CN105745074B - Base material, antibiotic slice, radiographic equipment, contact panel with antibiotic layer - Google Patents

Base material, antibiotic slice, radiographic equipment, contact panel with antibiotic layer Download PDF

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Publication number
CN105745074B
CN105745074B CN201580002693.0A CN201580002693A CN105745074B CN 105745074 B CN105745074 B CN 105745074B CN 201580002693 A CN201580002693 A CN 201580002693A CN 105745074 B CN105745074 B CN 105745074B
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silver
antibiotic layer
antibiotic
antiseptic
formula
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CN105745074A (en
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柴田路宏
永崎秀雄
成行书史
白土节子
大谷薰明
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Fujifilm Corp
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Fujifilm Corp
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Theoretical Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention provides the base material with antibiotic layer, antibiotic slice, radiographic equipment, the contact panel for possessing the antibiotic layer that can be shown antibacterial action in a short time and can maintain antibiotic property for a long time.The base material with antibiotic layer of the present invention has base material and is configured at least one of antibiotic layer of substrate surface, antibiotic layer has the 1st antiseptic comprising silver and the 2nd antiseptic that is different from the 1st antiseptic, including silver, silver content included in the antibiotic layer by per unit area be set to P and will using extract test the silver ion amount of per unit area that determines and be set to Q when, meet the relation of following formula (1) and formula (2).15.0≤the Q of (1) 6.0≤P/Q formulas of formula (2).

Description

Base material, antibiotic slice, radiographic equipment, contact panel with antibiotic layer
Technical field
The present invention relates to the base material with antibiotic layer, antibiotic slice, radiographic equipment and contact panel.
Background technology
Most cases can be implemented to process and assign various functions according to purpose to the surface of various product components.Wherein, In recent years, the technology for setting antibiotic layer in substrate surface is attracted attention.
For example, continuously contacting multiple patients mostly in medical treatment device used in medical scene.Further, since touch surface The surface of plate can directly be touched by uncertain many operators with finger, if therefore bacterium etc. exist in its surface colonization The risk of infectious disease.Therefore, by setting antibiotic layer on the surface of the various devices such as medical treatment device, bacterium increasing can be reduced Grow, disease infection risk.
As such a technology, for example, resist Patent Document 1 discloses the silver system for making silver complex be carried on silica-gel carrier Microbial inoculum, the slow release anti-biotic material for including silica gel and organic bond.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 09-131389 publications
The content of the invention
Invent problem to be solved
On the other hand, in recent years, in order to further improve various devices (such as medical treatment device, contact panel) using frequency Rate, it is desirable to antibacterial action is shown in shorter time.
Furthermore it is required that antibacterial action can be maintained for longer periods.
I.e., it is desirable to antibacterial action can be shown in a short time and the antibiotic layer of antibiotic property can be maintained for a long time.
The present inventor etc. is studied the base material with antibiotic layer described in patent document 1, as a result finds it not Above-mentioned important document can fully be met, it is necessary to further improvement.
It is an object of the invention to：In view of above-mentioned actual conditions and antibacterial action can be shown in a short time by providing to possess And the base material with antibiotic layer of the antibiotic layer of antibiotic property can be maintained for a long time.
In addition, being taken the photograph the present invention also aims to the radioactive ray for providing antibiotic slice and possessing the above-mentioned base material with antibiotic layer Image device and contact panel.
Means for solving the problems
The present inventor etc. has made intensive studies to above-mentioned problem, as a result finds to solve by following composition State problem.
(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 antiseptic comprising silver and the 2nd antiseptic that is different from above-mentioned 1st antiseptic, including silver,
Silver content included in the antibiotic layer by per unit area is set to P and will extract experiment survey using described later When the silver ion amount of fixed per unit area is set to Q, the relation of following formula (1) and formula (2) is met.
6.0≤the P/Q of formula (1)
15.0≤the Q of formula (2)
Wherein, P unit is ng/cm2, Q unit is ng/cm2。
(2) base material with antibiotic layer according to (1), it meets the relation of formula (3).
15.0≤Q≤25.0 of formula (3)
(3) base material with antibiotic layer according to (1) or (2), wherein,
Any one of 1st antiseptic comprising silver and in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antiseptic includes silver and the carrier including zeolite.
(4) base material with antibiotic layer according to any one of (1)~(3), wherein, antibiotic layer, which is included, has hydrophily The polymer of base.
(5) base material with antibiotic layer according to (4), wherein, hydrophily base includes polyoxy alkylidene.
(6) a kind of radiographic equipment, it has the base with antibiotic layer any one of (1)~(5) on surface Material.
(7) a kind of contact panel, it has the base material with antibiotic layer any one of (1)~(5) on surface.
