CN101564191A - Antibacterial and mildewproofing sheet - Google Patents
Antibacterial and mildewproofing sheet Download PDFInfo
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- CN101564191A CN101564191A CNA2008100923482A CN200810092348A CN101564191A CN 101564191 A CN101564191 A CN 101564191A CN A2008100923482 A CNA2008100923482 A CN A2008100923482A CN 200810092348 A CN200810092348 A CN 200810092348A CN 101564191 A CN101564191 A CN 101564191A
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- allyl isothiocyanate
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention produces an easily producible antibacterial and mildewproofing sheet releasing allyl isothiocyanate over a long period without thermally melting even by heating with a microwave oven, suppressing the releasing quantity of the allyl isothiocyanate when keeping in a refrigerator a freezer, and exhibiting antibacterial and mildewproofing effect releasing a sufficient amount of the allyl isothiocyanate after heating at low cost and with high producing efficiency. The allyl isothiocyanate is mixed with a urethane resin using an isocyanate-based urethane prepolymer having 500-10,000 molecular weight and an antibacterial and mildewproofing layer prepared by regulating the viscosity to take a value of 600 mPa.s to 2,500 mPa.s at any temperature of 40 to 60 DEG C is sandwiched between other layers. Thereby, a laminated sheet in which at least another sheet is an allyl isothiocyanate absorbing film is produced.
Description
Technical field
The present invention relates to use the antibacterial and mildewproofing sheet of allyl isothiocyanate.
Background technology
Known, the allyl isothiocyanate as the main component of scurvy grass, mustard has the antibacterial and mouldproof effect.Contain this allyl isothiocyanate and various antibacterial and mouldproof materials such as the film by slowly its release can being brought into play antibacterial effect, anti-mold effect or sheet thereby studying.
For example in patent documentation 1, put down in writing and allyl isothiocyanate has been contained in the polyurethane resin that is made of multi-functional isocyanates and polyalcohols and the polyurethane resin sheet that obtains.
In addition, put down in writing in patent documentation 2, the volatile medicine that is laminated with the gas permeation layer on the two sides that makes allyl isothiocyanate be contained in the mixture layer of rosin or rosin ester discharges tablet.
[patent documentation 1] Japanese patent laid-open 9-151317 communique
[patent documentation 2] Japan Patent spy opens the 2003-171208 communique
But, usually as patent documentation 1 be documented in when making allyl isothiocyanate be contained in polyurethane resin, if the polyurethane resin of low-molecular-weight isocyanates has been used in utilization, then cause viscosity to decline to a great extent by mixing with allyl isothiocyanate.When desiring to be coated in mixture on the film with so low viscous state, can adopt for example method of intaglio plate coating and so on, but because viscosity is low excessively, following problem can appear: can not guarantee necessary coating weight, perhaps to occur volume when stacked and curling uneven intermembranous, or mixture rises from the viscosity that laminated section spills up to mixture.
In addition, in making mixture the containing ratio of allyl isothiocyanate descend, during with full-bodied state coating, the necessary allyl isothiocyanate in order to keep giving full play to effect needs a large amount of polyurethane resins, therefore causes expensive.
In addition, when using the sheet of the resin sheet that only has one deck to make allyl isothiocyanate be contained in polyurethane resin and get, even also can continue to discharge allyl isothiocyanate, realize also can discharging under the also passable state of antibacterial and mouldproof effect at the allyl isothiocyanate that do not utilize that is in refrigeration, freezing preservation at low-temperature condition.Therefore, with heating such as electric stoves, when the situation after desiring to make it with this heating was brought into play the antibacterial and mouldproof effect, allyl isothiocyanate had but discharged and has been over food for refrigeration, freezing preservations back, exist when needs make its performance antibacterial and mouldproof effect, can not bring into play the situation of necessary effect.
On the other hand, as patent documentation 2 is put down in writing, used the tablet of rosin, because the easy heat fusing of rosin, therefore when being used as the emulsion sheet of feeder, have following problem: in case with food with heating such as electric stoves, then rosin fusion, resin spill from the sheet cross section and are attached on the food.
Summary of the invention
Therefore, the objective of the invention is to, cheap and obtain antibacterial and mildewproofing sheet with high efficiency, it is the antibacterial and mildewproofing sheet that discharges allyl isothiocyanate for a long time, promptly being used in food can heat fusing by heating such as electric stove yet, when refrigeration, the freezing preservation, reduce the burst size of allyl isothiocyanate, discharge the allyl isothiocyanate of abundant amount after the heating, can bring into play the antibacterial and mouldproof effect.
The present invention has solved above-mentioned problem by antibacterial and mildewproofing sheet as described below, the structure of this antibacterial and mildewproofing sheet is sandwiched between other layers for the antibacterial mildew inhibitor layer that is formed by the antibacterial and mouldproof mixture, other at least 1 layer is the allyl isothiocyanate adsorptivity film as PETG system film, described antibacterial and mouldproof mixture for allyl isothiocyanate with to have used number-average molecular weight be more than 500 and the polyurethane resin of 10000 following isocyanate-based carbamate prepolymers mixes and gets, and its viscosity during from arbitrary temperature of 40 ℃ to 60 ℃ is got the value more than the 600mPas and below the 2500mPas.
For molecular weight less than for 500 the isocyanate-based carbamate prepolymer, excess stickiness descends by mixing with allyl isothiocyanate, but mix with allyl isothiocyanate by isocyanate-based carbamate prepolymer with above-mentioned scope molecular weight, can be suppressed to above-mentioned range of viscosities, under the temperature range that allyl isothiocyanate is difficult to volatilize, can obtain the viscosity that is easy on sheet, apply, by this mixture is coated on the film, can be cheap and form the antibacterial and mouldproof layer efficiently.
In addition, other at least 1 layer that contains stacked of this antibacterial and mouldproof layer is allyl isothiocyanate adsorptivity film, and when preserving below normal temperature, the allyl isothiocyanate that discharges from the antibacterial mildew inhibitor layer is suppressed to discharge by the absorption of allyl isothiocyanate adsorptivity film.The allyl isothiocyanate of its absorption can be discharged during heating.Like this, be suppressed at the release in vain when not needing allyl isothiocyanate, when needs antibacterial and mouldproof effect, can discharge allyl isothiocyanate.
