JP2021130786A - Ink, bonding kit, bonding sheet, and method for producing bonding sheet - Google Patents

Abstract

To provide an ink that can be used for coloration of a biocompatible film containing regenerated cellulose and is useful for achieving coloration with high water resistance.SOLUTION: An ink 10 disclosed herein is an ink that colors a biocompatible film containing regenerated cellulose. The ink 10 contains water, a pigment, and a binder. The binder contains a polymer with an HSP value of 24 MPa1/2 or more and less than 31.0 MPa1/2.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to inks, sticking kits, sticking sheets, and methods of manufacturing sticking sheets.

Conventionally, a film for attaching to a living body containing regenerated cellulose is known.

For example, Patent Document 1 describes a membrane for biological attachment having a thickness of 20 nm or more and 1300 nm or less, which is composed of regenerated cellulose having a weight average molecular weight of 150,000 or more. This film for attaching to a living body can be attached to the skin without an adhesive, and even if it is attached to the skin for a long time, it is unlikely to give stress to the skin.

On the other hand, conventionally, inks having high biostability have been studied.

For example, Patent Document 2 describes an ink jet ink having high biostability. This inkjet ink contains pigments, acrylic particles, alcohol, and water. Alcohol contains trivalent alcohol. The alcohol content with respect to the total mass of the inkjet ink is 30% by mass or less. The amount of acrylic particles with respect to 10 parts by mass of the pigment is 0.5 to 10 parts by mass. Inkjet inks are negative for skin irritation. This inkjet ink can also be printed on a sheet made of a biocompatible material.

International Publication No. 2018/09/362 Japanese Unexamined Patent Publication No. 2017-057261

The present disclosure provides an ink that can be used for coloring a biocompatible film containing regenerated cellulose and is advantageous from the viewpoint of realizing coloring having high water resistance.

The ink in this disclosure is
An ink that colors biocompatible films containing regenerated cellulose.
water and,
With pigments
It contains a binder containing a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.}

The above ink can be used for coloring a biocompatible film containing regenerated cellulose, and is advantageous from the viewpoint of realizing coloring having high water resistance.

The figure which shows the ink in Embodiment 1 and the sticking kit in Embodiment 2. Graph showing the X-ray diffraction (XRD) pattern of natural cellulose Side view of the sticking sheet according to the third embodiment Side view of the sticking sheet according to the fourth embodiment

(Knowledge on which this disclosure was based)
At the time when the present inventors came up with the present disclosure, as described in Patent Document 1, there was a technique related to a bioadhesive film composed of regenerated cellulose. Cellulose is a naturally abundant organic polymer and is a polymer material that can be obtained at low cost. Cellulose has various useful properties such as being hydrophilic but insoluble in water and having biocompatibility. Therefore, cellulose is widely used, for example, in applications such as fibers for clothing and separation membranes such as dialysis membranes, and further application of cellulose is expected.

Cellulose processing technology is also being studied. For example, the film for attaching to a living body described in Patent Document 1 is produced by dissolving cellulose in an ionic liquid and processing it.

A biocompatible membrane containing regenerated cellulose is a highly safe membrane that does not easily exert physical or chemical stress on the living body even when it comes into contact with living tissues such as skin. Therefore, for example, it can be used as a biological attachment film that can be attached to a biological tissue such as skin. In that case, even if it is attached to the living tissue for a long time, it is difficult to give stress to the living tissue. If the biocompatible film can be colored, the use of the biocompatible film containing regenerated cellulose will be expanded. For example, it is conceivable to use a bio-adhesive film containing colored regenerated cellulose as a cosmetic sheet for protecting, coloring, or beautifying the skin. In addition, it is also conceivable to use a biocompatible membrane containing colored regenerated cellulose for attaching to articles such as clothing.

Patent Document 1 describes coloring a regenerated cellulose film. However, Patent Document 1 does not study any ink suitable for coloring a biocompatible film containing regenerated cellulose. The inkjet ink described in Patent Document 2 can also be printed on a sheet made of a biocompatible material. On the other hand, according to Patent Document 2, although the fixability of the ink jet ink to the filter paper has been evaluated, the fixability of the ink to the biocompatible film containing regenerated cellulose has not been evaluated. According to the study by the present inventors, a biocompatible film containing regenerated cellulose is colored with high water resistance by using an ink containing a pigment, an acrylic polymer, a trivalent alcohol, and water. It turns out that it is not always possible. As described above, the present inventors have discovered that it is not easy to color a biocompatible film containing regenerated cellulose with high water resistance, and in order to solve this problem, the present disclosure is made. It came to compose the subject.

Therefore, the present disclosure provides an ink that can be used for coloring a biocompatible film containing regenerated cellulose and is advantageous from the viewpoint of realizing coloring having high water resistance.

Hereinafter, embodiments will be described in detail with reference to the drawings. However, more detailed explanation than necessary may be omitted. For example, detailed explanations of already well-known matters or duplicate explanations for substantially the same configuration may be omitted. It should be noted that the accompanying drawings and the following description are provided for those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter described in the claims.

(Embodiment 1)
Hereinafter, the first embodiment will be described with reference to FIG.

[1-1. composition]
The ink 10 shown in FIG. 1 is an ink that colors a biocompatible film containing regenerated cellulose, and contains water, a pigment, and a binder. The binder contains a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.} The HSP value is the value of the Hansen solubility parameter. The HSP value can be determined by a method according to the description of Hansen Solubility Parameters: A User's Handbook, Second Edition. Charles M. Hansen.

The polymer contained in the binder is not limited to a specific polymer as long as it has an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.} The polymer may be an acrylic polymer. Acrylic polymers have high biosafety and have a carboxylic acid in their structure, so they are easily compatible with regenerated cellulose having hydrophilic groups. Further, the acrylic polymer can easily introduce various substituents and copolymerize with other monomers, and can easily control the physical properties.

The binder can be dissolved or stably dispersed in the ink 10, for example. The binder is dispersed in the ink 10, for example. In this case, the viscosity of the ink 10 tends to be lower than that in the case where the binder is dissolved in the ink 10. Therefore, it is easy to increase the density of the binder in the ink 10. In addition, since the viscosity of the ink 10 tends to be low, the method of applying the ink 10 to the biocompatible film containing regenerated cellulose is not limited to a specific method. For example, by emulsion-polymerizing an acrylic monomer, a dispersion in which a binder containing an acrylic polymer is dispersed in water can be obtained. The binder may be dissolved in the ink 10.

The acrylic polymer may be selected from the ingredients listed in the ingredient display name list of cosmetics based on the Pharmaceutical Affairs Law, or may be a known acrylic polymer used in cosmetics.

Examples of acrylic polymers are homopolymers of acrylic monomers, copolymers of two or more types of acrylic monomers, and copolymers of acrylic monomers and other monomers. The binder may contain only one kind of acrylic polymer, or may contain two or more kinds of acrylic polymers.

Examples of acrylic monomers include acrylate, methyl acrylate, ethyl acrylate, acrylate amide, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, N, N-dimethylaminoethyl acrylate, acrylonitrile, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, hydroxylopyl acrylate, glycidyl acrylate, propylene glycol monoacrylate, vinyl acetate, methacrylic acid. , Ethyl methacrylate, amide methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hydroxyethyl methacrylate, phenyl methacrylate, acrolein, crotonic acid, fumar Includes acids, dicarboxylic acids such as itaconic acid, and N, N-dimethylaminoethyl methacrylate or anhydrides thereof and partially / all esterified compounds.