(8) a kind of antibiotic slice, it includes antiseptic,
Antiseptic has the 1st antiseptic comprising silver and the 2nd antiseptic that is different from the 1st antiseptic, including silver,
Silver content included in the antibiotic slice by per unit area is set to P and will extract experiment survey using described later When the silver ion amount of fixed per unit area is set to Q, the relation of following formula (1) and formula (2) is met.
6.0≤the P/Q of formula (1)
15.0≤the Q of formula (2)
Wherein, P unit is ng/cm2, Q unit is ng/cm2。
(9) antibiotic slice according to (8), it meets the relation of formula (3).
15.0≤Q≤25.0 of formula (3)
(10) antibiotic slice according to (8) or (9), wherein,
Any one of 1st antiseptic comprising silver and in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antiseptic includes silver and the carrier including zeolite.
(11) antibiotic slice according to any one of (8)~(10), it also includes the polymer with hydrophily base.
(12) antibiotic slice according to (11), wherein, hydrophily base includes polyoxy alkylidene.
Invention effect
Antibacterial action is shown in a short time and antibiotic property can be maintained for a long time according to the present invention it is possible to provide and possess Antibiotic layer the base material with antibiotic layer.
In addition, it is also possible according to the present invention to provide antibiotic slice and possessing the radiography of the above-mentioned base material with antibiotic layer Device and contact panel.
Brief description of the drawings
Fig. 1 is the sectional view of an embodiment of the base material with antibiotic layer of the present invention.
Embodiment
Hereinafter, the base material with antibiotic layer, antibiotic slice, radiographic equipment and the contact panel of the present invention are said It is bright.
In addition, the number range for using "~" to represent in this specification refers to that the front and rear described numerical value comprising "~" is made For lower limit and the scope of higher limit.
One of characteristic point as the present invention, can enumerate using 2 kinds of antiseptics comprising silver and control to come from antibiotic layer Silver amount stripping quantity this point.Particular, it is found that：After the silver content P for being included the antibiotic layer of per unit area and utilization The silver ion amount Q for the per unit area that the extraction experiment stated is determined is adjusted to defined scope, can obtain required effect.
In addition, as the more excellent scheme of the present invention, the 1st antiseptic as described later can be enumerated and include silver and be selected from The scheme of the carrier of any one and the 2nd antiseptic comprising silver and including zeolite in calcium zinc orthophosphate activated by thallium and calcium phosphate.It has also been found that, In this case, from a part for the silver ion of the 1st antiseptic dissolution be again maintained in the 2nd antiseptic for the time being in porous In carrier, after the dissolution of silver ion from the 1st antiseptic terminates, be held in the porous carrier of the 2nd antiseptic silver from Son carries out dissolution, is achieved in silver ion and for longer periods continues dissolution.
Hereinafter, the base material with antibiotic layer of the present invention is described in detail first.
Fig. 1 is the sectional view of an embodiment of the base material with antibiotic layer of the present invention.As shown in figure 1, with antibiotic layer Base material 10 there is base material 12 and the antibiotic layer 14 that is configured on base material 12.In addition, antibiotic layer 14 can also be configured at base material 12 Surface at least a portion.
Hereinafter, each component is described in detail.
＜ base materials ＞
Base material plays the effect of support antibiotic layer, and there is no particular restriction for its species.In addition, as described later, base material can be with Constitute a part (such as front panel) for various devices.
There is no particular restriction for the shape of base material, can enumerate tabular, membranaceous, sheet, tubulose, threadiness, particle shape etc..This Outside, the substrate surface for configuring antibiotic layer described later can be tabular surface or concave surface, can also be convex surface.
There is no particular restriction for the material of composition base material, such as can enumerate metal, glass, ceramics, plastics (resin).Its In, from the aspect of operability, preferably plastics.In other words, preferred resin base material.
＜ antibiotic layers ＞
Antibiotic layer is to be configured at least a portion of substrate surface and the layer with antibacterial action.
Antibiotic layer at least have the 1st antiseptic (after, be also referred to as " the 1st antiseptic ") comprising silver and with the 1st antibacterial Agent is different, the 2nd antiseptic comprising silver (after, be also referred to as " the 2nd antiseptic ").That is, at least there are 2 kinds in antibiotic layer Silver-containing antibacterial agent (after, also it is referred to as " silver-series antibacterial agent ").
As the 1st antiseptic and the 2nd antiseptic, as long as comprising silver-colored (silver atoms), there is no particular restriction for its species.This Outside, also there is no particular restriction for silver-colored form, and the form such as with argent, silver ion, silver salt (including silver complex) includes silver. In addition, in this manual, silver complex is included in the range of silver salt.
