JP2006063241A - Multifunctional ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a multifunctional ink emitting negative ions and improved in both antimicrobial and deodorizing effects owing to photocatalytic activity in combination with the use of far-infrared rays radiating at the same time. <P>SOLUTION: The multifunctional ink is obtained by admixing a photocatalytically functional material into an ink composition comprising a macromolecular compound hard to be electrostatically charged, rare element-containing minerals, tourmaline or far-infrared radiating ceramics, and a pigment or dye. This multifunctional ink has both antimicrobial and deodorizing activities in combination with radiating negative ions and using far-infrared rays and antistaticity. A laminated material using this ink is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a multifunctional ink, and more particularly to a multifunctional ink and a laminate that can improve antibacterial and deodorizing effects by photocatalytic action as well as the amplification and sustaining of negative ions and the use of far infrared rays that are simultaneously emitted.

  In recent years, it has been known that negatively charged ions have various effects of healing the human body, improving the environment or improving health, and negative ions have antibacterial and deodorizing effects. In addition, far-infrared rays, which are generally known, have been reported to have a negative ion healing effect. In this way, various effects of negatively charged ions have attracted attention, such as sorrow, pleasant sleep, antitussive, antiperspirant, increased appetite, blood pressure drop, refreshing feeling, fatigue prevention, etc., or antibacterial, deodorizing effects, etc. Infrared rays have also been widely used for health treatment devices.

  In general, what is required of ink is a mixed composition of a resin composition and a pigment or dye that adheres to a substrate. Further, from the viewpoint of use, the ink is a general ink. For example, a printing ink is obtained by finely dispersing inorganic and organic pigments and lakes in an ink varnish. Printing inks are required to have an appropriate and uniform viscosity, dry as soon as possible after printing, and have no foul odor. In addition, as various special inks, there are inks that emit far-infrared mixed with far-infrared ceramics, and inks for health that contain catechins or peppers.

  On the other hand, from the viewpoint of people's living environment, negative ions and positive ions are always kept in parallel. For example, in a bad environment, negative ions and positive ions are likely to be offset, In the environment, the dramatic production and consumption of so-called synthetic substances, and their disposal, increase the positive ions and decrease the negative ions. ing. And if positive ions increase, it is said that abnormalities in the body and aging will progress. In recent years, our bodies, environment, food and water are weakly acidified, and the negative ions that are lacking there are produced and reduced to neutrality. It is said that it is the negative ion effect. Speaking of the improvement of the human body, this effect has been proven to be effective in activating rheumatic diseases, neuralgia, chronic diseases and the like by activating each tissue and autonomic nerve in the body.

In recent years, sick house syndrome has become a social problem even in the living environment, and people are also interested in antibacterial and deodorizing in daily life. When exposed to light, titanium oxide crystals kill E. coli and decompose formaldehyde, etc. In addition, photocatalytic active materials that have effects such as deodorization have attracted attention. Titanium oxide has been widely used as a white pigment, and it has been added and blended as an inorganic filler. However, in recent years, it has been used as a highly safe functional material using the photocatalytic activity of titanium oxide. Is attracting attention.

Many prior arts and patent documents of compositions having both antibacterial and deodorant properties are disclosed, and products are also sold in the market.
JP, 2001-335726, A In the above-mentioned patent documents 1, the present inventors etc. are mixed powders which contain the mineral which contains rare elements, and at least one of tourmaline or far-infrared ceramics in resin which is hard to be charged with static electricity. A multifunctional ink is disclosed, which is obtained by mixing a pigment and / or a dye with a resin composition in which is mixed.

When titanium oxide with a particle size of several to several hundreds nm called photocatalyst is exposed to ultraviolet rays such as sunlight, electrons are excited by the photoelectric effect, electrons and holes are generated, and the electrons reduce oxygen in the air. To superoxide ions, holes oxidize surface moisture and turn them into hydroxyl radicals. The superoxide ion and the hydroxyl radical show strong oxidizing power. When an organic substance adheres to the titania surface in this state, the superoxide ion decomposes the organic substance carbon and the hydroxyl radical takes hydrogen. Such a self-cleaning action is a mechanism that becomes an antibacterial action and a deodorizing action.

