JPH0813945B2 - Scented ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a scented ink, and a product printed or coated with the scented ink continues to emit a unique scent over a long period of time and has a new function. Value is added as a commercial product. Therefore, the present invention is applied to daily necessities, industrial products, advertising media, arts, etc., and its industrial application field is extremely wide.

[Prior Art] and [Problems to be Solved by the Invention] As a coating material containing a perfume, an adhesive material containing a cyclodextrin packaging compound as a fragrance (Japanese Patent Publication, Sho 58
-185372), emulsion adhesive containing inorganic porous material with adsorbed fragrance (Japanese Patent Publication No. S58-162677),
Known inks include those in which a fragrance is adsorbed on amorphous silica (Nippon Publication, Sho 59-145298), and inks containing a fragrance encapsulated with a gelatin film (Nippon Publication, Sho 61-243871). On the other hand, regarding a material in which a fragrance is adsorbed on a zirconium compound, there is only a technical result that has been developed through a series of researches by the present inventors, and an adsorbent of the fragrance on a hydrolyzate of a zirconate ester (Japanese Patent Publication No. −2312
2) and a mixture of a granular material in which a porous zirconium phosphate silicate compound is impregnated with a fragrance and a powder in which a fragrance is attached to an organic material (Nippon Patent Publication, Sho 62-4222). As a result of intensive studies conducted by the present inventors on a high-quality scented ink having a more effective performance than the above technical results and a curing method thereof, the present invention with extremely strictly limited conditions was completed. Has arrived.

[Means for Solving Problems] and [Function] That is, the present inventors have found that the present invention is a porous neutral zirconium having fine pores having a specific surface area of 200 to 600 m ² / g and a pH of 5 to 9. The inventors invented a scented ink obtained by covering the surface of a powder obtained by mixing 20 to 100 parts of a liquid fragrance with 100 parts of a compound powder, and kneading the powder with a radiation-curable resin composition of 100 to 500 parts.

The porous neutral zirconium compound powder is a zirconium compound powder having specific pores having a specific surface area of 200 to 600 m ² / g and a pH of 5 to 9, preferably 6 to 8,
The particle size is 0.05 to 20 microns, particularly preferably 0.3 to 5
It is a fine powder that is micron. Examples of the zirconium compound are zirconium oxide, zirconium hydroxyoxide, zirconia gel, organic acid zirconyl (poorly soluble), zirconium phosphate, zirconium silicate, zirconium borate, zirconium aluminate, zirconium phosphate silicate, zirconium antimonate, bismuth. Zirconium acid and the like, and industrially zirconium phosphate, zirconium silicate, zirconium phosphate silicate and partial hydrates thereof are advantageous. For example, zirconium phosphate silicate generally has a composition of Zr (PO ₄ ) _2y・ (SiO ₂ ) _z・ nH ₂ O (provided that y = 0.02) as disclosed in the literature (Japanese Patent Publication No. 59-26912). 〜2.00, z ＝ 0.05〜16.00, n ＝
0 to 10), which itself is provided in a form having a high adsorption activity. Moreover, even though it is highly acidic and most of it is insoluble in water when it is put into water, the pH of the aqueous solution is 1 to 5, which is a fragrance ingredient. It reacts and impairs aroma. And if it is desired to keep it neutral when it comes into contact with water, it is necessary to neutralize the acidic points of the zirconium silicate phosphate with a basic substance, and such a substance is used in the present invention. is there. For example, in the present invention, when ZrO ₂ is used as a reference, (ZrO ₂ ) ₁ (P ₂ O ₅ )
A composition _having a composition of _{0.8 to 1.0} (SiO ₂ ) _{1.0 to 2.0} (A ₂ O) _{0.1 to 0.4} (wherein A represents an alkali metal or ammonium ion) is particularly preferable. In this way, zirconium phosphate silicate adjusted to pH 5-9, preferably pH 6-8, and particularly preferably around 7 by appropriately neutralizing in consideration of the composition has a porosity, that is, a specific surface area of 400-450 m ² / g. Some powders have significant adsorption capabilities for liquid perfumes. It was also found that zirconium silicate, which is not neutral and has a high basicity, causes a partial decomposition and a condensation reaction of the fragrance component to remarkably change the fragrance tone. Therefore, in order to achieve the object of the present invention, it was necessary to pay particular attention to this point. The use ratios of the neutral zirconium compound powder, the liquid fragrance, and the radiation curable resin composition have been clarified through many experiments by the present inventors, and are based on 100 parts of the porous neutral zirconium compound powder. It was clarified that 20 to 100 parts of liquid fragrance and 100 to 500 parts of radiation curable resin composition were the ratios in the most excellent use range. If it deviates from this range, the balance of the performance of the scented ink will be lost, radiation curing will become difficult, the expected fragrance will not be emitted, and liquid fragrance will bleed on the printing surface or coating surface (bleed). As a result, air quality or photochemical reaction causes alteration of the perfume and formation of stains.

