid or bottle lid by means known per se. For example, in the case of a can lid, a sealant composition in the form of a coating liquid is injected from a nozzle into a groove in the can lid that rotates on a rotating chuck, and is dried to form a sealing gasket. In the case of bottle lids such as caps and crowns,
In addition to the methods described above, the sealant composition may be melt extruded onto the bottle lid and embossed while cooling.
It is packed in a predetermined shape. Of course, a powder or preform of the sealant composition is applied on the bottle lid,
It is also possible to form packing into a predetermined shape by stamping under heating and then cooling. Additionally, a packing or liner of the sealant composition may be produced outside the bottle lid and fitted onto the bottle lid. The excellent effects of the present invention will be explained with the following examples. Example 1 1 mole of hydroquinone and 238 g of a 37% formaldehyde aqueous solution are subjected to addition condensation at a reaction temperature of 90° C. in the presence of 0.01 mole of oxalic acid, and then hot water is poured into a reaction tank to obtain a hydroquinone formaldehyde resin.
At this time, the obtained resin had a number average molecular weight (n) of 1050 and a weight average molecular weight (n) of 1.10 as determined by the molecular weight measuring method shown below. Further, according to a potentiometric titration method using cesium nitrate, the resin contained 580 mmol of a phenol skeleton having a plurality of phenolic hydroxyl groups per ring per 100 g of resin solid content. This hydroquinone formaldehyde resin is a vinyl chloride resin for pasting, plasticity, stabilization,
A plastisol having the composition shown in Table 1 is made of a coloring agent.
This plastisol is applied to the inner surface of a glass bottle cap and heated at 200°C for 90 seconds to gel. The bottle was filled with air-saturated distilled water so that a head space of 25% of the bottle capacity remained, and the cap of the product of the present invention was tightened and sealed. The amount of oxygen in the headspace was measured over time using a gas chromatograph. 3
After a day, 30% of the oxygen had been consumed. In the comparison product, only a 4.5% decrease in oxygen was observed. Molecular Weight Measurement Method Hydroquinone formaldehyde resin was dissolved in tetrahydrofuran (THF) to a concentration of 1% to prepare a measurement solution. As an analytical column in a high performance liquid chromatograph device (Tosoh Model 8020)
One foot each of G1000H, G2000H, G3000H, and G4000H was connected and used for measurement. Measurement temperature is 40℃
The flow rate is 1 ml/min. 100μ of the measurement solution was injected into this device and the molecular weight distribution was measured. The calibration curve is based on standard monodisperse polystyrene with a molecular weight of 43,000.
23000, 11700, 5700, and 530, and the number average molecular weight and weight average molecular weight were calculated from this.

【table】

[Table] Example 2 A mixture of plastisol containing the hydroquinone/formaldehyde resin of Example 1 and 2 parts by weight of sodium hydrogen carbonate, an open-cell blowing agent, was similarly applied to the inner surface of a glass bottle cap and heated to gel. The resulting material was used as a lid for a glass bottle filled with air-saturated distilled water so that 1/3 of the bottle capacity remained as head space. The amount of oxygen consumed by using this cap was as shown in Figure 1. Further, air-saturated distilled water was filled so that no head space remained, and the amount of dissolved oxygen was determined using a dissolved oxygen meter. As shown in Figure 2, the initial amount of dissolved oxygen was 8.39 ppm, which decreased to 0.7 ppm after 3 days. Example 3 An oxygen-absorbing resin condensed from 1.0 mol of hydroquinone and 238 g of a 37% formaldehyde aqueous solution was mixed into a conventional liner composition consisting of low-density polyethylene, ethylene/propylene rubber, a colorant, a lubricant, and an antioxidant. was mixed in a proportion of 20 parts by weight. The mixture was melt extruded and embossed into liners on the inside of bottle caps. This cap was used as a lid for a container filled with air-saturated distilled water, and as shown in Figure 3, which compared the reduction in dissolved oxygen, it was more effective than a comparative product. Example 4 A 10% glycine-10% xylose solution was filled into a bottle, and a normal cap and the cap of Example 2 were attached to measure the degree of coloration. After 30 days of storage at 37°C, the coloring degree of the product of the present invention was found to be 0.9, compared to 1.6 for the normal product.

[Brief explanation of drawings]

Figure 1 shows the change over time in the amount of oxygen consumed when the sealant composition of the present invention is used in the lid of a glass bottle filled with air-saturated distilled water so that 1/3 of the bottle volume remains as head space. Figure 2 is a diagram showing the change over time in the amount of dissolved oxygen when the sealant composition of the present invention is used in the lid of a glass bottle filled with air-saturated distilled water so that no head paste remains. FIG. 3 is a diagram showing changes over time in the amount of dissolved oxygen when the sealant composition of the present invention and a comparative product are respectively applied to the lid of a container and the container is filled with air-saturated distilled water.

Claims (1)

[Scope of Claims] 1. An oxygen absorber made of a phenolic aldehyde resin having a plurality of phenolic hydroxyl groups per ring in the phenol skeleton is added to an elastomer polymer at a solid content of 100% of the solid content of the elastomer polymer.
A sealant composition for a can lid or bottle lid used for oxygen absorption in a sealed package, characterized in that the composition is blended in an amount of 0.1 to 50 parts by weight. 2 The phenol skeleton has the following formula wherein R represents a hydrogen atom, a hydroxyl group, an alkyl group, an amino group, or a halogen atom; the sealant according to claim 1, which is derived from a phenol containing a polyhydric phenol represented by: Composition. 3. Claims in which the phenol-aldehyde resin is a novolac-type phenol-aldehyde resin obtained by condensation polymerization of formaldehyde and a phenol component containing phenol having a plurality of phenolic hydroxyl groups per ring. The sealant composition according to item 1. 4. The phenol-aldehyde resin is a resol-type phenol-aldehyde resin obtained by polycondensation of a phenol component containing phenol having a plurality of phenolic hydroxyl groups per ring with a formaldehyde component and subsequent reduction. A sealant composition according to claim 1. 5 The phenolic aldehyde resin has a phenol skeleton having a plurality of phenolic hydroxyl groups per ring, per 100 grams of solid content of the resin.
The sealant composition according to claim 1, containing the sealant composition in an amount of from 850 mmol to 850 mmol. 6. The sealant composition of claim 1, wherein the phenolic aldehyde resin is present in the form of dispersed particles in the sealant composition. 7. The phenolic aldehyde resin is present in the sealant composition in the form of a solution.
The sealant composition described in . 8. The oxygen absorber of the composition further comprises a phenolic aldehyde resin and 1 to 1000 parts by weight of a water-insoluble solid electron-donating substance per 100 parts by weight of the phenolic aldehyde resin. Sealing composition. 9. The sealing composition according to claim 8, wherein the solid electron donating substance is an anion exchange resin, zinc oxide, magnesium oxide, calcium carbonate, zeolite, ammonia resol resin, melamine resin or urea resin. 10 Claim 1 in which the elastomer polymer is present in a plastisol system of vinyl chloride resin
The sealant composition described in . 11. The sealant composition of claim 1, wherein the elastomeric polymer is styrene-butadiene rubber.