Examples of other monomers copolymerizable with acrylic monomers include fluorine-based monomers such as styrene, vinyl acetate, silicone macromer, urethane and tetrafluoroethylene, chloride-based monomers such as ethylene, propylene and vinyl chloride, and alkoxysilanes. It is an unsaturated monomer.

The content of the binder in the ink 10 is not limited to a specific value. The content of the binder in the ink 10 is, for example, 40% by mass or less. In this case, the binder is less likely to aggregate in the ink 10.

Pigments are not limited to specific pigments. The pigment may be a known inorganic pigment or organic pigment. The type of pigment is determined, for example, according to the color and appearance required for coloring the biocompatible film containing regenerated cellulose. The term "pigment coloring" as used herein includes not only changing the color, texture, gloss, etc., but also changing the reflectance, refractive index, and transmittance of light from the outside to the object. The pigment may include a pigment for coloring the ink 10, an extender pigment, or a pearl pigment. The extender pigment, for example, adjusts the texture and gloss of the layer formed by the ink on the biocompatible film containing regenerated cellulose. The pearl pigment imparts luster to the layer formed by the ink on the biocompatible film containing regenerated cellulose. The ink may contain only one kind of pigment, or may contain two or more kinds of pigments.

The shape of the pigment is not limited to a specific shape. The shape of the pigment may be spherical, needle-shaped, rod-shaped, flake-shaped, fibrous, or amorphous. good.

Examples of pigments include the pigments shown below.
Inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate Inorganic brown pigments such as γ-iron oxide Inorganic yellow pigments such as yellow iron and ocher Inorganic black pigments such as black iron oxide and carbon black Titanium oxide Inorganic white pigments such as manganese violet and cobalt violet Inorganic purple pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate. Pigments Pigments made from various tar-based pigments Pigments made from various natural pigments Synthetic resin powders in which powder containing at least one of the above pigments is compounded with a resin

Examples of extender pigments are talc, kaolin, silicic anhydride, calcium carbonate, and magnesium carbonate. Examples of pearl pigments are titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica.

The water contained in the ink 10 functions as a solvent or a dispersion medium for the pigment and the binder. This water may be absorbed or volatilized by the biocompatible film containing regenerated cellulose after the ink 10 is applied to the film.

In ink 10, the ratio of the content of the binder to the content of the pigment is not limited to a specific value. The ratio is, for example, 0.1 or more and 8 or less on a mass basis.

Ink 10 may further contain at least one of a dihydric alcohol and a trihydric alcohol. The divalent alcohol is not limited to a specific alcohol. Examples of divalent alcohols are ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, butylene glycol, propylene diol, and hexane diol. Examples of trihydric alcohols are not limited to specific alcohols. The trihydric alcohol is, for example, an alcohol that is not irritating to the skin. An example of a trihydric alcohol is glycerin. Glycerin has high biosafety.

The ink 10 may further contain a dispersant. The dispersant disperses at least one of the pigment and the binder. The dispersant is not limited to a particular substance as long as it disperses at least one of the pigment and the binder. The dispersant may be a small molecule dispersant, a polymer dispersant, or an inorganic dispersant.

Small molecule dispersants are not limited to specific substances. Examples of low molecular weight dispersants are nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of nonionic surfactants are (poly) glycerin fatty acid ester, (poly) propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit tetraoleate, polyoxyethylene hydrogenated castor oil, (Poly) ethylene glycol fatty acid ester, polyoxyethylene sterol / hydrogenated sterol, polyoxyethylene lanolin / lanolin alcohol / honey wax derivative, and polyoxyethylene alkyl ether. Examples of polyoxyethylene alkyl ethers are polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and polyoxyethylene behenyl ether. Examples of anionic surfactants are alkyl sulfates, polyoxyethylene alkyl ether sulfates, sulfosuccinate salts, and alkylbenzene sulfonates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene sulfosuccinate alkyl ester salts, poly. Oxyalkylene alkyl phenyl ether sulfate, alkane sulfonate, acyl isethionate, acyl methyl taurate, higher fatty acid salt, polyoxyalkylene alkyl ether acetate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, acyl Glutamate, alanine derivative, glycine derivative, arginine derivative. Examples of cationic surfactants are fatty acid amidamine salts such as stearamidopropyldimethylamine and behenamidepropyldimethylamine, and monoalkyls such as cetrimonium chloride, stealtrimonium chloride, behentrimonium chloride and behentrimonium metosulfate. Type quaternary ammonium salt, dialkyl type quaternary ammonium salt such as distearyldimonium chloride and quotanium-18, benzalconium type quaternary ammonium salt such as dialkyl type quaternary ammonium salt, alkyltrimethylammonium chloride, alkoxypropyltrimethyl oxide Ammonium, dialkyldimethylammonium chloride, and alkylpyridium chloride. Examples of amphoteric surfactants are alkylamide propyl betaines, alkylcarboxybetaines, alkyldimethylaminoacetic acid betaines, alkyldimethylamine oxides, alkylamide propyl betaines, alkylamphoacetates, and diacetates.

The polymer dispersant is not limited to a specific substance. Examples of polymer dispersants include polyacrylic acid salts, styrene-maleic acid copolymers, carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, and cellulose derivatives such as hydroxypropyl methyl cellulose, polystyrene sulfonates, polyaspartic acid and salts thereof. , Polyglutamic acid and its salts, polyargicic acid and its salts, polyethylene glycol, polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, polyvinylpyrrolidone, polymer starch, soybean lecithin derivative, polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinyl Imidasoline, Satkinsan, Xanthan gum, and Chitosan.

The inorganic dispersant is not limited to a specific substance. Examples of inorganic dispersants are sodium hexametaphosphate, anhydrous sodium pyrophosphate, modified bennite, and synthetic hectorite.

The ink 10 may contain only one kind of dispersant, or may contain two or more kinds of dispersants. The dispersant may be selected from the ingredients listed in the ingredient labeling name list of cosmetics based on the Pharmaceutical Affairs Law, or may be a known compound used in cosmetics.

The ink 10 may contain other components. Examples of other ingredients are thickeners, pH regulators, UV absorbers, UV scatterers, antiseptic fungicides, oxygen scavengers, antioxidants, preservatives, anti-fading agents, defoamers, fragrances, etc. Valuable alcohols, and solvents or dispersion media other than alcohol and water.

The method for preparing the ink 10 is not limited to a specific method. Ink 10 can be prepared by thoroughly mixing components such as water, pigment, and binder. In this case, components other than water, pigments, and binders may be added as needed. The machine used for mixing is not limited to a specific machine. Examples of machines used for mixing are homogenizers, ball mills, sand mills, and homomixers.

[1-2. Effect, etc.]
As described above, in the present embodiment, the ink 10 is an ink that colors a biocompatible film containing regenerated cellulose, and contains water, a pigment, and a binder. The binder contains a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.}

Since the polymer contained in the binder is ^{less than 31.0 MPa 1/2} , when the biocompatible film containing regenerated cellulose is colored with ink 10, the affinity between the binder and water is low and the solidified product of ink 10 has water resistance. It tends to be highly sexual. On the other hand, when the polymer contained in the binder is 24 MPa ^1/2 or more, the affinity between the binder and the regenerated cellulose is easily maintained high. Therefore, it is easy to realize coloring having high water resistance for a biocompatible film containing regenerated cellulose.