As a result of searching for conditions that completely eliminate the above drawbacks, the present inventors stipulate the maintenance of the use ratio of each of the above raw materials in the present invention, and further guarantee the further effect of the present invention. As a means of enhancing the quality of the product, we have found a new method of covering the surface of powder containing a liquid fragrance with neutral zirconium compound powder with a hydrophobic film. A typical mix ratio of liquid fragrance is top note 15-35%, middle note 10-30
%, Base note 45-65%, but these can be adsorbed or sorbed on the neutral zirconium compound powder separately or simultaneously to form a powder. It may be found by microscopic examination that the surface of the powder that has adsorbed or sorbed this liquid fragrance, that is, has been impregnated with the liquid fragrance, is more or less wet with the liquid fragrance. When swimming into the resin composition, the scented ink was not completely cured by the irradiation of radiation, and on the other hand, it caused a change in scent tone. Such a phenomenon occurs not only when the ink is prepared but also during printing or application, and also during irradiation of radiation. In order to prevent such an aversive situation, it is necessary to cover the surface of the powder containing the liquid fragrance with a hydrophobic film. That is,
Organic film-forming substances that have no affinity for water, namely waxes, high boiling hydrocarbons, animal and vegetable oils, high boiling fluorinated oils, silicone oils, silane coupling agents, titanium coupling agents, zircon coupling agents, Polyolefin (oligomer), polyether (oligomer), polyester (oligomer), polyketone (oligomer), poly (meth) acrylate (oligomer), rosin, polystyrene, coumarone indene resin, petroleum resin, ketone resin, fluorine resin, silicone resin , Epoxy resin, phenolic resin, melamine resin, urea resin, polyamide, polyhalogenoolefin (oligomer), rubber, chlorinated rubber, cellulose or carbohydrate or their derivatives, polypeptide derivative, shellac (wax), polycarbonate, po Vinyl resin, it is important that'll covers the surface of the powder using a single or a mixture or mixtures thereof and perfume of such polyaromatic Chicks. This coating method includes a microencapsulation method in a liquid in a non-aqueous solvent, a fluid encapsulation method in which a liquid, a paste or a solution of a coating material is sprayed by flowing a powder, a spray dry method, or a coating material. There is an instant method in which a film is naturally or selectively formed on the surface of the powder by dissolving or dispersing it in a radiation curable resin composition and then adding the powder to this and stirring. . In particular, the instant method is convenient because the formation of the powder film and the kneading of the cured resin composition are carried out simultaneously. In the instant method, it is convenient to form a hydrophobic film by using a radiation curable resin composition having a relatively low molecular weight. However, when a delicate scent is required or when an expensive fragrance is used, the operation of covering the powder surface with a hydrophobic film in a separate process by the encapsulation method or the spray dry method is carefully performed. The method of doing is preferred.

In any case, the scented powder is stabilized at room temperature and under an air atmosphere by the above coating operation, but the amount of the coating substance used with respect to 100 parts of the neutral zirconium compound powder is (if the fragrance is contained, (Excluding this) 0.
1 to 10 parts, particularly preferably 0.5 to 5 parts are used.

