JP5098931B2 - Oil resistant cosmetics - Google Patents

Description

  The present invention relates to an application for which oil resistance and water resistance are required at the same time in wallpaper or the like, and relates to a cosmetic material that exhibits good oil resistance and water resistance by coating an aqueous dispersion without using a fluororesin.

  Oil-resistant paper, which has the function of suppressing oil penetration, is used for packaging and packaging of fried foods such as French fries, fat and fat foods such as butter, and other foods that contain oil such as cookies and pet food, and other labels and cosmetics. Is widely used.

  Such oil-resistant paper has the advantages of having high oil resistance and water resistance, low odor, and excellent printing suitability. An organic fluororesin such as an organic fluororesin-coated paper coated with a coating liquid containing it and having a paper base layer provided with oil resistance has become the mainstream.

Moreover, from the accumulation of organic fluororesin in the body, generation of harmful gas under high temperature conditions, etc., as an oil-resistant paper other than organic fluororesin, acrylic and styrene-acrylic having a glass transition point in the range of −25 to 30 ° C. Or a copolymer of olefin and maleic acid or a mixture of olefin and maleic acid and alkenyl succinic anhydride to 100 parts of a styrene-butadiene based synthetic resin emulsion or a mixture of these synthetic resin emulsions. There has been proposed an oil-resistant paper characterized in that a coating liquid in which 3 to 35 parts are mixed is applied to at least one surface of the front and back surfaces of the base paper by 2.0 to 10 g / m ² ( Patent Document 1). When an acrylic, styrene-acrylic or styrene-butadiene synthetic resin emulsion having a glass transition point in the range of −25 to 30 ° C. is used, the coating layer is provided with flexibility and heat sealability that is not damaged by bending, When 3 to 35 parts of an oil resistant agent obtained by copolymerizing olefin and maleic acid is added to 100 parts of the emulsion, oil resistance is imparted to the coating layer, and 3 to 150 inorganic pigments are added to 100 parts of the emulsion. It is described that the ink absorption can be imparted to the coating layer when the part is contained. It is described that the coating liquid may contain a surfactant, an organic solvent, etc. in order to improve the penetration into the paper base material layer. In the examples, a known oil resistance agent is added to the synthetic resin emulsion. A blended product is used.

  In addition, a resin coating layer was provided by polymerizing by irradiating an electron beam after depositing a resin monomer comprising a fluororesin monomer by vapor deposition on at least one side of the paper base layer to form a uniform film. There is also a characteristic oil-resistant paper (Patent Document 2). As an alternative to fluorinated oil-resistant agents, oil-resistant agents mainly composed of acrylic polymers marketed by external additives have problems such as a unique acrylic odor adhering to foods, and polyester-based oil-resistant agents also have good oil resistance. The oil-resistant paper according to the above is excellent in oil resistance and water resistance, has no odor, and has high ruled line oil resistance even when formed in a container.

  There is also an oil-resistant decorative printing sheet in which an ink layer having a color tone and a pattern is appropriately provided on at least one surface of a thin paper impregnated with an oil-resistant resin (Patent Document 3). A decorative material obtained by applying a decorative printing sheet obtained by applying a printed coloring pattern layer to one side of a thin paper by printing using a gravure printing method, etc. on a wooden substrate via an adhesive, or a transparent resin on the thin paper. Since the decorative material coated with a transparent protective resin layer is not oil resistant to the thin paper or the protective resin layer, the surface oil component of the decorative material may adhere to and contaminate the decorative material. However, according to the above configuration, damage to the ink layer due to external scratching stress or impact can be protected, and dust, dirt, oil, etc. adhering to the surface of the protective resin layer can be protected on the surface of the protective resin layer. It can be wiped off.

  Further, a wear-resistant resin layer formed from a coating composition containing a binder composed of a crosslinkable resin and spherical particles having a hardness higher than that of the crosslinkable resin is provided on the surface of the substrate, There is also a cosmetic material having a permeation-suppressing coating film that suppresses permeation of the wear-resistant resin composition and has oil resistance between the abrasion-resistant resin layer (Patent Document 4). When thin paper or highly permeable paper is used as the base material, there is a problem that the coating composition does not have the abrasion resistance due to the penetration of the resin, and further, the problem that the surface becomes rough due to the penetration. Patent Document 4 has been made in order to solve such drawbacks. It is said that by laminating a permeation-suppressing coating film having oil resistance, it is possible to provide a cosmetic material having excellent wear resistance and good design properties even when the base material is thin paper or highly permeable paper.