As in the present embodiment, the polymer may include an acrylic polymer.

As a result, the binder is easily dissolved or stably dispersed in the ink 10.

As in the present embodiment, in the ink 10, the ratio of the content of the binder to the content of the pigment may be 0.1 or more and 8 or less on a mass basis.

When the ratio of the content of the binder to the content of the pigment is 0.1 or more on a mass basis, it is easy to more reliably realize coloring having high water resistance to the biocompatible film containing regenerated cellulose. On the other hand, when the ratio of the content of the binder to the content of the pigment is 8 or less on a mass basis, it is easy to adjust the viscosity of the ink 10 to a desired range, and the coatability and printability of the ink 10 are improved. Easy to keep high.

As in the present embodiment, the ink 10 may further contain at least one of a dihydric alcohol and a trihydric alcohol.

As a result, volatilization of water contained in the ink 10 is suppressed, and a change in the concentration of the pigment in the ink 10 is unlikely to occur. Therefore, the ink 10 tends to have high storage stability.

As in this embodiment, the ink 10 may further contain a dispersant that disperses at least one of the pigment and the binder.

As a result, for example, the dispersibility of the pigment in the ink 10 tends to be high. Therefore, it is easy to apply the ink 10, and the color development of the solidified product of the ink 10 is likely to be good.

(Embodiment 2)
Hereinafter, the second embodiment will be described with reference to FIGS. 1 and 2.

[2-1. composition]
In FIG. 1, the sticking kit 1 includes an ink 10 and a biocompatible film 20. For a detailed description of the ink 10, the description of the first embodiment can be referred to. The biocompatible membrane 20 contains regenerated cellulose. The contact angle of water on the surface of the biocompatible film 20 is greater than 0 ° and less than 100 °. The contact angle of water on the surface of the biocompatible membrane 20 can be determined, for example, according to the θ / 2 method.

Regenerated cellulose means cellulose that does not have the crystal structure I peculiar to natural cellulose. The crystal structure of cellulose can be confirmed by, for example, the XRD pattern. FIG. 2 shows the XRD pattern of natural cellulose. This XRD pattern is a pattern obtained by using CuKα rays under the conditions of 50 kV and 300 mA. In this XRD pattern, peaks around 14-17 ° and 23 ° peculiar to the crystal structure I appear. On the other hand, regenerated cellulose often has a crystal structure II, having peaks near 12 °, 20 ° and 22 °, and no peaks near 14-17 ° and 23 °.

Since the regenerated cellulose does not have the crystal structure I peculiar to the natural cellulose, the crystallinity of the regenerated cellulose tends to be lower than the crystallinity of the natural cellulose. For this reason, regenerated cellulose contains a large amount of hydroxyl groups that are not involved in the formation of crystals, and thus easily retains a large amount of water. In addition, since regenerated cellulose can exert the humidity control function that is a characteristic of cellulose, it can prevent stuffiness and touch, and can retain a large amount of water in a state where there is little stress on the skin. Therefore, the biocompatible membrane containing regenerated cellulose has excellent moisturizing performance for the living body. Therefore, the biocompatible film 20 can be used as a biocompatible film.

The contact angle of water on the surface of the biocompatible film 20 may be 90 ° or less, 80 ° or less, or 75 ° or less.

The biocompatible membrane 20 is, for example, a self-supporting membrane. As used herein, the term "self-supporting membrane" means a membrane that can maintain its morphology as a membrane without a support. For example, when a part of the biocompatible membrane 20 is pinched with a finger or tweezers and the biocompatible membrane 20 is lifted, the biocompatible membrane 20 is not damaged and the biocompatible membrane 20 is formed without a support. The whole can be lifted.

The weight average molecular weight of the regenerated cellulose contained in the biocompatible membrane 20 is not limited to a specific value. Its weight average molecular weight is, for example, 150,000 or more. The weight average molecular weight of regenerated cellulose is, for example, 1,000,000 or less, preferably 500,000 or less, and more preferably 300,000 or less.

The thickness of the biocompatible film 20 is not limited to a specific value. Its thickness is, for example, 20 nm or more and 1300 nm or less. The thickness of the biocompatible membrane 20 is, for example, the arithmetic mean of the measured values at 10 or more randomly selected sites.

The crystallinity of the regenerated cellulose contained in the biocompatible membrane 20 is not limited to a specific value. Its crystallinity is, for example, 12% or less. The crystallinity of regenerated cellulose can be determined, for example, according to the method described in Park et al. "Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance" Biotechnology for Biofuels 2010, 3 10. According to this method, the crystallinity can be determined by the following formula (1). In formula (1), X is a peak area in the vicinity of 87 parts per million (ppm) to 93 ppm in the spectrum obtained by ^{solid 13 C-NMR measurement of a sample containing regenerated cellulose.} On the other hand, in the formula (1), Y is a peak area in the vicinity of 80 ppm to 87 ppm in the spectrum. It is considered that X is the peak area derived from the crystal structure and Y is the peak area derived from the amorphous structure.
Crystallinity [%] = {X / (X + Y)} x 100 Equation (1)

The biocompatible membrane 20 may contain a component effective for the living body. Ingredients that are effective for living organisms are not limited to specific ingredients. Examples of ingredients that are effective in the body are cosmetological ingredients, medicinal ingredients, and ingredients that protect the skin.

Examples of beauty ingredients are Arabic gum, tragacanto gum, galactan, guagam, carob gum, karaya gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassaw extract), starch (rice, corn, potato, wheat), succino Vitamin A such as glucan, casein, albumin, gelatin, mutin, chondroitin sulfate, xylitol, multitose, sodium pyrrolidone carboxylate, retinol, retinal, retinoic acid, vitamin B such as thiamine, riboflavin, pyridoxin, pyridoxamine, folic acid, ascorbic acid ( Vitamin C such as sodium), Vitamin D such as ergocalciferol and cholecalciferol, Vitamin E such as α-tocopherol, Vitamin K such as phylloquinone and menaquinone, Vitamin A derivative such as tretinoin and retinol palmitate, flusultiamine, etc. Vitamin B derivative, vitamin C derivative such as glyceryl ascorbic acid and ascorbyl tetrahexyl decanoate, vitamin D derivative such as dihydrotaxterol, vitamin E derivative such as α-tocopherol acetate, α-tocopheryl quinone, and α-tocopherol succinate. , Hydroquinone, polyphenols such as potassium 4-methoxysalicylate, lucinol, anthocyanin, disodium 3-succinyloxyglycyrrhetinate, placenta, dioxybenzone, 2-ethylhexyl 4-methoxysilicate, various amino acids, keratin, hydroxyapatite, phosphoric acid Ceramics such as tricalcium, calcium carbonate, alumina, zirconia, chitin, chitosan, arbutin, ellagic acid, kodiic acid, tranexamic acid, glycerol, sodium lactate, hyaluronic acid, ceramide, minoxidil, finasteride, collagen, elastin, various extracts, quen Acids, lecithin, carbomer, xanthan gum, dextran, palmitic acid, lauric acid, vaseline, titanium oxide, iron oxide, synthetic dyes, dyes, phenoxyethanol, fullerene, astaxanthin, coenzyme, human oligopeptides, glycerin, diglycerin, sorbitol, pyrrolidone carboxylic Acids, fatty acids polyglyceryl, polyglycerin, jojoba oil, trimethylglycine, mannitol, trehalose, glycosyl trehalose, purulan, erythritol, elastin, dipropylene glyco Glycol, butylene glycol, ethyl ethylhexanoate, sodium acrylate, disodium edetate, sucrose fatty acid ester, squalane, polyethylene glycol, polyoxyethylene hydrogenated castor oil, glycerin stearate, ethanol, polyvinyl alcohol, hydroxyethyl cellulose, triethyl Hexanoin, vegetable oils such as polyether-modified silicone, jojoba seed oil, and ectin.