The antibacterial and mildewproofing sheet that the present invention relates to because the viscosity when allyl isothiocyanate mixed with carbamate prepolymer is suitable, therefore easily on sheet coating contain the antibiotic layer of allyl isothiocyanate, easy manufacturing.In addition, the resin of mixing is the polyurethane resin after reaction makes it to solidify, and can not cause heat fusing under the common heating condition that carries out food processing, can keep the function as antibacterial and mildewproofing sheet.Therefore, if the antibacterial and mildewproofing sheet that this invention is related to is used for refrigerating at ordinary times, freezing preservation, edible before with the refrigeration of heating such as electric stove, the packing timber or the interior bag agent of frozen food, then when preserving, can suppress the release of allyl isothiocyanate, after heating need the antibacterial and mouldproof effect time can bring into play the antibacterial and mouldproof effect that allyl isothiocyanate produces.
Description of drawings
[Fig. 1] (a) be cut into antibacterial and mouldproof food that the schematic diagram, (b) of circular sheet will (a) moulding with glass stereogram
The schematic diagram, (b) that [Fig. 2] (a) is cut into the sheet of rectangle is with the antibacterial and mouldproof food of (a) moulding stereogram with cup
The specific embodiment
Below, the present invention will be described in detail.
The present invention is an antibacterial and mildewproofing sheet, wherein, by at least 1 layer beyond the formed stacked desurfacing of layer more than 3 layers be the antibacterial mildew inhibitor layer, other at least 1 layer is an allyl isothiocyanate adsorptivity film.At this, superficial layer is for constituting 2 layers on stacked surface.That is, above-mentioned antibacterial mildew inhibitor layer does not expose on the surface, but is sandwiched in other layers.
Above-mentioned antibacterial mildew inhibitor layer is formed by the antibacterial and mouldproof mixture of allyl isothiocyanate and polyurethane resin.By mixing with above-mentioned polyurethane resin, allyl isothiocyanate is fixed, along with the process of time can discharge the allyl isothiocyanate with antibacterial and mouldproof effect.
Above-mentioned polyurethane resin is formed by the isocyanate-based carbamate prepolymer, thereby be one-pack type (the humidity curable one component) urethane polymer that solidifies by contacting with airborne moisture, perhaps the isocyanate-based carbamate prepolymer is mixed with polyalcohols and must any kind of two-component-type urethane polymer.
Above-mentioned isocyanate-based carbamate prepolymer is to use the macromolecule after vulcabond with the NCO more than 2 or polyisocyanates make the carbamic acid polyisocyanate polyaddition, and aromatic diisocyanate and aliphatic diisocyanate are arranged.
As this aromatic diisocyanate, specifically can exemplify as diphenyl-methane 4,4 '-vulcabond, diphenyl-methane 2,4 '-vulcabond, diphenyl-methane 2,2 '-vulcabond or their mixture (MDI), m-phenylene diisocyanate, right-phenylene diisocyanate or their mixture, 4,4 '-diphenyl diisocyanate (NDI), 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI) or their mixture (TDI) etc.In addition, as aliphatic diisocyanate, can exemplify as trimethylene diisocyanate, butylidene vulcabond, hexylidene diisocyanate (HDI), pentylidene vulcabond, 1,2-, 2,3-or 1,3-butylidene vulcabond, 2,4,4-or 2,2,4-trimethyl hexylidene diisocyanate etc.
Wherein, if particularly for having the aromatic amino ester formate prepolymer of aromatic rings, even the blending ratio height of allyl isothiocyanate then, mixture is sclerosis easily also, therefore more preferably.On the other hand, if be aliphatic isocyanates urethane prepolymer, then when the blending ratio of allyl isothiocyanate was high, then mixture was non-sclerous sometimes.
The number-average molecular weight of above-mentioned isocyanate-based carbamate prepolymer need be preferably below 10000 for more than 500.If less than 500, then when mixing, can not obtain applying needed viscosity with allyl isothiocyanate, cause and can not apply.In addition, make it to react, can wait for, still because constantly being difficult to the viscosity maintenance of reaction is certain to reaching the needed viscosity of coating with the hydroxyl of airborne moisture polyol component, need to change applied thickness or change mechanical setting etc., might can not get the sheet of homogeneous.On the other hand, number-average molecular weight need be preferably below 5000 for below 10000.If surpass 10000, then too high might being difficult to of viscosity mixes with allyl isothiocyanate.
As above-mentioned polyalcohols, can exemplify as polyethers is that polyalcohols, polyester are polyalcohols, and they can use separately, also can and use.
Above-mentioned polyethers is that polyalcohols is the macromolecule that has a plurality of hydroxyls in the molecule and get by the ehter bond binding.As this polyethers is polyalcohols, can exemplify as the homopolymers of oxirane, expoxy propane, epoxy butane, oxolane, 3-methyltetrahydrofuran etc. or copolymer etc.
Above-mentioned polyester is that polyalcohols can get by the condensation reaction of polyacid and polyalcohol or the Arrcostab of polyacid and the ester exchange reaction of polyalcohol.As above-mentioned polyacid or its Arrcostab, can exemplify as phthalic acid or their dialkyls such as dimeric dibasic acid, phthalic acid, isophthalic acid, terephthalic acids, perhaps their mixture etc.In addition, as above-mentioned polyalcohol, can exemplify as ethylene glycol, diglycol, propane diols, 1,4-butanediol, 1,6-hexylene glycol, 1,7-heptandiol etc.
In addition, for above-mentioned isocyanate-based carbamate prepolymer, aromatic series is than the aliphatic fast trend that responds, and for above-mentioned polyalcohols, polyester system is than the polyethers system fast tendency that responds.Therefore, owing to the viscosity of solidification delay in suppressing to apply is risen, thereby above-mentioned aromatic isocyanate urethane prepolymer is polyalcohols combination with above-mentioned polyethers preferably, and above-mentioned in addition aliphatic isocyanates urethane prepolymer is the polyalcohols combination with above-mentioned polyester preferably.
The number-average molecular weight of above-mentioned polyalcohols is preferred more than 500, more preferably more than 1000.If less than 500, when then above-mentioned isocyanate-based carbamate prepolymer being mixed with allyl isothiocyanate, can not get applying needed viscosity sometimes, can not apply.In addition, make it the hydroxyl reaction that contains with above-mentioned polyalcohols, can wait for needed viscosity in reaching coating, but since reaction constantly carry out thereby be difficult to viscosity is kept certain, need to change applied thickness or change mechanical setting etc., might can not get the sheet of homogeneous.On the other hand, number-average molecular weight is preferred below 10000, more preferably below 5000.If surpass 10000, then be difficult to sometimes make it reaction with even mixing of the mixture of above-mentioned isocyanate-based carbamate prepolymer and allyl isothiocyanate.
