WO2008069149A1 - Fragrant sheet, fragrant article, and process for producing the same - Google Patents

Abstract

A fragrant product which retains a high-quality fragrance even during storage, has a surface gloss, is capable of high-precision image printing, and is portable and easy to use; and a process for producing the product. The product is a fragrant sheet which comprises a layer containing a fragrant ingredient and a support, the fragrant-ingredient-containing layer comprising a porous structure obtained by curing a polymerizable substance and a fragrant ingredient infiltrated therein. Also provided is a fragrant article which comprises the fragrant sheet and a bag holding the sheet therein and capable of preventing the fragrant ingredient from diffusing. The process for producing the fragrant sheet comprises: a step (A) in which a layer having a porous structure is formed on a support; and a step (B) in which a fragrant ingredient is infiltrated into the porous layer formed in the step (A) to form a fragrant-ingredient-containing layer.

Description

 Specification

 Fragrance sheet, fragrance article and method for producing the same

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a fragrance sheet, a fragrance article, and a method for producing the fragrance, and maintains a high-quality fragrance even during storage, has a glossy surface and enables high-definition printing, and is portable and easy to use. The present invention relates to a product and a manufacturing method thereof.

 Background art

 An aromatic bath is a method for obtaining various effects by smelling the scent of essential oil. Essential oils and their components are known to have sedative, sleep-inducing, arousal, analgesic, antibacterial, and deodorant effects depending on the type, and they are used according to the intended effect. Yes. In recent years, there has been a demand for a portable, simple and inexpensive aromatic bath product that can be used to easily perform an aromatic bath on the go and obtain the desired effect.

 The aromatic bath is sometimes performed with a single essential oil, but a plurality of essential oils are often mixed and used. Essential oils can be classified into top note, mid-no note, and base note depending on their volatilization rate. By selecting and blending each essential oil, it is possible to make it a well-balanced aromatic oil.

 In addition, products that have an essential oil storage section, an essential oil suction section, and a volatilization section have been developed for efficient volatilization, but they lacked portability in terms of structure, and further development was desired.

[0003] However, conventional fragrance products are made by volatilizing essential oils from hot water fiber, etc., kneaded into solids and volatilized, or directly percutaneously absorbed and / or volatilized into sheet packs. As a result, it was mainly the one that exhibited the effect, and the sheet-like and non-adhesive one was not common.

 [0004] In many cases, the sheet-like fragrance product has an infiltrating power of essential oils and the main surface is a fibrous material. For this reason, there are disadvantages such as a restriction on a high-definition printed image with low surface smoothness and a lack of fashionability with low gloss.

[0005] As a technique for solving such problems, a sheet-like fragrance is formed by an inkjet method. It is possible to develop a product. Patent Document 1 (Japanese Patent Application Laid-Open No. 2002-321445) proposes an ink jet recording material characterized by containing a fragrance in at least one of the layers constituting the ink jet recording material. According to the proposal, it is considered that a sheet-like fragrance product printed with high definition can be provided. However, as a result of a further trial by the present inventors, there is a problem that the fragrance changes when stored for a certain period of time. The problem of short sustainability became clear.

 [0006] In addition, a method for producing an inkjet recording material with a porous film formed of a polymerizable compound is described in Patent Document 2 (WO2006 / 101390Al). No mention is made.

 Patent Document 1: Japanese Patent Laid-Open No. 2002-321445

 Patent Document 2: International Publication No. 06/101390 Pamphlet

 Disclosure of the invention

 Problems to be solved by the invention

[0007] An object of the present invention is to provide a portable and easy-to-use fragrance product that maintains a high-quality fragrance even during storage, is glossy on the surface, and is capable of high-definition printing, and an inexpensive method for producing the fragrance product. It is.

 Means for solving the problem

As a result of intensive studies, the present inventors have found that a fragrance does not change even during storage by forming a porous structure with a polymerizable compound and incorporating a fragrance component therein. Furthermore, when the surface pore ratio of the fragrance component-containing layer was 0.3% or more and 20% or less, it was found that the fragrance half-life during use was long, and the present invention was completed.

That is, the present invention has the following configuration.

 <1> A fragrance sheet comprising a fragrance component-containing layer and a support, wherein the fragrance component-containing layer is impregnated with a fragrance component into a porous structure obtained by curing a polymerizable substance.

 <2> The aromatic component-containing layer is

 Applying a coating solution containing a polymerizable compound and a solvent to the support,

Polymerizing the polymerizable compound by radiation, thereby causing phase separation of the polymerized compound and the solvent; The fragrant sheet according to 1) above, which has a porous structure formed by removing the solvent by a drying step and / or a washing step.

 <3> The aromatic sheet according to the above item 2>, wherein the content of the polymerizable compound contained in the coating solution is 20 to 80% by weight.

 <4> V in the above <2> to <3>, wherein water is contained in an amount of 30% by weight or more based on the total amount of the solvent in the solvent contained in the coating solution. A fragrance sheet as described in 1.

 <5> V of <2> to <4> above, wherein the solvent contained in the coating solution contains a volatile co-solvent having a boiling point lower than that of water. Fragrance sheet

Yes

 <6> The fragrance sheet according to <1> to <5> above, wherein the film thickness of the fragrance component-containing layer is 5-300 m.

 <7> The aromatic sheet according to <1> to <6> above, wherein the wet porosity of the porous structure is 35 to 85%.

 <8> The fragrance sheet according to <2> to <7> above, wherein the average pore diameter of the porous structure is 0.001 to 2.0 m.

 <9> The aromatic sheet according to <1> to <8> above, wherein the weight average molecular weight of the polymerizable compound is 10,000 daltons or less.

 <10> The above <1> to <9, wherein the polymerizable compound is an unsaturated ethylene compound, and the unsaturated ethylene compound has one or a plurality of acrylate or metatalylate groups. > /! Fragrance sheet according to any of the above.

 <11> The fragrance sheet according to any one of <1> to <10>, wherein the porous structure comprises at least two chemically different layers.

 <12> The fragrance according to <2> to <11> above, wherein the radiation is electromagnetic radiation characterized in that the maximum emission wavelength is between 200 and 450 nm. Sheet.

<13> The aromatic sheet according to any one of <1> to <12> above, wherein the aromatic component contains at least one of limonene, linalool, linalyl acetate, and tervineol as a main component. <14> The aromatic sheet according to any one of <1> to <13> above, further comprising a laminate layer.

 <15> The aromatic sheet according to any one of <1> to <14> above, wherein the surface area ratio of the porous structure layer is 0.3% to 20%.

 <16> The above <1> to <15, wherein the photopolymerization initiator contained in the coating solution is α-hydroxyalkylphenone, acyl phosphine oxide, or a combination thereof. A fragrance sheet according to any one of the above.

 <17> A fragrance article comprising the fragrance sheet according to any one of <1> to <16>, which is contained in a bag capable of shielding diffusion of fragrance components.

 18> Step (i) of forming a layer having a porous structure on the support, and forming a fragrance component-containing layer by impregnating the layer having the porous structure formed in step (ii) with the fragrance component. The method for producing a fragrance sheet according to <1> to <16> above! /, Which includes a step (i).

 The invention's effect

 [0010] According to the present invention, there is provided a portable and easy-to-use fragrance product that maintains a high-quality fragrance even during storage, is glossy on the surface, and is capable of high-definition printing, and an inexpensive manufacturing method thereof. The power S to do.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The fragrance sheet of the present invention includes an fragrance component-containing layer and a support, and the fragrance component-containing layer is impregnated with a fragrance component in a porous structure obtained by curing a polymerizable substance.