Examples of medicinal ingredients are cepharanthin, rutin, isosorbide nitrate, indomethacin, finasteride, diflucortron valerate, acyclovir, ketoconazole, ketoprofen, diclofenac sodium, dexamethasone propionate, felbinac, clobetasol propionate, minoxidyl, loxoprofen. Methyl and tachlorimus.

An example of an ingredient that protects the skin is a sunscreen. Examples of sunscreen agents include UV absorbers such as dioxybenzone and 2-ethylhexyl 4-methoxycinnamate, and UV scatterers such as titanium oxide and zinc oxide.

The biocompatible membrane 20 may contain only one type of component effective for the living body, or may contain two or more types of components effective for the living body.

In the biocompatible membrane 20, the components effective for the living body exist in the voids inside the biocompatible membrane 20 in the form of a solid, a solution, a dispersion liquid, and an emulsion, for example.

[2-2. Effect, etc.]
As described above, in the present embodiment, the sticking kit 1 includes the ink 10 and the biocompatible film 20. The biocompatible membrane 20 contains regenerated cellulose. The contact angle of water on the surface of the biocompatible film 20 is greater than 0 ° and less than 100 °.

As a result, when the ink 10 is applied to the surface of the biocompatible film 20, the affinity between the biocompatible film 20 and the ink 10 is likely to be kept high. Therefore, it is easy to realize coloring having high water resistance for a biocompatible film containing regenerated cellulose.

As in the present embodiment, the weight average molecular weight of the regenerated cellulose contained in the biocompatible membrane 20 is 150,000 or more, and the biocompatible membrane 20 may have a thickness of 20 nm or more and 1300 nm or less.

As a result, although the biocompatible film 20 has a thickness of 20 nm or more and 1300 nm or less, a support is not required to maintain the shape of the biocompatible film 20. In other words, the biocompatible membrane 20 can be provided as a self-supporting membrane. Therefore, the biocompatible membrane 20 can be used for various purposes. Since the biocompatible film 20 has a thickness of 20 nm or more and 1300 nm or less, no adhesive is required to attach the biocompatible film 20 to the living body. Therefore, when the biocompatible film 20 is attached to the living body, there is less stress on the living body. Further, since the biocompatible membrane 20 contains regenerated cellulose having high humidity control performance and has a thickness of 1300 nm or less, stuffiness is reduced and the biocompatible membrane 20 can be used for a long period of time in a state of being attached to a living body. In addition, the biocompatible film 20 tends to be flexible, and the biocompatible film 20 tends to stick along the unevenness of the living body such as the cheek and the arm.

As in the present embodiment, the regenerated cellulose contained in the biocompatible membrane 20 may have a crystallinity of 12% or less.

As a result, the amount of hydroxyl groups involved in crystal formation in the biocompatible film 20 is small. Therefore, the adhesion of the biocompatible film 20 to the living body tends to be high. In addition, it has high moisturizing performance because it easily retains water. In addition, various functions can be added to the biocompatible membrane 20 by a method such as modification at the position of a hydroxyl group in regenerated cellulose.

As in the present embodiment, the biocompatible membrane 20 may contain a component effective for the living body.

Thereby, by attaching the biocompatible film 20 to the living body, it is possible to supply the components effective for the living body to the living body.

(Embodiment 3)
Hereinafter, the second embodiment will be described with reference to FIG.

[3-1. composition]
In FIG. 3, the sticking sheet 2a includes a biocompatible film 20 and a solidified ink 10a. For a detailed description of the biocompatible membrane 20, the description of the second embodiment can be referred to. The solidified product 10a contains a pigment and a binder, and forms at least a part of the surface of the sticking sheet 2a. The binder of the solidified product 10a contains a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.}

The solidified product 10a is, for example, a solidified product of ink 10. Therefore, the solidified product 10a may contain a component derived from the ink 10. For details of the binder contained in the solidified product 10a, refer to the description of the binder of the ink 10 in the first embodiment. For details of the pigment contained in the solidified product 10a, the description of the pigment of the ink 10 in the first embodiment can be referred to. In addition, the description of the first embodiment can be referred to for the quantitative relationship between the pigment and the binder.

The sticking sheet 2a can be manufactured, for example, by a method including the following steps (i) and (ii).
(I) The ink 10 is applied to the surface of the biocompatible film 20.
(Ii) The ink 10 applied to the surface of the biocompatible film 20 is dried.

In the step (i), the method of applying the ink 10 to the surface of the biocompatible film 20 is not limited to a specific method. Examples of such methods are gap coating, slot die coating, spin coating, bar coater coating, electrostatic spraying, spray coating, and printing. Examples of printing are screen printing, inkjet printing, flexographic printing, and gravure printing.

The number of times the ink 10 is applied to the surface of the biocompatible film 20 may be once or twice or more.

Regarding the step (ii), the method of drying the ink 10 is not limited to a specific method as long as water, alcohol and the like in the ink 10 can be removed. The method may be natural drying, or drying with heating or depressurization.

[3-2. Effect, etc.]
As described above, in the present embodiment, the sticking sheet 2a includes the biocompatible film 20 and the solidified ink 10a. The solidified product 10a contains a pigment and a binder, and forms at least a part of the surface of the sticking sheet 2a. A part of the pigment and the binder may be present in the film. The binder of the solidified product 10a contains a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.} The contact angle of water on the surface of the biocompatible film 20 is greater than 0 ° and less than 100 °.

As a result, when the ink 10 is applied to the surface of the biocompatible film 20, the affinity between the binder and water is low, and the affinity between the biocompatible film 20 and the solidified product 10a is likely to be kept high. Therefore, it is possible to provide a colored sticking sheet 2a having high water resistance.

As described above, in the present embodiment, the sticking sheet 2a is to apply the ink 10 to the surface of the biocompatible film 20 and to dry the ink 10 applied to the surface of the biocompatible film 20. It can be manufactured by the method including.

As a result, a colored sticking sheet 2a having high water resistance can be manufactured.

(Embodiment 4)
Hereinafter, the fourth embodiment will be described with reference to FIG.

[4-1. composition]
In FIG. 4, the sticking sheet 2b includes a base material 30, a biocompatible film 20, and a solidified ink 10a. For a detailed description of the biocompatible membrane 20, the description of the second embodiment can be referred to. For a detailed description of the solidified product 10a, the description of the third embodiment can be referred to.