In the case of the coating method in another step, the treated powder is put into the radiation curable resin composition in a dry atmosphere and kneaded. In this kneading, in addition to uniform dispersion of each component, mixing and adjustment of its concentration and viscosity, if necessary, mixing of leveling agent, addition of a small amount of fragrance, addition of filler powder, addition of sensitizer, antioxidation It is often carried out also as addition of an agent or a pigment, but if at least one of them is pre-blended in the cured resin composition, the operation of mixing or adding them is omitted. Of course, you can.

The radiation referred to in the present invention is mainly ultraviolet rays or electron beams, and in the case of ultraviolet rays, some visible rays or infrared rays may be mixed. As a general rule, the radiation-curable resin composition should not contain a low boiling point solvent, but it is acceptable to contain a small amount of solvent in order to facilitate the printing and coating operations. An ultraviolet curable resin is a binder resin component in ink that is cured by ultraviolet light, and as a component thereof, a (meth) acrylic acid ester oligomer,
Urethane-ized (meth) acrylic acid ester oligomers, polyfunctional (meth) acrylic acid oligomers, unsaturated polyesters, epoxy resins, epoxy-modified (meth) acrylic acid ester oligomers, etc. are used, and the solvent thereof is a reactive diluent. Is often used. In order to improve printability or paintability, an organic solvent may be added in some cases, but it is convenient for curing if the amount used is as small as possible.

If the fragrance is directly added to the ink as it is, without any treatment, as it has been done conventionally, polymerization due to radiation will be less likely to occur and the fragrance will be altered, so some addition of the fragrance component itself is required. Even if it is done, it should be added as little as possible. In particular, when a low boiling point fragrance is added, it should be added to the ink as fine particles of a fragrant powder or a fragrant paste containing cyclodextrin in principle and kneaded. The resin component of the ultraviolet curable ink is one which is rapidly cured by a photoreaction initiator, and its important ones are benzoin ether, α-acyloxime ester, acetophenone derivative, benzophenone derivative, benzyl ketal and ketone-amine system. Compounds, diazonium salts, etc. Curing by ultraviolet irradiation acts as a hydrogen abstracting agent like benzophenone or quinone to initiate polymerization, while Michler's ketone reacts in an excited intramolecular transfer state. Moreover, xanthone and fluorenone act as a hydrogen abstracting agent from an amine or a sulfur compound when an electron donor is present. Further, various commercially available sensitizers such as dyes absorb ultraviolet rays to be in an excited state and take a slightly different reaction route in the presence and absence of oxygen, but favorably proceed the polymerization. Dithiols and polythiols are often used as UV curing catalysts for epoxy resins.

The substrate used in the present invention refers to paper, fibers, plastics films, fabrics, plastics molded products, metals, ceramics, wood, bamboo materials, rubber products, leather products, etc., and when colored ink is used, it is a scent. Various patterns can be printed, and when a colorless ink is used, it can be applied with a scent. It is also possible to form a resin cured layer having a film thickness of 1 to 10 μm by printing or coating with the present fragrance ink and then further provide an overcoat layer to fulfill the role of surface protection. Printing or coating can be carried out by any of lithographic printing, letterpress printing, screen printing, gravure printing, offset printing, flexographic printing, transfer printing, coating method, inkjet printing, roller coating method and the like.

Since the curing of the ink of the present invention is often carried out by irradiation with ultraviolet rays, let us first explain this operation and the like. The ultraviolet irradiation is generally performed in the range of 0.5 to 5 seconds in many cases, and the irradiation time for one time tends to be shortened in the case of performing multilayer coating or multi-layer printing in which photopolymerization is performed many times. The UV curable ink used here is generally composed mainly of oligomers (photopolymerizable prepolymers) and monomers (reactive diluents, photopolymerizable monomers), and if necessary sensitizers (photopolymerization initiators) The amount added may be increased or decreased, and pigments, stabilizers, adhesiveness-imparting agents, antimisting agents, waxes, etc. may also be added. In lithographic printing using UV-curable ink, for example, its characteristics are utilized in carton printing. A typical composition of sheet-fed lithographic UV-curable ink for carton is epoxy acrylate.
40 parts, polyol acrylate 27 parts, photoinitiator 4
Parts, 4 parts of trimethylolpropane triacrylate, 0.1 part of methylhydroquinone, and 10 to 30 parts of pigments and the like. Then, the portion corresponding to the pigment in this formulation is replaced with the scented powder referred to in the present invention to form a scented ink.