On the other hand, an unsaturated carboxylic acid or its anhydride, an alkene having 2 to 6 carbon atoms and a specific (meth) acrylic acid ester or ester thereof are copolymerized with a predetermined composition, and the number average particle diameter is 1 μm or less. There is an aqueous dispersion of a polyolefin resin, which is an aqueous dispersion made of a polyolefin resin, and is substantially free of non-volatile aqueous additive (Patent Document 5). Under the present situation where the use of organic solvents is limited, an aqueous dispersion substantially free of non-volatile aqueous additive is provided, has a stable pot life, and has non-volatile aqueous additive. Since the agent is not substantially contained, it is possible to form a film excellent in water resistance without impairing the properties of the polyolefin resin.
JP 2004-19036 A JP 2006-022420 A JP-A-8-118554 JP 2000-211092 A Japanese Patent No. 3699935

  In recent years, the use of organic solvents tends to be restricted from the standpoints of environmental protection, resource conservation, dangerous goods regulations under the Fire Service Act, and workplace environment improvement. The method described in Patent Document 1 uses a surfactant or an organic solvent. If an oil-resistant cosmetic material having excellent oil resistance can be prepared without using these, it is excellent in environmental conservation. This also applies to Patent Document 3 and Patent Document 4.

  Moreover, the oil-resistant paper described in Patent Document 2 requires a vapor deposition step of a resin monomer composed of a fluororesin monomer and an electron beam irradiation step, is more expensive in raw material, and has a special manufacturing method. Therefore, development of oil-resistant paper obtained by a simpler method is desired.

  In addition, the oil-resistant decorative printing sheet of Patent Document 3 does not have an oil-resistant layer outside the printed layer or protective layer, which provides oil resistance to thin paper and protects the ink layer from damage due to scratching stress or impact. Therefore, there is a limit in preventing impregnation of the fat adhering to the printed layer, and it is difficult to prevent physical damage to the printed layer and the protective resin layer.

Moreover, since patent document 4 laminates | wears the abrasion-resistant resin composition which consists of a crosslinkable resin, in an Example, the resin is bridge | crosslinked by irradiating an electron beam, and a process is complicated.
In addition, the aqueous polyolefin resin dispersion described in Patent Document 5 is excellent in environmental conservation in that it does not substantially contain a non-volatile aqueous additive such as a surfactant, but it can produce a water-resistant coating but is oil-resistant. There is no description. Further, in the examples, an aqueous polyolefin resin dispersion is applied to a biaxially stretched PET film, but since it is an aqueous dispersion, it is applied to the paper base layer in order to prepare an oil-resistant paper base layer. If processed, it may impregnate and form a coating film.

The present invention has been made in view of the above situation, and an object thereof is to provide an oil-resistant cosmetic material that is inexpensive and has excellent oil resistance without using an organic fluororesin.
Moreover, an object of this invention is to provide the oil-resistant cosmetics obtained substantially from an organic solvent and a non-volatile water-izing auxiliary agent from a viewpoint of environmental conservation.

  As a result of detailed studies on the oil-resistant layer laminated on the paper base layer, the present inventors have found that a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass is a number average particle. The coating formed by applying an aqueous dispersion dispersed with a diameter of 1 μm or less has oil resistance, and the aqueous dispersion is prepared without substantially containing a non-volatile aqueous agent, and thus is excellent in environmental conservation. In general, a coating film cannot be formed because such an aqueous dispersion penetrates into the paper base layer. However, by applying the aqueous dispersion and drying at a predetermined temperature a predetermined number of times, A label capable of forming an oil-resistant layer and forming the oil-resistant layer on the surface of the printing layer, which is excellent in oil resistance and water resistance without forming an overcoat layer, and can also ensure a protective function of the printing surface. That it can be prepared May be formed oil layer on top of the coat layer, it found that thereby can impart oil resistance to the conventional decorative material, and completed the present invention.

That is, the present invention is an oil-resistant cosmetic material formed by laminating at least a paper base layer and an oil-resistant layer,
In the oil-resistant layer, the polyolefin copolymer resin containing unsaturated carboxylic acid or anhydride thereof in the range of 0.01 to 5% by mass is substantially free of non-volatile aqueous additive and has a number average particle diameter of 1 μm. The present invention provides an oil-resistant cosmetic material, which is obtained by applying and drying an aqueous dispersion liquid dispersed below.