In order to obtain above-mentioned two-component-type urethane polymer, can exemplify as above-mentioned isocyanate-based carbamate prepolymer and above-mentioned polyalcohols are preserved respectively, the side that its medium viscosity is high is with after allyl isothiocyanate evenly mixes, the method for mixing the opposing party again.In addition, also can add the arbitrarily additive that in general polyurethane resin use in the scope of the antibacterial and mouldproof effect of not damaging the antibacterial and mildewproofing sheet that the present invention relates to and viscosity is maintained in the limit of necessary scope this moment.In addition,, also the stabilizing agent that makes the allyl isothiocyanate stabilisation can be added, the cyclodextrin that makes it stabilisation as antioxidant, light stabilizer, with the allyl isothiocyanate inclusion etc. can be exemplified as employed additive in the purposes except that viscosity is adjusted.
With this allyl isothiocyanate, above-mentioned isocyanate-based carbamate prepolymer and above-mentioned polyethers is that polyalcohols or above-mentioned polyester are that polyalcohols mixes when obtaining the antibacterial and mouldproof mixture, preferably carries out so that allyl isothiocyanate is non-volatile at seal cavity.In addition, in order to obtain uniform mixture, also can be that polyalcohols or above-mentioned polyester are the polyalcohols heating with above-mentioned isocyanate-based carbamate prepolymer, above-mentioned polyethers, mix with allyl isothiocyanate with low viscosity state, be cooled to the optimum temperature that applies again.
In addition, in order to obtain above-mentioned one-pack type urethane polymer, can exemplify as being kept at above-mentioned isocyanate-based carbamate prepolymer, allyl isothiocyanate in the airtight container respectively in advance, after the use pipeline mixes in pipeline with mixer, apply, before with film-stack, give the method that moisture makes it to react; Or in advance with above-mentioned isocyanate-based carbamate prepolymer and allyl isothiocyanate after airtight container evenly mixes, give the method that moisture makes it to react equally.In addition, also can add the arbitrarily additive that in common polyurethane resin use in the scope of the antibacterial and mouldproof effect of not damaging the antibacterial and mildewproofing sheet that the present invention relates to and viscosity is remained in the limit of necessary scope this moment.
Any kind of situation for above-mentioned one-pack type urethane polymer and two-component-type urethane polymer, temperature is low more, the viscosity of the antibacterial and mouldproof mixture of gained is high more, yet be difficult to carry out temperature treatment summer, coating under the cryogenic conditions need change applied thickness or change mechanical setting etc., so might can not get uniform sheet.Therefore, coating temperature is preferably more than 40 ℃.On the other hand, if coating temperature surpasses 60 ℃, then can not ignore the evaporation capacity of allyl isothiocyanate, so application temperature need be for below 60 ℃.Above-mentioned antibacterial and mouldproof mixture must more than 40 ℃ and under the arbitrary temp of the temperature range below 60 ℃, have the viscosity that can apply at this.
This viscosity that can apply is necessary for more than the 600mPas.This be because, when less than 600mPas, viscosity is crossed and low is flowed easily, the result can not apply.Therefore, when viscosity is crossed low can not the coating, in above-mentioned temperature range, transfer to low temperature, thereby viscosity is applied after at least more than the 600mPas.Even if, then can not be used for the present invention if be cooled to 40 ℃ of viscosity still less than 600mPas.On the other hand, be necessary for below the 2500mPas.This is because if surpass 2500mPas, then viscosity is too high on the contrary, occurs sometimes carrying out the situation that scumbling is applied or the coating inequality occurred, maybe can not apply.Therefore, when viscosity is too high can not apply the time, transferring to high temperature in above-mentioned scope, is that maximum 2500mPas applies after following thereby make viscosity.Still surpass 2500mPas if be heated to 60 ℃ of viscosity, then can not be used for the present invention.
In addition, the weight mixing ratio of this allyl isothiocyanate and polyurethane resin is for any kind of situation of above-mentioned one-pack type urethane polymer and two-component-type urethane polymer, all be preferably 5: 95～35: 65, more preferably 10: 90～30: 70.If allyl isothiocyanate is less than 5: 95, then the duration that can bring into play the antibacterial and mouldproof effect or the burst size of gained antibacterial and mildewproofing sheet are very few, and effect is undesirable.On the other hand, if polyurethane resin is less than 35: 65, then the viscosity of antibacterial and mouldproof mixture declines to a great extent, and can not remain in the above-mentioned scope that can apply, perhaps fixing allyl isothiocyanate and might can't form above-mentioned antibacterial mildew inhibitor layer.Preferred 5: 95～15: 85 of weight mixing ratio when in addition, using aliphatic isocyanates urethane prepolymer.
Then, other at least 1 layer the above-mentioned allyl isothiocyanate adsorptivity film that forms stacked is described.Above-mentioned allyl isothiocyanate adsorptivity film is the allyl isothiocyanate adsorptivity film that can adsorb allyl isothiocyanate, can discharge adsorbed allyl isothiocyanate when heating.That is, when forming by three layers for above-mentioned stacked, at least one side who clips the sheet of above-mentioned antibacterial mildew inhibitor layer is an allyl isothiocyanate adsorptivity film.In addition, when above-mentioned stacked when forming more than four layers, the situation that has above-mentioned antibacterial mildew inhibitor layer and allyl isothiocyanate adsorptivity film directly to join, and the situation that other layers are arranged between itself and allyl isothiocyanate adsorptivity film, can easily adsorb the allyl isothiocyanate that discharges from above-mentioned antibacterial mildew inhibitor layer owing to directly join, therefore preferred.
If above-mentioned allyl isothiocyanate adsorptivity film is set at least 1 layer of stacked, then this antibacterial and mildewproofing sheet carry out cryopreserved below 10 ℃ environment or carry out can suppressing the release of allyl isothiocyanate in the environment below-18 ℃ of freezing preservation.Therefore, in that mushroom is almost inactive because temperature is low when not needing the refrigeration of antibacterial and mouldproof effect, freezing preservation, prevent to discharge allyl isothiocyanate in vain from the antibacterial and mildewproofing sheet that the present invention relates to.On the other hand, above-mentioned allyl isothiocyanate adsorptivity film can discharge the allyl isothiocyanate of absorption when heating.