 [0012] <Aromatic component-containing layer>

 In the present invention, the fragrance component-containing layer refers to a layer in which the fragrance component is retained. The holding state is not particularly limited, but it is preferably held in a state where droplets or a plurality of liquids are continuous. In the fragrance article of the present invention, the fragrance component-containing layer has a porous structure obtained by hardening a polymerizable substance. The aromatic component-containing layer is formed by impregnating the porous layer with an aromatic component.

In the fragrance sheet of the present invention, the porous layer may be a single layer or a plurality of layers. That is, it may consist of a plurality of layers that are chemically or physically different from each other. Form multiple layers Therefore, the printing component fixing function and glossiness are given to the uppermost layer, and the design ability is further improved with S.

 Here, chemical means a composition constituting a porous structure. Physical means porous pore diameter, membrane pressure, strength, and the like.

 The film thickness of the fragrance component-containing layer is 5 300 111 particles or more, 10 to; more preferably 150 m force S · Polymerizable compound

The polymerizable compound used in the present invention is a monomer or oligomer having a polymerizable group. It is preferable to have one or more polymerizable groups, more preferably two or more. Examples of the polymerizable group include a (meth) acrylate group, a butyl ether group, a butyl ester group, an alicyclic ether group (for example, an epoxy group, an oxetane group, etc.), etc. Polymerization used in the present invention For example, the compounds described in “Development of UV EB Curing Materials” (supervised by Yoneho Tabata, edited by Radtech Research Institute, CMC Publishing, 2003) can be used. Specific examples include, but are not limited to, epoxy compounds, oxetane derivatives, rataton derivatives, oxazoline derivatives, cyclic siloxanes, unsaturated ethylene compounds such as acrylates, metatalylates, poly-polythiols, butyl ethers, buramides, vinylolamines. , Aryl ethers, linole esters, linoleamines, maleic acid derivatives, itaconic acid derivatives, polybutadiene and styrene. Preferably, (meth) acrylate is used as the main compound, for example, alkyl- (meth) acrylate, polyester- (meth) acrylate, urethane- (meth) acrylate, polyether- (meth) acrylate, epoxy -(Meth) acrylate, polybutadiene-(Meth) acrylate, silicone one (meth) acrylate, melamine one (meth) acrylate, phosphazene one (meth) acrylate, (meth) acrylamide, and mixtures thereof It is done. These compounds can be added in the form of a monomer solution, monomer suspension, monomer dispersion, oligomer solution, oligomer suspension, oligomer dispersion, polymer solution, polymer suspension, or polymer dispersion. Preference is given to mono-, di- or polyfunctional unsaturated ethylene compounds having an attalylate group or a metatalylate group, which are used in one or more combinations. [0014] 'Solvent

 The coating liquid is preferably an aqueous base liquid. The solvent contained in the coating solution is most preferably water from the viewpoints of safety, environment, health and economy. From this viewpoint, the polymerizable compound of the present invention is preferably dissolved in water by 10 wt% or more.

 Many polymerizable compounds are generally lipophilic and often require a non-aqueous solvent to obtain a solution. If the miscibility in water is not sufficient to dissolve the polymerizable compound, one or more cosolvents are required. Due to the ability to dilute with water, the amount of co-solvent used can be kept low. The solvent preferably contains at least 30 wt% or more of water, more preferably 50 wt%.

 [0015] The co-solvent is preferably a polar volatile solvent because it can be removed in the drying step. Preferred co-solvents are lower alkyl alcohols, ketones, aldehydes, esters, alkoxy decane. The lower alkyl alcohol has a carbon atom number power of the alkyl chain of preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less. Specific examples include a mixed solvent of isopropanol and water. Other preferred cosolvents include methanol, ethanol, 1 propanol, acetone, ethyl acetate, dioxane, methoxyethanol, tetrahydrofuran, ethylene glycol, and dimethylformamide. The most preferred co-solvent is a solvent having a boiling point lower than that of water.

 [0016] Specific examples of the coating solution include a mixture of 10wt% CN132 and 27.5wt% CN435 and 62.5wt% water, 21.5wt% CN132 and 21.5wt% CN435 and 57wt% water. Mixture of 60wt% CN132 and 40wt% water, 49.75wt% CN132 and 49 · 75wt% water and 0.5wt% dodecyltrimethylammonium chloride to form porous preferable. CN132 and CN435 are polymerizable compounds that can be purchased from Cray Valley, France. CN132 is a low viscosity aliphatic epoxy acrylate. CN4 35 is ethoxylate trimethylolpropane tritalate.

 [0017] · Porous structure

A porous structure is formed by applying a coating solution containing a polymerizable compound on a support and curing it with radiation. Carefully adjust the concentration and composition of the polymerizable compound The selection causes phase separation between the crosslinked polymerizable compound and the solvent, and the solvent evaporates through a drying process to form a porous structure. Optionally, it can be cross-linked from a mixture of polymerizable compounds! /,! /, And the components can be washed and removed.

 The coating solution contains a polymerizable compound and a solvent, and in addition, a photopolymerization initiator, a surfactant, a non-polymerizable water-soluble polymer, and the like can be added.

[0018] The average pore diameter of the porous material is preferably 0 · 001–2.0 m, more preferably 0 · 003–1.0 m, and particularly preferably 0.01 to 0.7 m. The shape of the hole is not particularly limited, and may be rectangular, circular, or a combination thereof. It is preferable that the pores communicate with each other inside as soon as the aromatic component is absorbed.

 The wet porosity is preferably 5 to 90%. The wet porosity is determined by the following formula (wet film thickness / solid film thickness conversion X 100%)-100%

 The wet film thickness is determined by adding the swelling amount to the dry film thickness. The dry film thickness is determined by the SEM cross-sectional image. The amount of swelling is determined by recording the height of the layer swollen with water at 20 ° C using a probe. If the layer does not swell, the wet porosity is the same as the dry porosity. The wet porosity is preferably 35 to 85%, particularly preferably 50 to 85%.

In order to obtain the porous material of the present invention, it is necessary to carefully select a polymerizable compound and process conditions.

 In the present invention, the porous structure is formed by applying a coating liquid containing a polymerizable compound and a solvent to the support, polymerizing the polymerizable compound by radiation, and polymerizing the polymerizable compound and the solvent. It is preferable to form the phase by separating the solvent and removing the solvent by a drying step and / or a washing step.

In this case, a polymerizable compound (monomer, oligomer, prepolymer) is bridged by radiation to form a polymer. This step causes the growing polymer to be less soluble in the solvent, resulting in phase separation and separation of the polymer from the solvent. The polymer forms a network with micropores, and a solvent exists in the micropores. By removing the solvent in the drying process, a porous structure is formed. For removing the solvent, a washing step may be added before the drying step. Then remove the uncured composition by washing Also good. In order to obtain the best porous structure, the concentration of the polymerizable compound or the mixture of the polymerizable compounds in the coating solution is important. If the concentration is too low (20 wt% or less), the network structure will not be formed, and if the concentration is too high (80 wt% or more), there will be a different force S, a gelled layer will be formed, and pores will be formed after the drying process It cannot be made and does not have a porous structure. The concentration of the polymerizable compound in the coating solution is preferably 20 to 80 wt%, more preferably 30 to 60 wt%.

 [0020] The drying temperature is preferably set to a temperature at which the porous structure and the substrate do not deform or deteriorate. Although not particularly limited, 200 ° C or lower is preferable, 100 ° C or lower is more preferable, and 50 ° C or lower is particularly preferable. It is also preferable to reduce the humidity in order to increase the drying speed.