The base material 30 supports the biocompatible membrane 20 and the solidified product 10a. However, the base material 30 is not a support for maintaining the shape of the biocompatible film 20. The biocompatible film 20 is arranged between the base material 30 and the solidified product 10a in the thickness direction of the biocompatible film 20.

The material of the base material 30 is not limited to a specific material. The base material 30 is, for example, a sheet or a non-woven fabric. The base material 30 contains polyethylene, polypropylene, polyethylene terephthalate, nylon, acrylic resin, polycarbonate, polyvinyl chloride, acrylonitrile, butadiene, styrene (ABS) resin, polyurethane, synthetic rubber, cellulose, fluororesin, aramid, and polyimide. You may. The base material 30 may be a metal sheet or a glass sheet.

At least a part of the surface of the base material 30 may be chemically or physically surface-treated.

The planar shape of the base material 30 is, for example, the same as the planar shape of the biocompatible film 20.

(Other embodiments)
As described above, Embodiments 1, 2, 3, and 4 have been described as examples of the techniques disclosed in the present application. However, the technique in the present disclosure is not limited to this, and can be applied to embodiments in which changes, replacements, additions, omissions, etc. have been made. In addition, it is also possible to combine the components described in the above-described first, second, third, and fourth embodiments to form a new embodiment. Therefore, other embodiments will be illustrated below.

It was explained that in the first embodiment, the HSP value of the polymer contained in the binder is 24 MPa ^1/2 or more and ^{less than 31.0 MPa 1/2.} The upper limit value and the lower limit value of the HSP value of the polymer contained in the binder may be specified by any combination selected from the following numerical values.
^{25.0MPa 1/2, 28.5MPa 1/2, 29.7MPa 1/2} , 30.3MPa 1/2, 30.5MPa 1/2

In the second embodiment, it has been explained that the biocompatible film 20 can be used as a biocompatible film. The biocompatible membrane 20 may contain regenerated cellulose and the contact angle of water on the surface thereof may be larger than 0 ° and 100 ° or less. Therefore, the biocompatible film 20 may be a film that is attached to an article such as clothing. In this case, the biocompatible film 20 colored with the ink 10 can be used for decoration and protection of articles.

In the fourth embodiment, an example in which the planar shape of the base material 30 is the same as the planar shape of the biocompatible film 20 has been described. The planar shape of the base material 30 may be different from the planar shape of the biocompatible film 20. For example, a plurality of biocompatible films 20 may be arranged on a single base material 30.

The present disclosure will be described in more detail by way of examples. The present disclosure is not limited to the following examples. First, the evaluation method for each Example and each Comparative Example will be described.

<HSP value of polymer>
The HSP values of the polymers used to prepare the inks of Examples and Comparative Examples were determined by a method according to the description of Hansen Solubility Parameters: A User's Handbook, Second Edition. Charles M. Hansen. The solubility of each polymer at a concentration of 1% by weight in the solvent shown in Table 1 in which the values of the dispersion term δd, the polar term δp, and the hydrogen bond term δh are known was evaluated. From this result, the minimum value and the maximum value of the dispersion term δd, the polarity term δp, and the hydrogen bond term δh corresponding to the range of the solvent in which each polymer dissolves were determined. Then, the HSP value, which is an intermediate value, was calculated according to the equations (2) to (5). This is calculated using the software HSPiP 5 ^th Edition. The results are shown in Tables 2 to 8.
Variance term δd _{= (δd max −δd min} ) / 2 Equation (2)
Polarity term δp = (δp _max −δp _min ) / 2 Equation (3)
Hydrogen bond term δh = (δh _max −δh _min ) / 2 Equation (4)
(HSP value) ² = δd ² + δp ² + δh ² Equation (5)

<Water contact angle on the surface of the membrane>
The contact angle of water on the surface of the film used in Examples and Comparative Examples was determined using an automatic contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 2 to 8.

<Evaluation of water resistance>
^{After dropping 1 cm 3} of water on the decorative layer of the sheets according to each example and each comparative example, the tissue paper was pressed, and then the presence or absence of pigment adhesion on the tissue paper was confirmed, and the water resistance of the decorative layer was evaluated. The indexes for evaluating water resistance are as follows. The results are shown in Tables 2-9.
A: No pigment is attached to the tissue paper.
X: Pigment is attached to the tissue paper.

[Example 1]
<Ink preparation>
The contents of water, alcohol, pigment, and binder were adjusted as shown in Table 2, and these components were mixed to prepare the ink according to Example 1. Ultrapure water was used as water, and Zemea Select (1,3-propanediol) manufactured by Iwase Cosfa Co., Ltd. and glycerin (concentrated glycerin for cosmetics) manufactured by Kao Corporation were used as alcohols. Iron oxide yellow LL-100W manufactured by Titan Kogyo Co., Ltd. was used as the pigment. The primary particle size of this pigment was 100 nm. As a binder, Acrylate Copolymer Dermacryl AQF manufactured by Nurion Japan Co., Ltd. was used. The HSP value of this Acrylate copolymer was ^{25.0 MPa 1/2.}

<Preparation of regenerated cellulose membrane>
A cellulose solution was prepared by preparing cellulose derived from bleached pulp made from wood and having a purity of 90% or more and dissolving it in an ionic liquid. Next, a glass substrate having a flat surface was prepared. Next, a liquid film was formed on the glass substrate by applying a gap coating and applying a cellulose solution to the surface of the glass substrate. At this time, the size of the gap was adjusted so that the thickness of the regenerated cellulose film was the target thickness of 400 nm. After the formation of the liquid film, the glass substrate and the liquid film were sufficiently left to stand in an environment of a temperature of 25 ° C. and a relative humidity of 30% to 40% to gel the liquid film to obtain a polymer gel sheet. Then, the polymer gel sheet was washed with water to remove the ionic liquid from the polymer gel sheet. At this time, the glass substrate and the polymer gel sheet were immersed in ultrapure water, and the ultrapure water was replaced a plurality of times to wash the polymer gel sheet with water. An aqueous solution of a polyether-modified silicone KF-6012 (PEG / PPG-20 / 22 butyl ether dimethicone) manufactured by Shin-Etsu Chemical Co., Ltd. was prepared. Next, a laminate of the polymer gel sheet and the non-woven fabric was immersed in this aqueous solution. Next, the polymer gel sheet was taken out from the aqueous solution, and the polymer gel sheet was dried at a room temperature to obtain a regenerated cellulose film A. The thickness of the regenerated cellulose membrane A was measured using a stylus-type profiling system DEKTAK (registered trademark) manufactured by Car Nano Incorporated. As a result, the thickness of the regenerated cellulose membrane A was about 400 nm.