According to the present invention, by using a conventional aqueous polyolefin resin dispersion, it is possible to produce an oil-resistant cosmetic material using conventional equipment as it is and having excellent oil resistance.
The oil-resistant cosmetic material of the present invention can substantially reduce the burden on the environment without substantially containing a non-volatile aqueous additive.

  The oil-resistant decorative material of the present invention can be prepared with a simple layer structure, and the resulting cosmetic material is excellent in oil resistance and water resistance, and can be suitably used as wallpaper.

  The present invention is an oil-resistant decorative material formed by laminating at least a paper base layer and an oil-resistant layer, and the oil-resistant layer contains an unsaturated carboxylic acid or an anhydride thereof in a range of 0.01 to 5% by mass. The oil-resistant cosmetic, characterized in that the polyolefin copolymer resin containing is obtained by applying and drying an aqueous dispersion in which the number average particle size is 1 μm or less, substantially free of non-volatile aqueous auxiliary agent. It is a material.

(1) Structure of oil-resistant decorative material An example of a suitable aspect of the oil-resistant decorative material of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of an oil-resistant decorative material in which an oil-resistant layer (20) and a paper base layer (10) are laminated from the outer layer toward the inner layer. As shown in FIG. 2, a base layer (30) may be laminated on the surface of the paper base layer (10), and an oil resistant layer (20) may be laminated thereon. In addition, as shown in FIG. 3, the oil-resistant decorative material of the present invention has an oil-resistant layer (20), a printed layer (40), a base layer (30), and a paper base layer (10) from the outer layer toward the inner layer. May be stacked in this order. If it is this aspect, an oil-resistant layer (20) will also exhibit the function of an overcoat layer, and can protect a printing layer (40) appropriately. As shown in FIG. 4, the oil-resistant layer (20), the overcoat layer (50), the printing layer (40), the base layer (30), and the paper base layer (10) are arranged in this order from the outer layer to the inner layer. It may be laminated. By forming an oil-resistant layer on the surface of a conventional decorative material, a new oil-resistant decorative material can be obtained.

Since the oil-resistant cosmetic material of the present invention is excellent in water resistance and oil resistance, it can be suitably used for applications such as wallpaper where oil resistance and water resistance are required simultaneously.
(2) Paper base material layer The paper base material layer used by this invention can use what has bending resistance, rigidity, waist, intensity | strength, etc. As a paper base material layer, various paper base material layers, such as a pure white roll paper, a craft paper, a paperboard, a processed paper, a milk base paper, can be used, for example. The paper base layer may be a laminate of a plurality of these papers. Further, paper having a basis weight of about 10 to 500 g / m ² , preferably about 10 to 300 g / m ² can be used.

(2) Underlayer In the present invention, it is preferable to form an underlayer on the paper base layer and form a printing layer on the underlayer. As such a base layer, there is a clay coat layer. Since the paper base material layer has irregularities on its surface, a clear print surface cannot be formed when printing is directly performed on the paper base material layer. For this reason, the adhesion and design nature of a printing layer can be improved by forming a ground layer on a paper base material layer, and printing on it.

  The clay coat layer is obtained by applying a coating liquid containing clay to a paper base material layer, and laying clay particles on one side of the paper base material layer. The clay is not particularly limited as long as it is generally called clay, but kaolin, talc, bentonite, smectite, vermiculite, mica, chlorite, Kibushi clay, gairom clay, halloysite, mica, etc. are used. It is done. Of these, kaolin and talc are preferably used as the clay. Kaolin has excellent concealability and water absorption, and talc has low hardness (Mohs hardness 1) and excellent heat resistance. Improvement in dimensional stability can be expected.

  The clay coat layer preferably contains calcium carbonate, titanium dioxide, amorphous silica, expandable barium sulfate, satin white and the like as a pigment in addition to clay. By using calcium carbonate or titanium dioxide as the pigment, the smoothness of the surface of the clay coat layer can be increased and the concealability can be increased. Furthermore, calcium carbonate is preferably used because it is inexpensive.

  The coating liquid for coating the clay coat layer contains the above clay, a binder, and, if necessary, other pigments and additives in a solvent. As the solvent, water, alcohol or the like is usually used. As the binder, latex binders (eg, styrene butadiene latex, acrylic latex vinyl acetate latex), water-soluble binders (eg, starch (modified starch, oxidized starch, hydroxyethyl etherified starch, phosphate ester) Modified starch), polyvinyl alcohol, casein) and the like. Examples of additives that can be used include pigment dispersants, antifoaming agents, antifoaming agents, viscosity modifiers, lubricants, water resistance agents, water retention agents, coloring materials, and printability improvers.

