JP7421729B2 - Long-term retention sheet for aroma ingredients - Google Patents

Description

TECHNICAL FIELD The present invention relates to sheets and scented paper products containing scent components. The present invention also relates to a method of manufacturing a sheet containing a fragrance component and a method of manufacturing a scented paper product.

Paper products such as gift bags and gift bags are given a scent suitable for the occasion in which they are used, but these products have the problem of losing their scent during the period from purchase to use.

In order to solve this problem, it has been reported that the aroma components are retained for a long period of time by encapsulating them in resin capsules and applying force such as crushing or tearing them during use.

As a method for producing capsules containing such fragrance components, Patent Document 1 reports a method for producing microcapsules containing a fragrance having a CLogP value of 1.5 or less. Furthermore, Patent Document 2 describes that encapsulated fragrances can be produced by conventionally known methods such as interfacial polymerization and in-situ polymerization. However, such conventionally known methods for producing resin capsules require the use of organic solvents and pH adjustment, and require specialized equipment for production.

In addition, recent research reports have shown that cellulose nanofiber (CNF) is lightweight and has more than five times the strength of steel, and research has begun to explore the production and use of cellulose nanofiber (CNF) as a high-performance nanofiber obtained from plant resources. A lot of research is being done.

JP2019-167455A JP 2019-108562 Publication

An object of the present invention is to provide a sheet containing an aroma component that can retain the aroma component for a long period of time and can be manufactured without using an organic solvent or pH adjustment, and a scented paper product equipped with the sheet. shall be. Another object of the present invention is to provide a method for producing a sheet containing the above-mentioned aroma component and a method for producing the above-mentioned scented paper product.

Cellulose nanofibers made from wood pulp and bamboo have been reported to have gas barrier properties. From this, if cellulose nanofibers can envelop aroma components and form a sheet, it will be possible to retain the aroma components for a long period of time. Furthermore, cellulose nanofibers are composed of water and cellulose, and it is thought that they can be produced using existing paper processing equipment.

Therefore, as a result of extensive research in order to achieve the above objective, the inventors added and mixed an aromatic component into a suspension containing cellulose nanofibers, spread the mixed solution on a pulp sheet, and dried it. It was discovered that the sheet obtained by this method has oil sacs formed by cellulose nanofibers covering aroma components within the sheet, and is capable of retaining aroma components for a long period of time. Furthermore, the production method can be carried out without using an organic solvent or adjusting pH. In addition, the sheet obtained by this manufacturing method can retain aroma components for a long period of time, and can also release aroma components by tearing the sheet.

The present invention was completed based on these findings and further studies, and provides sheets, scented paper products, etc. that contain the following scent components.

Item 1. A sheet containing aromatic ingredients,
Contains aroma components and cellulose nanofibers,
A sheet in which the aroma component is encapsulated in the form of a capsule in which the liquid aroma component is covered with cellulose nanofibers.
Item 2. Item 2. The sheet according to Item 1, wherein the capsule has a diameter of 10 to 1000 μm.
Item 3. Item 3. The sheet according to item 1 or 2, wherein the aromatic component is released when the sheet is cut, pressed, or contains moisture.
Item 4. A scented paper product comprising the sheet according to any one of items 1 to 3.
Item 5. A method for manufacturing a sheet containing fragrance ingredients, including the following steps:
(1) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers, and (2) drying the mixed solution obtained in step (1), and adding a liquid aroma component to the cellulose nanofibers. A process of forming a sheet containing fragrance ingredients in the form of covered capsules.
Item 6. A method for producing scented paper products, including the following steps:
(A) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers,
(B) Coating the liquid mixture obtained in step (A) onto a paper base sheet, and (C) drying the liquid mixture coated on the base sheet in step (B). , a process of forming a paper product with a sheet containing a liquid aroma component in the form of a capsule covered with cellulose nanofibers.