In addition to overprinting a UV curable ink (herein referred to as UV curable varnish) using an offset printing machine, the UV curable varnish can be coated by a roll coater or a screen printing machine. An example of a typical photocurable resin composition for such an ultraviolet curable varnish for overprinting is as follows: epoxy acrylate (oligomer) 50 parts, trimethylolpropane triacrylate 30 parts, 1,6-hexanediol diacrylate 8
Parts, 2-hydroxy-2-methylpropiephenone 6 parts,
4,2-dimethoxy-2-phenylacetophenone 4 parts,
It is like a mixture of 1 part wax and 1 part diethanolamine.

Further, when the ink of the present invention is cured by an electron beam, it is not necessary to use a photopolymerization initiator or a sensitizer, and it can be applied within a short time even when using an opaque pigment, inner surface printing or inner surface coating. The purpose can be achieved. Regarding the basic binder resin component of ink, the case of electron beam curing and the case of ultraviolet curing are similar, and the raw materials are polyester (meth) acrylate, polyepoxy (meth) acrylate, polyurethane (meth) acrylate, poly Ether (meth) acrylate, polyol (meth) acrylate, epoxidized polybutadiene, unsaturated polyester, drying oil modified (meth) acrylate, polyethylene, polystyrene, polyvinyl chloride, polybutylene terephthalate, etc. are used, and the reactive diluent is Various polyfunctional (meth) acrylate monomers, di (meth) allyl-based monomers, tri (meth) allyl-based monomers and the like are used. Taking offset printing ink as an example, the pigment
Even if the content is 15 to 60%, electron beam curing occurs quickly.
And even if the ink contains powder with the surface of the fragrant powder covered with a hydrophobic film, it can cure the ink film without causing any problems within the normal curing conditions of 1 to 20 Mrad. is there.

Generally, in UV curing,
Although only 15 to 18% can be effectively used, it is said that 50 to 60% can be effectively used with the energy input by the electron beam accelerator.
The desired curing is completed within about 10 hours.

〔Example〕

The present inventors have conducted a number of experiments to clarify the superiority of the present invention. In order to further explain the technical content of the present invention, a representative few examples are selected from a large number of experimental examples below. Will be shown as an example. Therefore, the present invention should not be construed as being limited to only the examples, and it goes without saying that the embodiments can be arbitrarily modified and implemented without departing from the spirit and spirit of the present invention.

Example 1 Activated zirconium silicate phosphate having a specific surface area of 400 m ² / g and an average particle size of 0.5 micron (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., pH 7.0) was ignited and completely dehydrated. Fine powder
35g% of top notes, 20% by weight of middle notes and 45% by weight of base notes in 150g 40g of fragrance compounding
And stir vigorously in a nitrogen stream to make a powder.
Then, 20 g of the melted polyethylene oligomer and 10 g of the above rose-prepared fragrance are mixed into the above powder, and the mixture is stirred to give a scented composition covered with a scented film. Stabilized fragrant powder can be obtained by vigorously flowing this fragrant composition in a nitrogen stream and spraying a dilute dispersion of silicone wax to form a thin silicone wax film on the surface of the powder. When 230 g of this scented powder was sufficiently kneaded with 250 g of an ultraviolet curable ink (manufactured by Toka Dye Co., Ltd., UV Best Cure Modified Medium), a scented rose scented ink was obtained. This product can give a permanent rose scent to the printed matter by overcoating the surface of the printed matter and curing with UV.

