JP2925284B2 - Packaging material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a packaging material having excellent gas barrier properties during storage, good smoke properties, and no blocking in a hot water treatment step.

B. Prior Art In the manufacture of processed meat products represented by Bonless Ham, peach meat from which blood has been removed and deboned is immersed and pickled in a pickle solution consisting of salt, saltpeter, sugar and spices. Next, the meat is desalted with water, packed in a casing and smoked. Smoke uses smoke obtained from firewood or sawdust such as cherry blossoms, oaks and sugi, and is usually at a temperature of 10 to 120 ° C (can be divided into cold, warm, hot and roasting methods depending on the temperature). However, a hot-cooking method at 50 to 80 ° C is often used. The smoked ham is boiled in hot water for 30 minutes so that the central temperature is about 65 ° C, cooled, and further packaged and shipped.

In the case of using a non-permeable casing, it is necessary to adopt a liquid method of applying a liquid obtained by carbonizing wood such as cherry blossoms, oak, and ku in order to soak the smoke odor in the contents.
The process had to be complicated.

Conventionally, as a primary packaging material for processed meat products such as ham and sausage, natural casings such as sheep intestine, pig intestine, and cattle intestine,
Smokable casings such as collagen casings, cellulose casings, and fibrous casings, and non-permeable casings based on polyvinylidene chloride have been used.

For natural casings such as sheep, pig, and cow intestines, remove the intestinal tract membrane and the like adhering to the digestive tract of sheep, pigs, and cows, squeeze out the contents, remove the mucous membrane of the tube wall, and wash and salt. Although it has good smokeability and shrinkage, it has disadvantages such as low strength, high cost, poor gas barrier properties during storage, and inconsistent size and quality.

The collagen casing is a tube-shaped product of a collagen stock solution obtained from cow hide or the like, and has good smoke properties, but poor gas barrier properties during storage.
Under a high humidity condition such as a heating process, there were the drawbacks that gelatinization was likely to occur in the smokehouse and that the taste was poor due to the thickness.

Cellulose casing is a product obtained by coagulating viscose into a tube.It has good smokeability and suitability for filling machinery, but is non-edible, has poor gas barrier properties during storage, and peels small objects. There were drawbacks needed.

The fiber brass casing is made by applying and impregnating viscose on a nonwoven fabric such as manila hemp and solidifying and regenerating.It has good smokeability and filling machine suitability, but is non-edible and has a gas barrier during storage. There are drawbacks such as poor properties and the necessity of immersion in lukewarm water before use.

A fibrous casing coated with a vinylidene chloride copolymer latex to improve gas barrier properties during storage is already on the market, but has the problem of deteriorating smoke properties.

Polyvinylidene chloride-based non-permeable casing is a product obtained by blending a plasticizer and a stabilizer with a resin obtained by copolymerizing vinyl chloride and vinyl chloride, and molding it into a tube.The gas barrier property during storage is good. Yes, but not edible,
There were drawbacks such as poor smoke properties.

As described above, since a casing having a good smoke property has a poor gas barrier property at the time of storage, it is necessary to perform secondary packaging or repacking with a packaging material having a good gas barrier property at the time of storage. This was a major problem in terms of reduction and simplification of the process.

Ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) has poor gas barrier properties when wet and shows very good gas barrier properties when dry. Therefore, if the nonwoven fabric such as Manila hemp is applied and impregnated with viscose, and EVOH is laminated on the outside of the coagulated and regenerated fibrous casing, a product with good smoke properties and gas barrier properties during storage can be obtained, but In the middle of the hot water treatment process, there is a problem that EVOHs in the outer layer cause blocking. Conversely, if EVOH is laminated inside the fibrous casing, blocking does not occur in the hot water treatment process, but the problem that the gas barrier property during storage is not sufficiently improved because it is always in contact with wet contents. is there.

JP-A-56-163141 discloses a resin composition comprising 100 parts by weight of a water-soluble or water-dispersible vinyl alcohol-based polymer and 0.5 part by weight or more and less than 100 parts by weight of a water-soluble polyamide. There is a description used for adhesives. However, the invention states that the resin composition completely dissolves when immersed in water at 25 ° C., but uses a water-insoluble vinyl alcohol-based polymer and further blocks in a hot water treatment step. There is no description on preventing fiber optics or fibrous casing.

