CN105745074A - Substrate provided with antibacterial layer, antibacterial sheet, radiography device, and touch panel - Google Patents
Substrate provided with antibacterial layer, antibacterial sheet, radiography device, and touch panel Download PDFInfo
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- CN105745074A CN105745074A CN201580002693.0A CN201580002693A CN105745074A CN 105745074 A CN105745074 A CN 105745074A CN 201580002693 A CN201580002693 A CN 201580002693A CN 105745074 A CN105745074 A CN 105745074A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/728—Hydrophilic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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- Pest Control & Pesticides (AREA)
- Theoretical Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention provides: a substrate provided with an antibacterial layer, the substrate being provided with an antibacterial layer that promptly exhibits antibacterial action and that enables antibacterial properties to be maintained for a prolonged period of time; an antibacterial sheet; a radiography device; and a touch panel. This substrate provided with an antibacterial layer has a substrate and an antibacterial layer disposed on at least part of the surface of the substrate, wherein the antibacterial layer has a silver-containing first antibacterial agent, and a silver-containing second antibacterial agent that differs from the first antibacterial agent. Taking P to be the amount of silver per unit area included in the antibacterial layer and Q to be the amount of silver ions per unit area as measured using an extraction test, the relationships in formulae (1) and (2) are satisfied. (1) 6.0<=P/Q (2) 15.0<=Q.
Description
Technical field
The present invention relates to the base material of antibiotic layer, antibiotic slice, radiographic equipment and contact panel.
Background technology
The surface of various goods components can be implemented processing and give various function according to purpose by most cases.Wherein, in recent years, arrange the technology of antibiotic layer at substrate surface to attract attention.
Such as, multiple patient is mostly contacted continuously at the on-the-spot medical treatment device used of medical treatment.Further, since the surface of contact panel directly can be touched with finger by uncertain many operators, if therefore antibacterial etc. are at its surface colonization, then there is the risk caught.For this, by the surface configuration antibiotic layer at various devices such as medical treatment devices, it is possible to reduce bacterial multiplication, disease infect risk.
As this kind of technology, for instance Patent Document 1 discloses and make silver complex be carried on the silver-series antibacterial agent of silica-gel carrier, comprise the slow-releasing anti-biotic material of silica gel and organic bond.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 09-131389 publication
Summary of the invention
Invent problem to be solved
On the other hand, in recent years, in order to improve the use frequency of various device (such as medical treatment device, contact panel) further, it is desirable to show antibacterial action in shorter time.
Furthermore it is required that antibacterial action can for longer periods be maintained.
Namely, it is desirable to antibacterial action can be shown at short notice and the antibiotic layer of antibiotic property can be maintained for a long time.
The base material with antibiotic layer recorded in patent documentation 1 has been studied by the present inventor etc., found that it can not fully meet above-mentioned important document, it is necessary to further improve.
It is an object of the invention to: be provided with showing at short notice antibacterial action in view of above-mentioned practical situation and the base material with antibiotic layer of antibiotic layer of antibiotic property can be maintained for a long time.
Additionally, the present invention also aims to provide antibiotic slice and possess radiographic equipment and the contact panel of the above-mentioned base material with antibiotic layer.
For solving the means of problem
Above-mentioned problem is conducted in-depth research by the present inventor etc., found that above-mentioned problem can be solved by following composition.
(1) a kind of base material with antibiotic layer, it has base material and is configured at least one of antibiotic layer of substrate surface,
Antibiotic layer has the 1st antibacterial comprising silver and the 2nd different from above-mentioned 1st antibacterial, to comprise silver antibacterial,
When the silver content comprised in the antibiotic layer of per unit area being set to P and the silver ion amount utilizing the per unit area of extraction test determination described later being set to Q, meet below formula (1) and the relation of formula (2).
Formula (1) 6.0≤P/Q
Formula (2) 15.0≤Q
Wherein, the unit of P is ng/cm2, the unit of Q is ng/cm2。
(2) according to the base material with antibiotic layer described in (1), it meets the relation of formula (3).
Formula (3) 15.0≤Q≤25.0
(3) according to the base material with antibiotic layer described in (1) or (2), wherein,
1st antibacterial comprises silver and any one in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antibacterial comprises silver and includes the carrier of zeolite.
(4) according to the base material with antibiotic layer according to any one of (1)～(3), wherein, antibiotic layer comprises the polymer with hydrophilic base.
(5) according to the base material with antibiotic layer described in (4), wherein, hydrophilic base comprises polyoxy alkylidene.
(6) a kind of radiographic equipment, it has the base material with antibiotic layer according to any one of (1)～(5) on surface.
(7) a kind of contact panel, it has the base material with antibiotic layer according to any one of (1)～(5) on surface.
(8) a kind of antibiotic slice, it comprises antibacterial,
Antibacterial has the 1st antibacterial comprising silver and the 2nd different from the 1st antibacterial, to comprise silver antibacterial,
When the silver content comprised in the antibiotic slice of per unit area being set to P and the silver ion amount utilizing the per unit area of extraction test determination described later being set to Q, meet below formula (1) and the relation of formula (2).
Formula (1) 6.0≤P/Q
Formula (2) 15.0≤Q
Wherein, the unit of P is ng/cm2, the unit of Q is ng/cm2。
(9) according to the antibiotic slice described in (8), it meets the relation of formula (3).