Example 2 50 g of a fragrance mixture of 20 parts of benzyl acetate, 5 parts of jasmine absolute, 10 parts of phenylethyl alcohol, 15 parts of hydroxycitronellal, 10 parts of linalool and 3 parts of hexylcinnamic aldehyde are hydrogenated jojoba oil at 50 g and 60 ° C. Mix and stir to gradually cool to a solid, which is then ground at low temperature to a powder.
Dissolve 30 g of this powder in 50 g of methanol and add it to pH 6.5.
Activated zirconium silicate fine powder (Daiichi Rare Element Chemical Industry Co., Ltd., pH 6.5) is sprinkled on 100 g and mixed vigorously, then methanol is evaporated under low temperature and reduced pressure and then crushed to produce fragrant fine powder. Let body A.

By this operation, the hydrogenated jojoba oil phase-separates and floats on the surface of the fine powder A, and the surface of the fine powder A is conveniently and uniformly covered with the hydrogenated jojoba oil.

Meanwhile, geraniol 40 parts, phenylethyl alcohol 10
, Bulgarian Rose Absolute 10 parts, Geranium oil 8 parts and Oris oil 2 parts 80 g of a fragrance mixture to 100 g of activated zirconium silicate fine powder (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., pH 6.5) It is powder B when sprayed, mixed vigorously and left to stand until complete sorption. The powder is made to flow in a nitrogen stream, and a diluted pentane solution of microcrystalline wax is sprayed by a spray method and then dried to form a scented fine powder B by covering the surface of the powder with a thin wax film. Then, 50 g of the scented fine powder A and 50 g of the scented fine powder B are mixed to prepare a mixed scented fine powder. 100g of this mixed fragrant powder was used as an ultraviolet curing ink (Daika Seika Kogyo Co., Ltd., Seika Beam PHC-2300) 2
Add to 00g and knead thoroughly to make a uniform paste ink. This ink was a scented ink with an elegant Jasmine Rose scent. It overcoats the surface of prints and is UV cured to impart a semi-permanent Jasmine Rose fragrance to the prints.

Examples 3 to 31 (including Comparative Examples 1 to 17) To compare the effects of various porous neutral zirconium compound powders with the effects of other porous powders, powders having the properties shown in Table 1 (grains) An experiment was conducted by preparing a dehydrated product having a diameter of 0.5 to 3 microns. To 100 parts of these powders, rose base fragrance liquid (80 parts of phenylethyl alcohol, 5 parts of benzyl salicylate, 4 parts of ethylene brushlate, 2 parts of methylionone, 1 part of amylcinnamic aldehyde, 1 part of musk ambrette, 1 part of zudura A mixture of 1 part of betz oil, 1 part of UV stabilizer, and 5 parts of methanol) was spray-mixed, and methanol was evaporated under reduced pressure. Then, 3 parts of paraffin wax of Japanese Pharmacopoeia was used as a hydrophobic film agent on the powder. The solution dissolved in a small amount of petroleum ether is sprinkled, and the petroleum ether is evaporated by keeping it under reduced pressure with sufficient stirring. The resulting fragrant powder is put into 200 g of UV curable ink (UV best cure modified medium manufactured by Toka Dye Co., Ltd.) and kneaded sufficiently to obtain a rose-like fragrant fragrant ink for UV curing. It was This scented ink was applied to the surface of a postcard using an offset printing machine so as to have a thickness of 5 to 7 microns, irradiated with ultraviolet rays at 40 to 45 ° C. for 10 seconds to be cured, and then left in a room for 1 week. When the rose-like scent was tested, the results shown in Table 1 were obtained. Examples Nos. 3 to 21 in Table 1 are related to the results of the present invention, and Comparative Examples 1 to 17 are the results of experiments conducted for comparison with Examples.

In Table 1, the fragrance test results were determined by sensory-testing the scent of a postcard printed with scented ink by 5 male and 5 female panelists, and comparing it with the scent of the rose base fragrance liquid as a raw material. It is a thing. ⊚ indicates that 8 or more panelists and ∘ indicates that 6 or more panelists did not noticeably change the scent. Δ indicates that 5 or more panelists confirmed, and × indicates 8 or more panelists confirmed the change in the scent.