The blending ratio of the clay coating layer coating solution is not particularly limited, but is preferably about clay: pigment: binder = 1-20%: 50-90%: 10-30%. The coating method of the clay coat layer is not particularly limited, and a conventionally known coating method is used, but a coating method such as air knife coating, blade coating, short dwell coating, cast coating or the like is used. Although the coating amount and thickness of the clay coat layer are not particularly limited, the basis weight after drying is usually 5 to 40 g / m ² and preferably 10 to 40 g / m ² . In addition, as a paper base material layer and a clay coat layer, the material by which the clay coat layer was already formed in the paper base material layer can also be used.

  In the present invention, the base layer improves the adhesion between the paper base layer and the printed layer. In addition to the above-described clay coat layer, an isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium Anchor coat layers such as other and other anchor coating agents; primer layers mainly composed of polyurethane resins or polyester resins; sealing sealer layers; corona discharge treatment, ozone treatment, oxygen gas or nitrogen gas, etc. The pretreatment layer such as low temperature plasma treatment, glow discharge treatment, oxidation treatment using chemicals, etc., etc. may be performed.

(4) Oil-resistant layer In the oil-resistant decorative material of the present invention, the oil-resistant layer (20) is laminated at least on the paper base layer (10) (Fig. 1), but the base layer (30 on the paper base layer (10)). ) Is preferably laminated with an oil resistant layer (20) on the base layer (30) (FIG. 2). Moreover, a printing layer (40) may be further formed in the oil resistant decorative material (FIG. 3). By forming the oil resistant layer (20) on the upper layer of the print layer (40), the oil resistance can be secured and the surface of the print layer (40) can be physically protected. In this respect, the oil resistant layer and the overcoat layer are combined. The overcoat layer (50) may be laminated on the print layer (40), and then the oil resistant layer (20) may be formed on the overcoat layer (50) (FIG. 4).

  In the present invention, the oil-resistant layer has a number average particle diameter of a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, substantially free of non-volatile aqueous additive. Is obtained by coating and drying an aqueous dispersion in which is dispersed at 1 μm or less.

  The unsaturated carboxylic acid or anhydride thereof is a compound having at least one carboxyl group or acid anhydride group in the molecule, and specifically includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itacone. In addition to acids, itaconic anhydride, fumaric acid, crotonic acid and the like, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. The unsaturated carboxylic acid may be neutralized with a basic compound including an organic amine compound such as ammonia or triethylamine.

  In the present invention, in addition to the unsaturated carboxylic acid or its anhydride, alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, etc. may be mentioned, and a mixture thereof. It is preferable that these are further copolymerized.

  Further, in addition to the alkene having 2 to 6 carbon atoms, (meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethyl maleate, maleic acid Maleic acid esters such as diethyl and dibutyl maleate, (meth) acrylic acid amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc. It is preferable to copolymerize other copolymer components such as vinyl esters, vinyl alcohol obtained by saponifying vinyl esters with a basic compound, and mixtures thereof. In addition, the form of copolymerization is not limited, For example, any of random copolymerization, block copolymerization, graft copolymerization, etc. may be sufficient. In the present invention, a copolymer obtained by copolymerizing a terpolymer comprising ethylene, methyl acrylate or ethyl acrylate, and maleic anhydride in the above blending range is preferable.

  The blending ratio of the unsaturated carboxylic acid or anhydride (I), alkene (II) having 2 to 6 carbon atoms, and other copolymerization component (III) is 0.01 ≦ (I) / {(I) It is preferred that + (II) + (III)} × 100 <5 and (II) / (III) = 55/45 to 99/1. This is because an aqueous dispersion can be prepared substantially without the non-volatile aqueous agent. The nonvolatile aqueous auxiliary agent remains in the polyolefin copolymer resin even after the film is formed, and may plasticize the film to deteriorate the properties of the polyolefin copolymer resin, such as water resistance. In this case, since the non-volatile water-immobilizing aid is not substantially contained, the film properties, particularly water resistance and oil resistance are excellent. “Aqueous aid” refers to a drug or compound added for the purpose of promoting aqueousization or stabilizing the aqueous dispersion in the production of an aqueous dispersion. It means that it does not have a boiling point at pressure, or has a high boiling point (for example, 300 ° C. or higher) at normal pressure. The phrase “substantially free of non-volatile aqueous solubilizer” means that the non-volatile aqueous solubilizing aid is not actively added to the system and consequently does not contain them. Such nonvolatile aqueous auxiliary agent is particularly preferably zero content, but is contained in an amount of less than 0.1% by mass with respect to the polyolefin copolymer resin component as long as the effects of the present invention are not impaired. There is no problem. In addition, the acrylic ester unit may be converted into an acrylic acid unit by hydrolyzing only a part of the ester bond when the resin is made aqueous. In such a case, the change is taken into account. It suffices that the ratio of each component is within a specified range.