Formula (3) 15.0≤Q≤25.0
(10) according to the antibiotic slice described in (8) or (9), wherein,
1st antibacterial comprises silver and any one in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antibacterial comprises silver and includes the carrier of zeolite.
(11) according to the antibiotic slice according to any one of (8)～(10), it also comprises the polymer with hydrophilic base.
(12) according to the antibiotic slice described in (11), wherein, hydrophilic base comprises polyoxy alkylidene.
Invention effect
According to the present invention it is possible to be provided with showing at short notice antibacterial action and the base material with antibiotic layer of antibiotic layer of antibiotic property can be maintained for a long time.
It addition, it is also possible according to the present invention to provide antibiotic slice and possess radiographic equipment and the contact panel of the above-mentioned base material with antibiotic layer.
Accompanying drawing explanation
Fig. 1 is the sectional view of an embodiment of the base material with antibiotic layer of the present invention.
Detailed description of the invention
Hereinafter, illustrating with the base material of antibiotic layer, antibiotic slice, radiographic equipment and contact panel the present invention.
It addition, this specification uses "～" numerical range that represents refer to and comprise "～" the numerical value described in front and back as the scope of lower limit and higher limit.
As one of inventive feature point, can enumerate and use 2 kinds of antibacterial comprising silver and control the stripping quantity this point of the silver amount from antibiotic layer.Particular, it is found that: adjust the scope to regulation by the silver ion amount Q of the silver content P comprised by the antibiotic layer of per unit area and the per unit area utilizing extraction test determination described later, it is possible to obtain required effect.
It addition, as the more excellent scheme of the present invention, the 1st antibacterial as described later can be enumerated and comprise silver and any one and the 2nd antibacterial in calcium zinc orthophosphate activated by thallium and calcium phosphate comprise silver and include the scheme of carrier of zeolite.Also find, in this case, from the porous carrier that a part for the silver ion of the 1st antibacterial dissolution is again maintained in the 2nd antibacterial for the time being, after silver ion terminates from the dissolution of the 1st antibacterial, the silver ion being held in the porous carrier of the 2nd antibacterial carries out dissolution, is achieved in silver ion and for longer periods continues dissolution.
Hereinafter, first the base material with antibiotic layer of the present invention is described in detail.
Fig. 1 is the sectional view of an embodiment of the base material with antibiotic layer of the present invention.As it is shown in figure 1, the base material 10 with antibiotic layer has base material 12 and the antibiotic layer 14 being configured on base material 12.It addition, antibiotic layer 14 can also be configured at least some of of the surface of base material 12.
Hereinafter, each component is described in detail.
< base material >
Base material plays the effect supporting antibiotic layer, and there is no particular restriction for its kind.Additionally, as described later, base material may be constructed a part (such as front panel) for various device.
There is no particular restriction for the shape of base material, can enumerate tabular, membranaceous, lamellar, tubulose, threadiness, particle shape etc..Additionally, the substrate surface configuring antibiotic layer described later can be tabular surface, it is also possible to be concave surface, it is also possible to be convex surface.
There is no particular restriction for the material of composition base material, for instance can enumerate metal, glass, pottery, plastics (resin) etc..Wherein, from the aspect of operability, it is preferable that plastics.In other words, it is preferable that resin base material.
< antibiotic layer >
Antibiotic layer is to be configured at least some of of substrate surface and have the layer of antibacterial action.
Antibiotic layer at least has the 1st antibacterial (after, also referred to as " the 1st antibacterial ") comprising silver and different from the 1st antibacterial, to comprise silver the 2nd antibacterial (after, also referred to as " the 2nd antibacterial ").That is, at least there are 2 kinds of silver-containing antibacterial agents (after, also referred to as " silver-series antibacterial agent ") in antibiotic layer.
As the 1st antibacterial and the 2nd antibacterial, as long as comprising silver (silver atoms), there is no particular restriction for its kind.Additionally, the form of silver also there is no particular restriction, for instance comprise silver with forms such as argent, silver ion, silver salt (including silver complex).It addition, in this manual, silver complex is included in the scope of silver salt.
nullAdditionally，As silver salt，Include, for example: silver acetate、Acetopyruvic acid silver、Silver azide、Silver acetylide、Silver arsenate、Silver benzoate、Fluorine silver hydride、Silver bromate、Silver monobromide、Disilver carbonate、Silver chloride、Argentous chlorate.、Siliver chromate、Itrol.、Silver cyanate、Silver cyanide、(cis，Cis-1,5-cyclo-octadiene)-1,1,1,5,5,5-hexafluoroacetylacetonate keto acid silver、Silver diethyl dithio carbamate、Argentous fluoride (I)、Argentous fluoride (II)、7,7-dimethyl-1,1,1,2,2,3,3-seven fluoro-4,6-acetyl caproyl acid silver、Silver hexafluoroantimonate、Hexafluoroarsenate silver、Hexafluorophosphoric acid silver、Silver iodate、Silver iodide、Isothiocyanic acid silver、Silver potassium cyanide、Actol、Silver molybdate、Silver nitrate、Silver nitrite、Silver oxide (I)、Silver oxide (II)、Silver oxalate、Silver perchlorate、Perfluorobutyric acid silver、Perfluorinated acid silver、Silver manganate(VII).、Perrhenic acid silver、Silver phosphate、Silver picrate monohydrate、Silver propionate、Silver selenate、Silver selenide、Silver selenite、Silver sulfadiazine、Silver sulfate、Argentous sulfide.、Silver sulfite、Silver telluride、Silver tetrafluoroborate、Four iodo curium acid silver (acid of テ ト ラ ヨ De system キ ュ リ ウ system)、Four wolframic acid silver、Silver thiocyanate、P-methyl benzenesulfonic acid silver、Silver trifluoromethanesulfonate、Silver trifluoroacetate and silver vanadate etc..