In addition, as silver salt, such as can enumerate：Silver acetate, acetopyruvic acid silver, silver azide, silver acetylide, silver arsenate, Silver benzoate, fluorine silver hydride, silver bromate, silver bromide, silver carbonate, silver chlorate, silver chlorate, siliver chromate, silver citrate, silver cyanate, Silver cyanide, (cis, cis-1,5- cyclo-octadiene) -1,1,1,5,5,5- hexafluoroacetylacetonate ketone acid silver, diethyl-dithio ammonia Base silver formate, silver fluoride (I), silver fluoride (II), the fluoro- 4,6- acetyl caproyls of 7,7- dimethyl -1,1,1,2,2,3,3- seven 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, perfluor third Sour silver, silver permanganate, perrhenic acid silver, silver orthophosphate, silver picrate monohydrate, silver propionate, silver selenate, silver selenide, silver selenite, Flamazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, the tetraiodo close silver-colored (the テ ト ラ ヨ ー De of curium acid System キ ュ リ ウ ム Suan Silver), four wolframic acid silver, silver thiocyanate, p-methyl benzenesulfonic acid silver, silver trifluoromethanesulfonate, silver trifluoroacetate and vanadic acid Silver etc..
In addition, as one of silver complex, histidine silver complex, methionine silver complex, cysteine can be enumerated Silver complex, aspartic acid silver complex, 2-pyrrolidone-5-carboxylic acid's silver complex, oxo-tetrahydrofuran carboxylic acid silver complex or imidazoles Silver complex etc..
As the 1st antiseptic and the 2nd antiseptic, the antiseptic of the organic system such as can enumerate above-mentioned silver salt and comprising rear The antiseptic of the inorganic system for the carrier stated, there is no particular restriction for its species.
Wherein, from can show in a short time antibacterial action, and/or can maintain for a long time antibiotic property in terms of (with Afterwards, also it is referred to as " aspect for making the effect of the present invention more excellent ") set out, the 1st antiseptic and the 2nd antiseptic are preferably comprising load Body and the silver-colored silver-colored load carriers being carried on carrier.
There is no particular restriction for the species of carrier, can enumerate：Calcium zinc orthophosphate activated by thallium, calcium phosphate, basic zirconium phosphate, aluminum phosphate, calcium silicates, work Property charcoal, activated alumina, silica gel, zeolite, hydroxyapatite, titanium phosphate, potassium titanate, oxidizing aqueous bismuth, oxidizing aqueous zirconium, neatly Stone etc..In addition, as zeolite, such as can enumerate：The natural zeolites such as chabasie, modenite, erionite, clinoptilolite；A types boil The synthetic zeolites such as stone, X-type zeolite, y-type zeolite.
There is no particular restriction for the average grain diameter of above-mentioned silver-colored load carriers, from make the present invention effect it is more excellent in terms of go out Hair, more preferably preferably 0.1~10 μm, 0.1~2 μm.In addition, above-mentioned average grain diameter is：Utilize measurement microscope at least 10 The diameter of individual arbitrary silver-colored load carriers simultaneously carries out these diameters obtained by arithmetic average to be worth.
In addition, as set forth above, it is possible to including silver with any form in silver ion, argent and silver salt.
It is used as the suitable form of the 2nd antiseptic, it is preferable to use porous body (such as zeolite, basic zirconium phosphate, aluminum phosphate, silicic acid Calcium) it is used as the silver-colored load carriers of carrier.
In addition, as the most suitable form of the 1st antiseptic and the 2nd antiseptic, from making the more excellent side of the effect of the present invention Face is set out, and the 1st antiseptic is included silver and any one in calcium zinc orthophosphate activated by thallium and calcium phosphate and the 2nd antiseptic bag Argentiferous and the carrier including zeolite.In other words, the 1st antiseptic be comprising any one in calcium zinc orthophosphate activated by thallium and calcium phosphate, With the silver-colored silver-colored supported catalyst for being carried on the carrier, the 2nd antiseptic is to include the carrier of zeolite and be carried on the carrier Silver-colored silver-colored supported catalyst.
There is no particular restriction for silver-colored content in 1st antiseptic and the 2nd antiseptic, for example, in above-mentioned silver-colored load carriers In the case of, silver-colored content is preferably 0.1~30 mass %, more preferably 0.3~10 matter relative to silver-colored load carriers gross mass Measure %.
There is no particular restriction for the total content of above-mentioned 1st antiseptic and above-mentioned 2nd antiseptic in antibiotic layer, from making the present invention The more excellent aspect of effect set out, preferably so that silver reaches 0.0001~1 mass % relative to the content of antibiotic layer gross mass The mode of (preferably 0.001~0.1 mass %) makes antibiotic layer contain the 1st antiseptic and the 2nd antiseptic.
In addition, the silver amount in antibiotic layer refers to the silver-colored total amount in silver and the 2nd antiseptic in the 1st antiseptic.