When estimated from the antibacterial action and deodorant action in Patent Document 1 above, an approximation point is seen in the mechanism principle, and the resin composition itself in the publication has a continuous emission of electrons, whereas a photocatalyst. Is similar to the fact that electrons are emitted by sunlight and the excitation of both electrons contributes.

However, in the above patent, the release of negative ions and the emission of far-infrared radiation and antibacterial and collecting properties can work together, but the antibacterial and deodorizing properties are at a moderate level compared to the former. It is a little less. In addition to the release of negative ions and far-infrared radiation, the antibacterial and deodorant multifunctional functions can be exhibited together, but the antibacterial and deodorant needs in particular are required. Therefore, it is difficult to select a combination that can exert the desired antibacterial and deodorant effects.

  When the main purpose is antibacterial effect and deodorizing effect, the multifunctional ink and the photocatalyst have moderate antibacterial performance in antibacterial effect, while deodorizing effect can be obtained at low concentration. However, at high concentrations, it is difficult to obtain deodorant performance. In addition, the photocatalyst deodorizes only the portion where the malodorous component is adhered and adhered, and does not deodorize a wide range of malodor in the air.

  Recently, hospital infections, food poisoning in the food industry, and infectious diseases in the livestock industry have become social problems. Medical equipment, medical clothing, and food-related products must be at a high level of sterilization and sterilization, not antibacterial. If it is, it cannot be manufactured and used.

In addition, titanium oxide as a photocatalyst has the following problems. (1) There is no effect in the dark at night when sunlight and other ultraviolet rays do not hit. (2) When mixed with or brought into contact with a resin, the organic resin is decomposed and deteriorated, so its use is limited.

It has become necessary to solve the above-mentioned problems of the antibacterial effect and the deodorizing performance, which are the above problems, and the photocatalyst.

  In view of the above problems, the present invention includes (1) a polymer compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared radiation ceramics, and a pigment and / or A multifunctional ink in which a photocatalytic functional material is added to and mixed with a resin composition containing a dye. (2) A photocatalytic functional material is applied to the surface treated with a multifunctional ink containing a polymer compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared radiation ceramic. The present invention provides a multifunctional ink laminate processed with a coating material dispersed in an inorganic binder.

  In the present invention, as this theoretical elucidation, it is speculated that ion-focused static electricity is established, positive ions in the air are selectively focused with a composite material charged with negative static electricity, and an air environment containing only negative ions is created. At the same time, far infrared rays are also radiated. Furthermore, by adding photocatalytic titanium oxide, the production of positive ions is greatly reduced, and the negative ion effect can be exhibited more. Far-infrared radiation hardly changes, and thus, a large amount of negative ions are emitted by excitation or amplification, and at the same time a far-infrared effect is obtained. In addition to the negative-ion effect and the far-infrared effect, antibacterial and deodorant properties are patented. 1, in the middle low level, the synergistic effect is estimated by the selection of the photocatalytic functional material and the specified additive composition, and the multifunctional function capable of exhibiting the triple effect of antibacterial and deodorizing effect coexisting with the photocatalytic activity function Has reached the configuration of the ink and its laminate.

  The above-mentioned multifunctional ink and laminate material continuously release a large amount of negative ions, and simultaneously amplify and radiate far infrared rays, and simultaneously amplify and release superoxide ions and hydroxyl radicals. A high bactericidal effect was obtained, and at the same time, a substance capable of deodorizing high-concentration malodorous components was found, and a function capable of exerting an effect even in a dark place where sunlight did not enter, which was a great difficulty of photocatalytic functional materials, was found. .

  In the present invention, lacquer, varnish, resin emulsion, water-soluble resin, solvent-based synthetic resin, solventless UV resin, and the like can be used as the resin for ink.