In addition, as an example of silver complex, histidine silver complex, methionine silver complex, cysteine silver complex, aspartic acid silver complex, 2-pyrrolidone-5-carboxylic acid's silver complex, oxo-tetrahydrofuran silver carboxylate complex or imidazoles silver complex etc. can be enumerated.
As the 1st antibacterial and the 2nd antibacterial, for instance the antibacterial of the antibacterial that can enumerate the organic system of above-mentioned silver salt etc. and the inorganic system comprising carrier described later, there is no particular restriction for its kind.
Wherein, from can show at short notice antibacterial action and/or can maintain for a long time antibiotic property aspect (after, also referred to as " making the aspect that the effect of the present invention is more excellent ") set out, the 1st antibacterial and the 2nd antibacterial are preferably the silver-colored silver-colored load carriers comprising carrier and being carried on carrier.
There is no particular restriction for the kind of carrier, can enumerate: calcium zinc orthophosphate activated by thallium, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicates, activated carbon, activated alumina, silica gel, zeolite, hydroxyapatite, titanium phosphate, potassium titanate, oxidizing aqueous bismuth, oxidizing aqueous zirconium, brucite etc..It addition, as zeolite, for instance can enumerate: the natural zeolites such as chabasie, modenite, erionite, clinoptilolite；The synthetic zeolites such as type A zeolite, X-type zeolite, y-type zeolite.
There is no particular restriction for the mean diameter of above-mentioned silver load carriers, from the aspect that the effect making the present invention is more excellent, it is preferred to 0.1～10 μm, more preferably 0.1～2 μm.It addition, above-mentioned mean diameter is: the diameter utilizing measurement microscope at least 10 arbitrary silver load carriers the value these diameters being carried out arithmetic average and obtaining.
It addition, as set forth above, it is possible to comprise silver with any form in silver ion, argent and silver salt.
Applicable form as the 2nd antibacterial, it is preferable to use porous body (such as zeolite, zirconium phosphate, aluminum phosphate, calcium silicates) is as the silver-colored load carriers of carrier.
Additionally, it is best suitable for form as the 1st antibacterial and the 2nd antibacterial, from the aspect that the effect making the present invention is more excellent, it is preferable that make the 1st antibacterial comprise silver and any one and the 2nd antibacterial in calcium zinc orthophosphate activated by thallium and calcium phosphate comprise silver and include the carrier of zeolite.In other words, the 1st antibacterial be comprise in calcium zinc orthophosphate activated by thallium and calcium phosphate any one and be carried on the silver-colored supported catalyst of silver of this carrier, the 2nd antibacterial is the silver-colored supported catalyst of the carrier that comprises and include zeolite and the silver being carried on this carrier.
There is no particular restriction for the content of the silver in the 1st antibacterial and the 2nd antibacterial, for instance, when above-mentioned silver load carriers, the content of silver is preferably 0.1～30 mass % relative to silver load carriers gross mass, more preferably 0.3～10 mass %.
There is no particular restriction for above-mentioned 1st antibacterial in antibiotic layer and the total content of above-mentioned 2nd antibacterial, from the aspect that the effect making the present invention is more excellent, it is preferable that so that the mode that silver reaches 0.0001～1 mass % (preferably 0.001～0.1 mass %) relative to the content of antibiotic layer gross mass makes antibiotic layer contain the 1st antibacterial and the 2nd antibacterial.
It addition, the silver amount in antibiotic layer refers to the silver in the 1st antibacterial and the total amount of the silver in the 2nd antibacterial.
Additionally, there is no particular restriction for the content of the 1st antibacterial (or the 2nd antibacterial) in antibiotic layer, more excellent from the mechanical strength making antibiotic layer and make the aspect that the effect of the present invention is more excellent, relative to antibiotic layer gross mass, it is preferably 0.001～10 mass %, it is more preferably 0.01～5 mass %, more preferably 0.01～3 mass %, it is particularly preferred to be 0.01～1 mass %.
Antibiotic layer can comprise the composition beyond the 1st above-mentioned antibacterial and the 2nd antibacterial.
Such as, the polymer (after, also referred to as " hydrophilic polymer ") with hydrophilic base can be comprised in antibiotic layer.By comprising hydrophilic polymer in antibiotic layer such that it is able to make antibiotic layer show hydrophilic more preferably, and can be easier to remove the polluter being attached on antibiotic layer by using the washing of water etc..
There is no particular restriction for the kind of hydrophilic base, for instance can enumerate: polyoxy alkylidene (such as polyoxyethylene, polyoxypropylene, oxygen ethylidene carry out block or the random polyoxy alkylidene being combined into oxygen propylidene), amino, carboxyl, the alkali metal salt of carboxyl, hydroxyl, alkoxyl, amide groups, carbamoyl, sulfoamido, sulfamoyl, sulfonic group, sulfonic alkali metal salt etc..Wherein, from the aspect that the effect making the present invention is more excellent, it is preferable that polyoxy alkylidene.