[0021] The solubility of the polymerizable compound greatly affects the performance of the porous surface. When it is desired to impart high gloss to the porous surface, the polymerizable compound is preferably a clear solution. When the mat surface is desired, a turbid liquid may be used as appropriate.

 [0022] In order to cause a rapid phase separation with a large solubility difference between the first compound and the polymer obtained by polymerization, it is preferable that the molecular weight of the first compound is not too large. By selecting the above, a porous polymer having a high molecular weight can be obtained. The molecular weight of the polymerizable monomer or oligomer is preferably 10,000 daltons or less, more preferably 5000 daltons or less, and particularly preferably 1000 daltons or less.

 As a specific example, in the case of epoxydiatalylate (CN132, Cray Valley), 23-53 wt% is preferred in water / isopropanol (weight ratio 6:;! ~ 4: 1) 28-48 wt 33 to 43 wt% is particularly preferred. The central value of epoxydiatalylate, 38 wt%, is different for different polymerizable compounds and mixtures of polymerizable compounds. When a part of epoxy diatalylate is replaced with a polymerizable compound that dissolves more in water, the power to increase the water / isopropanol ratio and the concentration of the polymerizable compound can be increased.

Yes

[0023] The concentration can also be changed by changing the monomer system or solvent system or adding an additive. For example, if you want to set the center value at 50 wt%, use CN132 and CN435 at 1: 1, or use CN132 alone to make the solvent 9: 1 water / isopropanol, This is possible by adding a surfactant such as tilamonium chloride or sodium dodecylbenzenesulfonate. If you want to set the center value at 60 wt%, CN132 can be used with water alone.

 In addition, if polyurethane acrylate is cured at the same concentration as epoxydiatalate, a porous membrane can be obtained. Although it is not possible to predict the center value for all polymerizable compound and solvent combinations, it is possible to determine the concentration to obtain porosity for each polymerizable compound, which also indicates that This suggests the importance of selecting the concentration of the compound. As an aid to the selection of the polymerizable compound and the solvent, it is possible to cite the open mouth patent No. 216622 (cloud point method) and the US registered patent No. 3823027 (noh, nsen method).

[0024] Photopolymerization initiator

 It is preferable that a photopolymerization initiator is mixed in the coating solution. Preferably, it is mixed immediately before application. A photoinitiator is required when the applied mixture is cured by UV or visible light.

 A preferable ratio of the photopolymerization initiator to the polymerizable compound is 0.1 wt% to 10 wt%, more preferably 0.5 wt% to 5 wt% by weight.

 Preferred photopolymerization initiators are radical type, cation type, and anion type photopolymerization initiators.

 [0025] Examples of intramolecular cleavage type photopolymerization initiators include α-hydroxyalkyl ketones such as 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl] 2 methylol-1-propanone (Irgaqure 2959, Ciba 1) Hydroxy 1 cyclohexyl 1 phenyl ketone (Ir gaqurel 84, Ciba), 2 Hydroxy 1 2-Methyl 1-Phenyl 1-propanone (SarcureSR1173, Saromer), Oligo [2 Hydroxy 1 2 Methyl 1— {4— (1-methyl butyl) phenyl} propanone] (SarcureSR1130, manufactured by Sartomer), 2-hydroxy-2-methyl-1- (4-ter butyl-) phenylpropane 1-on, etc. The compounds described in Item 11, lines 8 to 29 of International Patent Publication No. 2006-101390 are listed.

[0026] Examples of hydrogen abstraction type photopolymerization initiators include benzophenone derivatives such as benzo Examples include Huenon (AdditolBP, manufactured by UCB), 4-hydroxybenzophenone, 3-hydroxybenzophenone, etc. In addition, International Patent No. 2006—101390, line 12, line 1 to line 1, line 3, line 3 And the compounds described.

 [0027] In the case where the polymerizable compound is atallate, ditalylate, tritalylate, or polyfunctional atalylate, an intramolecular cleavage type photopolymerization initiator is preferred. In particular, a-hydroxyalkylphenone, for example, 2-hydroxy 1-Methyl 1-phenylpropane 1-one, 2-hydroxy 2-methyl 1- (4-ter-butyl-) phenylpropane 1-one, 2-hydroxy 1- [4 -— (2 Hydroxy Ethoxy) phenyl] 2 methylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, oligo [2-hydroxy-2-methyl-11 {4 (1 methylbuyl) phenyl} propanone] are preferred examples. Or acylphosphine oxides, for example 2, 4, 6 trimethylbenzoyl phenylphosphine oxide, ethyl 2, 4, 6 trimethylbenzoyl roof Alkenyl phosphine oxide, bis (2, 4, 6 trimethylbenzoyl I le) phenylalanine phosphine oxide.

[0028] In the case of multilayer coating, it is preferable to determine the amount of photopolymerization initiator for each layer. For example, in a multilayer structure, in order to cure efficiently with a low photopolymerization initiator concentration, it is preferable that the uppermost photopolymerization initiator is different from the lower photopolymerization initiator. In general, some initiators are known to work efficiently in the top layer and some initiators in the lower layer. The lower layer photopolymerization initiator preferably has an absorption spectrum that does not completely overlap with the absorption spectrum of the upper layer photopolymerization initiator. The maximum absorption wavelength of the uppermost photopolymerization initiator and the lowermost photopolymerization initiator preferably has a difference of at least 20 nm. When a UV light source is used as the light source, several different wavelength light sources can be selected. With the optimal combination of UV light source and photopolymerization initiator, the light source reaches the lower layer so that the lower layer photopolymerization initiator works. Specific examples of light sources include the H bulb provided by Fusion UV System, which provides light sources with maximum emission wavelengths of 220 nm, 255 nm, 300 nm, 310 nm, 365 nm, 405 nm, 435 nm, 550 nm, and 580 nm. . 200 nm to 450 nm is the most important for the curing reaction. It is clear that the spectrum of the UV light source and the spectrum of the photoinitiator need to overlap sufficiently. If they overlap sufficiently, thicker films can be cured with the same light source intensity. Also different types of photopolymerization By using an initiator, it is possible to control V, gloss and porosity, which cannot be controlled with a single photoinitiator.

 [0029] The porous structure layer of the present invention preferably has a surface porosity of 0.3% to 20%.

 5% to 19% is more preferred 1.0% to 18.5% is particularly preferred. The surface open area ratio is determined by the ratio of the surface area (projected area) of the opening of the hole to the total surface area (projected area). The total projected area and the surface area of the hole opening are measured by surface SEM images. The surface porosity can be changed depending on the time from application of a coating solution containing a polymerizable compound to curing by radiation and the intensity of radiation irradiation during curing. The preferred value varies depending on the type of polymerizable compound and the type of radiation. As a specific example, when CN132 or CN435 is used as the polymerizable compound, the time from application to curing is preferably 1 to 60 seconds. 1 second ~ 45 seconds are more preferred 1 to 30 seconds is particularly preferred.

 [0030], surfactant

 A surfactant can be added to the coating solution as a wetting agent of an aqueous composition, as a surface tension adjusting agent, or for other purposes such as imparting gloss. As the surfactant, a noion surfactant, an ionic surfactant, an amphoteric surfactant, or a combination thereof can be used.

 [0031] Preferred nonionic surfactants include ethoxylate alkylphenones, ethoxylate aliphatic alcohols, ethylene oxide / propylene oxide block copolymers, fluoroalkyl ethers, and the like.