Japanese Patent Application Laid-Open No. 57-212269 discloses a highly water-absorbing polymer as a main component, which is insoluble in water and has a water absorption of 0.5%.
There is a description of a swellable coating composition obtained by mixing a solution in which a polymer capable of forming a film is dissolved in an organic agent.
However, there is no description in the invention of preventing blocking in the hot water treatment step or of a fibrous casing.

Japanese Patent Application Laid-Open No. 55-34956 discloses that a film of a molten composition of EVOH and nylon does not whiten even during heat sterilization and retains good gas barrier properties during storage. However, the invention does not relate to water- or alcohol-soluble nylon or to a fibrous casing.

Japanese Patent Application Laid-Open No. 62-225535 discloses EVOH having an ethylene content of 20 to 60 mol% and a saponification degree of a vinyl acetate component of 90 mol% or more, nylon, and a water solution of a Group I or Group II metal of the Periodic Table. A process for obtaining a film from a solution using a neutral salt is described. However, the present invention relates to improvement of high-speed stretchability by heating, and there is no description about prevention of blocking in a so-called hot water process or a fibrous casing.

As described above, a casing having a constant product size and quality, excellent in smoke property, suitability for filling machine, and good in gas barrier property during storage has not yet been developed, and there is a long-awaited demand in the industry.

C. Problems to be Solved by the Invention The present invention has a constant product size and quality, is excellent in smokeability and filling machine suitability, has no blocking in a hot water treatment process, and has a gas barrier property in storage. And a casing for processed meat products such as ham and sausage.

D. Means for Solving the Problems As a result of intensive studies based on recognition of the above problems, the present inventors have found that EVOH 60 to 98% by weight having an ethylene content of 20 to 65 mol% and water or alcohol soluble Nylon 40-2
By weight, the packaging material having a resin composition layer consisting of the resin composition layer on the outer surface of the fibrous casing has excellent smokeability and suitability for a filling machine, has a uniform size and quality, and has no blocking in the hot water treatment process. In addition, it has good gas barrier properties during storage, and is excellent as a temporary packaging material for processed meat products such as ham and sausage.
The present invention has been completed.

Hereinafter, the present invention will be described in more detail. In the present invention, a fibrous casing is a packaging material in which a fibrous base material is coated or impregnated with a polymer substance. Impregnated and dried after solidification, regeneration, water washing, desulfurization, water washing, and softening processes. For example, Mitron of Fujimori Kogyo Co., Ltd., Toho Casing of Mima Trading Co., Ltd., Osaka Chemical Alloy Co., Ltd. ) Which are sold under a trade name such as Art Fibers.

In the present invention, EVOH is typically a saponified ethylene-vinyl acetate copolymer, having an ethylene content of 20 to 65 mol%, preferably 20 to 50 mol%, and a degree of saponification of the vinyl acetate component. 90 mol% or more, preferably 95 mol%
That is all. If the ethylene content is less than 20 mol%, the gas barrier property at high humidity decreases. On the other hand, if the content exceeds 65 mol%, not only sufficient gas barrier properties cannot be obtained, but also the storage stability of the solution deteriorates. Further, even when the degree of saponification is less than 90 mol%, the gas barrier property at high humidity is reduced.

EVOH also contains a small amount of propylene, isobutene,
Α-olefins such as methylpetene-1, hexene and octene, unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride, salts thereof, partial and complete esters thereof, nitriles thereof, amides thereof and anhydrides thereof , An unsaturated sulfonic acid, a salt thereof, and a copolymerization component such as a vinylsilane-based compound such as vinyltrimethoxysilane.

In addition, EVOH consists of two or more EVs with different ethylene copolymerization ratios.
It may be a mixture of OH or a mixture of two or more EVOHs having different degrees of polymerization. Both the ethylene copolymerization ratio and the degree of polymerization may be different.

