JP6071102B2 - Wrapping paper - Google Patents

Description

  The present invention relates to a novel paper wrapper.

  Conventional wrapping paper (also referred to as release paper) generally employs, for example, a paper / water-soluble resin / silicone configuration (Patent Document 1). However, this configuration conforms to the standard for potassium permanganate consumption (dissolution test) stipulated in Ministry of Health and Welfare Notification No. 370 (final revision: Ministry of Health, Labor and Welfare Notification No. 201 of March 31, 2006). Not done. The test method of this standard is a test method in which an organic substance that migrates from a sample to water is oxidized with potassium permanganate and the amount thereof is measured as potassium permanganate consumption. In applications such as foods and medicines, it is preferable to conform to the above-mentioned standard, and when it does not conform to this standard, there is a possibility that organic substances may be mixed into foods, pharmaceuticals and the like.

JP-A-6-306797

  As a result of investigations and researches by the present inventors, the reason why the wrapping paper having the above configuration does not conform to the standard of potassium permanganate consumption is that water-soluble resin in the wrapping paper (generally polyvinyl alcohol: PVA). ). For this reason, although it is anticipated that the above-mentioned standards will be met if a water-soluble resin is not used, another problem arises that if the water-soluble resin is not used, the article to be packaged adheres to the wrapper.

  Therefore, a main object of the present invention is to provide a paper wrapper that is difficult to adhere to a package and that conforms to the standard of potassium permanganate consumption (dissolution test).

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a specific layer structure, and has completed the present invention.

That is, the present invention relates to the following wrapper.
1. 1) paper, 2) a polyolefin layer laminated on the front surface of the paper, 3) a wrapping paper comprising a silicone layer laminated on the polyolefin layer,
Aluminum foil is further laminated on the back of the paper, the aluminum foil is a soft foil,
The polyolefin layer comprises an aqueous dispersion of a) a copolymer metal salt ionomer of a polyolefin hydrocarbon and an unsaturated carboxylic acid, b) an ethylene vinyl acetate copolymer resin, c) a low density polyethylene, or d) a low molecular weight polyethylene. Formed using
A wrapping paper used to wrap food directly so that the aluminum foil is on the outer surface side.
2. Item 4. The paper wrapper according to Item 1, wherein the paper has a basis weight of 10 to 50 g / m ² .
3. Item 3. The wrapping paper according to Item 1 or 2, wherein the aluminum foil has a thickness of 5 to 25 µm.
4). Item 4. The paper wrapper according to any one of Items 1 to 3, wherein the consumption amount of potassium permanganate in the paper wrapper is 10 μg / mL or less.

  According to the present invention, since it has good releasability, it has a characteristic that the packaged contents (contents) are difficult to adhere, and also conforms to the standard of potassium permanganate consumption (dissolution test). Paper can be provided. In particular, regarding the peelability, not only the initial peelability is excellent, but also good peelability can be maintained even after long-term storage or even in an environment where the temperature (temperature) and humidity are high. Moreover, since it conforms to the standard of potassium permanganate consumption (dissolution test), higher safety can be exhibited.

  The wrapping paper of the present invention having such characteristics can be suitably used as a wrapping paper for foods, pharmaceuticals or chemicals, for example. In particular, as food, it is also suitable for packaging sweets such as chewing gum and soft candy.

It is a figure which shows an example of the laminated constitution of the wrapper of this invention. It is a figure which shows an example of the laminated constitution of the wrapper of this invention.

  The paper wrapper of the present invention is a paper wrapper comprising 1) paper, 2) a polyolefin layer laminated on the front surface of the paper, and 3) a silicone layer laminated on the polyolefin layer, wherein the polyolefin layer Is formed using an aqueous dispersion of polyolefin.

  FIG. 1 shows the basic layer configuration of the paper wrapper of the present invention. A polyolefin layer 2 is laminated on the front surface of the paper 1. Further, a silicone layer 3 is laminated on the polyolefin layer. The paper wrapper of the present invention is particularly characterized in that the polyolefin layer 2 is formed using an aqueous polyolefin dispersion. 1 is used, the silicone layer 3 side is the inside, and the paper 1 side is the outside. That is, a packaged item (contents) such as food and medicine may be placed on the silicone layer 3 and wrapped. A known method can be adopted as the wrapping method (packaging method) itself.

  In addition to the basic layer configuration described above, other layers may be laminated on the wrapper of the present invention. For example, as shown in FIG. 2, an aluminum foil 4 may be laminated on the back surface of the paper 1. In this case, the paper 1 and the aluminum foil 4 can be laminated via an adhesive layer (not shown). Hereinafter, the layer configuration of the wrapper of the present invention will be described.