There is no particular restriction for the structure of the main chain of hydrophilic polymer, for instance can enumerate polyurethanes, poly-(methyl) acrylate, polystyrene, polyester, polyamide, polyimides, polyureas etc..
It addition, poly-(methyl) acrylate is the concept comprising both polyacrylate and polymethacrylates.
One of applicable form as hydrophilic polymer, can enumerate monomer (after, also referred to as " the hydrophilic monomer ") polymerization making to have above-mentioned hydrophilic base and the polymer that obtains.
Hydrophilic monomer refers to the compound with above-mentioned hydrophilic base and polymerism base.Hydrophilic base as defined above.
There is no particular restriction for the quantity of the hydrophilic base in hydrophilic monomer, shows hydrophilic aspect more preferably from making antibiotic layer, it is preferred to more than 2, more preferably 2～6, more preferably 2～3.
There is no particular restriction for the kind of polymerism base, for instance can enumerate free-radical polymerised base, cationically polymerizable base, anionic polymerisation base etc..As free-radical polymerised base, (methyl) acryloyl group, acrylamido, vinyl, styryl, pi-allyl etc. can be enumerated.As cationically polymerizable base, vinyl ether group, epoxy ethyl, oxetanylmethoxy etc. can be enumerated.Wherein, it is preferable that (methyl) acryloyl group.
It addition, (methyl) acryloyl group is the concept comprising both acryloyl group and methylacryloyl.
There is no particular restriction for the quantity of the polymerism base in hydrophilic monomer, from the aspect that the mechanical strength of the antibiotic layer making gained is more excellent, it is preferred to more than 2, more preferably 2～6, more preferably 2～3.
One of applicable form as hydrophilic monomer, can enumerate the compound shown in below formula (1).
[changing 1]
In formula (1), R1Represent substituent group (substituent group of 1 valency).There is no particular restriction for the kind of substituent group, can enumerate known substituent group, for instance can enumerate: can have heteroatomic alkyl (such as alkyl, aryl), above-mentioned hydrophilic base etc..
R2Represent polymerism base.Polymerism base as defined above.
L1Represent the concatenating group of singly-bound or divalent.There is no particular restriction for the kind of the concatenating group of divalent, for instance can enumerate-O-,-CO-,-NH-,-CO-NH-,-COO-,-O-COO-, alkylidene, arlydene, heteroaryl and their combination.
L2Represent polyoxy alkylidene.Polyoxy alkylidene refers to the group shown in below formula (2).
Formula (2) *-(OR3)m-*
In formula (2), R3Represent alkylidene (such as ethylidene, propylidene).M represents the integer of more than 2, it is preferred to 2～10, more preferably 2～6.It addition, * represents binding site.
N represents the integer of 1～4.
When obtaining hydrophilic polymer, it is possible to and with above-mentioned hydrophilic monomer and other monomers (not comprising the monomer of hydrophilic base).I.e., it is possible to the hydrophilic polymer making hydrophilic monomer and (monomer beyond the hydrophilic monomer) copolymerization of other monomers and obtaining.
There is no particular restriction for the kind of other monomers, as long as have the known monomer of polymerism base, can be suitable for using.Polymerism base as defined above.
Wherein, from the aspect that the mechanical strength making antibiotic layer is more excellent, it is preferable that have the polyfunctional monomer of more than 2 polymerism bases.Polyfunctional monomer plays a role as so-called cross-linking agent.
There is no particular restriction for the quantity of the polymerism base comprised in polyfunctional monomer, the aspect more excellent from the mechanical strength making antibiotic layer and the aspect of operability, it is preferred to 2～10, more preferably 2～6.
As polyfunctional monomer, for instance trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, tetramethylol methane tetraacrylate can be enumerated.
There is no particular restriction for the mixing ratio (quality of the quality of hydrophilic monomer/other monomers) of hydrophilic monomer and other monomers (especially polyfunctional monomer), from the hydrophilic aspect being easily controlled antibiotic layer, it is preferably 0.01～10, more preferably 0.1～10.
Additionally, there is no particular restriction for the content of the above-mentioned hydrophilic polymer in antibiotic layer, from the aspect that the removability made by washing the polluter removed on antibiotic layer is more excellent, relative to antibiotic layer gross mass, it is preferably more than 50 mass %, it is more preferably more than 70 mass %, more preferably more than 90 mass %.
(manufacture method of antibiotic layer)
There is no particular restriction for the manufacture method of antibiotic layer, it is possible to adopts known method.Include, for example: the compositions comprising the 1st above-mentioned antibacterial and the 2nd antibacterial is coated the method forming antibiotic layer on base material；By the method etc. of the assigned position that the antibiotic slice comprising the 1st antibacterial and the 2nd antibacterial additionally made is attached on base material.
Wherein, from being easier to adjust the aspect of the thickness of antibiotic layer, concave-convex surface, preferred: the compositions (solidification compound) comprising above-mentioned hydrophilic monomer and the 1st antibacterial and the 2nd antibacterial is coated on base material assigned position and is formed film, and film is implemented cured, it is consequently formed the method (rubbing method) of antibiotic layer.