In addition, there is no particular restriction for the content of the 1st antiseptic (or the 2nd antiseptic) in antibiotic layer, from making antibiotic layer Mechanical strength is more excellent and the more excellent aspect of effect of the present invention is set out, and relative to antibiotic layer gross mass, is preferably 0.001~10 mass %, more preferably 0.01~5 mass %, more preferably 0.01~3 mass %, particularly preferably 0.01~1 mass %.
The composition beyond above-mentioned the 1st antiseptic and the 2nd antiseptic can be included in antibiotic layer.
For example, in antibiotic layer can include with hydrophily base polymer (after, be also referred to as " hydrophilic polymer Thing ").By including hydrophilic polymer in antibiotic layer, so as to make antibiotic layer show more preferably hydrophily, and can It is easier to remove the polluter being attached on antibiotic layer by using the washing of water etc..
There is no particular restriction for the species of hydrophily base, for example, can enumerate：Polyoxy alkylidene (such as polyoxyethylene, polyoxy Propylidene, oxygen ethylidene and oxygen propylidene carry out block or the polyoxy alkylidene being randomly combined into), amino, carboxyl, carboxyl Alkali metal salt, hydroxyl, alkoxy, amide groups, carbamoyl, sulfoamido, sulfamoyl, sulfonic group, sulfonic alkali gold Belong to salt etc..Wherein, from making the more excellent aspect of effect of the present invention, preferably polyoxy alkylidene.
There is no particular restriction for the structure of the main chain of hydrophilic polymer, for example, can enumerate polyurethanes, poly- (methyl) Acrylate, polystyrene, polyester, polyamide, polyimides, polyureas etc..
In addition, poly- (methyl) acrylate is the concept for including both polyacrylate and polymethacrylates.
One of suitable form as hydrophilic polymer, can enumerate make with above-mentioned hydrophily base monomer (after, Referred to as " hydrophilic monomer ") polymer obtained by polymerization.
Hydrophilic monomer refers to the compound with above-mentioned hydrophily base and polymerism base.Hydrophily base is as defined above institute State.
There is no particular restriction for the quantity of hydrophily base in hydrophilic monomer, more preferably hydrophilic from antibiotic layer is shown Aspect is set out, preferably more than 2, more preferably 2~6, more preferably 2~3.
There is no particular restriction for the species of polymerism base, for example, can enumerate free-radical polymerised base, cationically polymerizable base, the moon Photopolymerizable base etc..As free-radical polymerised base, (methyl) acryloyl group, acrylamido, vinyl, benzene second can be enumerated Alkenyl, pi-allyl etc..As cationically polymerizable base, vinyl ether group, epoxy ethyl, oxetanylmethoxy etc. can be enumerated.Wherein, It is preferred that (methyl) acryloyl group.
In addition, (methyl) acryloyl group is the concept for including both acryloyl group and methylacryloyl.
There is no particular restriction for the quantity of polymerism base in hydrophilic monomer, from make gained antibiotic layer mechanical strength more Excellent aspect is set out, preferably more than 2, more preferably 2~6, more preferably 2~3.
One of suitable form as hydrophilic monomer, can enumerate the compound shown in following formula (1).
【Change 1】
In formula (1), R1Represent substituent (substituent of 1 valency).There is no particular restriction for the species of substituent, can enumerate known Substituent, can for example enumerate：Can having heteroatomic alkyl (such as alkyl, aryl), above-mentioned hydrophily base.
R2Represent polymerism base.Polymerism base is as defined above.
L1Represent the concatenating group of singly-bound or divalent.There is no particular restriction for the species of the concatenating group of divalent, can for example enumerate- O- ,-CO- ,-NH- ,-CO-NH- ,-COO- ,-O-COO-, alkylidene, arlydene, heteroaryl and they Combination.
L2Represent polyoxy alkylidene.Polyoxy alkylidene refers to the group shown in following formula (2).
Formula (2) *-(OR3)m- *
In formula (2), R3Represent alkylidene (such as ethylidene, propylidene).M represents more than 2 integer, preferably 2~10, More preferably 2~6.In addition, * represents binding site.
N represents 1~4 integer.
When obtaining hydrophilic polymer, above-mentioned hydrophilic monomer can be used together and other monomers (do not include hydrophily base Monomer).I.e., it is possible to using make hydrophilic monomer with it is hydrophilic obtained by other monomers (monomer beyond hydrophilic monomer) copolymerization Property polymer.
There is no particular restriction for the species of other monomers, as long as the known monomer with polymerism base, you can suitably make With.Polymerism base is as defined above.
Wherein, it is preferably many with more than 2 polymerism bases from making the more excellent aspect of the mechanical strength of antibiotic layer Functional monomer.Polyfunctional monomer plays a role as so-called crosslinking agent.
There is no particular restriction for the quantity of polymerism base included in polyfunctional monomer, from making the mechanical strength of antibiotic layer more Excellent aspect and the aspect of operability are set out, preferably 2~10, more preferably 2~6.