In the present invention, any of inorganic pigments and organic pigments can be used as the pigment. Examples of inorganic pigments include petals, barium yellow, ultramarine blue, cobalt green, and carbon black.
Examples of organic pigments include thioindigo maroon, Hansa yellow, phthalocyanine green, and aniline black.

  As the dye, a direct dye, a metal-containing dye, a reactive dye, or the like can be used.

  In the present invention, examples of the photocatalytic functional material include anatase-type titanium oxide, brookite-type titanium oxide, and apatite-coated titanium oxide. As the particle diameter, those pulverized to 5 to 200 nm can be used. Most preferably, 6 to 30 nm is advantageous in promoting excitation of electrons. Further, in gas purification with titanium oxide for photocatalysts, those having a large specific surface area and a large amount of adsorption are suitable, and a specific surface area of 50 square meters / g or more is also advantageous in promoting excitation of electrons. .

  The photocatalytic functional material can be added and mixed in a range not exceeding 50% by weight, preferably 2 to 50% by weight, and most preferably 2 to 30% by weight, so as not to reduce the production of negative ions. Is advantageous. This is because if the blending amount of the photocatalytic functional material exceeds 50% by weight, it affects the mixing with other components and does not contribute to the desired photocatalytic effect.

In the present invention, as the far-infrared ceramic, silica-based and alumina-based ceramics and ceramics containing silica, alumina, iron oxide, magnesium oxide, sodium oxide, and iron oxide can be used. Most preferably, among the ceramics of the above components, the use of a ceramic that emits far-infrared rays having a wavelength of 2 to 50 μm at an emissivity of 50 or more in the normal temperature body temperature range is to amplify the generation of negative ions. It is beneficial.

  Commercially available products containing the above components include the trade name Serajit manufactured by OKI Trading Co., Ltd., which is useful for amplifying negative ions and simultaneously emitting far infrared rays.

  Most preferably, the average particle size of about 10 microns is useful for mixing and printing as the particle size of the powder.

  In the present invention, organosilica sol, colloidal silica, water-soluble alkali silicate, alkoxysilane, lithium silicate, chromic acid, cement and the like can be used as the inorganic binder. Most preferably, organosilica sol and colloidal silica are more advantageous because they hardly inhibit the photoexcitation action.

  In the present invention, as printing ink in the processing method, any of screen ink, gravure ink, inkjet ink, offset ink, hot stamp ink, pad ink, UV ink, textile printing ink, etc. Can also be used for.

  The present invention includes (1) a resin composition containing a polymer compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared ceramic, and a pigment and / or a dye. Multifunctional ink with a photocatalytic functional material added and mixed. (2) The photocatalytic functional material is inorganic on the surface treated with a multifunctional ink containing a polymer compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared ceramic. It is a multifunctional ink laminate processed with a coating material dispersed in a binder. The multifunctional ink greatly reduces positive ions, generates negative ions continuously and in large quantities, and simultaneously amplifies and emits far-infrared rays, and at the same time, photocatalytic superoxide ions and hydroxyl radicals are generated. It can be amplified to greatly improve antibacterial and deodorizing effects, and has excellent effects as a printing ink for sterilizing products, deodorizing products, medical clothing, food products, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples.

Preparation of Samples As the compounding materials shown in Tables 1 and 2, silicon emulsion, trade name SE1980, manufactured by Toray Dow Corning Silicon Co., Ltd. was used. As the far-infrared ceramic, the trade name Serajit ALF9, manufactured by OKI Trading Co., Ltd. was used. As the photocatalyst, trade name PC-101, titanium oxide having an average particle diameter of 20 microns manufactured by Titanium Industry was used. Colloidal silica was used as the inorganic binder.

  Formulation (1)

配合処方（２）

Formulation (2)

表１及び表２に示す実施例１，２、３、４、５、６、７，８の所定量を配合した混合物を、３Ｌ真空攪拌機ダルトンにて、１時間攪拌混合した。

The mixture which mix | blended the predetermined amount of Example 1, 2, 3, 4, 5, 6, 7, 8 shown in Table 1 and Table 2 was stirred and mixed by 3 L vacuum stirrer Dalton for 1 hour.