Comprise the 1st antibacterial and the 2nd antibacterial in the composition, but other compositions (other monomers above-mentioned, lubricant, solvent (water or organic solvent)) can also be comprised.
It addition, polymerization initiator can be comprised in the composition.By comprising polymerization initiator, so that the polymerization in film more efficiently carries out, form the antibiotic layer of mechanical strength.There is no particular restriction for the kind of polymerization initiator, it is possible to use the kind that the method choice of cured is best, for instance can select thermal polymerization, Photoepolymerizationinitiater initiater.More specifically, can enumerate the aromatic series ketone such as benzophenone, phenyl phosphine oxide, Alpha-hydroxy alkyl phenones based compound (BASFIRGACURE184,127,2959, DAROCUR1173 etc.), phenyl phosphine oxide based compound (MAPO:BASFLUCIRINTPO, BAPO:BASFIRGACURE819) etc..
There is no particular restriction for the content of the polymerization initiator comprised in compositions, relative to gross mass 100 mass parts of hydrophilic monomer and other monomers, it is preferred to 0.1～15 mass parts, more preferably 1～6 mass parts.
There is no particular restriction for the method for coating composition, it is possible to adopts known coating process.
Additionally, the method for cured there is no particular restriction, heat treated or photo-irradiation treatment can be enumerated.
(characteristic of antibiotic layer)
There is no particular restriction for the average thickness of antibiotic layer, from the aspect of mechanical property and antibiotic property, it is preferred to 0.5～20 μm, more preferably 1～10 μm.
It addition, the assay method of the average thickness as antibiotic layer, the sample strip of antibiotic layer is embedded in resin, utilizes microtome to cut out section, utilize scanning electron microscope that the section cut out is observed and measured.Measure the thickness of any 10 positions of antibiotic layer, these thickness are carried out arithmetic average.
There is no particular restriction for the water contact angle on antibiotic layer surface, from the aspect that removability is more excellent, antibiotic property is more excellent making utilization washing etc. remove the polluter on antibiotic layer, it is preferably less than 40 °, more preferably less than 30 °, more preferably less than 25 °.There is no particular restriction for lower limit, and from the aspect of the material behavior used, the situation of more than 5 ° is more.
It addition, in this specification, water contact angle is measured based on the sessile drop method of JISR3257:1999.Measure and use NIC Co., Ltd. LSE-ME1 (software 2winmini).More specifically, use pure water, at room temperature 20 DEG C, on the antibiotic layer surface keeping level, drip drop 2 μ l, and measure the contact angle in the moment of 20 seconds after the drop wise addition.
The < base material > with antibiotic layer
The silver content comprised in the antibiotic layer of per unit area is being set to P (ng/cm2) and the silver ion amount utilizing the following per unit area extracting test determination is set to Q (ng/cm2) time, the base material with antibiotic layer with base material described above and antibiotic layer meets below formula (1) and the relation of formula (2).
Formula (1) 6.0≤P/Q
Formula (2) 15.0≤Q
Hereinafter, first, the assay method of above-mentioned P and Q is described in detail.
Silver content P (the ng/cm comprised in the antibiotic layer of per unit area2) refer to and the silver comprised in antibiotic layer is measured (ng) area (cm divided by the interarea of antibiotic layer2) value of gained.It addition, the area of the interarea of antibiotic layer refers to: the area of the interarea 14a with base material 12 side opposite side of antibiotic layer 14 in Fig. 1.
The value of silver content P is more big, it is meant that silver amount contained in antibiotic layer is more many, as long as the size of silver content P meets the relation of above-mentioned formula (1), then there is no particular restriction, from the aspect that the effect making the present invention is more excellent, it is preferred to 90ng/cm2Above, more preferably 120ng/cm2Above.There is no particular restriction for the upper limit, from the view point of prevent variable color or the embrittlement of film, it is preferred to 10000ng/cm2Below, more preferably 1000ng/cm2Below.
Assay method about silver content P, use is adjusted to the antibiotic layer of prescribed level (area), utilize atomic absorption spectrum (IENA cotrAA700) to measure the silver amount in antibiotic layer, by the silver amount of gained divided by above-mentioned area, obtain silver content P.More specifically, the silver all dissolutions making to comprise in antibiotic layer, use the solution of gained to carry out above-mentioned atomic absorption spectrum, and obtain silver amount according to the standard curve made in advance, by the gained silver amount area divided by antibiotic layer, obtain silver content P.As the method making the silver all dissolutions comprised in antibiotic layer, the wet type ashing usually used as the pre-treatment in inorganic analysis is known is used to process.
Hereinafter, the method extracting test is described in detail.
In extracting test, use 1/500 broth medium specified in JISZ2801:2010 as extracting solution.The temperature of this extracting solution is controlled at 35 ± 1 DEG C, make with the antibiotic layer (example 1: the area of antibiotic layer: 4cm in the base material of antibiotic layer2(2cm × 2cm)) contact 1 hour with extracting solution (liquid measure: 9mL).It addition, as the method making antibiotic layer contact with extracting solution, it is possible to implement the method for the base material of impregnated tape antibiotic layer in extracting solution.
Then, after terminating at 1 hour, reclaim the base material with antibiotic layer from extracting solution, measure the silver ion amount (ng) being extracted in extracting solution.About the mensuration of the silver ion amount in extracting solution, use atomic absorption spectrum (device name IENA cotrAA700) to implement, and obtain silver ion amount according to the standard curve made in advance.