 [0032] Preferable ionic surfactants include, but are not limited to, alkyltrimethylammonium salts, alkylbenzildimethylammonium salts, and alkylpyridinium salts, where they are included in the alkyl chain. The number of carbon atoms is preferably from 8 to 22, more preferably from 12 to 18; The surfactant may be silicon-based or fluorine-based.

[0033] Preferable fluorosurfactants include fluoro C2-C20 alkyl carboxylic acid and its salt, N-perfluorooctane sulfonate disodium glutamate, etc., in addition, item 16 of International Patent Publication 2006-101390. List the compounds listed in the 11th to 40th lines. [0034] Preferable silicon surfactants include polysiloxanes such as polysiloxane polyoxyalkylene copolymers. Other such copolymers include dimethylsiloxane methyl (polyoxyethylene) copolymer, dimethylsiloxane-methyl (polyoxyethylene polyoxypropylene) siloxane copolymer, trisiloxane and polyether copolymer. And trisiloxane alkoxylate, and siloxane propoxylate, which is a copolymer of siloxane and polypropylene oxide. The siloxane copolymer may be a random copolymer, an alternating copolymer, a graft copolymer, or a block copolymer. The polyether siloxane copolymer is preferably 100 to 10,000 weight S in weight average molecular weight. Examples of the polyether siloxane copolymer include the compounds described in International Patent No. 2006-101390, item 17 lOfi to 20th mesh.

Yes

 [0035] The preferred addition amount of the surfactant is preferably 0.01 to 2% of the dry weight of the layer.

~ 0.5% is more preferred.

[0036] Water-soluble polymer

 The fragrance component-containing layer of the present invention may contain a non-polymerizable water-soluble polymer or a hydrophilic polymer. The non-polymerizable water-soluble polymer is added to the mixture of polymerizable compounds before or after curing. You can impregnate the dried porous membrane or apply it as a water-soluble polymer solution before drying! /.

 The addition amount of the water-soluble polymer is preferably 40% or less of the dry weight of the porous layer, and more preferably 0.5 to 10%.

 Specific examples of the water-soluble polymer include polybulal alcohol, polybutylpyrrolidone, polyethylene oxide, polypropylene oxide, polyethylene glycol, polybutyl ether, gelatin and the like, and in addition, paragraph 18 of International Patent Publication 2006-101390. No. 13 to No. 19 8 No., No. 19 No. 10 to No. 20 No. 11 Neighboring polymers are listed and are listed with a force S.

When adding a non-polymerizable water-soluble polymer, it is preferable to add a crosslinking agent. The amount of added calories is preferably not more than 20 wt% of the amount of the polymer contained in the layer, more preferably 0.5 to 5 wt%. As an example of the cross-linking agent, International Patent No. 2006—101390, paragraph 20, line 23-2 Examples include the compounds described in Item 1, Line 16.

 [0037] <Support>

 The support that can be used in the present invention is not particularly limited, and either a transparent support made of a transparent material such as plastic or an opaque support made of an opaque material such as paper can be used. In the present invention, a resin-coated support in which a thermoplastic resin layer is provided on both surfaces of a substrate such as paper is preferable.

 [0038] The support used in the present invention is preferably a water-resistant support. It may be transparent or opaque. The thickness of the water-resistant support is preferably about 50 to 200 111. In particular, for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, celluloid and other resin films, and polyolefin resin-coated paper. In addition, a support in which paper is coated (laminated) with a polyolefin resin such as polyethylene or polypropylene, and a glass plate can also be used.

 [0039] The highly glossy opaque support preferably has a glossiness of 40% or more on the surface on which the fragrance component-containing layer is provided. The glossiness is a value determined according to the method described in JIS P-8142 (75-degree specular gloss test method for paper and board). Specific examples include the following supports.

[0040] For example, high gloss paper support such as baryta paper used for art paper, coated paper, cast coated paper, silver salt photographic support, etc .; polyesterols such as polyethylene terephthalate (PET), nitro Cellulose esters such as cenololose, cenololose acetate, cenololose acetate, tyrate, polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and other plastic films are made opaque by adding white pigments (surface) (It may be calendered.) A highly glossy film; or a white pigment on the surface of a highly glossy film containing various paper supports, the transparent support or the white pigment. Examples thereof include a support provided with a polyolefin coating layer which may or may not be contained. A white pigment-containing foamed polyester film (for example, foamed PET in which polyolefin fine particles are contained and voids are formed by stretching) is also suitably exemplified. [0041] Examples of the resin-coated support include thermoplastic resins on both sides of a highly glossy paper substrate such as art paper, coated paper, cast-coated paper, baryta paper used for silver salt photographic support, and the like. Preferable examples include those provided with a layer and resin-coated paper used for photographic paper for silver salt photography.

 The fragrance sheet of the present invention preferably has at least one laminate layer between the fragrance component-containing layer and the support, or on the side opposite to the direction component-containing layer of the support. In the case of the opposite side, the outermost surface or the outermost surface may not be used.

 The laminate layer is mainly a polymer film that imparts base material penetration resistance and crease resistance. The material is not particularly limited as long as it is a hydrophobic polymer. For example, polyethylene, Examples thereof include thermoplastic polymer films such as polyurethane. The thickness of the laminate layer is not particularly limited, but is preferably δ ^ ιη˜;! OO ^ m, and more preferably 10 ^ m˜60 μm.

 [0042] The thickness of the opaque support is not particularly limited.

 300 m is preferred.

 [0043] The surface of the support may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment or the like in order to improve wettability and adhesion. Good.

 [0044] Hereinafter, the polyolefin resin-coated paper will be described in detail.

 As the base paper constituting the polyolefin resin-coated paper, a generally used paper with no particular limitation can be used, but a smooth base paper such as that used for a photographic support is more preferable. As the pulp composing the base paper, natural pulp, recycled pulp, synthetic pulp, etc. are used alone or in combination.

 This base paper is mixed with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, dye, etc., which are generally used in papermaking.

[0045] The thickness of the base paper is not particularly limited, but a paper having good surface smoothness such as a paper that is compressed by applying pressure in a calendar or the like during paper making or after paper making is preferred. The amount is preferably 30 ~ 250g / m ² ! / ヽ.

[0046] As the resin of the resin-coated paper, a polyolefin resin or a resin curable with an electron beam is used. That power S. Polyolefin resins include copolymers of two or more of olefins such as low density polyethylene, high density polyethylene, polypropylene, polybutene, and polypentene, or ethylene propylene copolymers, and mixtures thereof. Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

[0047] Further, in the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc, and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, stearin Fatty acid metal salts such as aluminum oxide and magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine, cecilian blue, and phthalocyanine blue, cobalt violet, fast violet, manganese It is preferable to add various additives such as magenta pigments and dyes such as purple, fluorescent brighteners and ultraviolet absorbers in appropriate combinations.

 [0048] The resin-coated paper as a support preferably used in the present invention is produced by a so-called extrusion coating method in which, in the case of a polyolefin resin on a traveling base paper, a heat-melted resin is cast. The both surfaces are covered with resin. In the case of a resin that is cured by an electron beam, the resin is applied with a commonly used coater such as a gravure coater or a blade coater, and then irradiated with an electron beam to cure and coat the resin. Moreover, it is preferable to subject the base paper to an activation treatment such as corona discharge treatment or flame treatment before coating the resin on the base paper. The surface (surface) to which the fragrance component-containing layer of the support is applied has a glossy surface, a matte surface, etc., depending on the application, and the glossy surface is particularly advantageous. Although it is not necessary to coat the back surface with resin, it is preferable to coat resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and an active treatment such as corona discharge treatment or flame treatment can be applied to the front surface or both of the front and back surfaces as required. The thickness of the resin coating layer is not particularly limited, but it is generally coated on the front or back and back to a thickness of 5 to 50 mm 111.