Since the sheets and paper products of the present invention cover the aroma components with cellulose nanofibers, it is possible to retain the aroma components trapped inside for a long time, and when force such as tearing the sheet is applied, the aroma components are released. It has the property of emitting . Furthermore, the sheets and paper products of the present invention can be manufactured without the need for operations such as the use of organic solvents or pH adjustment, and can also be manufactured using existing paper processing equipment.

2 is a photograph showing the sheet surface observed with a microscope in Example 1. 1 is a photograph showing an oil sac (before rupture) observed with a microscope in Example 1. 1 is a photograph showing an oil sac (after rupture) observed with a microscope in Example 1. 3 is a photograph showing the sheet surface observed with a microscope in Example 2. 3 is a photograph showing the sheet surface observed with a microscope in Example 3. 2 is a graph showing the measurement results of limonene concentration before and after tearing the sheet in Test Example 1.

Embodiments of the present invention will be described below.

Note that in this specification, the term "comprise" includes the meanings of "essentially consist of" and "consist of".

The sheet containing the aroma component of the present invention is
Contains aroma components and cellulose nanofibers,
The aroma component is characterized in that it is encapsulated in the form of a capsule in which the liquid aroma component is covered with cellulose nanofibers.

Cellulose nanofibers are fine cellulose fibers that can be obtained by refining (defibrating) pulp fibers. Examples of raw materials for cellulose nanofibers include cellulose derived from plants such as wood and bamboo, and microorganisms, with wood and bamboo being preferred. Pulp fibers used as raw materials for cellulose nanofibers include, for example, hardwood kraft pulp (LKP) such as hardwood bleached kraft pulp (LBKP), hardwood unbleached kraft pulp (LUKP), softwood bleached kraft pulp (NBKP), and softwood unbleached kraft pulp. Chemical pulp such as softwood kraft pulp (NKP) such as kraft pulp (NUKP); stone ground pulp (SGP), pressurized stone ground pulp (PGW), chemical ground pulp (CGP), refiner ground pulp (RGP), ground pulp (GP), thermoground pulp (TGP), thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), bleached thermomechanical pulp (BTMP), and other mechanical pulps; used tea paper, used kraft envelope paper, used newspaper paper, and used magazine paper. , used paper pulp manufactured from used leaflet paper, used office paper, plain old paper, used corrugated paper, Kent used paper, imitation used paper, used land deed paper, recycled used paper, etc.; deinked pulp (DIP) made by deinking used paper pulp, etc. Can be mentioned. These pulp fibers may be used alone or in combination of two or more.

The method for producing cellulose nanofibers is not particularly limited, and various known methods can be used. For example, defibration may be performed by mechanical treatment of pulp in a water-dispersed state, or defibration may be performed after chemical treatment such as enzyme treatment, acid treatment, TEMPO catalytic oxidation, or phosphoric acid esterification.

Examples of defibration methods using mechanical processing include a grinder method in which pulp fibers are ground between rotating grindstones, a counter-impingement method using a high-pressure homogenizer, and a pulverization method using a ball mill, roll mill, cutter mill, etc. .

The content of cellulose nanofibers in the sheet containing the aroma component of the present invention is not particularly limited, and is usually 50 to 99% by mass, preferably 75 to 90% by mass.

Flavor components are not particularly limited, and include, for example, natural fragrances, animal fragrances, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musks, etc. .

Examples of natural fragrances include orange oil, lime oil, lemon oil, petitgrain oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil, abyss oil, anise oil, bay oil, bore rose oil, ylang-ylang oil, Geranium oil, citronella oil, peppermint oil, mentha oil, spearmint oil, lemongrass oil, eucalyptus oil, patchouli oil, jasmine oil, rose oil, cedar oil, vetiver oil, galbanum oil, oakmoss oil, pine oil, camphor oil, sandalwood essential oils such as camphor oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, and thyme oil.

Examples of animal flavorings include java incense, beaver incense, einko incense, and dragon incense.