  In the present invention, a small amount of other monomers such as dienes, (meth) acrylonitrile, vinyl halides, halogenated vinylidenes, carbon monoxide and sulfur disulfide may be copolymerized. The resulting polyolefin resin preferably has a melt flow rate of 0.01 to 500 g / 10 min at 190 ° C. and a load of 2160 g, which is a measure of molecular weight.

  The number average particle diameter (hereinafter referred to as mn) of the polyolefin resin particles is 1 μm or less from the viewpoint of improving the storage stability of the aqueous dispersion. The weight average particle diameter (hereinafter, mw) is preferably 1 μm or less. The degree of particle dispersion (mw / mn) is preferably 1 to 3 from the viewpoint of storage stability of the aqueous dispersion and low-temperature film-forming properties.

  Further, the content of the polyolefin copolymer resin in the aqueous dispersion can be appropriately selected depending on the film forming conditions, the desired thickness and performance of the resin film, and is not particularly limited, but the viscosity of the coating composition is moderate. 1 to 60% by mass, more preferably 3 to 55% by mass, still more preferably 5 to 50% by mass, and particularly preferably 10 to 45% by mass.

  In the aqueous dispersion used in the present invention, the carboxyl group in the polyolefin resin may be neutralized with a basic compound. As such a basic compound, ammonia or an organic amine compound that volatilizes during film formation is preferable from the viewpoint of water resistance of the film, and an organic amine compound having a boiling point of 30 to 250 ° C. is particularly preferable. Examples of such organic amine compounds include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. The addition amount of the basic compound is 0.5 to 3.0 times equivalent to the carboxyl group in the polyolefin resin.

  It is preferable to add an organic solvent at the time of aqueous formation in order to promote the aqueous formation of the polyolefin resin and reduce the dispersed particle size. The amount of the organic solvent used is preferably 40% by mass or less, more preferably 3 to 30% by mass in the aqueous medium.

  Specific examples of such organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert. -Alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, tetrahydrofuran Ethers such as dioxane, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, Esters such as methyl pionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol , Glycol derivatives such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, and 3 Examples include methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like. Among them, those having a boiling point of 30 to 250 ° C are preferable, those having 50 to 200 ° C Is particularly preferred. These organic solvents may be used in combination of two or more. In addition, when the boiling point of the organic solvent is less than 30 ° C., the ratio of volatilization when the resin is made aqueous increases, and the efficiency of aqueous formation may not be sufficiently increased. An organic solvent having a boiling point exceeding 250 ° C. is difficult to be scattered from the resin film by drying, and the water resistance of the film may be deteriorated. Among the above organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, and the like are highly effective in promoting the aqueous formation of the resin and are easy to remove the organic solvent from the aqueous medium. Dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether are preferable, and ethanol, n-propanol, and isopropanol are particularly preferable from the viewpoint of low temperature drying property.

  As described above, the aqueous dispersion used in the present invention is composed of at least a polyolefin copolymer resin and water, and further contains the organic solvent. The water content at that time is 40 to 99. % By mass, preferably 40 to 90% by mass, more preferably 50 to 90% by mass.

  The method for obtaining the aqueous dispersion comprising the polyolefin copolymer resin is not particularly limited. For example, the polyolefin copolymer resin having the above composition in the form of particles or powder having a particle diameter of 1 cm or less, preferably 0.8 cm or less, basic The compound, water, and, if necessary, the organic solvent are heated and stirred in a container that can be sealed. As the container, a solid / liquid stirring device or an emulsifier can be used, and it is preferable to use a device capable of pressurization of 0.1 MPa or more. Aqueous dispersion can be achieved even with low-speed stirring that allows the resin to float in an aqueous medium, so that an aqueous dispersion can be produced even with a simple apparatus. Stir and mix at a temperature of 40 ° C. or lower, and then maintain the temperature in the tank at 80 to 200 ° C. and continue stirring for 5 to 120 minutes to sufficiently make the polyolefin copolymer resin aqueous and obtain an aqueous dispersion. be able to.