Paper Paper (or papers) used in known or commercially available packaging materials can be used for the paper used in the wrapper of the present invention. For example, high-quality paper, glassine paper, craft paper, pure white roll paper, imitation paper, western paper, Japanese paper, various coated papers, and the like can be used. The basis weight of the paper is preferably about 10 to 50 g / m ^{2 in} terms of strength, flexibility and cost.

  The thickness of the paper to be used is not limited, but is usually about 10 to 100 μm, particularly 15 to 60 μm.

Polyolefin layer Polyolefin constituting the polyolefin layer includes, for example, ionomer, ethylene vinyl acetate copolymer resin, polyethylene (high density polyethylene, low density polyethylene, low molecular weight polyethylene (weight average molecular weight: several thousand), linear linear low At least one type such as a density polyethylene) or a polypropylene type can be suitably used. As the ionomer, known or commercially available products including modified ionomers can be used. For example, polyolefin ionomer, fluorine ionomer, polystyrene ionomer, polyester ionomer, (meth) acrylic ionomer, and the like can be used. Of these, polyolefin ionomers are preferred. Examples of the polyolefin ionomer include a copolymer metal salt of an olefinic hydrocarbon such as ethylene, propylene, and butene and an unsaturated carboxylic acid (acrylic acid, methacrylic acid, etc.). Commercially available products of such ionomers can also be used, and examples thereof include “High Milan” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) having methacrylic acid as an acidic monomer. In the present invention, at least one of an ionomer system, an ethylene vinyl acetate copolymer resin system, and a polyethylene system can be more suitably used from the viewpoint of easily forming a polyolefin coating film and having an excellent sealing effect on paper.

  The thickness of the polyolefin layer is not limited, but is generally about 0.3 to 5 μm, particularly 0.5 to 3 μm.

  In the paper wrapper of the present invention, the polyolefin layer is particularly formed using an aqueous polyolefin dispersion. That is, an aqueous dispersion in which the above polyolefin is dispersed in water is used. The concentration of the aqueous dispersion (the solid content concentration of the polyolefin) is not particularly limited and can be appropriately set according to the type of polyolefin to be used, but is usually about 50 to 600 g / L, particularly 150 to 450 g / L. It is preferable to do. In addition to polyolefins, surfactants, colorants, anti-settling agents and the like can be added as appropriate to the aqueous dispersion as needed. In particular, environmental protection, workability (working environment), food safety, etc. From the standpoint of properties, an aqueous dispersion containing no surfactant and organic solvent is preferred. Commercially available products can also be used as the aqueous polyolefin dispersion containing no surfactant and organic solvent. As such a commercially available product, for example, a trade name “CHEMIPARL (registered trademark)” (manufactured by Mitsui Chemicals) series can be suitably used.

The method for forming the polyolefin layer is not particularly limited, and for example, the polyolefin layer can be formed as a coating film by forming a coating film of the aqueous dispersion and drying it. The coating film may be formed by a known method, for example, die coating, dip coating, knife coating, river roll coating, spray coating, gravure coating, roll coating, doctor coating, bar coating. Various coating methods such as the above, and printing methods can be appropriately employed. Although the drying temperature after application | coating is not restrict | limited in particular, Generally it is preferable to set it as about 80-120 degreeC. In the wrapping paper of the present invention, by using such a coating film, it is possible to effectively realize appropriate adhesive strength with paper and silicone, content peelability, low potassium permanganate consumption, and the like. In forming the coating film, 0.3 to 3 g / ^{m 2} approximately by weight after drying the coating amount of the aqueous polyolefin dispersion is preferably in particular a 0.5 to 2 g / ^{m 2.} By setting within this range, the sealing effect on the paper can be obtained, and the non-adhesiveness (peelability) of the contents can be more effectively exhibited. Further, since the weight is low (thickness is thin), packaging suitability such as mechanical cutting suitability and folding suitability (fold holding ability) can be further satisfied.

Silicone layer For the formation of the silicone layer, silicone used in ordinary release paper or the like can be used. For example, at least one of polydimethylsiloxane, polyphenylmethylsiloxane, polyalkylalkenylsiloxane, polyalkylhydrogensiloxane, and the like can be suitably used. These can also use a commercial item. Examples of commercially available products include silicone “SRX345” manufactured by Toray Dow Corning Co., Ltd., silicone “TPR6722” manufactured by Momentive Performance Materials Japan GK, “X-52-195” manufactured by Shin-Etsu Chemical Co., Ltd., and the like. be able to.