It addition, when measuring silver ion amount, in order to improve the stability of mensuration, it is preferable that as needed in extracting solution adds nitric acid (about 1mL).
Then, by the silver ion amount of gained divided by the contact area of antibiotic layer and extracting solution (when above-mentioned example 1, for 4cm2), calculate the silver ion amount Q (ng/cm of per unit area2).Antibiotic layer refers to, with the contact area of extracting solution, the area that antibiotic layer surface contacts with extracting solution when making antibiotic layer contact with extracting solution, for instance refer to the area of the interarea 14a with base material 12 side opposite side of antibiotic layer 14 in Fig. 1.
The silver ion amount Q of gained represents the silver ion degree from antibiotic layer dissolution (extraction) herein, meets the relation of below formula (2).Formula (2) refers to that Q is 15.0ng/cm2Above.
Formula (2) 15.0≤Q
Wherein, from the aspect that the effect making the present invention is more excellent, it is preferable that meet the relation of formula (3).
Formula (3) 15.0≤Q≤25.0
And then, from the aspect that the effect making the present invention is more excellent, Q is preferably 17.0～24.0ng/cm2, more preferably 19.0～21.0ng/cm2。
At silver ion amount Q less than 15.0ng/cm2Time, the antibiotic property in the short time is poor.
Above-mentioned silver content P and silver ion amount Q meets the relation of below formula (1).Formula (1) refers to that P/Q is more than 6.0.It addition, P/Q is by the P value divided by Q gained.
Formula (1) 6.0≤P/Q
Wherein, from the aspect that the effect making the present invention is more excellent, P/Q is preferably more than 7.0, more preferably more than 10.0.There is no particular restriction for the upper limit, from the aspect that the lasting effect of antibiotic property is saturated, it is preferred to less than 20.0, more preferably less than 15.0.
When P/Q is less than 6, it is impossible to show, in long-time, the antibiotic property specified.
The above-mentioned base material with antibiotic layer can apply to various uses, and can be configured at various device (surface of device).I.e., it is possible to the front panel as each device uses.Surface configuration has the device of this base material with antibiotic layer can obtain the antibiotic property in the short time and long-time interior antibiotic property.
Device as the base material applied with antibiotic layer, for instance radiographic equipment, contact panel etc. can be enumerated.It addition, when being applied to these devices, a part (front panel) for the various devices supporting antibiotic layer can serve as base material.
It addition, above-mentioned antibiotic layer can also use as antibiotic slice himself.Constituting of antibiotic slice is identical with above-mentioned antibiotic layer, it is possible to use antibiotic slice replaces antibiotic layer to implement said extracted test.That is, make above-mentioned regulation extracting solution contact with antibiotic slice, and measure the silver ion amount in extracting solution of being extracted into, by the value of the gained contact area divided by antibiotic slice Yu extracting solution, as long as making the silver ion amount of the per unit area of gained in above-mentioned prescribed limit.
Embodiment
Hereinafter, the present invention will be described in more detail to utilize embodiment, but the present invention is not by the restriction of these embodiments.
(preparation of solidification compound)
By each composition mixing shown below, prepare into solidification compound.
Hydrophilic monomer: MiramerM4004 (TOYOCHEMICALSCO., LTD. system) 76 mass parts
Cross-linking agent: A-DPH (chemical industry Co., Ltd. of Xin Zhong village system) 21 mass parts
Polymerization initiator: IRGACURE (BASF AG's system) 3 mass parts
Solvent composition (1): methanol 15 mass parts
Solvent composition (2): propylene glycol monomethyl ether 35 mass parts
(preparation of antibacterial)
(the 1st antibacterial: comprise the antibacterial of the silver being carried on calcium zinc orthophosphate activated by thallium)
Make calcium hydroxide, zinc oxide and phosphatase reaction, obtain phosphate.It is added to silver nitrate, carries out washing, filter, dry, broken, thus obtain the 1st antibacterial (silver load carriers).The mean diameter of the 1st antibacterial of gained is 1 μm, and silver ion content is equivalent to 3 mass %.
(the 2nd antibacterial: comprise the antibacterial of the silver being carried on zeolite)
Make zeolite contact with silver nitrate aqueous solution, and make in zeolite can ion and the silver ion displacement of ion exchange, thus obtain the 2nd antibacterial.The mean diameter of the 2nd antibacterial of gained is 1.51 μm, and silver ion content is equivalent to 0.5 mass %.
< embodiment and comparative example >
Relative to all solids composition 100 mass parts of the above-mentioned solidification compound prepared, the ratio (mass parts) shown in table 1 is added the 1st antibacterial and the 2nd antibacterial and mixes, and prepares into the solidification compound that antibiotic layer is formed.
The antibiotic layer formation solidification compound of gained is coated POLYCARBONATE SHEET (Asahi Glass CARBOGLASSCFR110C), after making it dry 30 minutes at 60 DEG C, utilize UV to irradiate and make monomer cure, it is consequently formed antibiotic layer, is fabricated to evaluate sample (base material with antibiotic layer).
< evaluates >
Use the embodiment of gained and the evaluation sample of comparative example, carry out following evaluation.Result is concluded and is shown in table 1.