When needs antibacterial and mouldproof effect, by the heating antibacterial and mildewproofing sheet, above-mentioned allyl isothiocyanate adsorptivity film discharges adsorbed allyl isothiocyanate.In addition, d/d allyl isothiocyanate is not directly to discharge from above-mentioned allyl isothiocyanate adsorptivity film side, is mostly to discharge via the superficial layer of antibacterial mildew inhibitor layer from opposition side.This is owing to following reason causes, the density unevenness of absorption allyl isothiocyanate is even in the whole film, and the concentration of position that approaches above-mentioned antibacterial mildew inhibitor layer is higher, in addition, even be heated, above-mentioned allyl isothiocyanate adsorptivity film also is difficult to see through allyl isothiocyanate.In addition, concentrate on allyl isothiocyanate near a side of above-mentioned antibacterial mildew inhibitor layer compared with seeing through whole film, be back to above-mentioned antibacterial mildew inhibitor layer easilier, recently increase from the burst size of the face of above-mentioned allyl isothiocyanate adsorptivity film side from the burst size of the face of opposition side.
In addition, the allyl isothiocyanate of release is not the time to discharge outside sheet in heating quickly, though but when heating, discharge to a certain degree, after heating, also continue slowly to discharge in normal temperature environment following cooling period.This as mentioned above, is not directly to discharge from above-mentioned allyl isothiocyanate adsorptivity film owing to following reason causes, but discharges via the face of above-mentioned antibacterial mildew inhibitor layer from opposition side, and therefore life period postpones during discharging.
By this allyl isothiocyanate adsorptivity film is placed the surface, add the antibacterial and mildewproofing sheet that the present invention relates to food, discharge allyl isothiocyanate when then refrigerating is preserved hardly, after heating need the antibacterial and mouldproof effect time, can discharge allyl isothiocyanate.
Specifically, the maximal absorptive capacity of allyl isothiocyanate is 30mg/m under the preferred 30 ℃ environment of above-mentioned allyl isothiocyanate adsorptivity film
2More than and 3000mg/m
2Below, transit dose on the one of allyl isothiocyanate is 5g/m down at 30 ℃
2Following film.These values are above-mentioned antibacterial and mildewproofing sheet to be used to refrigerate, during the food of freezing preservation, can fully to suppress the value of the waste burst size of allyl isothiocyanate under common preservation environment.Under this temperature,,, also can suppress breeding of bacterium or mould propagation even therefore do not discharge allyl isothiocyanate because nearly all bacterium or mould activity are suppressed.Because this holding time is long,, then when needs antibacterial and mouldproof effect, but can not discharge if therefore discharge allyl isothiocyanate in vain.From the allyl isothiocyanate that above-mentioned antibacterial mildew inhibitor layer discharges, can suppress the consumption in vain of allyl isothiocyanate by above-mentioned allyl isothiocyanate adsorptivity film absorption thus.
In addition, the assay method at the above-mentioned maximal absorptive capacity of this regulation is undertaken by following method.
In glass system drier, add to make allyl isothiocyanate with respect to its volume needed allyl isothiocyanate of vapour pressure that reaches capacity, with 100cm
2Each film be arranged in the drier in the mode that does not contact allyl isothiocyanate.With this glass system drier in 30 ℃ down place 7 days after, take out each film, wipe allyl isothiocyanate with tissue paper at the film surface sweating.Afterwards, each film was placed 1 hour under 30 ℃, each film is reclaimed in the allyl isothiocyanate volatilization back that surplus is adhered to, and uses carrene as extracting solvent again, utilize the residual quantity in the gas chromatography determination film, try to achieve this value as the maximal absorptive capacity that will measure to film.
In addition, the assay method at the above-mentioned transit dose of this regulation is undertaken by following method.
In stainless steel moisture vapor transmission cup (cylindric), add allyl isothiocyanate 1g, place the film of measuring, place again and have, carry out fixing seal with the same area of peristome, with the ring of the peristome of shape at its peristome.Through the time measure the weight of moisture vapor transmission cup, it is reduced the allyl isothiocyanate transit dose of weight as the above-mentioned peristome area of unit.
On the other hand, above-mentioned allyl isothiocyanate adsorptivity film must can discharge the allyl isothiocyanate of absorption through heating, specifically, preferably under the heating environment more than 60 ℃, can discharge the allyl isothiocyanate adsorptivity film more than 40% of the allyl isothiocyanate of absorption.This temperature is the temperature with the food of heating such as electric stove refrigeration, freezing preservation the time.Like this,, around food, supply with the gas of allyl isothiocyanate, can bring into play antibacterial and mouldproof effect protection food by discharging, see through allyl isothiocyanate.
As the PETG system film that is above-mentioned allyl isothiocyanate adsorptivity film, can use for example biaxial tension PETG, amorphous polyethylene terephthalate, glycol modification copolymerization PETG etc.PETG system film has the character of absorption allyl isothiocyanate under the normal temperature, if heat then the structural relaxation of film, can discharge adsorbed allyl isothiocyanate.
When using PETG system film, more than the preferred 7 μ m of the thickness of film as above-mentioned allyl isothiocyanate adsorptivity film.If less than 7 μ m, then not only adding has pleat man-hour easily, and because adsorbance is insufficient, therefore can not get sufficient antibacterial and mouldproof effect sometimes when needed.On the other hand, be preferably below the 50 μ m.If surpass 50 μ m, then price is very high, can not use in price sometimes.Specifically, for the PETG system film of thickness 25 μ m, maximal absorptive capacity is about 400mg/m
2About.In addition, when using PETG system film on the two sides, see through in order to make allyl isothiocyanate, the preferably thin person of single face is more than the preferred 7 μ m and below the 12 μ m.
In addition, clamp the sheet of two layers of formation of the both sides of above-mentioned antibacterial mildew inhibitor layer, its at least one sheet is the allyl isothiocyanate permeability film that can be fully sees through allyl isothiocyanate, the film of preferably guaranteeing the transit dose of allyl isothiocyanate, can regulating according to the purposes of the antibacterial and mildewproofing sheet that the present invention relates to.
Particularly preferably be, above-mentioned antibacterial mildew inhibitor layer is clamped by above-mentioned allyl isothiocyanate adsorptivity film and above-mentioned allyl isothiocyanate permeability film.If above-mentioned allyl isothiocyanate adsorptivity film directly is layered on the above-mentioned antibacterial mildew inhibitor layer, then allyl isothiocyanate is slowly adsorbed, and in addition, the allyl isothiocyanate of absorption is difficult to discharge.Relative therewith, because allyl isothiocyanate permeability film adsorbs repeatedly and discharges, therefore most being adsorbed to the above-mentioned allyl isothiocyanate adsorptivity film of the allyl isothiocyanate that discharges from above-mentioned antibacterial mildew inhibitor layer of result, adsorbance is more than allyl isothiocyanate permeability film.Therefore, the over half of allyl isothiocyanate that above-mentioned antibacterial mildew inhibitor layer had can be adsorbed, allyl isothiocyanate minimizing in vain can be suppressed.