  The thickness of the silicone layer can be adjusted as appropriate, but is usually about 0.01 to 5 μm, particularly 0.1 to 3 μm.

The method for forming the silicone layer is not limited, and a coating film of silicone or a solution thereof may be formed on paper, dried and cured. As a method for forming the coating film, the same methods as the coating method, the printing method and the like mentioned in the case of the polyolefin layer can be adopted. In the case of employing a silicone solution, the silicone may be dissolved in an organic solvent such as toluene and coated using the solution. The coating amount of the silicone is 0.01 to 3 g / ^{m 2} on a dry weight after, particularly preferably a 0.1 to 1.5 g / ^{m 2.} By setting the amount to be applied, more excellent peelability and the like can be exhibited. In general, after the coating film is formed, it may be cured by heat drying. In this case, the drying temperature is usually preferably 100 ° C or higher, more preferably 140 to 170 ° C. For example, it can be effectively dried and cured by spraying hot air adjusted to the above temperature range on the coating film.

Other Layers In the wrapper of the present invention, an aluminum foil, an adhesive layer, and the like can be laminated as necessary in addition to the basic layer configuration as described above. For example, an aluminum foil can be laminated on the back surface of paper (the surface on which the polyolefin layer is not laminated).

  When aluminum foil is used for the wrapping paper of the present invention, known aluminum foil (including aluminum alloy foil) can be used. In particular, an aluminum foil made of a material such as 1N30, 1070, 8021, and 8079 defined by JIS or the like can be suitably used. Moreover, although the tempering can use any of hard foil, semi-hard foil, or soft foil, it is preferable to use soft foil in terms of adhesiveness or flexibility. The thickness of the aluminum foil is not particularly limited, but is preferably about 5 to 25 μm in that barrier properties, strength, flexibility and the like can be appropriately obtained. The aluminum foil may be subjected to embossing, primer treatment, anchor coat treatment, printing, overcoat treatment, etc., as used in known packaging materials.

In the wrapping paper of the present invention, an adhesive layer may be interposed between the layers. For example, when laminating an aluminum foil on paper, it is preferable to use an adhesive. The adhesive is not particularly limited as long as it is an adhesive used in a known packaging material. For example, water glass, polyethylene, polyurethane, polyacryl, polyester, epoxy, polyvinyl acetate, cellulose A laminating adhesive such as a glass-based adhesive can be used as appropriate. The coating amount of the adhesive is not limited, but the coating amount after drying is preferably about 0.5 to 5 g / m ² in that desired adhesive strength, flexibility and the like can be appropriately obtained.

Potassium permanganate consumption The potassium permanganate consumption in the paper wrapper of the present invention is 10 μg / mL or less. Since it has such a low consumption, higher safety can be exhibited. For this reason, it can be suitably used as a food or pharmaceutical wrapping paper that requires a high degree of safety. The measuring method of potassium permanganate consumption can be implemented by the method of Test Example 3 described later.

  The features of the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples.

Example 1
Water glass (coating amount after drying) with one side of a 6.5 μm thick aluminum foil (1N30 soft foil) and one side of paper (made by Daio Paper Co., Ltd., trade name “Burger Wrap”, basis weight 21 g / m ² ) 3 g / m ² ) was used for bonding by a wet laminating method. The other side of the paper was coated with an ionomer aqueous dispersion (trade name “Chemical S300”, manufactured by Mitsui Chemicals, application amount after drying 1 g / m ² ), and then dried at 100 ° C. Furthermore, after coating the surface of the polyolefin-based aqueous dispersion with silicone (Momentive Performance Materials Japan GK, trade name “TPR6722 / CM670”, coating amount after drying 0.5 g / m ² ), 150 Drying was carried out at 0 ° C. to produce a paper wrapper of Example 1.

Example 2
Example similar to Example 1 except that the ionomer aqueous dispersion was changed to an acrylic-modified ionomer aqueous dispersion (trade name “Chemical SA 100” manufactured by Mitsui Chemicals, application amount after drying 1 g / m ² ). 2 wrappers were made.

Example 3
Except for changing the ionomer aqueous dispersion to an ethylene vinyl acetate copolymer resin aqueous dispersion (trade name “Chemical V300” manufactured by Mitsui Chemicals, Ltd., application amount after drying 1 g / m ² ), the same as in Example 1. Thus, a wrapping paper of Example 3 was produced.

Example 4
The ionomer aqueous dispersion was replaced with a low-density polyethylene aqueous dispersion (trade name “Chemical M200” (polyethylene density: 0.92 g / cm ³ , manufactured by Mitsui Chemicals, Inc., coating amount after drying 1 g / m ² )). Example 4 was made in the same manner as Example 1 except that.