(mensuration of silver content P)
25cm is reached according to the size (area) making antibiotic layer2Mode cut the evaluation sample being fabricated in above-described embodiment and comparative example.Afterwards, the sample of gained is carried out wet type ashing process, and limit uses the standard curve made in advance, and lateral dominance atomic absorption spectrum (IENA cotrAA700) obtains silver content (ng), by the value of the gained area divided by antibiotic layer, obtain silver content P (ng/cm2)。
(mensuration of silver ion amount Q)
4cm is reached according to the size (area) making antibiotic layer2Mode cut the evaluation sample being fabricated in above-described embodiment and comparative example.By the evaluation sample of cutting dipping 1 hour in bacterium solution (in JISZ2801:2010 1/500 broth medium of regulation) 9ml at 35 DEG C.Adding nitric acid 1ml in this bacterium solution, limit uses the standard curve made in advance, and lateral dominance atomic absorption spectrum (IENA cotrAA700) obtains silver ion amount, by the value of the gained area divided by antibiotic layer, obtains silver ion amount Q (ng/cm2)。
(antibiotic property (initial stage antibiotic property))
About antibiotic property evaluation, according to the evaluation methodology recorded in JISZ2801:2010,24 hours times of contact in bacterium solution were changed to 1 hour, implement test.Measure the bacterium number (individual/cm after each test2), evaluate according to following benchmark.Strain uses coliform.In order to validation test is set up, the POLYCARBONATE SHEET (Asahi Glass CARBOGLASSCFR110C) being not provided with antibiotic layer is evaluated simultaneously, confirms the bacterium number (individual/cm after contacting 1 hour2) it is 6.2 × 102(individual/cm2) more than.In actual use, it is preferable that " A " or " B ".
" A ": bacterium number is less than 1/cm2
" B ": bacterium number is 1/cm2Less than 10/cm2
" C ": bacterium number is 10/cm2Above
(the antibiotic property evaluation after endurancing)
In order to whether the evaluation sample made according to above-mentioned steps can be obtained Long-term Anti bacterium property it is evaluated, implements following endurancing.Generally, it is configured at the antibiotic layer of component surface once attachment dirt, most cases water wiping, causes that silver-colored dissolution now is in water, become the main cause that antibiotic property reduces.As can be seen here, if the antibiotic property of excellence also can be shown after following abrasion test, then also can long term maintenance antibiotic property when using antibiotic layer.
About endurancing, when the antibiotic layer surface imposed load 500g to the evaluation sample (base material with antibiotic layer) being fabricated to according to above-mentioned steps with after wet cloth friction 36000 times, utilize the method described in above-mentioned (antibiotic property) to implement the evaluation experimental of antibiotic property, and evaluated according to following benchmark.Strain uses coliform.Wet cloth uses the mylar (goods name ANTICON) being soaked with pure water.In actual use, it is preferable that " A " or " B ".
" A ": bacterium number is less than 1/cm2
" B ": bacterium number is 1/cm2Less than 10/cm2
" C ": bacterium number is 10/cm2Above
" silver containing ratio (wt%) " in table 1 refers to the silver that comprises in the antibiotic layer ratio (quality %) relative to antibiotic layer gross mass.
[table 1]
As shown in table 1, it is possible to confirm: the base material with antibiotic layer of present invention antibiotic property at short notice is excellent, and antibiotic property is also excellent for a long time.Especially confirm: when P/Q is more than 10 as shown in embodiment 2～4, obtain more excellent effect.
On the other hand, in the comparative example 1～8 being unsatisfactory for regulation important document, do not obtain required effect.
Symbol description
10 base materials with antibiotic layer
12 base materials
14 antibiotic layers
Claims (12)
1. the base material with antibiotic layer, it has base material and is configured at least one of antibiotic layer of described substrate surface,
Described antibiotic layer has the 1st antibacterial comprising silver and the 2nd different from described 1st antibacterial, to comprise silver antibacterial,
When the silver content comprised in the described antibiotic layer of per unit area being set to P and the silver ion amount of the per unit area extracting test determination below utilization being set to Q, meet below formula (1) and the relation of formula (2),
Formula (1) 6.0≤P/Q
Formula (2) 15.0≤Q
Wherein, the unit of P is ng/cm2, the unit of Q is ng/cm2,
Additionally, described extraction test is following test: in use JISZ2801:2010,1/500 broth medium of defined is as extracting solution, and the temperature of described extracting solution is controlled at 35 ± 1 DEG C, make described to contact 1 hour with the described antibiotic layer in the base material of antibiotic layer with described extracting solution, measure the silver ion amount being extracted in described extracting solution, by the value of the gained contact area divided by described antibiotic layer Yu described extracting solution, obtain the silver ion amount Q of per unit area.
2. the base material with antibiotic layer according to claim 1, it meets the relation of formula (3),
Formula (3) 15.0≤Q≤25.0.
3. the base material with antibiotic layer according to claim 1 and 2, wherein,
Described 1st antibacterial comprises silver and any one carrier in calcium zinc orthophosphate activated by thallium and calcium phosphate,
Described 2nd antibacterial comprises silver and includes the carrier of zeolite.
4. the base material with antibiotic layer according to any one of claims 1 to 3, wherein, described antibiotic layer comprises the polymer with hydrophilic base.
5. the base material with antibiotic layer according to claim 4, wherein, described hydrophilic base comprises polyoxy alkylidene.