In addition, the layer of clamping the both sides of above-mentioned antibacterial mildew inhibitor layer also can be an allyl isothiocyanate permeability film, during this situation, at arbitrary layer the stacked above-mentioned allyl isothiocyanate adsorptivity film in the outside at least.At this moment, with regard to above-mentioned allyl isothiocyanate adsorptivity film, only adsorb the almost part through the above-mentioned allyl isothiocyanate permeability of side film of the impartial allyl isothiocyanate that discharges, therefore the adsorbance minimizing of above-mentioned allyl isothiocyanate adsorptivity film of two sides from above-mentioned antibacterial mildew inhibitor layer.
Specifically, above-mentioned allyl isothiocyanate permeability film is to transit dose every day preferred 10g/m under 30 ℃ of allyl isothiocyanate
2More than and 200g/m
2Below.If less than 10g/m
2, then transit dose is very few, can not give full play to the antibacterial and mouldproof effect sometimes.On the other hand, if surpass 200g/m
2, then transit dose is too much, and the duration becomes too short.
As above-mentioned allyl isothiocyanate permeability film, can use polyolefin mesentery, cellophane film.As the polyolefin mesentery, can exemplify as polypropylene system films such as biaxially oriented polypropylene film, un-stretched polypropylene film, polyethylene system film etc.Wherein optimization polypropylene system film, more preferably Biaxially oriented polypropylene system film.In addition, there is no particular limitation for the thickness of above-mentioned allyl isothiocyanate permeability film, and it is above and below the 80 μ m to be preferably 9 μ m, and more preferably 12 μ m are above and below the 60 μ m.If less than 9 μ m, then cross the thin problem that may occur on the intensity.On the other hand, if surpass 80 μ m, then antibacterial and mildewproofing sheet curls easily, or permeability might be undesirable.In addition, owing to these allyl isothiocyanate permeability films are provided with for allyl isothiocyanate is seen through, therefore, the maximal absorptive capacity of allyl isothiocyanate is the smaller the better, specifically, the maximal absorptive capacity of allyl isothiocyanate is 200mg/m under 30 ℃ condition
2Below.As this sheet, the glassine paper of for example thick 24 μ m is 50mg/m
2About.
As the method for utilizing above-mentioned allyl isothiocyanate adsorptivity film or above-mentioned allyl isothiocyanate permeability film to clamp above-mentioned antibacterial mildew inhibitor layer, can exemplify as the above-mentioned antibacterial and mouldproof mixture of coating on a slice in these films, make a slice film be bonded in method on the formed above-mentioned antibacterial mildew inhibitor layer again.In addition, the method as the above-mentioned antibacterial and mouldproof mixture of coating on above-mentioned film can exemplify as adjusting coating amount according to the gap between roller or its rotating speed, applies the method for above-mentioned antibacterial and mouldproof mixture when carrying out transfer printing repeatedly; Certain clearance is set adjusts the method etc. that coating amount carries out the transfer printing coating.As this applying device, can exemplify as the stacked machine of non-solvent, reverse coating machine, lip formula coating machine etc.
When the above-mentioned antibacterial and mouldproof mixture of coating forms above-mentioned antibacterial mildew inhibitor layer on above-mentioned film,, preferably under room temperature or heated condition, carry out the slaking of a few days in order to make the polyurethane resin sclerosis.If directly or across allyl isothiocyanate permeability film apply above-mentioned antibacterial mildew inhibitor layer on allyl isothiocyanate adsorptivity film, then allyl isothiocyanate is adsorbed in the above-mentioned allyl isothiocyanate adsorptivity film between this maturation period.
The above-mentioned coating amount that contains the above-mentioned antibacterial mildew inhibitor layer of polyurethane resin is preferably 0.5g/m
2More than, more preferably 1g/m
2More than.If less than 0.5g/m
2, then the amount of antibacterial mildew inhibitor is very few, and the effect of gained antibacterial and mildewproofing sheet is undesirable sometimes.On the other hand, if be 3g/m
2With next preferred, 2g/m more preferably
2Below.If surpass 3g/m
2, then the uneven possibility height that curls takes place in the layer of the both sides that join with above-mentioned antibacterial mildew inhibitor layer, also might become the reason that causes pleat in addition.
In addition, after being coated to above-mentioned antibacterial mildew inhibitor layer on the above-mentioned allyl isothiocyanate adsorptivity film, by above-mentioned allyl isothiocyanate permeability rete is laminated on the face with above-mentioned antibacterial mildew inhibitor layer opposition side, can utilize above-mentioned allyl isothiocyanate adsorptivity film and above-mentioned allyl isothiocyanate permeability film to clamp above-mentioned antibacterial mildew inhibitor layer.On the contrary, also can after above-mentioned antibacterial mildew inhibitor layer being coated on the above-mentioned allyl isothiocyanate permeability film, make above-mentioned allyl isothiocyanate adsorptivity rete be laminated to the face of opposition side again.
In addition, also can be at the stacked above-mentioned allyl isothiocyanate permeability film of the one side of above-mentioned antibacterial mildew inhibitor layer, superficial layer with two sides becomes above-mentioned allyl isothiocyanate adsorptivity film again, yet, if two sides' superficial layer is above-mentioned allyl isothiocyanate adsorptivity film, even then heating also can make allyl isothiocyanate discharge hardly.Therefore at least one side who is preferably superficial layer is above-mentioned allyl isothiocyanate permeability film, directly above-mentioned antibacterial mildew inhibitor is stacked on this film layer by layer.
In addition, for the release by allyl isothiocyanate continues performance antibacterial and mouldproof effect, the burst size of the allyl isothiocyanate of needed antibacterial and mildewproofing sheet per unit area of the antibacterial and mildewproofing sheet that the present invention relates to and time per unit is preferably 3mg/m
2More than hour.This be because, if less than 3mg/m
2Hour, then Fa Hui antibiotic property might be undesirable.On the other hand, burst size is preferably 1000mg/m
2Below hour.This be because, if surpass 1000mg/m
2Hour, then might on food, adsorb taste or influence taste.These duration and burst size can wait according to the permeability of the proportion of the coating amount of above-mentioned antibacterial mildew inhibitor layer, above-mentioned allyl isothiocyanate, above-mentioned allyl isothiocyanate permeability film and adjust.