In the present invention, any nylon soluble in water or alcohol can be used as long as it is soluble in water or alcohol, but the following are typical examples. That is, dodecylenediamine, hexamethylenediamine, piperazine, tetramethylenediamine, trimethylenediamine, ethylenediamine, m-
Diamine components such as xylylenediamine and p-xylylenediamine, and aminocarboxylic acid components such as γ-butyrolactam, δ-valerolactam, ε-caprolactam, ω-laurolactam, ω-aminoundecanoic acid, ω-aminododecanoic acid, etc. And terephthalic acid, isophthalic acid, various naphthalene dicarboxylic acids, azelaic acid, sebacic acid, pimelic acid, adipic acid, glutaric acid, nylon obtained from polycarboxylic acid components such as succinic acid as raw materials,
Preferably 10 to 90% by weight in the molecule, preferably 20 to 80%
Nylon having 2% by weight of ether bonds, 2 per molecule
Nylon having ester bonds of .about.70 mol%, preferably 5-50 mol%, i) sulfonic acid groups in the molecule of 1-50 mol%, preferably 2-25 mol%, ii) alkali metal salt of sulfonic acid Iii) Nylon having a sulfonic acid derivative such as a salt of one or more amine derivatives selected from ammonia, primary amine, secondary amine and tertiary amine and sulfonic acid, and an ammonium salt in the molecule Nylon having a nitrogen atom of a type is desirable.

Nylon having an ether bond in the molecule thereof can be obtained by using any polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol when obtaining nylon by condensation polymerization. Akira
It is manufactured by a method known in JP-A-60-161453 and JP-A-60-163952.

Nylon having an ester bond in the molecule of 1,3-cyclohexanedimethanol, ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol, hexamethylene It can be obtained by using any polyhydric alcohol component such as glycol, glycerin, and pentaerythritol. Furthermore, ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, tetramethylene glycol,
Polyhydric alcohol components such as neopentyl glycol, diethylene glycol, hexamethylene glycol, 1,3-cyclohexanedimethanol, glycerin, pentaerythritol, and δ-valerolactone, ε-caprolactone, ω-laurolactone, ω-hydroxyundecanoic acid, ω-hydroxydodecanoic acid, a hydroxycarboxylic acid component such as p-hydroxybenzoic acid, and terephthalic acid;
By an ester-amide exchange reaction of nylon with any polyester obtained from polycarboxylic acid components such as isophthalic acid, various naphthalene dicarboxylic acids, azelaic acid, sebacic acid, pimelic acid, adipic acid, glutaric acid, succinic acid, etc. Are also obtained, JP-A-49-44098, JP-A-51-125194, JP-A-56-88428 and JP-T-61-501515.
It is manufactured by a known method.

Nylon having a sulfonic acid derivative in its molecule also includes sodium 2,5- or 3,5-dicarboxybenzenesulfonate, 2,5- or 3,5 during condensation polymerization.
-Sodium dicarboxymethylbenzenesulfonate,
Sodium 2,5- or 3,5-dicarbomethoxybenzenebenzenesulfonate, sodium 2,5- or 3,5-dicarbomethoxymethylbenzenesulfonate, furthermore, a sodium salt of the above compound with an alkali metal such as potassium, ammonia, It can be obtained by using an arbitrary sulfonic acid derivative such as a primary amine, a secondary amine, a compound substituted with a tertiary amine, etc., by a method known in JP-B-49-27522 and JP-A-49-27523. Manufactured.

Nylon having an ammonium salt type nitrogen atom in the molecule of N, N'-bis (carboxymethyl) piperazine, N, N'-bis (2-carboxyethyl) piperazine, N, N '-Bis (carboxymethyl) methylamine, N, N'-bis (2-carboxyethyl) methylamine, N, N'-dimethyl-N, N'-bis (carboxymethyl) ethylenediamine, N, N'-dimethyl It is obtained by using an arbitrary tertiary amine derivative such as -N, N'-bis (2-carboxyethyl) ethylenediamine, and is produced by a conventional method.

EV with nylon soluble in water or alcohol
When used in combination with OH, blocking in the hot water treatment step can be prevented.

The blend ratio of nylon soluble in water or alcohol is 40 to 2% by weight, preferably 30 to 10% by weight.
If the blend ratio of nylon is less than 2% by weight, the effect of preventing blocking in the hot water treatment step is not sufficient. Meanwhile, 40
If the content is more than 10% by weight, the gas barrier property is greatly reduced.