Examples of aldehydes include undecylenaldehyde, laurylaldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral, citronellal, ethylvanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, Examples include aldehyde, octanal, ligustral, lireal, liral, tripral, vanillin, helional, and the like.

Examples of phenols include eugenol, isoeugenol, and the like.

Examples of alcohols include bacdanol, citronellol, dihydromircenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, Santarex, terpineol, tetrahydrolinalol, phenylethyl alcohol, and the like.

Examples of the ethers include cedranbar, grisalva, methyleugenol, methylisoeugenol, and the like.

Examples of esters include cis-3-hexenyl acetate, cis-3-hexenylpropionate, cis-3-hexenyl salicylate, p-cresyl acetate, pt-butylcyclohexyl acetate, amyl acetate, methyl dihydrojas Monate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl carbinyl acetate, erica propionate, ethyl acetoacetate, erica acetate, geranyl Acetate, geranyl formate, hedione, linalyl acetate, β-phenylethyl acetate, hexyl salicylate, styralyl acetate, terpinyl acetate, vetivery acetate, ot-butylcyclohexyl acetate, manzanate, allylheptanoate, etc. It will be done.

Examples of hydrocarbons include d-limonene, α-pinene, β-pinene, myrcene, and the like.

Examples of ketones include α-ionone, β-ionone, methyl-β-naphthylketone, α-damascone, β-damascone, δ-damascone, cis-jasmone, methylionone, allylionone, cashmeran, dihydrojasmone, and isoee. Examples include Super, Beltfix, Isolone Diphoranone, Corebon, Rosephenone, Raspberry Ketone, and Dynascon.

Examples of the lactones include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroxan.

Examples of musks include cyclopentadecanolide, ethylene brasylate, galaxolide, musk ketone, tonalide, and nitro musks.

These aroma components can be used alone or in combination of two or more.

The content of the aroma component in the sheet containing the aroma component of the present invention is not particularly limited, and is usually 1 to 50% by mass, preferably 10 to 25% by mass.

The sheet of the present invention may contain other components in addition to aroma components and cellulose nanofibers, such as binders, pigment dispersants, thickeners, fluidity improvers, Antifoaming agents, foam suppressants, mold release agents, penetrants, colored dyes, colored pigments, optical brighteners, ultraviolet absorbers, antioxidants, preservatives, waterproofing agents, and the like can be mentioned.

The aroma component is encapsulated in the form of a capsule in which the liquid aroma component is covered with cellulose nanofibers. As described above, the sheet of the present invention is characterized in that the aroma component is maintained in a liquid state and encapsulated in the capsule. Since the aroma components are encapsulated in cellulose nanofiber capsules that have gas barrier properties, the aroma components can be retained for a long period of time. Further, the diameter of the capsule is not particularly limited, and is, for example, 10 to 1000 μm, preferably 100 to 500 μm.

When the sheet of the present invention is cut, pressed, or exposed to moisture, the capsule containing the aroma component is broken and the aroma component contained therein is released, thereby generating a scent. That is, the fragrance component can be retained for a long period of time and the fragrance can be generated when necessary.

The thickness of the sheet containing the aroma component of the present invention is not particularly limited, and is usually 10 to 1000 μm, preferably 200 to 500 μm.

Further, the scented paper product of the present invention is characterized in that it includes a sheet containing the above-mentioned scent component.

Such paper products are not particularly limited, and include, for example, wrapping paper such as food wrapping paper, envelopes, gift bags, gift bags, noshi, mizuhiki, greeting cards, message cards, pamphlets, business cards, book covers, and synthetic paper. , Japanese paper, label paper, printing paper, grease absorbing paper, air filters, masks, disposable diapers, etc.

For example, if the paper product is an envelope, a gift bag, a gift bag, a noshi, etc., the sheet containing the scent component is cut when the package is opened, so that a scent is generated when the package is opened. be able to. Furthermore, when the paper product is a mask or the like, the capsule containing the fragrance component can be broken down to generate a fragrance by absorbing moisture during use.