Yes

[0049] For the support in the present invention, various types of backcoat layers can be coated for antistatic properties, transport properties, anticurling properties, and the like. The backcoat layer has an inorganic antistatic agent. An antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant, and the like can be contained in an appropriate combination.

[0050] As a material that can be used for the transparent support, a material that is transparent and can withstand radiant heat when used in an OHP or a backlight display is preferable. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Of these, polyesters are preferred, and polyethylene terephthalate is particularly preferred. The thickness of the transparent support is not particularly limited, but is preferably 50 to 200 mm in terms of easy handling.

 [0051] Next, the resin-coated paper will be described in detail. As the base paper, wood pulp is used as the main raw material, and if necessary, paper is made using synthetic pulp such as polypropylene or synthetic fibers such as nylon and polyester in addition to wood pulp. As the wood pulp, LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used. Power S, SBK-rich LBKP, NBSP, LBSP, NDP, LDP It is preferable to use it. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less. The pulp is preferably a chemical pulp with low impurities (sulfate pulp sulfite pulp), and a pulp having a whiteness improved by bleaching is also useful.

 [0052] In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc, and titanium oxide, paper strength enhancers such as starch, polyacrylamide, and polybum alcohol, fluorescent whitening Agents, moisture retention agents such as polyethylene glycols, dispersants, softening agents such as quaternary ammonium can be added as appropriate.

[0053] The freeness of the pulp used for papermaking is preferably 200 to 500 ml according to the CSF regulations, and the fiber length after beating is a 24 mesh residual mass% defined by JIS P-8207 and 42%. A sum of 30% to 70% of the mass% of the mesh residue is preferred. The mass% of the 4 mesh residue is preferably 20% by mass or less. The basis weight of the base paper is preferably 30 to 250 g, particularly 50 to 200 g force << preferably. The thickness of the base paper is preferably 40 to 250 mm 111. The base paper can be given a high smoothness by calendering at the paper making stage or after paper making. Dense base paper The degree is generally 0.7 to 1; 2 g / m ² (JIS P-8118) is common. Further, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JI SP-8143.

 [0054] As a surface sizing agent that may be coated with a surface sizing agent, the same sizing agent that can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS P-8113.

 [0055] The surface side of the base paper can be generally coated with polyethylene. Polyethylene is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDP E), but some other LLDPE, polypropylene, etc. can also be used.

 [0056] In particular, the polyethylene layer on the side on which the fragrance component-containing layer is formed is composed of rutile or anatase type titanium oxide, fluorescent whitening agent, ultramarine in polyethylene as widely used in photographic paper. Those having improved opacity, whiteness and hue are preferred. Here, the content of titanium oxide is generally preferably 3 to 20% by mass, more preferably 4 to 13% by mass with respect to polyethylene. The thickness of the polyethylene layer is not particularly limited, but is preferably 10 to 50 111 for both the front and back layers. Further, an undercoat layer can be provided on the polyethylene layer in order to provide adhesion with the aromatic component-containing layer. The undercoat layer is preferably an aqueous polyester, gelatin, or PVA. The thickness of the undercoat layer is preferably 0.0;! To 5 〜m.

 [0057] Polyethylene-coated paper can be used as glossy paper, or V can be obtained with ordinary photographic printing paper by carrying out a loose molding process when polyethylene is melt-extruded onto the base paper and coated. Those having a matte or silky surface can also be used.

[0058] A back coat layer can be provided on the support, and examples of components that can be added to the back coat layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the knock coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and silicic acid. White inorganic materials such as aluminum, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, ritbon, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide Pigments, styrenic plastic pigments, Examples thereof include organic pigments such as acrylic plastic pigment, polyethylene, microcapsule, urea resin, and melamine resin.

 [0059] Examples of the aqueous binder used in the knock coat layer include a styrene / maleic acid salt copolymer, a styrene / acrylate copolymer, a polybutyl alcohol, a silanol-modified polybulal alcohol, starch, and a cationized starch. Water-soluble polymers such as casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, and polybutylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistant agent.

 [0060] <Aroma component>

 Preferred examples of the fragrance component used in the present invention include essential oils, synthetic fragrances, animal fragrances, active ingredients and simple compounds thereof, and essential oils or effective ingredients contained in essential oils are preferred.

 [0061] The essential oils used in the present invention include, for example, ylang ylang essential oil, geranium essential oil, lavender essential oil, jasmine essential oil, chamomile essential oil, raventin essential oil, hyssop essential oil, rose essential oil, neroli essential oil, cedarwood essential oil, eucalyptus essential oil , Cypress essential oil, cypress essential oil, sandalwood essential oil, juniper essential oil, tea tree essential oil, pine essential oil, pachiyuri essential oil, orange essential oil, grapefruit essential oil, lime essential oil, lemongrass essential oil, lemon essential oil, citronella essential oil, bergamot essential oil, peppermint essential oil, rosemary Examples include natural essential oils such as essential oil, claric essential oil, clove essential oil, thyme essential oil, fennel essential oil, marjoram essential oil, melissa essential oil, rosewood essential oil, basil essential oil, bate essential oil, cinnamon essential oil. Of these, ylang ylang essential oil, geranium essential oil, cedarwood essential oil, eucalyptus essential oil, cypress essential oil, orange essential oil, grapefruit essential oil, lime essential oil, peppermint essential oil, and rosemary essential oil are preferred. A combination of these essential oils may be used.

[0062] The active ingredient contained in the essential oil includes, for example, linalool, linalyl acetate, 1-limonene, 1-menthol, α-pinene, β-pinene, citranole, cineole, d-camphor, zimonore, eugnole, caye Hyanoredehydr, Camazulene, Tsunanore-4, Bonore Neo 1 , A-terpineol, β-tervineol, terpineol-4, geraniol, nero lnole, α-santa ronore / 3-santa ronore, carotonore, cedronorole, biridifloro 1 ole, sclareol, safrole, apiol, myristicin, methylcavicol, annel , Sclareol oxide, manoyl oxide, citronellal and the like. You can also use a combination of these active ingredients.

 [0063] In the present invention, it is preferable that the aromatic component contains at least one of limonene, linalool, linalyl acetate, and terbineol as a main component. Here, the main component is specifically 15% by mass or more based on the total fragrance component.

[0064] V, which is not limited as the coating amount of the fragrance component, is preferably 0.1 to 50 g / m ² , more preferably 0.5 to 25 g / m with respect to the area (horizontal projection area) of the fragrance sheet. ² , more preferably 2 to 10 g / m ² is preferably applied.

 [0065] <Creation of aromatic sheet>

 The fragrance sheet of the present invention contains a fragrance component-containing layer and a support, and the fragrance component-containing layer impregnates a porous structure with the fragrance component. That is, the method for producing a fragrance sheet of the present invention comprises a step (A) of forming a layer having a porous structure on a support, and a layer formed in step (A) by impregnating the fragrance component with the fragrance component. Including the step (B) of forming the component-containing layer

Yes

 When the fragrance sheet is printed, either the fragrance component or the printing component may be applied or dried at the same time, but preferably, the fragrance component is applied after the printing component is applied. I prefer to do it.