In the present invention, the alcohol means a monohydric alcohol such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, and a polyhydric alcohol such as ethylene glycol and glycerin. And ethanol, n-propanol and t-butanol are preferred.

In the present invention, as a method of obtaining a resin composition layer composed of EVOH and nylon, a resinous material of EVOH and nylon is obtained by a method using a Banbury mixer, a single-screw or twin-screw extruder, a Brabender plastograph, or the like. , A method of dissolving it in a water-alcohol mixed solvent to form a solution, dissolving EVOH in a water-alcohol mixed solvent, dissolving nylon in a water-alcohol mixed solvent, water or alcohol, and mixing those solutions And a method of simultaneously dissolving a mixture of EVOH and nylon in a mixed solvent of water and alcohol to form a solution, and laminating the obtained solution by solution coating.

Further, the resin composition of the present invention includes various additives such as an antioxidant, an ultraviolet absorber, a coloring agent, a slip agent, an antistatic agent, a plasticizer, and various kinds of polyolefins as long as the present invention is not impaired. You may mix resin. The proportion of these components is at most 20% by weight, preferably at most 15% by weight, based on the whole composition.

Here, the mixing ratio of each component of the water-alcohol mixed solvent is 10 to 70% by weight of water and 90 to 30% by weight of alcohol.
Water-alcohol mixed solvents include carboxylic acids such as formic acid and acetic acid, phenol, and the like, as long as the present invention is not impaired.
One or more of phenols such as cresol, amines such as ethylenediamine and trimethylenediamine, amides such as dimethylacetamide and N-methylpyrrolidone, and dimethylsulfoxide may be mixed.

Further, a surfactant, a leveling agent, a coloring agent, an antifoaming agent, and the like may be mixed with the water-alcohol mixed solvent as long as the present invention is not impaired.

As a method of laminating a resin composition layer composed of EVOH and nylon and a fibrous casing, a solution of a water-alcohol mixed solvent of the resin composition is coated on the outer surface or both surfaces of the fibrous casing, and then the solvent is evaporated. To form a resin composition layer.
At this time, in order to improve the interlayer adhesion between the resin composition layer and the fibrous casing layer, it is preferable that the layers are laminated via a polyester-based or urethane-based two-component curable adhesive.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

All parts and percentages are by weight unless otherwise specified.

E. Examples Example 1 In 90 parts of a mixed solvent containing 35% of water and 65% of n-propanol, an ethylene content of 32 mol% and a degree of saponification of a vinyl acetate component were added.
8 parts of EVOH with 99.5 mol%, MI (value measured at 190 ° C. under a load of 2160 g, the same applies hereinafter) of 1.4 g / 10 min, and water-soluble nylon (AQ nylon P-70 manufactured by Toray Industries, Inc .; ether-modified nylon) ) And 0.05 part of a leveling agent (Toray Silicone Co., Ltd. SH28PA) are added, and the mixture is stirred at 80 ° C for 2 hours.
A clear solution having a solid content of 10% was prepared.

Fibrous casing (manila hemp nonwoven fabric coated and impregnated with viscose, coagulated and regenerated), polyester adhesive (main agent: 100 parts of Adcoat AD-335A manufactured by Toyo Morton Co., Ltd., curing agent: Toyo Morton C Co., Ltd.
AT-10 (6 parts), diluting solvent: methyl ethyl ketone / toluene = 1/1) was applied and dried (solid content: 2 g / m ² ). Further, the resin composition solution is applied thereon, dried and then heated at 160 ° C. for 1 hour.
Heat treatment was performed for 3 minutes to obtain a 3 μm-thick EVOH laminate.

After the laminate is immersed in hot water of 100 ° C for 5 minutes,
Blocking did not occur even if the H faces were pressed.

The amount of oxygen gas permeation at 20 ° C and 85% RH (Mod
OX-TRAN 10 / 50A manufactured by ern Controls)
It was as good as 3 ml / m ² · day · atmospheric pressure.

Compared with the original uncoated fibrous casing, the suitability for filling the EVOH-coated fibrous casing was not deteriorated, and the smokeability by the hot-cooking method was good and had the same performance.