As the concrete using method of the antibacterial and mildewproofing sheet that the present invention relates to, can exemplify as being used to cover the top or whole packing of food, to the method for food performance antibacterial and mouldproof effect or freshness maintenance effect etc.The antibacterial and mildewproofing sheet that the present invention relates to is owing to used above-mentioned polyurethane resin, therefore under the condition of the general heating of carrying out food with electric stove etc., can heat fusing, can keep the antibacterial mildew inhibitor layer, discharge allyl isothiocyanate continuously by the direction certain time that needs, the antibacterial and mouldproof effect to packaged food is continued at single or double.
In addition because at least one side's face is become above-mentioned allyl isothiocyanate adsorptivity film, therefore at normal temperature, refrigeration, can discharge allyl isothiocyanate ground hardly when freezing and continue preservation.Promptly, if in the packing of food, use above-mentioned antibacterial and mildewproofing sheet, perhaps it is put in advance the packing of food, then can deposit as follows: before the temperature of food descends, discharge the allyl isothiocyanate of absorption in the allyl isothiocyanate permeability film, performance antibacterial and mouldproof effect, under refrigeration, such mushroom is difficult to breed when freezing state, allyl isothiocyanate can not discharge in vain.After heated foods such as electric stove, when distance eats certain interval of time, reach the propagable temperature of mushroom during this, but should the stage discharge the fully allyl isothiocyanate of amount from above-mentioned antibacterial and mildewproofing sheet, thus can suppress mushroom breeding, keep the environment of health.
In addition, when being used for this packing, if the layer of above-mentioned allyl isothiocyanate adsorptivity film uses to be positioned at than above-mentioned antibacterial mildew inhibitor layer mode more in the outer part, then more suitable, this be because, even there is the release after the heating, but few through the allyl isothiocyanate of above-mentioned allyl isothiocyanate adsorptivity film, almost be face release entirely from opposition side.
In addition, shape as the antibacterial and mildewproofing sheet that the present invention relates to, can exemplify as forming the shape of food containers by following moulding, described being shaped to: antibacterial and mildewproofing sheet is heated after the temperature that reaches easy deformation the vacuum forming of the antibacterial and mildewproofing sheet vacuum attraction being carried out moulding in the concavity mould; Or heat and reach after the temperature that to be out of shape thermoforming that the concavity mould antibacterial and mildewproofing sheet used after heating and convex mold heated carry out moulding simultaneously etc.These for example can will cut the shape that conglobate above-mentioned antibacterial and mildewproofing sheet is made the described cup of Fig. 1 (b) type shown in Fig. 1 (a), the above-mentioned antibacterial and mildewproofing sheet that will cut into rectangle shown in Fig. 2 (a) is molded into the shape of dish-type shown in Fig. 2 (b).Carry out moulding if particularly cut into rectangle as shown in Figure 2, then can not have utilize lavishly through stacked and sheet.
[embodiment]
Below, be described more specifically the present invention by embodiment.At first, film, polyurethane resin and the allyl isothiocyanate that uses described.
PET#25 ... Japan's weaving (strain) system: PETG system film (allyl isothiocyanate adsorptivity film), thick 25 μ m
OPP#20 ... Japan's weaving (strain) system: Biaxially oriented polypropylene system film (allyl isothiocyanate permeability film), thick 20 μ m
The first aromatic isocyanate urethane prepolymer ... the military field chemistry of Mitsui (strain) system: ケ ネ one ト A-242A number-average molecular weight (Mn): 1268 (two-component-type carbamate prepolymers)
High molecular weight polyether is a polyalcohols ... the military field chemistry of Mitsui (strain) system: ケ ラ Star Network XA-244B number-average molecular weight (Mn): 3254
The second aromatic isocyanate urethane prepolymer ... the military field chemistry of Mitsui (strain) system: ケ ネ one ト A-260 number-average molecular weight (Mn): 2129 (one-pack type carbamate prepolymers)
Allyl isothiocyanate ... Japan's terpene chemistry (TERPENE) (strain) system
In addition, the mensuration of above-mentioned number-average molecular weight is to use gel permeation chromatography (GPC), measures under the following conditions.
Device: TOSOH (strain) corporate system HLC-8120GPC
Post: TOSOH (strain) corporate system TSK-GEL α-M
Phase flows: 0.5mol/l NaNO
3Dimethyl sulfoxide (DMSO) (DMSO) solution
Detector: differential refractive index meter (RI)
Flow velocity: 1ml/min
Column temperature: 40 ℃
Number-average molecular weight (Mn): be converted into polyethylene glycol (PEG)
[manufacturing of antibacterial and mildewproofing sheet and burst size test]
(embodiment 1)
With the first aromatic isocyanate urethane prepolymer, high molecular weight polyether is that polyalcohols and allyl isothiocyanate mix according to 75: 10: 15 weight mixing ratio, and the viscosity when making 40 ℃ is the antibacterial and mouldproof mixture of 1040mPas.At this moment, (strain) eastern machine U.S. (ト キ メ Star Network) system Brookfield viscometer is used in viscosimetric analysis.Utilize the stacked machine of non-solvent of Fuji's mechanical industry (strain) system, on PET#25 with 1.8g/m
2Coating amount apply this antibacterial and mouldproof mixture, form the antibacterial mildew inhibitor layer.The OPP#20 that on the face opposite of this antibacterial mildew inhibitor layer, fits with PET#25, obtain forming by 3 layers, superficial layer is the antibacterial and mildewproofing sheet of allyl isothiocyanate permeability film.
＜normal temperature is preserved test 〉
100 of the antibacterial and mildewproofing sheets of gained are put into the aluminium oxide bag to be sealed, in 40 ℃ of thermostats, preserve after 1 month, to test body, to be cut into 10cm * 16cm square, be arranged under 30 ℃, 25%RH, calm condition, after utilizing Hewlett-Packard system gas-chromatography HP 6890 to measure 1 hour, the content of allyl isothiocyanate in sheet after 3 hours, after 6 hours, after 24 hours, content when beginning to volatilize is as residual rate 100%, and separately content is converted into residual rate, shows the result in table 1.
[table 1]
| Elapsed time (hr) | 0 | 1 | 3 | 6 | 24 |
| Embodiment 1 | 100.0％ | 88.6％ | 85.7％ | 82.9％ | 80.0％ |
| Comparative example 1 | 100.0％ | 34.2％ | 12.8％ | 4.2％ | 0.0％ |
| Embodiment 2 | 100.0％ | 85.1％ | 83.2％ | 81.2％ | 78.1％ |
＜freezing preservation test 〉
Above-mentioned test body is placed in-18 ℃ the freezer, measures the remaining quantity of the allyl isothiocyanate after 7 days, after 14 days, after 30 days, after 60 days, be converted into residual rate equally.It is the results are shown in table 2.