 When the aromatic component impregnated layer has a porous structure, the permeation of the aromatic component is accelerated and the aromatic component can be efficiently applied. Note that this impregnation step of the fragrance component is more effective when impregnating the fragrance component after printing because the soaking of the scent component is slower than the non-printing portion. Both of them have the same effect on improving production efficiency even after printing.

In the fragrance sheet of the present invention, the fragrance component infiltrates and penetrates into the capillary pores formed by the porous structure of the fragrance component impregnated layer. The aromatic component is volatilized from the gas-liquid interface. Therefore, the retention of fragrance components in this case involves solidification and packaging. I need an excessive system such as a bunch!

 The fragrance sheet of the present invention preferably takes a form used by fragrance immediately after opening, and is impregnated with a highly volatile fragrance component.

 After the fragrance component is impregnated in the fragrance sheet, it is preferably volatilized until saturated in a force bag packed in a bag capable of shielding the diffusion of the fragrance component described later. Furthermore, the aromatic component is gradually evaporated without applying an external pressure even after opening. The volatilization weight curve depends on the aroma component composition, temperature and humidity environment, etc., but volatilizes at least 10% by mass at the time of opening and 40% by mass after opening for 30 minutes with respect to the coating amount at the time of manufacture. It is preferable. Therefore, it is important that the coated surface is dried immediately after the fragrance component is applied.

 In the present invention, since the fragrance component is applied in a liquid or dispersed liquid form, it is preferable to have a drying step after the fragrance component is applied. Furthermore, since the fragrance component has sufficient volatility at normal temperature and pressure, in order to constantly impregnate the prescribed coating amount and proceed to the next step, the coated surface is dried and I like it! /

 The dryness of the coated surface can be judged by the fact that it is not wet by human sensory evaluation and that polyethylene or the like is not in close contact. However, if it is overdried, the problem arises that the required amount of fragrance component cannot be applied. Therefore, the surface of the impregnated component impregnated surface is dry, and the best condition is to contain the aromatic component in the internal porous layer.

[0066] The method of incorporating the fragrance component into the fragrance component-containing layer is not particularly limited. For example, the fragrance component is held in the form of droplets instead of microcapsules or the like in the porous material of the fragrance component-containing layer. It is preferable. When used, it volatilizes from the surface due to the volatility of the fragrance component and emits a fragrance.

[0067] In the present invention, the method of impregnating the aromatic component is not particularly limited, and for example, a known coating method can be used. For example, gravure coating, wire bar coating, blade coating, spray coating, curtain coating, spin coating, stripe coating from a nozzle, etc. can be mentioned, and bar coating and blade coating are preferable. The fragrance component can be immersed in the stock solution, or it can be diluted and impregnated in organic soluble U. Preferred examples of the organic homogeneous U include ethanol.

<Embodiment> It is desirable that the fragrance sheet impregnated with the fragrance component should be a fragrance article with a bag (packaging material) that can shield the diffusion of the fragrance component attached or contained (packed)! The packaging material is preferably a film-like material capable of shielding a fragrance (fragrance shielding film), and is not particularly limited as long as it can shield the fragrance, but is suitably used such as a polyester film, a polyethylene film, a polypropylene film, and an aluminum film. . A multilayer film combining these is also preferably used. The bag for shielding the fragrance is not particularly limited as long as it can shield the fragrance, but it is suitably used for bag strength obtained by processing a polyester film, a polyethylene film, a polypropylene film, an aluminum film or the like into a bag shape. A bag obtained by processing a multilayer film combining these into a bag shape is also preferably used.

 The packaging material desirably has a gas barrier property, and more desirably has a metal layer having a thickness of 2 to 15 m, more preferably 4 to 10 m. Example

 [0069] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. In the examples, “part” and “%” are based on mass.

Yes

 [0070] (Production of support)

 Wood pulp consisting of 100 parts of LBKP is beaten to 300 ml of Canadian freeness with a double disc refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anion polyacetamide, polyamide polyamine epoxy hydrin 0. 1 part and 0.5 part of cationic polyacrylamide were added in an absolutely dry mass ratio to the pulp, and weighed with a long paper machine to produce 205 g / m 2 of base paper.

[0071] In order to adjust the surface size of the above base paper, 0.04% of a fluorescent whitening agent (“Whitex BB” manufactured by Sumitomo Chemical Co., Ltd.) was added to a 4% aqueous solution of polybutyl alcohol, and this was completely dried. The base paper was impregnated with a mass conversion of 0.5 g / m ² , dried, and then subjected to a calendering process to obtain a base paper adjusted to a density of 1.05 g / ml.

[0072] After the corona discharge treatment was performed on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 19 m using a melt extruder to form a mat surface. A resin layer was formed (hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back side is further subjected to corona discharge treatment. After that, as an antistatic agent, aluminum oxide (“Alumina Sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd.) are used. (Snowtex 0)) was dispersed in water at a mass ratio of 1: 2 so that the dry mass was 0.2 g / m ² .

 [0073] Further, after the corona discharge treatment was performed on the felt surface (surface) side where the resin layer was not provided, anatase-type titanium dioxide 10%, a trace amount of ultramarine blue, and a fluorescent brightening agent 0.01% (With polyethylene) and MFR (melt flow rate) 3 · 8 low density polyethylene is extruded to a thickness of 40 πι using a melt extruder to form a high gloss thermoplastic layer. (This high gloss surface is hereinafter referred to as a “front surface”) and used as a support.

Yes

 [0074] <Preparation of coating solution for forming porous layer>

 A coating solution was prepared as follows.

 (Coating solution A) 38 g of epoxy ditalylate (CN132, manufactured by Cray Valley) was dissolved in a mixture of 14 g of isopropanol and 50.5 g of water.

 (Coating solution B) 38 g of epoxydiatalylate (CN132, manufactured by Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureTM2959, manufactured by CIBA Specialty Chemicals) mixed with 14 g of isopropanol and 49.9 g of water Dissolved in.

 (Coating Solution C) 2 g of glycidyl metatalylate was added to 200 g of a 10% solution of bovine-derived alkali gelatin (MW 10k Daiton) (pH adjusted to 9). The mixture was stirred at 40 ° C. for 2 hours to introduce C—C double bonds.

 (Coating solution D) A mixture of 38 g of epoxydiatalylate (CN132, Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureTM2959, CIBA Specialty Chemicals) of 14 g of isopropanol and 32.4 g of water Dissolved in. To the solution, 5 g of the solution C and 10 g of a 3% solution of a fluorosurfactant (Zonyl ™ FSN100, manufactured by Dupont) were added.

(Coating solution E) 22.5 g of epoxy diatalylate (CN132, manufactured by Cray Valley), 15 g of ethoxylate tritalate (CN435, manufactured by Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureT M2959, CIBA Specialty Chemicals) 11.25g isopropanol and 36.25g water Dissolved in the mixture. To the mixture, 5 g of the solution C and 10 g of a 3% solution of a fluorosurfactant (Zonyl ™ FSN100, manufactured by Dupont) were added.

[0075] (Coating solution F) 18 g of epoxydiatalylate (CN132, manufactured by Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureTM2959, manufactured by CIBA Specialty Chemicals) 17.8 g of isopropanol and 63.6 g In a mixture of water.

 (Coating solution G) A mixture of 81 g of epoxydiatalylate (CN132, manufactured by Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureTM2959, manufactured by CIBA Specialty Chemicals) of 4 g of isopropanol and 14.4 g of water. Dissolved in.