  The mixed examples 1, 2, 3, 4, 5, and 6 were applied to a glass wool non-woven fabric by a pasting machine and a petiole pattern was printed by a screen printing machine. As a coating amount at that time, a two-layer processed nonwoven fabric coated at 50 g / square meter and dried in a drying furnace at 400 degrees for 20 minutes was used.

  Samples of this two-layer nonwoven fabric were designated as Examples 9 and 10.

Ion measurement and far-infrared measurement Ion measurement and far-infrared measurement of the samples of Examples 1 to 4 and Examples 9 and 10 were performed.

  As an ion measurement method, an ion tester 900 manufactured by Kobe Radio Co., Ltd. was used as a small ion measurement, and the average number of negative ions and positive ions per 3 minutes / cc was measured at room temperature 25 ° C., humidity 60%, sample 20 cm square. .

  For the total ion measurement, an air ion tester ITC-201A manufactured by Andes Electric was used, and the average production amount / cc of negative ions and positive ions for 3 minutes was measured in the same atmosphere.

  In the far-infrared measurement, a far-infrared emissivity at a sample temperature of 35 ° C. was measured using an FTIR measuring instrument, JIR-E500.

  The results are shown in Table 3.

実施例１〜４及び実施例９，１０の小イオン測定及び総イオン測定の結果、実施例１〜４の樹脂組成物に光触媒及びアパタイト被覆酸化チタン配合が、プラスイオンを大量に減少させて、マイナスイオンを大量に生成させていた。実施例９，１０においても、プラスイオンを大幅に減少させて、マイナスイオンを生成させていた。
遠赤外線の放射においても、いずれの実施例も高放射で放射していた。

As a result of small ion measurement and total ion measurement in Examples 1 to 4 and Examples 9 and 10, the photocatalyst and the apatite-coated titanium oxide compound were added to the resin compositions in Examples 1 to 4 to reduce positive ions in a large amount. A large amount of negative ions was generated. Also in Examples 9 and 10, the positive ions were significantly reduced to generate negative ions.
Even in the far-infrared radiation, all the examples radiated with high radiation.

Comparative example

  Samples of Comparative Examples 1, 2, 3, and 4 were prepared in the same manner as in Examples 1 to 4, using the formulation shown in Examples 5, 6, 7, and 8 as sample preparation methods.

  Ion measurement and far-infrared measurement of the comparative example were performed in the same manner as in the examples.

  The results are shown in Table 4.

実施例と比較例の小イオン測定結果および総イオン測定結果から明らかなように、樹脂組成物に光触媒酸化チタンを加えることで、プラスイオン生成が大幅に減少することになり、よりマイナスイオン効果を発揮できるものになった。

As is clear from the small ion measurement results and the total ion measurement results of the examples and the comparative examples, the addition of photocatalytic titanium oxide to the resin composition significantly reduces the production of positive ions, thereby further reducing the negative ion effect. It became something that can be demonstrated.

  In the far-infrared rays, high radiation was maintained almost unchanged.

Practical application test Using the samples prepared in the examples and comparative examples, an antibacterial test and a deodorization test are performed to clarify the present invention.

Antibacterial test An antibacterial test was conducted by the Japan Spinning Inspection Association, a public testing organization.

ｌｏｇＢ−ｌｏｇＡ＝２．７ 有効
殺菌活性値＝ｌｏｇＡ−ｌｏｇＣ
静菌活性値＝ｌｏｇＢ−ｌｏｇＣ As an antibacterial test method, in accordance with JIS-L1902 quantitative test method, as environmental conditions,
(1) Daylight irradiation, (2) Darkness without illumination. MRSA (resistant Staphylococcus aureus) was used as a test strain. The test results are shown in the table below.
(Test results)
(1) During daylight irradiation

logB-logA = 2.7 effective bactericidal activity value = logA-logC
Bacteriostatic activity value = log B-log C