In the present invention, the aqueous dispersion thus obtained has a coating amount of 0.1 to 100 g / m ² , more preferably 0.1 to 80 g / m when dried on the paper base layer or the underlayer. It is formed by coating, heating and drying so as to be ² .

(6) Other layers A desired printed layer can be formed on the oil-resistant decorative material of the present invention. The print layer may be formed on any layer, but is preferably on the base layer.

  As the printing layer, for example, a normal gravure ink composition, an offset ink composition, a relief printing ink composition, a screen ink composition, and other ink compositions are used on a paper base layer or an undercoat layer. For example, by using gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, by forming a desired printed pattern consisting of characters, figures, patterns, symbols, etc. Can be configured.

  In the oil-resistant cosmetic material of the present invention, a glued wallpaper to be applied to the wall by applying a paste to the back surface of the cosmetic material when the decorative material is applied, an adhesive wallpaper that peels off the release paper on the back surface to expose the adhesive surface, and adheres, It can be prepared to any pressure-sensitive wallpaper or the like that pressurizes to break down the microcapsules on the back surface and discharges the adhesive to adhere. Depending on the format of such a label, an adhesive layer, a release paper layer, and the like can be laminated.

(7) Method for Producing Oil-Resistant Cosmetic Material The method for producing the oil-resistant cosmetic material of the present invention is not limited. However, the paper base layer contains 0.01 to 5% by mass of unsaturated carboxylic acid or its anhydride. The polyolefin copolymer resin contained in is coated and dried with an aqueous dispersion in which the number average particle diameter is 1 μm or less without substantially containing a non-volatile aqueous additive, and the aqueous dispersion is coated and dried. , 1 to 5 times to form an oil-resistant layer, thereby producing a method for producing an oil-resistant cosmetic material.

In the present invention, as described above, the base layer may be laminated on the paper base material layer. When the aqueous dispersion is applied to the base layer on the paper base layer, the oil-resistant layer can be formed by a single application and drying. Since the binder contained in the underlayer prevents the aqueous dispersion from being impregnated into the paper base material layer, it is considered that an oil-resistant layer is formed by one coating and drying. The application amount of the aqueous dispersion is 0.01 to 100 g / m ² , more preferably 0.05 to 80 g / m ² , and particularly preferably 0.1 to 50 g / m ² when dried.

  Also, when forming an oil-resistant layer on the printed layer, when forming an oil-resistant layer on the overcoat layer, the oil-resistant layer can be laminated in the same manner as when forming the oil-resistant layer on the underlayer. it can.

  On the other hand, when the aqueous dispersion is applied to the paper base layer, the application and drying are performed twice or more, more preferably 2 to 5 times, particularly preferably 3 to 3, although depending on the paper base used. Repeat 5 times. Since the aqueous dispersion contains water in the range of 40 to 99% by mass, the aqueous dispersion is absorbed from the unevenness on the surface of the paper base material layer, and oil resistance is ensured by one application and drying. Is difficult. However, it has been found that oil resistance can be ensured by forming the aqueous dispersion film a plurality of times. Therefore, when the aqueous dispersion is applied directly to the paper base layer and when the aqueous dispersion is applied to the base layer, the amount of coating required to ensure oil resistance may differ. is there.

For example, when applying to a paper base material layer, the aqueous dispersion is applied in a dry amount, 0.01 to 50 g / m ² , more preferably 0.05 to 20 g / m ² , particularly preferably, After coating at 0.1 to 10 g / m ² , the coating is dried to form a coating, and then the aqueous dispersion is coated at a dry coating amount of 0.01 to 50 g / m ² , more preferably 0.05. It is applied at -20 g / m ² , particularly preferably 0.1-10 g / m ² and dried, and this is repeated. In the case of direct application to the paper base material layer, the coating amount at the time of drying of the aqueous dispersion is finally 0.01 to 100 g / m ² , more preferably 0.05 to 80 g / m ² , Particularly preferably, the oil resistance can be ensured by laminating so as to be 0.1 to 50 g / m ² . The coating and drying conditions are not particularly limited as long as a film is formed.