^{A sample for solid 13} C-NMR measurement was prepared from the regenerated cellulose film A, ^{and solid 13} C-NMR measurement was performed ^{using this sample to obtain a solid 13} C-NMR spectrum. Solid ¹³ C-NMR measurements were made by Varian Unity Inova-400 and Doty Scientific, Inc. The procedure was performed according to the CP / MAS method using a 5 mm CP / MAS probe manufactured by Japan. The measurement conditions are MAS speed: 10 kHz, room temperature (25 ° C.), sample rotation speed: 10 kHz, observation width: 30.2 kHz, observation center: 96 ppm, observation frequency: 100.574 MHz, and CP pulse ( ¹ H → ¹³ C). ) Method, observation nucleus 90 ° pulse: 3.9 microseconds, 1H excitation pulse: 3.8 microseconds, contact time: 2.0 ms, waiting time: 10 seconds or more, total number of times: 8,000 times I set it. It was confirmed that ^{the solid 13} C-NMR spectrum of regenerated cellulose measured by the CP method under these conditions ^{closely matches the solid 13} C-NMR spectrum measured by the DD (Dipolar De couple) method with a sufficient relaxation time. rice field. Based on the obtained solid ¹³ C-NMR spectrum, the crystallinity of the regenerated cellulose contained in the regenerated cellulose film A was determined according to the above formula (1). The crystallinity was 0%.

The regenerated cellulose membrane A was immersed in water, taken out, and the weight M2 of the regenerated cellulose membrane after immersion was measured. Further, the weight M1 of the regenerated cellulose membrane before immersion was measured before the regenerated cellulose membrane was immersed in water. The water absorption rate of the regenerated cellulose membrane A was determined according to the following formula (6).
Water absorption rate [%] = {(M2-M1) / M1} x 100 formula (6)

<Making a sheet>
The ink according to Example 1 was applied to the surface of the regenerated cellulose film A with a squeegee to form a coating film, and the coating film was dried at room temperature for 1 day to form a decorative layer on the regenerated cellulose film. In this way, the sheet according to Example 1 was obtained.

[Example 2]
The ink according to Example 2 was prepared in the same manner as in Example 1 except that iodosol GH810F, which is an alkyl copolymer ammonium acrylate manufactured by AkzoNobel, was used as the binder. The HSP value of iodosol GH810F was 28.5 MPa ^1/2 . A sheet according to Example 2 was obtained in the same manner as in Example 1 except that the ink according to Example 2 was used instead of the ink according to Example 1.

[Example 3]
The ink according to Example 3 was prepared in the same manner as in Example 1 except that iodosol G41F, which is a styrene / alkyl acrylate copolymer ammonium manufactured by AkzoNobel, was used as a binder. The HSP value of iodosol G41F was 29.7 MPa ^1/2 . A sheet according to Example 3 was obtained in the same manner as in Example 1 except that the ink according to Example 3 was used instead of the ink according to Example 1.

[Example 4]
The ink according to Example 4 was prepared in the same manner as in Example 1 except that Vinizol 1086WP, which is an acrylates copolymer ammonium manufactured by Daido Kasei Co., Ltd., was used as a binder. The HSP value of Vinizol 1086WP was 30.3 MPa ^1/2 . A sheet according to Example 4 was obtained in the same manner as in Example 1 except that the ink according to Example 4 was used instead of the ink according to Example 1.

[Example 5]
The ink according to Example 5 was prepared in the same manner as in Example 1 except that iodosol 34F, which is an alkyl copolymer ammonium acrylate manufactured by AkzoNobel, was used as the binder. The HSP value of iodosol 34F was 30.5 MPa ^1/2 . A sheet according to Example 5 was obtained in the same manner as in Example 1 except that the ink according to Example 5 was used instead of the ink according to Example 1.

[Comparative Example 1]
An ink according to Comparative Example 1 was prepared in the same manner as in Example 1 except that Dytozol 3000SLPN, which is an Acrylate copolymer manufactured by Daito Kasei Co., Ltd., was used as a binder. The HSP value of Dytosol 3000SLPN was 23.0MPa ^1/2 . A sheet according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the ink according to Comparative Example 1 was used instead of the ink according to Example 1.

[Comparative Example 2]
An ink according to Comparative Example 2 was prepared in the same manner as in Example 1 except that Vinizol 2140LH, which is an Acrylate / VA copolymer manufactured by Daido Kasei Co., Ltd., was used as a binder. The HSP value of Vinizol 2140LH was 31.0 MPa ^1/2 . A sheet according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the ink according to Comparative Example 2 was used instead of the ink according to Example 1.

[Comparative Example 3]
An ink according to Comparative Example 3 was prepared in the same manner as in Example 1 except that polyvinyl alcohol (PVA) manufactured by Wako Pure Chemical Industries, Ltd. was used as the binder. The HSP value of this polyvinyl alcohol was 34.0 MPa ^1/2 . A sheet according to Comparative Example 3 was obtained in the same manner as in Example 1 except that the ink according to Comparative Example 3 was used instead of the ink according to Example 1.

[Comparative Example 4]
The ink according to Comparative Example 4 was prepared in the same manner as in Example 1 except that Metrose SM4000, which is a methyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd., was used as the binder. The HSP value of Metrose SM4000 was 34.4MPa ^1/2 . A sheet according to Comparative Example 4 was obtained in the same manner as in Example 1 except that the ink according to Comparative Example 4 was used instead of the ink according to Example 1.

[Examples 6 to 10]
Example 1, Example 2, Example 3, Example 4, and Example 5 except that Typake CR-50, which is titanium oxide manufactured by Ishihara Sangyo Co., Ltd., was used as the pigment instead of iron yellow oxide. In the same manner, the inks according to Example 6, Example 7, Example 8, Example 9, and Example 10 were prepared, respectively. The primary particle size of Typake CR-50 was 250 nm. Example 6 in the same manner as in Example 1 except that the inks according to Example 6, Example 7, Example 8, Example 9, and Example 10 were used instead of the ink according to Example 1. , Example 7, Example 8, Example 9, and Example 10 were obtained.

[Comparative Examples 5 to 8]
Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 except that Typake CR-50 was used as the pigment instead of iron yellow oxide, respectively, in Comparative Example 5 and Comparative Example 6, respectively. , Comparative Example 7, and Comparative Example 8 were prepared. Comparative Example 5 and Comparative Example 6 are the same as in Example 1 except that the inks according to Comparative Example 5, Comparative Example 6, Comparative Example 7, and Comparative Example 8 were used instead of the ink according to Example 1, respectively. , Comparative Example 7 and Comparative Example 8 were obtained.

As shown in Tables 2 and 3, the water resistance of the decorative layer in the sheets according to Examples 1 to 10 was good. On the other hand, it was difficult to say that the water resistance of the decorative layer in the sheets according to Comparative Examples 1 to 8 was good. It is suggested that the polymer contained in the binder in the ink for forming the decorative layer has ^{an HSP value of 24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2} , which is advantageous for enhancing the water resistance of the decorative layer. Was done.

[Examples 11 to 14]
The polymer gel sheet obtained in the same manner as in Example 1 was washed with water in the same manner as in Example 1. Next, the polymer gel sheet was immersed in a solution of triethylhexanoin manufactured by Nisshin Oillio Group. Then, the polymer gel sheet was taken out from the solution, and the polymer gel sheet was naturally dried at room temperature to obtain a regenerated cellulose film B. The contact angle of water on the surface of the regenerated cellulose membrane B was 32 °.

Examples 11, 12, and Examples, respectively, in the same manner as in Example 1, Example 2, Example 3, and Example 4, except that the regenerated cellulose film B was used instead of the regenerated cellulose film A. Sheets 13 and 14 according to Example 14 were prepared.