Example 5
Example Example 1 except that the ionomer aqueous dispersion was changed to a low molecular weight polyethylene aqueous dispersion (manufactured by Mitsui Chemicals, trade name “Chemipearl W300”, coating amount after drying 1 g / m ² ). 5 wrappers were produced.

Comparative Example 1
Water glass (coating amount after drying) with one side of a 6.5 μm thick aluminum foil (1N30 soft foil) and one side of paper (made by Daio Paper Co., Ltd., trade name “Burger Wrap”, basis weight 21 g / m ² ) 3 g / m ² ) to form a paper wrapper of Comparative Example 1. (No coating agent)

Comparative Example 2
Implemented except that instead of the polyolefin-based aqueous dispersion, a commercially available PVA (polyvinyl alcohol) coating solution (manufactured by Taisei Kayaku Co., Ltd., trade name “Martite TX-320”, coating amount after drying 1 g / m ² ) was used. A wrapper of Comparative Example 2 was produced in the same manner as Example 1.

Comparative Example 3
Implemented except that instead of the polyolefin-based aqueous dispersion, a commercially available PVA (polyvinyl alcohol) coating solution (manufactured by Taisei Kayaku Co., Ltd., trade name “NL-05 aqueous solution”, coating amount after drying 1 g / m ² ) was used. A wrapper of Comparative Example 3 was produced in the same manner as Example 1.

Comparative Example 4
Water glass (coating amount after drying) with one side of a 6.5 μm thick aluminum foil (1N30 soft foil) and one side of paper (made by Daio Paper Co., Ltd., trade name “Burger Wrap”, basis weight 21 g / m ² ) 3 g / m ² ) was used for bonding by a wet laminating method. After coating with silicone (Momentive Performance Materials Japan GK, trade name “TPR6722 / CM670”, coating amount 0.5 g / m ² after drying) on the other side of the paper, it was dried at 150 ° C. for comparison. The wrapper of Example 4 was produced.

Test Example 1 <Peelability test>
To the wrapping paper (length 50 mm × width 72 mm) produced in Examples 1 to 5 and Comparative Examples 1 to 4, “Watering Kiss Mint Gum (Lyche & Lemon, Muscat & Muscat)” manufactured by Ezaki Glico Co., Ltd. Directly wrap the aluminum foil on the outer surface, store it for 3 days in an atmosphere of 40 ° C and 90% RH under a pressure of 1 kPa from above, and then use the fingers to wrap the paper and the gum. The releasability was examined (n = 3). The results are shown in Table 1. The evaluation method is “○” when the gum can be easily taken out without adhering / adhering to the wrapper, and “when the gum adheres / adheres to the wrapper and a part of the wrapper is torn” “×”.

Test Example 2 <Adhesion strength test>
Preparation of Specimen X: Soft candy (Morinaga Confectionery Co., Ltd.) A4 size plain paper was placed on an A4 size aluminum flat plate, the end was fixed with cellophane tape, and cut in half at the center in the longitudinal direction 6 cuts × 8 rows (= 48 pieces) were arranged on plain paper with the cut surface of “Haichu (Grape)” manufactured by the company facing up (top). Furthermore, the wrapping paper (width 25 mm × length 300 mm) produced in Examples 1 to 5 and Comparative Examples 1 to 4 is arranged in the row direction on the cut surface of the soft candy so that the aluminum foil of the wrapping paper is on the top (top direction) The end was fixed with cellophane tape so that the wrapper would not sag. Let X be the specimen prepared so far.

  Preparation of test auxiliary body Y: On a separately prepared A4 size aluminum flat plate, a peeled surface of glassine silicon paper of about A4 size was placed upward (upward direction), and the end was fixed with cellophane tape. The test auxiliary body prepared here is set to Y.

  Preparation of adhesion strength test body Z: The test auxiliary body Y is placed on the test body X prepared above (on the aluminum foil) so that the peel surface of the test auxiliary body Y prepared above is below (ground direction). It was placed upside down, and weights (500g weight x 4 pieces) were placed near the four corners of the A4 size aluminum plate from above (top direction).

  The adhesion strength test body Z in this state was inserted into a polyethylene bag with a chuck of about A3 size, and then the chuck was closed and sealed. In this state, after holding in a constant temperature bath at a temperature of 40 ° C. for 24 hours, the adhesion strength test specimen Z was taken out of the bag, the weight was removed, and then left at room temperature for about 5 hours.