Examples 22 to 26 100 g of active zirconium aluminate powder (pH 7.2) having a specific surface area of 440 m ² / g and an average particle size of 1.7 microns was sprayed with 90 g of the perfume shown in Table 2 and vigorously in a closed container for 5 hours. After stirring and cooling, the powder was dried under reduced pressure in a desiccator kept at 0 ° C to obtain a powder from which ethanol was removed. Next, Freon solution containing 2% of fluororesin oligomer 300m
When this powder is put into a l, cooled to -20 ° C, and left overnight with stirring, a powder with the surface of the fragrant powder covered with a fluororesin is obtained. It is stabilized by filtering and drying. It becomes a fragrant powder. 100 g of this scented powder is put into 150 g of UV curable ink (UV best cure modified medium manufactured by Toka Dye Co., Ltd.) and sufficiently kneaded to obtain a scented ink corresponding to the raw material perfume. When there is a concern about discoloration of perfume fragrance due to ultraviolet rays by this method, an ultraviolet stabilizer (for example, Tinuvin manufactured by Ciba Geigy) may be added to the perfume in a small amount in advance. If this scented ink is mixed with a coloring ink, a scented ink of each color is obtained. Table 2 shows the results of a sensory test of the scent tone after overcoating a business card with this scented ink and curing with ultraviolet rays in the same manner as in Examples 3 to 21.

However, although the sensory test was the same as in Examples 3 to 21, it was found that a part of the top notes of the perfume volatilized due to the experimental operation, and the fragrance balance was changed by this amount. A business card printed with this scented ink was placed in a vinyl passport and left in a drying room, where it fragranced for about 6 months (the aroma changes slightly, but the characteristics of the perfume are retained. Was done). This experiment was applied to leather gloves, silk gloves, glass broaches, metal earrings, etc., and good results were obtained.

Example 27 According to the method shown in Examples 22 to 26, 100 g of activated zirconium silicate powder (pH 7.2) was impregnated with 30 g of Bulgaria rose absolute, and the surface of the powder was coated with a fluororesin to give a stable fragrance. Use powder. 100 g of this scented powder was mixed with 100 g of acrylic modified alkyd resin, 20 g of trimethylolpropane triacrylate, and 20 g of titanium white to form a paste, which was then applied onto a polyvinyl chloride sheet colored in black, and the same sheet was placed on top. And stack from top to bottom. When this laminated sheet is irradiated with an electron beam of 10 Mrad within the shortest possible time using an electron beam accelerator (300 KV), a fragrant ink cured product is laminated as an intermediate layer to form a plastic sheet. Cut this one properly and lay down
If processed into a ruler or bookmark (bookmark), the fragrance of rose oil will be released over a long period of time, doubling the commercial value as a stationery item.

〔The invention's effect〕

The scented ink of the present invention can be easily cured after being attached to a substrate such as a paper product, a plastic product, a textile product, a rubber product, a leather product, a metal product, a ceramic product, a woodwork product by a printing method or a coating method. You can The scent contained in the scented ink rarely changes during curing and thereafter, and can be emitted over a long period of time. Its scent is not only aromatic, but medicinal,
It is also applied to odors for sterilization, insecticide, deodorization (for masking), etc. Therefore, this product may be applied to a wide range of fields from daily necessities, cosmetics, food packaging materials, cads, publications, agricultural products, hospital products, store products to various industrial products, and its effectiveness is immense. It is considered to be

Claims (1)

[Claims] 1. A powder comprising 100 parts of a porous neutral zirconium compound powder having a specific surface area of 200 to 600 m ² / g and a pH of 5 to 9 and 20 to 100 parts of a liquid fragrance. Radiation-curable resin composition 100-500 that covers the body surface with a hydrophobic film
A fragrant ink characterized by being kneaded with a part.