[Comparative Examples 9 to 12]
Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 except that the regenerated cellulose membrane B was used instead of the regenerated cellulose film A, respectively, in Comparative Example 9, Comparative Example 10, and Comparative Example, respectively. A sheet according to 11 and Comparative Example 12 was prepared.

Table 4 shows the evaluation results of the water resistance of the decorative layer in the sheets according to Examples 11 to 14 and the sheets according to Comparative Examples 9 to 12. As shown in Table 4, the water resistance of the decorative layer in the sheets according to Examples 11 to 14 was good. On the other hand, it was hard to say that the water resistance of the decorative layer in the sheets according to Comparative Examples 9 to 12 was good. It is suggested that the polymer contained in the binder in the ink for forming the decorative layer has ^{an HSP value of 24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2} , which is advantageous for enhancing the water resistance of the decorative layer. Was done.

[Example 15]
The polymer gel sheet obtained in the same manner as in Example 1 was washed with water in the same manner as in Example 1. Next, the polymer gel sheet was immersed in an aqueous solution of glycerin. Then, the polymer gel sheet was taken out from the aqueous solution, and the polymer gel sheet was naturally dried at room temperature to obtain a regenerated cellulose film C. The contact angle of water on the surface of the regenerated cellulose film C was 4 °. In addition, the crystallinity of the regenerated cellulose in the regenerated cellulose membrane C was 0%, and the water absorption rate of the regenerated cellulose membrane C was 171%.

A sheet according to Example 15 was prepared in the same manner as in Example 3 except that the regenerated cellulose film C was used instead of the regenerated cellulose film A.

[Example 16]
The polymer gel sheet obtained in the same manner as in Example 1 was washed with water in the same manner as in Example 1. Next, the polymer gel sheet was immersed in an aqueous solution of sodium lactate manufactured by Musashino Chemical Research Institute. Then, the polymer gel sheet was taken out from the aqueous solution, and the polymer gel sheet was naturally dried at room temperature to obtain a regenerated cellulose film D. The contact angle of water on the surface of the regenerated cellulose membrane D was 12 °.

A sheet according to Example 16 was prepared in the same manner as in Example 3 except that the regenerated cellulose film D was used instead of the regenerated cellulose film A.

[Example 17]
The polymer gel sheet obtained in the same manner as in Example 1 was washed with water in the same manner as in Example 1. Next, the polymer gel sheet was immersed in a solution of eco-oil RS, which is a jojoba seed oil manufactured by Higher Alcohol Industry Co., Ltd. Then, the polymer gel sheet was taken out from the solution, and the polymer gel sheet was naturally dried at room temperature to obtain a regenerated cellulose membrane E. The contact angle of water on the surface of the regenerated cellulose film E was 68 °. In addition, the crystallinity of the regenerated cellulose in the regenerated cellulose membrane E was 1.8%, and the water absorption rate of the regenerated cellulose membrane E was 128%.

A sheet according to Example 17 was prepared in the same manner as in Example 3 except that the regenerated cellulose film E was used instead of the regenerated cellulose film A.

[Comparative Example 13]
The polymer gel sheet obtained in the same manner as in Example 1 was washed with water in the same manner as in Example 1. Next, the polymer gel sheet was immersed in a solution of dimethyl silicone oil KF-96h-10,000 cs manufactured by Shin-Etsu Chemical Co., Ltd. Then, the polymer gel sheet was taken out from the solution, and the polymer gel sheet was naturally dried at room temperature to obtain a regenerated cellulose film F. The contact angle of water on the surface of the regenerated cellulose film F was 101 °.

A sheet according to Comparative Example 13 was produced in the same manner as in Example 3 except that the regenerated cellulose film F was used instead of the regenerated cellulose film A.

Table 5 shows the evaluation results of the water resistance of the decorative layer in the sheets according to Examples 3, 13, 15 to 17 and the sheets according to Comparative Example 13. As shown in Table 5, the water resistance of the decorative layer in the sheet according to each example was good. On the other hand, it was hard to say that the water resistance of the decorative layer in the sheet according to Comparative Example 13 was good. It was suggested that the contact angle of water on the surface of the regenerated cellulose film is larger than 0 ° and 100 ° or less, which is advantageous for enhancing the water resistance of the decorative layer.
It is probable that in the sheet according to Comparative Example 13, the affinity between the regenerated cellulose film F and the ink was low, and the adhesion between the decorative layer and the regenerated cellulose film F was low. Therefore, it is considered that the decorative layer of the sheet according to Comparative Example 13 was easily peeled off by water.

[Examples 18 to 21]
Inks according to each of Example 18, Example 19, Example 20, and Example 21 were prepared in the same manner as in Example 2 except that the content of the binder was adjusted as shown in Table 6. In addition, in the same manner as in Example 2, the inks according to Example 18, Example 19, Example 20, and Example 21 were used instead of the ink according to Example 2, respectively. 18, Sheets of Example 19, Example 20, and Example 21 were obtained.

[Comparative Example 14]
The ink according to Comparative Example 14 was prepared in the same manner as in Example 2 except that the binder was not added. Sheets according to Comparative Example 14 were obtained in the same manner as in Example 2 except that the ink according to Comparative Example 14 was used instead of the ink according to Example 2.

As shown in Table 6, the water resistance of the decorative layer in the sheet according to each example was good. On the other hand, it was hard to say that the water resistance of the decorative layer in the sheet according to Comparative Example 14 was good. It was suggested that the inclusion of the binder in a predetermined content with respect to the content of the pigment is advantageous in enhancing the water resistance of the decorative layer.

[Examples 22 to 24]
Example 22, Example 23, and Example 24, respectively, in the same manner as in Examples 1, 3, and 5, except that the content of each component was adjusted as shown in Table 7 without adding alcohol. The ink according to the above was prepared. Example 22, Example 23, and Example 23, respectively, in the same manner as in Example 1, except that the inks according to Example 22, Example 23, and Example 24 were used instead of the ink according to Example 1. A sheet according to Example 24 was obtained.

[Example 25]
The ink according to Example 25 was prepared in the same manner as in Example 24, except that the content of each component was adjusted as shown in Table 7 by adding a dispersant without adding alcohol. A sheet according to Example 25 was obtained in the same manner as in Example 1 except that the ink according to Example 25 was used instead of the ink according to Example 1. Anionic surfactants and amphoteric surfactants were used as dispersants. Di (2-ethylhexyl) sulfosuccinate Na was used as the anionic surfactant, and betaine lauryldimethylaminoacetate was used as the amphoteric surfactant.

[Comparative Examples 15 to 18]
Comparative Example 15, Comparative Example 16, and Comparative Example, respectively, in the same manner as in Comparative Examples 1, 2, 3, and 4, except that the content of each component was adjusted as shown in Table 8 without adding alcohol. 17 and the ink according to Comparative Example 18 were prepared. Comparative Example 15 and Comparison are carried out in the same manner as in Example 1 except that the inks according to Comparative Example 15, Comparative Example 16, Comparative Example 17, and Comparative Example 18 were used instead of the ink according to Example 1, respectively. Sheets according to Example 16, Comparative Example 17, and Comparative Example 18 were obtained.