As polyfunctional monomer, for example, it can enumerate trimethylolpropane trimethacrylate, tetramethylol methane tetrapropylene acid Ester, dipentaerythritol acrylate, tetramethylol methane tetraacrylate.
Hydrophilic monomer and the mixing ratio (quality of hydrophilic monomer/other lists of other monomers (especially polyfunctional monomer) The quality of body) there is no particular restriction, from the hydrophilic aspect for being easily controlled antibiotic layer, preferably 0.01~10, it is more excellent Elect 0.1~10 as.
In addition, there is no particular restriction for the content of above-mentioned hydrophilic polymer in antibiotic layer, from make by wash remove it is anti- The more excellent aspect of removability of polluter on bacterium layer is set out, relative to antibiotic layer gross mass, preferably 50 mass % with On, 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, can be using known method.It can such as enumerate：It will include above-mentioned The 1st antiseptic and the composition of the 2nd antiseptic be coated on the method for forming antibiotic layer on base material；By including for making in addition The antibiotic slice of 1st antiseptic and the 2nd antiseptic is attached at method of assigned position on base material etc..
Wherein, from thickness, the concave-convex surface aspect for being easier adjustment antibiotic layer, preferably：Above-mentioned parent will be included The composition (solidification compound) of aqueous monomers and the 1st antiseptic and the 2nd antiseptic be coated on the assigned position on base material and Film is formed, and curing process is implemented to film, the method (rubbing method) of antibiotic layer is consequently formed.
The 1st antiseptic and the 2nd antiseptic are included in the composition, but can also include other compositions (other above-mentioned lists Body, lubricant, solvent (water or organic solvent)).
In addition, polymerization initiator can be included in the composition.By comprising polymerization initiator, so that poly- in film Conjunction is more efficiently carried out, and forms the antibiotic layer of mechanical strength.There is no particular restriction for the species of polymerization initiator, it is possible to use The optimal species of the method choice of curing process, for example, can select thermal polymerization, Photoepolymerizationinitiater initiater.It is more specific and Speech, can enumerate the aromatic series such as benzophenone, phenyl phosphine oxide ketone, Alpha-hydroxy alkyl phenones based compound (BASF IRGACURE184,127,2959, DAROCUR1173 etc.), phenyl phosphine oxide based compound (MAPO：BASF LUCIRIN TPO、 BAPO：BASF IRGACURE 819) etc..
There is no particular restriction for the content of polymerization initiator included in composition, relative to hydrophilic monomer and other lists The mass parts of gross mass 100 of body, more preferably preferably 0.1~15 mass parts, 1~6 mass parts.
There is no particular restriction for the method for coating composition, can be using known coating method.
In addition, there is no particular restriction for the method for curing process, heating or photo-irradiation treatment can be enumerated.
(characteristic of antibiotic layer)
There is no particular restriction for the average thickness of antibiotic layer, from mechanical property and antibiotic property aspect, preferably 0.5~ 20 μm, more preferably 1~10 μm.
In addition, the assay method of the average thickness as antibiotic layer, the sample strip of antibiotic layer is embedded in resin, utilize Slicer cuts out section, and the section cut out is observed and determined using SEM.Determine any of antibiotic layer These thickness are carried out arithmetic average by the thickness of 10 positions.
There is no particular restriction for the water contact angle of antibacterial layer surface, from make using washing etc. remove antibiotic layer on polluter The aspect that removability is more excellent, antibiotic property is more excellent set out, preferably less than 40 °, more preferably less than 30 °, further it is excellent Elect less than 25 ° as.There is no particular restriction for lower limit, and from used material property aspect, more than 5 ° of situation is more.
In addition, in this specification, water contact angle is based on JIS R 3257：1999 sessile drop method is measured.Measure makes With NIC Co. Ltd. systems LSE-ME1 (software 2win mini).More specifically, using pure water, in holding at 20 DEG C of room temperature In the antibacterial layer surface of level be added dropwise the μ l of drop 2, and determine after the drop wise addition 20 seconds at the time of contact angle.
Base material ＞s of the ＜ with antibiotic layer
Silver content included in the antibiotic layer by per unit area is set to P (ng/cm2) and will be carried using following The silver ion amount of the per unit area of experiment measure is taken to be set to Q (ng/cm2) when, with base material and antibiotic layer described above Base material with antibiotic layer meets the relation of following formula (1) and formula (2).
6.0≤the P/Q of formula (1)
15.0≤the Q of formula (2)
Hereinafter, first, above-mentioned P and Q assay method is described in detail.
Silver content P (ng/cm included in the antibiotic layer of per unit area2) refer to the silver amount included in antibiotic layer (ng) divided by antibiotic layer interarea area (cm2) obtained by value.In addition, the area of the interarea of antibiotic layer refers to：Antibacterial in Fig. 1 The area with the interarea 14a of the side opposite side of base material 12 of layer 14.