[table 2]
| The process fate (my god) | 0 | 7 | 14 | 30 | 60 |
| Embodiment 1 | 100.0％ | 87.9％ | 88.0％ | 87.2％ | 87.2％ |
| Comparative example 1 | 100.0％ | 32.6％ | 8.6％ | 0.0％ | 0.0％ |
| Embodiment 2 | 100.0％ | 84.3％ | 82.9％ | 78.6％ | 79.0％ |
＜heat resistant test 〉
(Sharp's (strain) system: RE-M20) heating is 1 minute, observes appearance change, the film on top layer is stretched along 180 ° of directions carry out disbonded test simultaneously with the electric stove of specified output 500W with the antibacterial and mildewproofing sheet of gained.Results verification does not have appearance change, and in addition, the breaking of film of top layer face only appears in not fusion of polyurethane resin in disbonded test.
Release test after the＜heating 〉
Above-mentioned test body and the cup that the water of 50cc is housed were together put into above-mentioned electric stove heating after 2 minutes, under 30 ℃, the calm condition of 25%RH, place the test body, through the time measure the content of allyl isothiocyanate, being converted into the allyl isothiocyanate before heating is 100% residual rate.It is the results are shown in table 3.
[table 3]
| Elapsed time (hr) | Before electric stove | Behind electric stove | 1 | 3 | 6 | 24 |
| Embodiment 1 | 100.0％ | 83.6％ | 47.3％ | 31.9％ | 29.2％ | 27.4％ |
| Comparative example 1 | 100.0％ | 2.1％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ |
| Embodiment 2 | 100.0％ | 79.3％ | 45.5％ | 34.3％ | 30.8％ | 30.2％ |
| Embodiment 3 | 100.0％ | 85.4％ | 47.8％ | 30.5％ | 30.4％ | 28.8％ |
Antibiotic property test after the＜heating 〉
To put into same container (250ml) through the rice 80g of sterilization treatment, the colibacillary bacterium liquid of the 20 μ l that drip respectively in 20 positions on rice surface through sterilization treatment.At once above-mentioned antibacterial and mildewproofing sheet is cut into afterwards that 60mm * 100mm is square to be placed on the rice, closes the lid, preserved 6 hours in 30 ℃.Reclaim whole 80g rice after 6 hours, measure the Escherichia coli bacterium number in the rice.In addition, also measure the situation of not placing antibacterial and mildewproofing sheet of contrast as a comparison.It is the results are shown in table 4.In addition, the unit in the table is (a CF U/80g rice).
[table 4]
| Elapsed time (hr) | 0 | 6 |
| There is not antibiotic | 3.7×10 3 | 6.9×10 5 |
| Embodiment 1 | 3.7×10 3 | 3.3×10 3 |
| Comparative example 1 | 3.7×10 3 | 7.5×10 5 |
| Embodiment 2 | 3.7×10 3 | 4.1×10 3 |
| Embodiment 3 | 3.7×10 3 | 3.8×10 3 |
(comparative example 1)
PET#25 with OPP#20 replacement embodiment 1 measures equally.Show the result in table 1～4.In addition, carry out heat run similarly to Example 1, confirming does not have appearance change, and the breaking of film of superficial layer only appears in not fusion of polyurethane resin in disbonded test.
(embodiment 2)
The second aromatic isocyanate urethane prepolymer and allyl isothiocyanate are mixed according to 80: 20 weight mixing ratio, and the viscosity when being manufactured on 40 ℃ is the antibacterial and mouldproof mixture of 1290mPas.Under 40 ℃ with this antibacterial and mouldproof mixture with 1.8g/m
2Coating amount be coated on the PET#25, form the antibacterial mildew inhibitor layer.OPP#20 fits on the face opposite with PET#25 of this antibacterial mildew inhibitor layer, placed 2 down at 40 ℃, make antibacterial mildew inhibitor layer sclerosis, form constitute by 3 layers, superficial layer is by allyl isothiocyanate permeability film with as the film formed antibacterial and mildewproofing sheet of PETG system of allyl isothiocyanate adsorptivity film.Carry out similarly to Example 1 mensuration for this sheet.It is the results are shown in table 1～4.
(embodiment 3)
Use the antibacterial and mildewproofing sheet of the embodiment 1 of the rectangle of indulging 70mm * horizontal 100mm, utilize the continuous vacuum forming machine HVF of (having) テ ラ ダ キ カ イ system, make Fig. 2 (b) shapes of containers of dark 10mm, carry out release test and antibiotic property test after the heating in the test of embodiment 1.It is the results are shown in table 3,4.
(result)
Preserve in the test at normal temperature, embodiment 1 and 2 sheet are irrelevant with the kind of carbamate prepolymer, under 30 ℃ through 24 hours after maintenance about 80%, the two sides is that sheet allyl isothiocyanate in 24 hours of the comparative example 1 of PP all is released (table 1).
In freezing preservation test, decline to a great extent than rate of release with 30 ℃ environment facies, all discharge with the allyl isothiocyanate in 30 days of the sheet of comparative example 1 and to compare, the allyl isothiocyanate that embodiment 1 and 2 sheet kept more than 7 one-tenth on 30th, even afterwards again through 30 days, also keep the allyl isothiocyanate (table 2) of amount much at one.Think that this is most being adsorbed, fixing by PET#25 owing to the allyl isothiocyanate that discharges from the antibacterial mildew inhibitor layer.
In the release test after heating, the sheet of comparative example 1 is released at the just more than half allyl isothiocyanate in heating back at once, for the sheet of embodiment 1 and 2, and compares after the firm heating, the amount that discharges in 24 hours afterwards is more, and the heating back slowly discharges allyl isothiocyanate from PET#25 as can be known.In addition, for embodiment 3 with the sheet vacuum forming of embodiment 1, also with embodiment 1 much at one, can slowly discharge allyl isothiocyanate.
In the antibiotic property test, do not see antibacterial effect for comparative example 1, the mushroom breeding, and for embodiment 1 to 3, the viable count of mushroom does not almost change after 6 hours, can suppress breeding.