 (Coating solution H) 22.5 g of ethoxylate (9) trimethylolpropane (SR502, manufactured by Sartomer), 15 g of ethoxylate tritalylate (CN435, manufactured by Cray Valley) and 0.6 g of photopolymerization initiator (IrgacureTM2959, CIBA Specialty Chemicals) was dissolved in a mixture of 17.5 g isopropanol and 44.5 g water.

 (Coating solution I) Photopolymerization of 22.5 g of ethoxylate (10) bisphenol diatalylate (SR602, Sartomer) and 15 g of ethoxylate tritalylate (CN435, Cray Valley) was started. The agent (IrgacureTM2959, manufactured by CIBA Specialty Chemicals) was dissolved in a mixture of 25.0 g isopropanol and 37.0 g water.

 (Coating ί) 37.5g of pentaerythritol triatalylate (SR444, manufactured by Sartomer) and 1.0g of photopolymerization initiator (IrgacureTM2959, manufactured by CIBA Specialty Chemicals) mixed with 31.0g of isopropanol and 31.0g of water Dissolved in the liquid.

[0076] (Coating liquid K) 37.5 g of tri (propylene glycol) glycerol diatalylate (manufactured by Sigma Aldrich) and l.Og photopolymerization initiator (IrgacureTM2959, CIBA Specialty Chemicals) 25.0 g of isopropanol And 37.0 g of water in a mixture.

 (Coating solution L) 22.5 g of tri (propylene glycolanol) glycerol diatalylate (Sigma A1 drich), 15 g of ethoxylate tritalylate (CN435, Cray Valley) and 0.6 g of photopolymerization initiator ( IrgacureTM2959, manufactured by CIBA Specialty Chemicals) was dissolved in a mixture of 20.0 g of isopronool V and 42.0 g of water.

(Coating solution M) 22.5 g of tetra (ethylene glycol) diatalylate (Sigma Aldrich) and 15 g of ethoxylate tritalylate (CN435, Cray Valley) and 0.6 g of photopolymerization The initiator (Irgacure ™ 2959, manufactured by CIBA Specialty Chemicals) was dissolved in a mixture of 20.0 g isopropanol and 42.0 g water.

 (Coating solution N) Based on the description in paragraph [0070] of JP-A-2002-321445, except that β-naphthylethyl ether was changed to lavender essential oil.

 (Coating solution Ο) Lavender essential oil was removed from the coating solution Ν and adjusted.

[0077] (Coating solution Ρ) 217. 3 g of epoxydiatalate (CN132, manufactured by Cray Valley), 144.9 g of ethoxylate tritalate (CN435, manufactured by Cray Valley) and 9.7 g of 2 parts Cryroylamido-2-methylmonopropanesulfonic acid (AAMPSA, Sigma Aldrich) and 5.8 g of photoinitiator (IrgacureTM2959, CIBA Specialty Chemicals) 108.7 g of isoprononol and 467.9 g of water And 45.7 g of IN—NaOH were dissolved in a mixed solution.

 (Coating solution Q) 217 · 3 g of epoxy diatalylate (CN132, manufactured by Cray Valley), 144.9 g of ethoxylate tritalylate (CN435, manufactured by Cray Valley) and 9.7 g of 2-atallyloylamino Do-2-methyl-propanesulfonic acid (AAMPSA, Sigma Aldrich) and 5.8 g of photoinitiator (IrgacureTM2959, CIBA Specialty Chemicals), 108.7 g of isoprononol, 470.8 g of water and 45 g Dissolved in 7 g IN—NaOH mixture.

 (Coating solution R) 1.3 g of glycidyl metatalylate (GMA, manufactured by Sigma Aldrich) and 11.7 g of gelatin (ImagerTMHB, manufactured by Stoess) were dissolved in 87 g of water. 11 • lg of polyamide beads (manufactured by Orgasol2001TM Arkema, average particle size 10 m) were dispersed in the solution with a dissolver.

 (Coating solution S) 217 · 3 g of epoxy diatalylate (CN132, manufactured by Cray Valley), 144.9 g of ethoxylate tritalate (CN435, manufactured by Cray Valley) and 9.7 g of 2-acryloylamine Do-2-methylmonopropane sulfonic acid (AAMPSA, Sigma Aldrich) and 2.9 g of photoinitiator (IrgacureTM2959, CIBA Specialty Chemicals), 108.7 g of isoprononol, 470.8 g of water, 36. Dissolved in 9 g IN-NaOH mixture. The coating solution R24.6 g was added to the solution.

<Formation of porous layer> After the corona discharge treatment was applied to the above support pair, a porous layer was obtained by applying, curing and drying as follows using a slide bead coater.

(Porous sheet 1) Coating solution A was applied at 50 cc / m ² . Thereafter, an electron beam of 180 keV 90 kGy was irradiated using P-200 (manufactured by ESI) in an inert gas (N 2). Then, it was dried at 40 ° C for 2 minutes.

(Porous sheet 2) The coating liquid B was applied at 50 cc / m ² . Thereafter, UV light of 0 · 18 Jm ² was irradiated using H-bulb of Light Hammer 6 (Fusion UV Systems). Then, it was dried at 40 ° C for 2 minutes.

 (Porous sheet 3) In the same manner as in application example 2, coating liquid D was applied instead of coating liquid B.

(Porous sheet 4) In the same manner as in application example 2, coating liquid E was applied instead of coating liquid B.

(Porous sheet 5) In the same manner as in application example 2, coating solution F was applied instead of coating solution B

(Porous sheet 6) In the same manner as in application example 2, coating liquid G was applied instead of coating liquid B.

(Porous sheet 7) Coating solution B was applied at 25 cc / m ² by a multilayer coating method, and coating solution E was applied at 25 cc / m ^{2 on the} upper layer. Thereafter, UV light of 0.4 Jm ² was irradiated using H_b ulb of Light Hammer 6 (Fusion UV Systems). Then, it was dried at 40 ° C for 2 minutes.

 (Porous sheet 8) In the same manner as in application example 2, coating liquid H was applied instead of coating liquid B.

(Porous sheet 9) In the same manner as in application example 2, coating liquid I was applied instead of coating liquid B. (Porous sheet 10) In the same manner as in application example 2, coating ί was applied instead of coating liquid B

(Porous sheet 11) In the same manner as in Application Example 2, a coating solution was applied instead of the coating solution.

(Porous sheet 12) In the same manner as in Application Example 2, the coating liquid L was applied instead of the coating liquid. (Porous sheet 13) In the same manner as in Application Example 2, coating solution M was applied instead of coating solution B.

 (Porous sheet 14) A coating solution according to the description in paragraph [0069] of JP-A-2002-321445

N was applied.

 (Porous sheet 15) In the same manner as in Application Example 14, coating liquid O was applied instead of coating liquid N.

(Porous sheet 16) Coating solution P was applied at the lowermost layer, coating solution Q was applied as the intermediate layer, and coating solution S was applied at the uppermost layer at 40, 15, and 5 cc / m ² , respectively. Then, it performed using Light HammerTM10 (made by Fusion UV Systems). The relative intensity of the lamp was 70%. The time from application to curing was 14 seconds. After curing, it was dried at 40 ° C for 3 minutes.

 (Porous sheet 17) By the same method as porous sheet 16, the time from application to curing was reduced to 8.5.

 (Porous sheet 18) By the same method as for porous sheet 16, the time from coating to curing was reduced by 11.5.

 (Porous sheet 19) In the same manner as the porous sheet 16, the relative lamp intensity was 100%, and the time from application to curing was 11.5 seconds.

 (Porous sheet 20) In the same manner as for porous sheet 16, the relative lamp intensity was 60%, and the time from coating to curing was 1.2 seconds.