  Thereafter, the test auxiliary body Y is also removed, and one row of the soft candy in the test piece X and the set of wrapping paper thereon are separated for each row, and a tensile tester is used for the adhesion strength between the soft candy and the wrapping paper. And measured in the 90 ° peeling direction (tensile speed 100 mm / min, N = 3 average value). The results are shown in Table 1. The adhesion strength is 1.5 N / 25 mm width or less, which is a level that does not cause a problem. “Unpeelable” means that the soft candy or paper wrapper was broken or broken, and could not be measured.

Test Example 3 <Measurement of consumption of potassium permanganate>
The measurement of potassium permanganate consumption is as follows: “Standard equipment for foods, additives, etc. (Ministry of Health and Welfare Notification No. 370 of 1959) 3D D 2 Synthetic resin equipment or container packaging (category: operating temperature 100 In accordance with the following test method, the measurement was performed on each wrapping paper produced in Examples 1 to 5 and Comparative Examples 2 to 4. In Comparative Example 1, since the elution surface is paper, this measurement is not performed. The results are shown in Table 2.

Water that was cut out so that the single-sided area of the wrapping paper was 50 cm ² , the aluminum foil surface side was closely fixed to a metal jig preheated to 60 ° C., and then preheated to 60 ° C. By immersing in 100 ml and holding for 30 minutes, elution is performed to obtain each test solution.

  Put 100 ml of water in an Erlenmeyer flask, 5 ml of aqueous sulfuric acid solution diluted with 2 volumes of water per 1 volume of concentrated sulfuric acid, and 5 ml of 0.002 mol / l potassium permanganate solution, boil for 5 minutes, then discard the solution and wash with water. . Take 100 ml of the test solution in this Erlenmeyer flask, add 5 ml of the same sulfuric acid aqueous solution as above, add 10 ml of 0.002 mol / l potassium permanganate solution, and boil for 5 minutes by heating. Subsequently, heating is stopped, 10 ml of a 0.005 mol / l sodium oxalate solution is immediately added for decolorization, and titration is performed with a 0.002 mol / l potassium permanganate solution until the slight red color remains without disappearing.

Separately, a blank experiment is performed in the same manner, and the potassium permanganate consumption (abbreviated as K) is obtained by the following equation.

K (μg / ml) = ((ab) × 0.316 × f × 1000) / 100

a: Titration volume of 0.002 mol / l potassium permanganate solution in this test (ml)
b: Titration amount of 0.002 mol / l potassium permanganate solution in the blank test (ml)
f: Factor of 0.002 mol / l potassium permanganate solution

  It turns out that Examples 1-5 and the comparative example 4 are adapted to the synthetic resin general specification (10 microgram / ml or less) of Ministry of Health and Welfare No. 370 in 1959.

  From the above results, it can be seen that Examples 1 to 5 of the present invention show good results with no problem in all of peelability, adhesion strength, and potassium permanganate consumption, and are suitable for wrapping paper. On the other hand, the wrapping paper of Comparative Example 1 has problems in terms of peelability and adhesion strength, and is not suitable for wrapping paper. Comparative Example 2 and Comparative Example 3 have problems in terms of consumption of potassium permanganate, and are not suitable for wrapping foods such as confectionery. The wrapping paper of Comparative Example 4 shows no problem in terms of initial peelability and potassium permanganate consumption, but shows that the peelability does not last after storage for a long period of time or in an environment where the temperature (temperature) is high. This is also unsuitable as a wrapper for foods such as confectionery.

  As described above, the wrapping paper of the present invention maintains not only the initial peelability but also the peelability even after long-term storage or in an environment where the temperature (temperature) is high. It has the feature that there are few elutions of organic substances that are less harmful to the human body.

Claims (4)

1) paper, 2) a polyolefin layer laminated on the front surface of the paper, 3) a wrapping paper comprising a silicone layer laminated on the polyolefin layer,
Aluminum foil is further laminated on the back of the paper, the aluminum foil is a soft foil,
The polyolefin layer comprises an aqueous dispersion of a) a copolymer metal salt ionomer of a polyolefin hydrocarbon and an unsaturated carboxylic acid, b) an ethylene vinyl acetate copolymer resin, c) a low density polyethylene, or d) a low molecular weight polyethylene. Formed using
A wrapping paper used to wrap food directly so that the aluminum foil is on the outer surface side. The basis weight of the paper is 10-50 g / m ² The wrapper according to claim 1, wherein The wrapping paper according to claim 1 or 2, wherein the aluminum foil has a thickness of 5 to 25 µm. The paper wrapper in any one of Claims 1-3 whose potassium permanganate consumption in a paper wrapper is 10 microgram / mL or less.