  The aqueous dispersion can be applied to the surface of various substrates by, for example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, or brush coating. After uniformly coating and setting near room temperature as necessary, it can be formed by adhering to a uniform resin film on the surface of various substrates by subjecting it to drying or drying and baking and a heat treatment agent. it can. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected depending on the characteristics of the substrate to be coated, the type of the curing agent described later, the blending amount, etc. Is preferably 30 to 250 ° C, more preferably 60 to 230 ° C, particularly preferably 80 to 210 ° C, and the heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, and more preferably 5 seconds to 10 minutes is particularly preferred. In addition, when a crosslinking agent is added, in order to sufficiently advance the reaction between the carboxyl group in the polyolefin and the crosslinking agent, it is desirable to appropriately select the heating temperature and time depending on the type of the crosslinking agent.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
Example 1
An aqueous dispersion of polyolefin copolymer resin containing 2% by mass of maleic anhydride (number of dispersed resins) in a clay coat layer of single-sided clay coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ) (Average particle size 0.6 μm, non-volatile water-immobilizing aid not used, water content 60 mass%) was applied and dried with Meyer bar # 3 so that the thickness when dried was 1.6 g / m ^2. An oil-resistant cosmetic material was obtained.

  Put about 2g of butter (manufactured by Snow Brand Milk Products Co., Ltd.) on the coating layer side of this oil-resistant cosmetic material and make it into a circle with a diameter of about 3cm, 5 hours at room temperature, 18 hours at room temperature, 20 minutes at 40 ° C. The degree of penetration of the later butter was observed.

(Comparative Example 1)
Using a single-sided clay-coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ) and placing the butter on the clay-coated layer side of this comparative oil-resistant cosmetic material, The state of soaking was evaluated. The results are shown in Table 1.

(Comparative Example 2)
The non-clay coat layer of single-sided clay-coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ) was dried with the aqueous dispersion used in Example 1 having a thickness of 1.6 g / m ^2. It was applied and dried to obtain a comparative oil resistant cosmetic material.

Butter was placed on the aqueous dispersion coating layer side of this comparative oil-resistant cosmetic material, and the butter penetration state was evaluated in the same manner as in Example 1. The results are shown in Table 1.
(Comparative Example 3)
The non-clay coat layer of single-sided clay-coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ) was dried with the aqueous dispersion used in Example 1 having a thickness of 1.6 g / m ^2. Then, this operation was performed twice to obtain a comparative oil resistant cosmetic material.

Butter was placed on the aqueous dispersion coating layer side of this comparative oil-resistant cosmetic material, and the butter penetration state was evaluated in the same manner as in Example 1. The results are shown in Table 1.
(Example 2)
On the non-coated layer of single-sided clay-coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ), the aqueous dispersion used in Example 1 had a thickness of 1.6 g / m ² when dried. Then, this operation was performed three times to obtain an oil-resistant cosmetic material.

Butter was placed on the aqueous dispersion coating layer side of this oil resistant cosmetic material, and the butter penetration state was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Moreover, 1 drop of methylene blue aqueous solution was dripped on the aqueous dispersion coating layer side of the oil-resistant cosmetic material, and the penetration degree of the water drop after 5 minutes at room temperature was observed. The results are shown in Table 2.

(Comparative Example 4)
Using a single-sided clay-coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ), put the butter on the non-clay coat layer side, and soak the butter in the same manner as in Example 1. Evaluated. The results are shown in Table 1.

Further, one drop of methylene blue aqueous solution was dropped on the non-clay coat layer side of the comparative oil-resistant decorative material, and the operation was performed in the same manner as in Example 2 to observe the degree of penetration of water drops. The results are shown in Table 2.
(Comparative Example 5)
Using a general-purpose oil-resistant paper using a fluororesin, butter was placed on the coating layer side, and the butter penetration state was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 6)
Using a general-purpose oil-resistant paper using a fluororesin, butter was placed on the non-coated layer side of the coated paper, and the penetration state of the butter was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Further, one drop of methylene blue aqueous solution was dropped on the non-coating layer side of the comparative oil-resistant decorative material, and the operation was performed in the same manner as in Example 2 to observe the degree of penetration of water drops. The results are shown in Table 2.
(Example 3)
Printing was performed by a gravure printing method using a normal gravure ink composition on a clay coat layer of single-sided clay coated paper (Hokuetsu Paper Co., Ltd., NEW Tough Ivory: basis weight 260 g / m ² ). Printing was performed on the clay coat layer from dark to light, in black, indigo, red, yellow, and white.

Subsequently, an aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride (number average particle diameter of the dispersed resin 0.6 μm, non-volatile aqueous solubilizing agent not used, moisture content 60 on the printed layer) Mass%) was applied and dried with a Mayer bar # 3 so that the thickness upon drying was 1.6 g / m ² to obtain an oil-resistant cosmetic material.