Comparative Example 1 The procedure of Example 1 was repeated, except that 2 parts of water-soluble nylon was not added.

Although the oxygen gas permeation amount of the laminate was as good as 11 ml / m ² · day · atm, it was not usable due to blocking by hot water.

Example 2 Example 1 was the same as Example 1 except that “2 parts of water-soluble nylon” was changed to “2 parts of alcohol-soluble nylon (AQ nylon K-80 manufactured by Toray Industries, Inc., copolymerized nylon)”.
It went according to.

The laminate did not cause blocking by hot water. Moreover, the oxygen gas permeation amount at 20 ° C. and 85% RH of the laminate was as good as 14 ml / m ² · day · atmospheric pressure.

Compared with the original uncoated fibrous casing, the suitability for filling the EVOH-coated fibrous casing was not deteriorated, and the smokeability by the hot-cooking method was good and had the same performance.

Comparative Example 2 In Example 1, "water 35% and n-propanol 65%
EVO containing 90 parts of a mixed solvent containing ethylene and 32 mol% of ethylene, saponification degree of vinyl acetate component of 99.5 mol% and MI of 1.4 g / 10 min
H "was changed to" EVOH 90 parts of a mixed solvent containing 20% water and 80% n-propanol and an ethylene content of 68 mol%, a saponification degree of vinyl acetate component of 97 mol%, and an MI of 38 g / 10 min EVOH ". Example 1 was repeated except that the heat treatment at 160 ° C. for 1 minute was changed to “heat treatment at 110 ° C. for 1 minute”.

The laminate did not cause blocking by hot water. However, the amount of oxygen gas permeated at 20 ° C. and 85% RH of the laminate was 83 ml / m ² · day · atmospheric pressure, which was largely inferior to that of stored products.

Example 3 In Example 1, "EVO of 32 mol%, saponification degree of vinyl acetate component of 99.5 mol%, MI of 1.4 g / 10 min EVO"
H was changed to "EVOH with ethylene content 27 mol%, saponification degree of vinyl acetate component 99.7 mol%, MI 1.6 g / 10 min" and "Heat treatment at 160 ° C for 1 minute" was changed to "170 The procedure was performed in the same manner as in Example 1 except that the heat treatment was changed to "C for 1 minute."

The laminate did not cause blocking by hot water. In addition, the oxygen gas permeation amount of the laminate at 20 ° C. and 85% RH was as good as 11 ml / m ² · day · atmospheric pressure.

Compared with the original uncoated fibrous casing, the suitability for filling the EVOH-coated fibrous casing was not deteriorated, and the smokeability by the hot-cooking method was good and had the same performance.

Comparative Example 3 In 90 parts of water, the polymerization degree was 500 and the saponification degree of the vinyl acetate component was 98.3.
7 mol% of polyvinyl alcohol, 845 parts of ε-caprolactam, hexamethylene diammonium hadipate 5
90 parts, dimethyl 5-potassium sulfoisophthalate 218
And 3 parts of a sulfonic acid-modified nylon obtained from 132 parts of a 65% aqueous solution of hexamethylenediamine were stirred at 90 ° C. for 3 hours to obtain a transparent solution having a solid content of 10%. Hereinafter, a laminate was obtained according to Example 1.

In the laminate, the resin composition layer was eluted by hot water, and an improved fibrous casing made by storage was not obtained.

F. Effects of the Invention According to the present invention, the product size and quality are constant,
A casing for processed meat products such as ham and sausage can be obtained which is made of smoke, has excellent filling machine suitability, has no blocking during boil treatment, and has a good gas barrier property during storage.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 B65D 67/00-79/02 B65D 65/00-65/46 B65D 85 / 50

Claims (2)

(57) [Claims] 1. Ethylene having an ethylene content of 20 to 65 mol%.
A packaging material having a resin composition layer (A) composed of 60 to 98% by weight of a vinyl alcohol copolymer and 40 to 2% by weight of nylon soluble in water or alcohol on the outer surface of a fibrous casing (B). 2. The packaging material according to claim 1, wherein the layer (A) is laminated on the outer surface of the fibrous casing (B) through an adhesive layer.