Since the sheets and paper products of the present invention cover the aroma components with cellulose nanofibers, it is possible to retain the aroma components trapped inside for a long period of time, and when force such as tearing the sheet is applied, the aroma components are released. A fragrance can be generated by releasing ingredients.

The sheet containing the aroma component of the present invention can be manufactured by a method including the following steps.
(1) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers, and (2) drying the mixed solution obtained in step (1), and adding a liquid aroma component to the cellulose nanofibers. A process of forming a sheet containing fragrance ingredients in the form of covered capsules.

Moreover, the scented paper product of the present invention can be manufactured by a method including the following steps.
(A) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers,
(B) Coating the liquid mixture obtained in step (A) onto a paper base sheet, and (C) drying the liquid mixture coated on the base sheet in step (B). , a process of forming a paper product with a sheet containing a liquid aroma component in the form of a capsule covered with cellulose nanofibers.

The solvent in the suspension containing cellulose nanofibers is not particularly limited, and is usually water. The content of cellulose nanofibers in the liquid mixture is, for example, 0.05 to 5% by mass, and the content of aroma components is, for example, 0.05 to 5% by mass.

The mixed liquid may contain other components in addition to the aroma component and cellulose nanofibers, such as a binder, a pigment dispersant, a thickener, a fluidity improver, and an antifoaming agent. agents, foam suppressants, mold release agents, penetrants, colored dyes, colored pigments, optical brighteners, ultraviolet absorbers, antioxidants, preservatives, waterproofing agents, and the like.

The method of adding and mixing the aroma component into the suspension containing cellulose nanofibers is not particularly limited, and various known mixing methods such as a mixer or a shaker can be used.

The base sheet used in the above step (B) is made of paper, and refers to the portion of various paper products to which the liquid mixture is applied in order to impart a fragrance. The base sheet may have one layer or multiple layers of two or more layers.

Coating of the liquid mixture can be performed using a known coating machine. Examples of such coating machines include blade coaters, air knife coaters, roll coaters, brush coaters, kiss coaters, squeeze coaters, curtain coaters, die coaters, 2-roll size press coaters, gate roll coaters, blade metal ring coaters, and rod coaters. Examples include a metal ring coater, a bar coater (clearance bar), a gravure coater, a dip coater, a comma coater, and the like.

The amount of the mixed liquid to be applied is not particularly limited, and is usually such that the sheet containing the aroma component formed has a thickness of 10 to 1000 μm, preferably 200 to 500 μm.

The method for drying the liquid mixture is not particularly limited, and various known methods can be used. Examples of such a drying method include a method of drying in an oven, a method of drying in air, and the like.

In step (2) above, when drying the liquid mixture obtained in step (1), it is desirable to dry the liquid mixture after forming it into a sheet.

According to the above-described manufacturing method, the sheets and scented paper products containing aroma components of the present invention can be manufactured without the need for operations such as the use of organic solvents or pH adjustment, and can also be manufactured using existing paper processing equipment. Since it can be manufactured, it can be manufactured by a simple method and is also excellent in terms of manufacturing cost.

Examples are given below to explain the present invention in more detail. However, the present invention is not limited to these Examples in any way.

Example 1
In Example 1, 40 g of a CNF aqueous dispersion (bamboo CNF defibration degree B manufactured by Chuetsu Pulp Co., Ltd.) prepared to have a solid content concentration of approximately 1% and 0.5 g of citrus essential oil (Himekozo (registered trademark) yuzu essential oil) were mixed into 50 g. ml centrifuge tube, shake for 10 minutes with a shaker (SRR-2 manufactured by As One), spread on a pulp sheet, and dry overnight in a dryer (AFO-82 manufactured by AGC Techno Glass) at 50℃. I let it happen.

Visual observation of the dried sheet revealed citrus essential oil sacs covered with cellulose nanofibers within the sheet.