Claims (10)
1. an antibacterial and mildewproofing sheet is characterized in that,
By 1 layer outside layer stacked desurfacing that forms more than 3 layers is the antibacterial mildew inhibitor layer that is formed by the antibacterial and mouldproof mixture, described antibacterial and mouldproof mixture is to be that the isocyanate-based carbamate prepolymer below 10000 forms more than 500 polyurethane resin mixes with allyl isothiocyanate and gets by number-average molecular weight, and described antibacterial and mouldproof mixture is under 40 ℃ to 60 ℃ arbitrary temp, viscosity is got the following value of the above 2500mPas of 600mPas
Other at least 1 layer is by forming as adsorbing the PETG system film that allyl isothiocyanate and heating the time can discharge the allyl isothiocyanate adsorptivity film of allyl isothiocyanate.
2. an antibacterial and mildewproofing sheet is characterized in that,
By 1 layer outside layer stacked desurfacing that forms more than 3 layers is the antibacterial mildew inhibitor layer that is formed by the antibacterial and mouldproof mixture, described antibacterial and mouldproof mixture is to be the isocyanate-based carbamate prepolymer below 10000 more than 500 with number-average molecular weight, by number-average molecular weight is that the polyethers below 10000 is a polyalcohols more than 500, polyester is the polyurethane resin that polyalcohols or this two kinds of polyalcohols form, mix with allyl isothiocyanate and get, described antibacterial and mouldproof mixture is under 40 ℃ to 60 ℃ arbitrary temp, viscosity is got the following value of the above 2500mPas of 600mPas
Other at least 1 layer is by forming as adsorbing the PETG system film that allyl isothiocyanate and heating the time can discharge the allyl isothiocyanate adsorptivity film of allyl isothiocyanate.
3. antibacterial and mildewproofing sheet as claimed in claim 1 or 2 is characterized in that,
The one deck at least that joins with described antibacterial mildew inhibitor layer is formed by allyl isothiocyanate permeability film.
4. antibacterial and mildewproofing sheet as claimed in claim 3 is characterized in that,
Per 1 day allyl isothiocyanate transit dose of described allyl isothiocyanate permeability film is 1g/m down at 30 ℃
2Above 200g/m
2Below.
5. as claim 3 or 4 described antibacterial and mildewproofing sheets, it is characterized in that,
Described allyl isothiocyanate permeability film is the polyolefin mesentery.
6. antibacterial and mildewproofing sheet as claimed in claim 5 is characterized in that,
Described polyolefin mesentery is formed by polypropylene system film or polyethylene system film.
7. as each described antibacterial and mildewproofing sheet in the claim 1～6, it is characterized in that,
The maximal absorptive capacity that described allyl isothiocyanate adsorptivity film is an allyl isothiocyanate under 30 ℃ environment is 30mg/m
2Above 3000mg/m
2Following film,
Under the heating environment more than 60 ℃, can being released more than 40% of the allyl isothiocyanate of absorption.
8. as each described antibacterial and mildewproofing sheet in the claim 1～7, it is characterized in that,
The thickness of described PETG system film is below the above 50 μ m of 7 μ m.
9. an antibacterial and mouldproof food is characterized in that with cup,
Use in the claim 1～8 each described antibacterial and mildewproofing sheet to carry out moulding and get.
10. the antibacterial and mouldproof method of a food is characterized in that,
Use each described antibacterial and mildewproofing sheet or the described antibacterial and mouldproof food of claim 9 cup in the claim 1～8, when preserving, adsorb the allyl isothiocyanate that discharges from described antibacterial mildew inhibitor layer with described allyl isothiocyanate adsorptivity film,
During heating or through the preheating of food the allyl isothiocyanate of absorption is discharged from described allyl isothiocyanate adsorptivity film, thus to described antibacterial and mildewproofing sheet or antibacterial and mouldproof food with the food of cup heating, on every side food or they both bring into play the antibacterial and mouldproof effect.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007121783 | 2007-05-02 | ||
| JP2007121783A JP5038014B2 (en) | 2007-05-02 | 2007-05-02 | Antibacterial mold sheet |
| JP2007-121783 | 2007-05-02 |
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| CN101564191A true CN101564191A (en) | 2009-10-28 |
| CN101564191B CN101564191B (en) | 2012-05-23 |
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| CN2008100923482A Expired - Fee Related CN101564191B (en) | 2007-05-02 | 2008-04-22 | Antibacterial and mildewproofing sheet |
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|---|---|
| JP (1) | JP5038014B2 (en) |
| KR (1) | KR101451670B1 (en) |
| CN (1) | CN101564191B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106508957A (en) * | 2016-11-28 | 2017-03-22 | 武亦然 | Mildew-resistant card device used in clothes, making method thereof, and mildew-resistant composition |
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| JP6680632B2 (en) * | 2016-06-24 | 2020-04-15 | 小島プレス工業株式会社 | Sustained release film |
| KR102507418B1 (en) | 2020-12-31 | 2023-03-07 | 이동신 | Controlling and deodorizing fungus production and reducing VOC |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5880150A (en) * | 1993-11-10 | 1999-03-09 | The Green Cross Corporation | Antimicrobial agent containing allyl isothiocyanate and method for controlling release speed of allyl isothiocyanate |
| WO1995017819A1 (en) * | 1993-12-28 | 1995-07-06 | Rengo Co., Ltd. | Controlled-release ait preparation, process for producing the same, and use thereof |
| JP3070033B2 (en) * | 1996-02-19 | 2000-07-24 | 三洋化成工業株式会社 | Antibacterial film |
| JP4448209B2 (en) * | 1999-06-07 | 2010-04-07 | リンテック株式会社 | Volatile drug sustained release sheet and method for producing the same |
| KR100460021B1 (en) * | 1999-08-25 | 2004-12-04 | 다이이치 고교 세이야쿠 가부시키가이샤 | Gel-like resin molded object and volatile gel-like packaged drug and method of preparing the same |
| JP4190349B2 (en) * | 2002-05-31 | 2008-12-03 | レンゴー株式会社 | Isothiocyanate-containing composition |
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2007
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106508957A (en) * | 2016-11-28 | 2017-03-22 | 武亦然 | Mildew-resistant card device used in clothes, making method thereof, and mildew-resistant composition |
| CN106508957B (en) * | 2016-11-28 | 2019-02-22 | 武亦然 | For the mould proof card device and preparation method, mould proof composition in clothes |
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| KR101451670B1 (en) | 2014-10-16 |
| JP2008273120A (en) | 2008-11-13 |
| CN101564191B (en) | 2012-05-23 |
| KR20080097915A (en) | 2008-11-06 |
| JP5038014B2 (en) | 2012-10-03 |
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