Silver content P value is bigger, it is meant that contained silver amount is more in antibiotic layer, as long as silver content P size is met The relation of formula (1) is stated, then there is no particular restriction, from making the more excellent aspect of effect of the present invention, preferably 90ng/cm2 More than, more preferably 120ng/cm2More than.There is no particular restriction for the upper limit, excellent from the viewpoint of the discoloration or embrittlement for preventing film Elect 10000ng/cm as2Hereinafter, more preferably 1000ng/cm2Below.
On silver content P assay method, using the antibiotic layer for being adjusted to prescribed level (area), atomic absorption light is utilized The silver amount in (IENA cotrAA700) measure antibiotic layer is composed, by the silver amount of gained divided by above-mentioned area, silver content P is obtained.More Specifically, the whole dissolutions of the silver included in antibiotic layer are made, the solution obtained by use carries out above-mentioned atomic absorption spectrum, and root Silver-colored amount is obtained according to the good standard curve of pre-production, by gained silver amount divided by the area of antibiotic layer, silver content P is obtained.As making The method of the whole dissolutions of silver included in antibiotic layer, using usually as the wet type ash known to the pre-treatment in inorganic analysis Change is handled.
Hereinafter, the method for extracting experiment is described in detail.
In experiment is extracted, JIS Z 2801 are used：1/500 broth medium is used as extraction specified in 2010 Liquid.By the temperature control of the extract solution at 35 ± 1 DEG C, make the antibiotic layer (example 1 in the base material with antibiotic layer：The area of antibiotic layer： 4cm2(2cm × 2cm)) and extract solution (liquid measure：9mL) contact 1 hour.In addition, being used as the side for making antibiotic layer be contacted with extract solution Method, it is possible to implement the method for the base material of impregnated tape antibiotic layer in extract solution.
Then, after 1 hour terminates, the base material with antibiotic layer is reclaimed from extract solution, measure is extracted into extract solution Silver ion amount (ng).On the measure of the silver ion amount in extract solution, atomic absorption spectrum (device name IENA systems are used CotrAA700) to implement, and silver ion amount is obtained according to the good standard curve of pre-production.
In addition, when determining silver ion amount, in order to improve the stability of measure, preferably being added as needed in extract solution Nitric acid (about 1mL).
Then, by the silver ion amount divided by antibiotic layer of gained and the contact area of extract solution (in the case of above-mentioned example 1, For 4cm2), calculate the silver ion amount Q (ng/cm of per unit area2).The contact area of antibiotic layer and extract solution refers to make antibacterial The layer area that antibacterial layer surface is contacted with extract solution when being contacted with extract solution, for example refer to antibiotic layer 14 in Fig. 1 with base material 12 The interarea 14a of side opposite side area.
The silver ion amount Q of gained represents that silver ion, from the degree of antibiotic layer dissolution (extraction), meets following formula (2) herein Relation.Formula (2) refers to that Q is 15.0ng/cm2More than.
15.0≤the Q of formula (2)
Wherein, from making the more excellent aspect of the effect of the present invention, the relation of formula (3) is preferably met.
15.0≤Q≤25.0 of formula (3)
And then, from making the more excellent aspect of the effect of the present invention, Q is preferably 17.0~24.0ng/cm2, more preferably For 19.0~21.0ng/cm2。
It is less than 15.0ng/cm in silver ion amount Q2When, the antibiotic property in the short time is poor.
Above-mentioned silver content P and silver ion amount Q meets the relation of following formula (1).Formula (1) refers to that P/Q is more than 6.0. In addition, P/Q is by the value obtained by P divided by Q.
6.0≤the P/Q of formula (1)
Wherein, from making the more excellent aspect of effect of the present invention, P/Q is preferably more than 7.0, more preferably 10.0 with On.There is no particular restriction for the upper limit, from the lasting effect saturation aspect of antibiotic property, and preferably less than 20.0, more preferably Less than 15.0.
In the case where P/Q is less than 6, it is impossible to antibiotic property as defined in showing in a long time.
The above-mentioned base material with antibiotic layer can apply to various uses, and can be configured at the various devices (table of device Face).I.e., it is possible to be used as the front panel of each device.The device that surface configuration has the base material with antibiotic layer can be obtained The antibiotic property in antibiotic property and long-time in short time.
As the device of base material of the application with antibiotic layer, such as can enumerate radiographic equipment, contact panel.Separately Outside, in the case of applied to these devices, base material can be served as by supporting a part (front panel) for the various devices of antibiotic layer.