[Comparative Examples 19 and 20]
Comparative Examples 19 and 20, respectively, were described in the same manner as in Comparative Examples 15 and 16, except that the content of each component was adjusted as shown in Table 8 by adding a dispersant without adding alcohol. The ink was prepared. Sheets according to Comparative Example 19 and Comparative Example 20 were obtained in the same manner as in Example 1 except that the inks according to Comparative Example 19 and Comparative Example 20 were used instead of the ink according to Example 1, respectively. As the dispersant, the anionic surfactant and the amphoteric surfactant used in the preparation of the ink according to Example 25 were added.

<Evaluation of dispersibility>
The dispersibility of the inks according to Examples 22 to 25 and the pigments in Comparative Examples 15 to 20 was evaluated. When the ink was stirred after the ink was prepared and the pigment was uniformly mixed, and no precipitation of the pigment was confirmed even after 1 hour from the stirring, the dispersibility was evaluated as "A". On the other hand, when the ink was stirred after the preparation of the ink, the pigment was uniformly mixed, but when the precipitation of the pigment was confirmed within 1 hour from the stirring, the dispersibility was evaluated as "B". The results are shown in Tables 7 and 8.

As shown in Table 7, the water resistance of the decorative layer in the sheet according to each example was good. On the other hand, as shown in Table 8, it was difficult to say that the water resistance of the decorative layer in the sheet according to each comparative example was good. Even if alcohol is not added to the ink, it is advantageous for the polymer contained in the binder in the ink ^{to have an HSP value of 24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2 in} order to improve the water resistance of the decorative layer. It was suggested that there is.

The comparison between Examples 22 to 24 and Example 25 suggests that the pigment can be satisfactorily dispersed in the ink by adding the dispersant.

[Comparative Example 21]
A filter paper, which is a natural cellulose having a thickness of 140 μm, was prepared. Since the filter paper is natural cellulose, it is a material having a crystal structure I. The crystallinity of cellulose having a crystal structure I contained in the filter paper was 26%. The water absorption rate of the filter paper was 99.6%. A sheet according to Comparative Example 21 was obtained in the same manner as in Comparative Example 2 except that this filter paper was used instead of the regenerated cellulose film A.

[Comparative Example 22]
A PET film having a thickness of 116 μm was prepared. The water absorption rate of the PET film was 0.20%. A sheet according to Comparative Example 22 was obtained in the same manner as in Comparative Example 2 except that this PET film was used instead of the regenerated cellulose film A.

As shown in Table 9, the decorative layer formed on the filter paper and the PET film by the ink according to Comparative Example 2 showed good water resistance. On the other hand, it was hard to say that the decorative layer formed on the regenerated cellulose film A by the ink according to Comparative Example 2 had good water resistance. Therefore, it was suggested that even an ink showing good fixability to filter paper and PET film does not always show good fixability to regenerated cellulose.

<Evaluation of adhesion to the skin>
The adhesion of the regenerated cellulose film A, the regenerated cellulose film C, the regenerated cellulose film E, the filter paper in Comparative Example 21, the PET film in Comparative Example 22, and the test piece of the polylactic acid sheet having a thickness of 410 nm to the skin is as follows. Evaluated as. A small amount of commercially available lotion was applied on the skin inside the upper arm of the subject, and each test piece was attached onto it. After 8 hours in that state, it was confirmed whether or not the test piece had fallen off the skin. Based on the confirmation result, the adhesion of each test piece to the skin was evaluated according to the following indexes. The results are shown in Table 10. The water content of the polylactic acid sheet was 0.3%.
A: The test piece has not fallen off the skin X: The test piece has fallen off the skin

<Evaluation of skin stress>
The skin stress of the regenerated cellulose film A, the regenerated cellulose film C, the regenerated cellulose film E, the filter paper in Comparative Example 21, the PET film in Comparative Example 22, and the test piece of the polylactic acid sheet having a thickness of 410 nm was evaluated as follows. bottom. A small amount of water was applied to the skin inside the upper arm of the subject, and a test piece was attached onto the skin. After 1 hour had passed in that state, it was confirmed whether or not there was any discomfort such as stuffiness and abnormalities such as redness of the skin. Based on the confirmation result, the skin stress of each test piece was evaluated according to the following indexes. The results are shown in Table 10.
A: No abnormality X: There is an abnormality

As shown in Table 10, it was suggested that the test piece of the regenerated cellulose film had better adhesion to the skin and less skin stress than the test piece of the filter paper, the PET film, and the polylactic acid sheet.

The ink of the present disclosure can realize coloring with high water resistance by being applied to a biocompatible film containing regenerated cellulose. The sticking sheet thus obtained can be used by sticking to a living body such as skin, and is useful for skin protection, coloring, beautification and the like.

1 Sticking kit 2a, 2b Sticking sheet 10 Ink 10a Ink solidified 20 Film 30 Base material

Claims (16)

An ink that colors biocompatible films containing regenerated cellulose.
water and,
With pigments
Contains a binder containing a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.}
ink. The ink according to claim 1, wherein the polymer contains an acrylic polymer. The ink according to claim 1 or 2, wherein the ratio of the content of the binder to the content of the pigment is 0.1 or more and 8 or less on a mass basis. The ink according to any one of claims 1 to 3, further containing at least one of a divalent alcohol and a trihydric alcohol. The ink according to any one of claims 1 to 4, further containing a dispersant that disperses at least one of the pigment and the binder. The ink according to any one of claims 1 to 5 and
With a biocompatible membrane containing regenerated cellulose,
The contact angle of water on the surface of the biocompatible film is greater than 0 ° and less than 100 °.
Sticking kit. The regenerated cellulose has a weight average molecular weight of 150,000 or more and has a weight average molecular weight of 150,000 or more.
The biocompatible film has a thickness of 20 nm or more and 1300 nm or less.
The sticking kit according to claim 6. The application kit according to claim 6 or 7, wherein the regenerated cellulose has a crystallinity of 12% or less. The application kit according to any one of claims 6 to 8, wherein the biocompatible film contains an ingredient effective for a living body. It is a sticking sheet
Biocompatible membrane containing regenerated cellulose and
A solidified ink containing a pigment and a binder and forming at least a part of the surface of the sticking sheet.
The contact angle of water on the surface of the biocompatible film is greater than 0 ° and less than 100 °.
The binder contains a polymer having an HSP value of ^{24 MPa 1/2} or more and ^{less than 31.0 MPa 1/2.}
Sheet for sticking. The sticking sheet according to claim 10, wherein the polymer contains an acrylic polymer. The sticking sheet according to claim 10 or 11, wherein the ratio of the content of the binder to the content of the pigment in the solidified product is 0.1 or more and 8 or less on a mass basis. The regenerated cellulose has a weight average molecular weight of 150,000 or more and has a weight average molecular weight of 150,000 or more.
The biocompatible film has a thickness of 20 nm or more and 1300 nm or less.
The sticking sheet according to any one of claims 10 to 12. The sticking sheet according to any one of claims 10 to 13, wherein the regenerated cellulose has a crystallinity of 12% or less. The sticking sheet according to any one of claims 10 to 14, wherein the biocompatible film contains an ingredient effective for a living body. Applying the ink according to any one of claims 1 to 5 to the surface of a biocompatible film containing regenerated cellulose,
Including drying the ink applied to the surface.
The contact angle of water on the surface is greater than 0 ° and less than 100 °.
A method of manufacturing a sticking sheet.

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