In addition, as a result of observing the obtained sheet with a digital microscope (KH-8700 manufactured by Hirox Japan), the size of the oil capsule was approximately 100 μm to approximately 1000 μm in diameter (Figure 1), and it was found that the size of the oil sac was approximately 100 μm to approximately 1000 μm in diameter. However, as liquid came out (Figures 2 and 3), it was confirmed that it contained essential oil.

Example 2
Example 2 was the same as Example 1, except that the CNF aqueous dispersion was replaced with Chuetsu Pulp Co., Ltd.'s bamboo CNF defibration degree B, and Sugino Machine Co., Ltd.'s CNF BiNFs BMa with the solid content concentration adjusted to about 1% was used. A sheet was prepared using the same process as above. Observation of the prepared sheet with a digital microscope confirmed the presence of citrus essential oil covered with cellulose nanofibers within the sheet (Figure 4).

Example 3
Example 3 was the same as Example 1, except that the CNF aqueous dispersion was replaced with Chuetsu Pulp Co., Ltd.'s bamboo CNF defibration degree B, and CNF derived from high-pressure homogenizer-treated pulp whose solid content concentration was adjusted to about 1% was used. A sheet was produced by performing the same treatment. Observation of the prepared sheet with a digital microscope confirmed the presence of citrus essential oil covered with cellulose nanofibers within the sheet (Figure 5).

Example 4
In Example 4, 80 g of a CNF aqueous dispersion (Bamboo CNF defibration degree B manufactured by Chuetsu Pulp Co., Ltd.) whose solid content concentration was adjusted to about 1% and 0.5 g of citrus essential oil (Himekozo (registered trademark) Yuzu essential oil) were mixed into 200 g. After weighing the mixture into a ml beaker and stirring for 1 minute using a hand mixer (THM250N manufactured by Tescom Electric Co., Ltd.), half the amount was spread on a pulp sheet and dried overnight in a dryer at 50°C.

Visual observation of the dried sheet revealed citrus essential oil sacs covered with cellulose nanofibers within the sheet.

Test example 1
The shelf life of the aroma components of the sheet obtained in Example 4 was evaluated. The sheet was placed in a 500 ml Erlenmeyer flask and the inside was purged with nitrogen gas. After standing at about 25° C. for 15 minutes, the concentration of limonene present in the gas phase was measured using a gas chromatograph mass spectrometer (JMS-AMSUN200, manufactured by JEOL Ltd.). The sheet obtained in Example 4 was torn at 16 minutes and the limonene concentration was measured in the same manner.

The results are shown in FIG. Before tearing the sheet, the limonene concentration was less than 1 mg/L, but after tearing, approximately 20 mg/L of limonene was present, confirming that the aroma components were retained inside the sheet. It was done.

Claims (6)

A sheet containing aromatic ingredients,
Contains aroma components and cellulose nanofibers,
A sheet in which the aroma component is encapsulated in the form of a capsule in which the liquid aroma component is covered with cellulose nanofibers. The sheet according to claim 1, wherein the capsule has a diameter of 10 to 1000 μm. The sheet according to claim 1 or 2, wherein the aromatic component is released when the sheet is cut, pressed, or moistened. A scented paper product comprising the sheet according to any one of claims 1 to 3. A method for manufacturing a sheet containing fragrance ingredients, including the following steps:
(1) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers, and (2) drying the mixed solution obtained in step (1), and adding a liquid aroma component to the cellulose nanofibers. A process of forming a sheet containing fragrance ingredients in the form of covered capsules. A method for producing scented paper products, including the following steps:
(A) A step of adding and mixing an aroma component into a suspension containing cellulose nanofibers,
(B) Coating the liquid mixture obtained in step (A) onto a paper base sheet, and (C) drying the liquid mixture coated on the base sheet in step (B). , a process of forming a paper product with a sheet containing a liquid aroma component in the form of a capsule covered with cellulose nanofibers.