In addition, above-mentioned antibiotic layer its own can also be used as antibiotic slice.The composition of antibiotic slice and above-mentioned antibacterial Layer is identical, and antibiotic slice can also be used to replace antibiotic layer to implement said extracted experiment.That is, above-mentioned regulation extract solution is made with resisting Bacterium piece is contacted, and determines the silver ion amount being extracted into extract solution, the contact by the value divided by antibiotic slice of gained with extract solution Area, as long as making the silver ion amount of the per unit area of gained in above-mentioned prescribed limit.
Embodiment
Hereinafter, using embodiment, the present invention will be described in more detail, but the present invention is not limited by these embodiments It is fixed.
(preparation of solidification compound)
Each composition as shown below is mixed, solidification compound is prepared into.
Hydrophilic monomer：Miramer M4004 (TOYO CHEMICALS CO., LTD. system) 76 mass parts
Crosslinking agent：A-DPH (Xin Zhong villages chemical industry Co. Ltd. system) 21 mass parts
Polymerization initiator：IRGACURE (BASF AG's system) 3 mass parts
Solvent composition (1)：The mass parts of methanol 15
Solvent composition (2)：The mass parts of propylene glycol monomethyl ether 35
(preparation of antiseptic)
(the 1st antiseptic：Include the silver-colored antiseptic for being carried on calcium zinc orthophosphate activated by thallium)
Make calcium hydroxide, zinc oxide and phosphatase reaction, obtain phosphate.Silver nitrate is added thereto, is washed, mistake Filter, it is dry, broken, thus obtain the 1st antiseptic (silver-colored load carriers).The average grain diameter of 1st antiseptic of gained is 1 μm, silver Ion concentration is equivalent to 3 mass %.
(the 2nd antiseptic：Include the silver-colored antiseptic for being carried on zeolite)
Zeolite is contacted with silver nitrate aqueous solution, and the ion exchangeable ion in zeolite is replaced with silver ion, Thus the 2nd antiseptic is obtained.The average grain diameter of 2nd antiseptic of gained is 1.51 μm, and silver ion content is equivalent to 0.5 matter Measure %.
＜ embodiments and comparative example ＞
Relative to the mass parts of all solids composition 100 of the above-mentioned solidification compound prepared, according to the ratio shown in table 1 Example (mass parts) is added the 1st antiseptic and the 2nd antiseptic and mixed, and is prepared into the curability combination of antibiotic layer formation Thing.
The antibiotic layer formation of gained is coated on POLYCARBONATE SHEET (Asahi Glass CARBOGLASS with solidification compound CFR110C), make it after 60 DEG C are dried 30 minutes, make monomer cure using UV irradiations, be consequently formed antibiotic layer, be fabricated to and comment Valency sample (base material with antibiotic layer).
＜ evaluates ＞
The evaluation sample of embodiment and comparative example obtained by use, has carried out following evaluation.As a result conclude and be shown in table 1.
(silver content P measure)
25cm is reached according to the size (area) of antibiotic layer is made2Mode cut in above-described embodiment and comparative example and be fabricated to Evaluation sample.Afterwards, wet type ashing processing is carried out to the sample of gained, side uses the good standard curve of pre-production, lateral dominance Silver content (ng) is obtained with atomic absorption spectrum (IENA cotrAA700), the value of gained divided by the area of antibiotic layer are obtained Silver content P (ng/cm2)。
(silver ion amount Q measure)
4cm is reached according to the size (area) of antibiotic layer is made2Mode cut in above-described embodiment and comparative example and be fabricated to Evaluation sample.By the evaluation sample of cutting in bacterium solution (JIS Z 2801 at 35 DEG C：1/500 common meat specified in 2010 Soup culture medium) impregnate 1 hour in 9ml.Nitric acid 1ml is added into the bacterium solution, side uses the good standard curve of pre-production, lateral dominance Silver ion amount is obtained with atomic absorption spectrum (IENA cotrAA700), by the value of gained divided by the area of antibiotic layer, silver is obtained Ionic weight Q (ng/cm2)。
(antibiotic property (antibiotic property at initial stage))
On antibiotic property evaluation, according to JIS Z 2801：Evaluation method described in 2010, during by contact in bacterium solution Between be changed within 24 hours 1 hour, implement experiment.Determine bacterium number (individual/cm after each experiment2), enter according to following benchmark Evaluation is gone.Strain uses coliform.In order to which validation test is set up, while the POLYCARBONATE SHEET (rising sun nitre to being not provided with antibiotic layer Son CARBOGLASS CFR110C processed) evaluated, confirm bacterium number (individual/cm after contacting 1 hour2) it is 6.2 × 102(individual/ cm2) more than.In actual use, preferably " 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/cm2More than
(the antibiotic property evaluation after endurancing)
Evaluate, implement in order to which long-term antibiotic property whether can be obtained to the evaluation sample made according to above-mentioned steps Following endurancing.Generally, the antibiotic layer for being configured at component surface once adheres to dirt, and most cases are wiped with water, are led Silver-colored dissolution now is caused into water, the main cause reduced as antibiotic property.As can be seen here, if after following abrasion experiment Excellent antibiotic property can be shown, then can also maintain antibiotic property for a long time when using antibiotic layer.