  Put about 2g of butter (manufactured by Snow Brand Milk Products Co., Ltd.) on the coating layer side of this oil-resistant cosmetic material and make it into a circle with a diameter of about 3cm, 5 hours at room temperature, 18 hours at room temperature, 20 minutes at 40 ° C. The degree of penetration of the later butter was observed.

In addition, one drop of methylene blue aqueous solution was dropped on the oil resistant layer of the oil resistant cosmetic material, and the same level of water droplets was observed as in Example 2. The results are shown in Table 2.
The printed layer was physically protected from the oil resistant layer.

（結果）
（１） 実施例１、比較例１、比較例６の結果から、クレーコート層に前記水性分散液を塗工する場合には、フッ素樹脂を使用することなく、かつ実質的に不揮発水性化助剤を配合することなく、１回の塗工でフッ素樹脂による耐油コート紙（比較例６）と同程度の耐油性に優れる耐油層を形成することができた。

(result)
(1) From the results of Example 1, Comparative Example 1, and Comparative Example 6, when the aqueous dispersion was applied to the clay coat layer, a non-volatile aqueous solution assistant was used without using a fluororesin. An oil-resistant layer having excellent oil resistance comparable to that of an oil-resistant coated paper made of a fluororesin (Comparative Example 6) could be formed by one coating without blending an agent.

  (2) From the results of Comparative Examples 2 to 4, Comparative Example 6, and Example 2, when the aqueous dispersion is applied to a paper substrate, a fluororesin is used by applying and drying three times. An oil-resistant layer comparable to that of an oil-resistant coated paper made of a fluororesin (Comparative Example 6) could be formed without adding a non-volatile water-based auxiliary.

(3) From the results in Table 2, it was found that the oil-resistant layer of the present invention was excellent in water resistance even when directly laminated on the paper base material layer.
(4) From the result of Example 3, the oil-resistant layer could be formed by applying the aqueous dispersion on the print layer. It was estimated that the printed layer was physically protected by the oil resistant layer.

  INDUSTRIAL APPLICATION This invention can manufacture the oil-resistant cosmetics which are excellent in oil resistance, without using a fluororesin and substantially mix | blending non-volatile water-izing auxiliary agent.

FIG. 1 is a cross-sectional view of an oil-resistant decorative material of the present invention in which an oil-resistant layer (20) is laminated on a paper base layer (10). FIG. 2 is a cross-sectional view of the oil-resistant decorative material of the present invention on which a paper base layer (10), a base layer (30), and an oil-resistant layer (20) are formed. FIG. 3 is a cross-sectional view of the oil-resistant decorative material of the present invention in which a paper base layer (10), a base layer (30), a printed layer (40), and an oil-resistant layer (20) are sequentially laminated. FIG. 4 shows the oil-resistant makeup of the present invention in which a paper base layer (10), a base layer (30), a printed layer (40), a tail-AB-coat layer (50), and an oil-resistant layer (20) are laminated in this order. It is sectional drawing of material.

Explanation of symbols

10 ... paper substrate layer,
20 ... oil resistant layer,
30 ... Underlayer,
40 ... printing layer,
50 ... Underlayer

Claims (5)

It is an oil-resistant decorative material formed by laminating at least a paper base layer and an oil-resistant layer,
In the oil-resistant layer, the polyolefin copolymer resin containing unsaturated carboxylic acid or anhydride thereof in the range of 0.01 to 5% by mass is substantially free of non-volatile aqueous additive and has a number average particle diameter of 1 μm. An oil-resistant cosmetic material obtained by applying and drying the aqueous dispersion liquid dispersed below.   The oil-resistant cosmetic material according to claim 1, wherein the paper base material layer has a base layer on one side, and the oil-resistant layer is laminated on the base layer.   The oil-resistant cosmetic material according to claim 2, wherein the oil-resistant decorative material further includes a printing layer, the printing layer is formed on the underlayer, and the oil-resistant layer is laminated on the printing layer. Sex cosmetics.   The oil-resistant decorative material further has an overcoat layer, and a printed layer and an overcoat layer are formed in this order on the foundation layer, and the oil-resistant layer is laminated on the overcoat layer. The oil-resistant cosmetic material according to claim 3, wherein The oil-resistant cosmetic material according to any one of claims 1 to 3, wherein the coating amount of the aqueous dispersion in the oil-resistant layer is 0.1 to 100 g / m ² when dried.

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