[Test example]

 The table shows the film thickness, wet porosity, average pore diameter, average molecular weight of the polymerized compound, and surface porosity of the prepared porous sheet. The film thickness was measured from the SEM cross-sectional image. The wet porosity was measured by the following method. The average pore diameter and the surface area ratio were measured from SEM surface images. Wet porosity = (wet film thickness / solid content coating amount conversion X 100%) — 100% The wet film thickness was determined by adding the swelling amount to the dry film thickness. The dry film thickness is determined by the SEM cross-sectional image. The amount of swelling was determined by recording the height of the layer swollen with water at 20 ° C with a probe.

[0083] [Table 1] table 1

 [0084] <Production of aromatic products>

 After the porous sheets obtained from the above were cut into a size of 5.5 cm × 9.1 cm, the fragrance component was applied with a blade coater to give a fragrance sheet. Lavender essential oil was used as an aromatic component. In addition, after cutting, an image of a lavender field was printed using an inkjet printer (PM A950, manufactured by Seiko Epson Corporation), and then a mixed essential oil based on Lavender mono essential oil was applied with a blade coater to obtain a directional sheet. The porous sheet 14 was cut into 5.5 × 9.1 cm and used as an aromatic sheet.

 After the fragrance component was applied to the obtained fragrance sheet, the surface was visually checked for dryness, and the fragrance sheet was packed in a packaging material (STRONG PACK, manufactured by Meiwa Packs) to obtain an fragrance product.

 [0085] (Test example)

 Aroma products obtained from the above, 25 ° C 60% RH '7 days, 25. C60% RH. 20th, 25th. C6 0% RH-80 days, 40 ° C27% RH '7 days, 60 ° C12% RH' 7 days After storage, the packaging material was opened and the odor was confirmed. For fragrance products 16-29, the lavender was also visually evaluated for blurring in one field.

 The test results are shown below. V and evaluation were based on the following judgment.

 ◯: The same as the applied aromatic component

Δ: In addition to the same odor as the applied fragrance component, it has a sour odor with discomfort. X: Sickness with discomfort!

 1: Indicates that an aromatic sheet cannot be produced.

[Table 2]

From the results of the test examples, it has been clarified that the fragrance sheet having the fragrance component-containing layer of the present invention does not change the fragrance even when stored for a long time, and can enjoy the same odor as the applied fragrance component. In Comparative Examples 5, 6, 20, and 21, the fragrance component did not permeate when the fragrance component was applied, so that the fragrance sheet could not be produced. This is presumably because the aroma component was not absorbed because the porous structure was not formed. Comparative Examples 13, 14, and 29 are uncomfortable with storage time I couldn't enjoy sour!

 As for the blur of the lavender field painting, no blur was observed except in Comparative Examples 20 and 21.

[0088] (Test Example 2)

 Aromatic products obtained from the above;! ~ 4, 7 ~; 15, 30-34 were opened one day after packing, and volatilization of aroma components was evaluated by weighing. Weighing was performed 5, 10, 15, 30, 60, 120, 240, and 360 minutes after opening. The half-life of highly volatile components was calculated using data of 5, 10, and 15 minutes, and the half-life of low-volatile components was calculated using data of 120, 240, and 360 minutes. The half-life is calculated by the following procedure. The logarithmic value of the gravimetric data is taken on the vertical axis, and time is plotted on the horizontal axis to obtain a straight line. The disappearance rate constant k of the fragrance component is determined from the slope of this straight line. The half-life tl / 2 is determined by the following equation.

 tl / 2 = 0.693 / k

[0089] [Table 3]

 Table 3

 [0090] From the results of the test examples, the aromatic sheet containing the aromatic component-containing layer having a surface porosity of 0.3% to 20% according to the present invention has a large half-life for both high-volatile components and low-volatile components. It became clear that the fragrance can be enjoyed for a long time.

[0091] This application is a Japanese patent application filed on Nov. 30, 2006. Japanese Patent Application No. 2006-323756, and This is based on Japanese Patent Application No. 2007-094375 filed on March 30, 2007, the contents of which are incorporated herein by reference.

Industrial applicability

 The present invention provides a fragrance sheet that does not change fragrance even when stored for a long period of time.

Claims

The scope of the claims

 [I] A fragrance sheet comprising a fragrance component-containing layer and a support, wherein the fragrance component-containing layer is impregnated with a fragrance component into a porous structure obtained by curing a polymerizable substance.

 [2] The aromatic component-containing layer is

 Applying a coating solution containing a polymerizable compound and a solvent to the support,

 Polymerizing the polymerizable compound by radiation, thereby causing phase separation of the polymerized compound and the solvent;

 2. The fragrance sheet according to claim 1, which has a porous structure formed by removing the solvent by a drying step and / or a washing step.

[3] The fragrance sheet according to [2], wherein the content of the polymerizable compound contained in the coating solution is 20 to 80% by weight.

[4] In the solvent contained in the coating solution, water is contained in an amount of 30% by weight or more based on the total amount of the solvent! /. Fragrance sheet.

[5] The fragrance sheet according to any one of [2] to [4], wherein the solvent contained in the coating solution contains a volatile cosolvent having a boiling point lower than that of water.

[6] The film thickness of the aromatic component-containing layer is 5 to 300 111,

V, Fragrance sheet according to any of the above.

 [7] The wet porosity of the porous structure is 35 to 85%,

V, Fragrance sheet according to any of the above.

 [8] The average pore diameter of the porous structure is 0.001 to 2.0 m.

The fragrance sheet in any one of -7.

[9] The weight average molecular weight of the polymerizable compound is 10,000 daltons or less.

The fragrance sheet according to any one of claims 1 to 8.

[10] The claim characterized in that the polymerizable compound is an unsaturated ethylene compound, and the unsaturated ethylene compound has one or more acrylate or metatalylate groups; The fragrance sheet according to crab.

[II] The aromatic sheet according to any one of claims 1 to 10, wherein the porous structure is composed of at least two chemically different layers.

[12] The fragrance sheet according to any one of [2] to [11], wherein the radiation is an electromagnetic radiation characterized by having a maximum emission wavelength of 200 to 450 nm.

 [13] The fragrance sheet according to any one of V to V of claim 12, wherein the fragrance component contains at least one of limonene, linalool, linalyl acetate, and tervineol as a main component.

 14. The fragrance sheet according to any one of claims 1 to 13, further comprising a laminate layer.

 15. The fragrance sheet according to V of claim 1-14, wherein the porous structure layer has a surface porosity of 0.3% to 20%.

 [16] The photopolymerization initiator contained in the coating solution is α-hydroxyalkylphenone, or acylylphosphine oxide, or a combination thereof. The fragrance sheet in any one.

 [17] An fragrance article according to any one of [1] to [16], wherein the fragrance sheet according to any one of claims 1 to 16 is contained in a bag capable of shielding diffusion of fragrance components.

 [18] Step (i) of forming a layer having a porous structure on the support, and impregnating the layer having the porous structure formed in step (ii) with an aromatic component to form an aromatic component-containing layer The method for producing a fragrance sheet according to any one of claims 1 to 16, comprising a step (i).

 [19] Step (i) for forming a layer having a porous structure on the support, step (i) for printing on the layer having a porous structure formed in step (ii), and step (ii) The fragrance sheet according to any one of claims 1 to 17, further comprising a step (C) of forming a fragrance component-containing layer by impregnating a layer having a porous structure formed in the step (ii) with a fragrance component after Manufacturing method.