6. a radiographic equipment, it has the base material with antibiotic layer according to any one of Claims 1 to 5 on surface.
7. a contact panel, it has the base material with antibiotic layer according to any one of Claims 1 to 5 on surface.
8. an antibiotic slice, it comprises antibacterial,
Described antibacterial has the 1st antibacterial comprising silver and the 2nd different from described 1st antibacterial, to comprise silver antibacterial,
When the silver content comprised in the described antibiotic slice of per unit area being set to P and the silver ion amount of the per unit area extracting test determination below utilization being set to Q, meet below formula (1) and the relation of formula (2),
Formula (1) 6.0≤P/Q
Formula (2) 15.0≤Q
Wherein, the unit of P is ng/cm2, the unit of Q is ng/cm2,
Additionally, described extraction test is following test: in use JISZ2801:2000,1/500 broth medium of defined is as extracting solution, and the temperature of described extracting solution is controlled at 35 ± 1 DEG C, described antibiotic slice is made to contact 1 hour with described extracting solution, measure the silver ion amount being extracted in described extracting solution, by the value of the gained contact area divided by described antibiotic layer Yu described extracting solution, obtain the silver ion amount of per unit area.
9. antibiotic slice according to claim 8, it meets the relation of formula (3),
Formula (3) 15.0≤Q≤25.0.
10. antibiotic slice according to claim 8 or claim 9, wherein,
Described 1st antibacterial comprises silver and any one carrier in calcium zinc orthophosphate activated by thallium and calcium phosphate,
Described 2nd antibacterial comprises silver and includes the carrier of zeolite.
11. the antibiotic slice according to any one of according to Claim 8～10, it also comprises the polymer with hydrophilic base.
12. antibiotic slice according to claim 11, wherein, described hydrophilic base comprises polyoxy alkylidene.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-069275 | 2014-03-28 | ||
| JP2014069275A JP6092144B2 (en) | 2014-03-28 | 2014-03-28 | Substrate with antibacterial layer, antibacterial sheet, radiation imaging device, touch panel |
| PCT/JP2015/059454 WO2015147201A1 (en) | 2014-03-28 | 2015-03-26 | Substrate provided with antibacterial layer, antibacterial sheet, radiography device, and touch panel |
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| CN105745074A true CN105745074A (en) | 2016-07-06 |
| CN105745074B CN105745074B (en) | 2017-09-19 |
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| CN201580002693.0A Active CN105745074B (en) | 2014-03-28 | 2015-03-26 | Base material, antibiotic slice, radiographic equipment, contact panel with antibiotic layer |
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| Country | Link |
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| JP (1) | JP6092144B2 (en) |
| CN (1) | CN105745074B (en) |
| TW (1) | TW201538319A (en) |
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| JP6590687B2 (en) * | 2015-12-24 | 2019-10-16 | 平岡織染株式会社 | Resin composition for tent structure film material |
| WO2019188353A1 (en) * | 2018-03-29 | 2019-10-03 | 富士フイルム株式会社 | Antibacterial composition, antibacterial film, substrate with antibacterial film |
| JP2023027804A (en) * | 2021-08-18 | 2023-03-03 | 株式会社ダイセル | Antiviral molding and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159741A (en) * | 1994-10-05 | 1997-09-17 | 东陶机器株式会社 | Antibacterial solid, process for producing the same, and method of utilizing the same |
| JPH11314963A (en) * | 1999-03-11 | 1999-11-16 | Toto Ltd | Multifunctional material having antibacterial property |
| US20090123723A1 (en) * | 2007-11-14 | 2009-05-14 | Holger Kliesch | Antimicrobially Modified, Biaxially Oriented Polyester Film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304619A (en) * | 1994-05-11 | 1995-11-21 | Aica Kogyo Co Ltd | Production of antimicrobial polyester decorative sheet |
| JP2002179514A (en) * | 2000-12-11 | 2002-06-26 | Nisshin Steel Co Ltd | Antifungal agent, method of producing the same and antifungal resin composition |
| CN103459512B (en) * | 2011-02-15 | 2016-08-10 | 东洋制罐集团控股株式会社 | Antibacterial resin composition |
| WO2014025040A1 (en) * | 2012-08-09 | 2014-02-13 | 王子ホールディングス株式会社 | Antibacterial transparent film and antibacterial adhesive sheet |
-
2014
- 2014-03-28 JP JP2014069275A patent/JP6092144B2/en active Active
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2015
- 2015-03-26 WO PCT/JP2015/059454 patent/WO2015147201A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159741A (en) * | 1994-10-05 | 1997-09-17 | 东陶机器株式会社 | Antibacterial solid, process for producing the same, and method of utilizing the same |
| JPH11314963A (en) * | 1999-03-11 | 1999-11-16 | Toto Ltd | Multifunctional material having antibacterial property |
| US20090123723A1 (en) * | 2007-11-14 | 2009-05-14 | Holger Kliesch | Antimicrobially Modified, Biaxially Oriented Polyester Film |
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| Publication number | Publication date |
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| JP2015189152A (en) | 2015-11-02 |
| WO2015147201A1 (en) | 2015-10-01 |
| JP6092144B2 (en) | 2017-03-08 |
| CN105745074B (en) | 2017-09-19 |
| TW201538319A (en) | 2015-10-16 |
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