On endurancing, in the antibacterial of the evaluation sample (base material with antibiotic layer) to being fabricated to according to above-mentioned steps After being rubbed 36000 times with wet cloth in the state of layer surface imposed load 500g, implemented using the method described in above-mentioned (antibiotic property) The evaluation experimental of antibiotic property, and evaluated according to following benchmark.Strain uses coliform.Wet cloth is using being soaked with pure water Mylar (product name ANTICON).In actual use, preferably " 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/cm2More than
" silver-colored containing ratio (wt%) " in table 1 refers to ratio of the silver relative to antibiotic layer gross mass included in antibiotic layer (quality %).
【Table 1】
As shown in table 1, it can confirm that：The antibiotic property of the base material with antibiotic layer of the present invention in a short time is excellent, and Prolonged antibiotic property is also excellent.Especially confirm：In the case where P/Q is more than 10 as shown in embodiment 2~4, obtain To more excellent effect.
On the other hand, in the comparative example 1~8 of regulation important document is unsatisfactory for, required effect is not obtained.
Symbol description
10 base materials with antibiotic layer
12 base materials
14 antibiotic layers

Claims (10)

1. a kind of base material with antibiotic layer, it has base material and is configured at least one of antibiotic layer of the substrate surface,
The antibiotic layer has the 1st antiseptic comprising silver and the 2nd antiseptic that is different from the 1st antiseptic, including silver,
1st antiseptic includes silver and any one carrier in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antiseptic includes silver and the carrier including zeolite,
Silver content included in the antibiotic layer by per unit area is set to P and surveyed being tested using following extraction When the silver ion amount of fixed per unit area is set to Q, the relation of following formula (1) and formula (2) is met,
6.0≤the P/Q of formula (1)
15.0≤the Q of formula (2)
Wherein, P unit is ng/cm2, Q unit is ng/cm2,
In addition, described extract experiment to test as follows：Use JIS Z 2801：The 1/500 ordinary broth training of defined in 2010 Base is supported as extract solution, and by the temperature control of the extract solution at 35 ± 1 DEG C, is made described in the base material with antibiotic layer Antibiotic layer is contacted 1 hour with the extract solution, determines the silver ion amount in the extract solution of being extracted into, by the value of gained divided by The contact area of the antibiotic layer and the extract solution, obtains the silver ion amount Q of per unit area.
2. the base material according to claim 1 with antibiotic layer, it meets the relation of formula (3),
15.0≤Q≤25.0 of formula (3).
3. the base material according to claim 1 or 2 with antibiotic layer, wherein, the antibiotic layer is included with hydrophily base Polymer.
4. the base material according to claim 3 with antibiotic layer, wherein, the hydrophily base includes polyoxy alkylidene.
5. a kind of radiographic equipment, it has the base according to any one of claims 1 to 4 with antibiotic layer on surface Material.
6. a kind of contact panel, it has the base material according to any one of claims 1 to 4 with antibiotic layer on surface.
7. a kind of antibiotic slice, it includes antiseptic,
The antiseptic has the 1st antiseptic comprising silver and the 2nd antiseptic that is different from the 1st antiseptic, including silver,
1st antiseptic includes silver and any one carrier in calcium zinc orthophosphate activated by thallium and calcium phosphate,
2nd antiseptic includes silver and the carrier including zeolite,
Silver content included in the antibiotic slice by per unit area is set to P and surveyed being tested using following extraction When the silver ion amount of fixed per unit area is set to Q, the relation of following formula (1) and formula (2) is met,
6.0≤the P/Q of formula (1)
15.0≤the Q of formula (2)
Wherein, P unit is ng/cm2, Q unit is ng/cm2,
In addition, described extract experiment to test as follows：Use JIS Z 2801：The 1/500 ordinary broth training of defined in 2010 Base is supported as extract solution, and by the temperature control of the extract solution at 35 ± 1 DEG C, the antibiotic slice is contacted with the extract solution 1 hour, the silver ion amount being extracted into the extract solution is determined, by the value of gained divided by the antibiotic slice and the extract solution Contact area, obtain the silver ion amount of per unit area.
8. antibiotic slice according to claim 7, it meets the relation of formula (3),
15.0≤Q≤25.0 of formula (3).
9. the antibiotic slice according to claim 7 or 8, it also includes the polymer with hydrophily base.
10. antibiotic slice according to claim 9, wherein, the hydrophily base includes polyoxy alkylidene.
CN201580002693.0A 2014-03-28 2015-03-26 Base material, antibiotic slice, radiographic equipment, contact panel with antibiotic layer Active CN105745074B (en)

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