（２）光無し（暗闇）

(2) No light (darkness)

上記の抗菌試験から明らかなように、実施例と比較例を比較すると、樹脂組成物よりも相当高い抗菌性を示し、殺菌レベルの性能を有するものとなった。また、光の無い環境でも、余り低下することなく抗菌性を維持していた。
それに対し、光無しの環境では、比較例３，４の光触媒のみの試料では、全く効果が見られなかった。これらの効果は、樹脂組成物のマイナスイオン増幅をする遠赤外線と、光触媒の相互作用が働くことによって、相乗効果が推定され、抗菌効果を大幅に向上させたことは明らかである。

As is clear from the above antibacterial test, when Examples and Comparative Examples were compared, the antibacterial property was considerably higher than that of the resin composition, and it had a sterilization level performance. Further, even in an environment without light, the antibacterial property was maintained without much deterioration.
On the other hand, in the environment without light, the sample of Comparative Examples 3 and 4 only had no effect at all. It is clear that the synergistic effect is estimated and the antibacterial effect is greatly improved by the interaction between the far infrared rays that amplify the negative ions of the resin composition and the photocatalyst.

Deodorization test The detector tube method was used as the deodorization test.

  As a test method, 5 cm square and gas of samples of Examples and Comparative Examples were injected into 5 liters of tetrabag, and the gas concentrations after 30 minutes and 1 hour were measured using a detector tube. The malodor rate (%) was converted. The environmental conditions were (1) daylight irradiation and (2) dark without illumination.

  Ammonia was used as the gas type. The control material is a blank containing no sample.

Ammonia gas initial concentration 200ppm, gas amount 600ml
Deodorization rate% = [(control gas concentration−sample gas) / control gas concentration] × 100 (1) Daylight irradiation As a result, the control gas concentration after 30 minutes 190 ppm
Control gas concentration 170ppm after 1 hour

（２）照明無し闇黒
その結果、３０分後のコントロールガス濃度 １９０ｐｐｍ
１時間後のコントロールガス濃度 １７０ｐｐｍ

(2) Darkness without illumination As a result, the control gas concentration after 30 minutes 190ppm
Control gas concentration 170ppm after 1 hour

上記、消臭試験結果から明らかなように、実施例及び比較例と比較して、高濃度のアンモニアガス濃度でも、実施例では、効率よく分解消臭したことが明らかとなった。また、光無しの環境条件でも、大差なく効率よく分解消臭したことが明らかとなった。

As is clear from the results of the above deodorization test, it was revealed that even in a high concentration of ammonia gas compared to the examples and comparative examples, the examples achieved efficient odor elimination in the examples. In addition, it became clear that even in environmental conditions without light, the odor was eliminated efficiently without much difference.

  Only the photocatalysts of Comparative Examples 3 and 4 did not deodorize at all.

Claims (6)

Add a photocatalytic functional material to an ink composition that contains a polymer compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared radiation ceramics, and a pigment or dye. Multi-functional ink that mixes and emits negative ions and emits far-infrared rays and has antibacterial and deodorizing effects. The multifunctional ink according to claim 1, wherein the photocatalytic functional material is photocatalytic titanium oxide. The multifunctional ink according to claim 1, wherein the photocatalytic functional material is apatite-coated titanium dioxide. The multifunctional ink according to any one of claims 1 to 3, wherein the photocatalytic functional material has an average particle diameter of 6 to 30 nm and a specific surface area of 50 square meters / g or more made of photocatalytic titanium oxide. The multifunctional ink according to any one of claims 1 to 4, wherein the photocatalytic functional material is added and mixed in a range of weight percent not exceeding 2 wt%. It is treated with an ink composition containing a pigment and / or a dye containing at least one of a high molecular compound that is not easily charged with static electricity, a mineral containing rare elements, and at least one of tourmaline or far-infrared radiation ceramics. A multifunctional ink laminate, wherein the photocatalytic functional material is processed on a surface with a coating material in which an inorganic binder is dispersed.