CN101995447A - Moisture absorbent having self- and multi-indicating ability and preparation method thereof - Google Patents
Moisture absorbent having self- and multi-indicating ability and preparation method thereof Download PDFInfo
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- CN101995447A CN101995447A CN2009101761206A CN200910176120A CN101995447A CN 101995447 A CN101995447 A CN 101995447A CN 2009101761206 A CN2009101761206 A CN 2009101761206A CN 200910176120 A CN200910176120 A CN 200910176120A CN 101995447 A CN101995447 A CN 101995447A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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Abstract
The present invention relates to a moisture absorbent having self- and multi-indicating ability and a preparation method thereof. Provided is the moisture absorbent that a self- and multi-indicating agent is uniformly distributed to the surface of the moisture absorbent, composed of the self- and multi-indicating agent formed by a mixture of pyoktanin blue and quinaldine red in a proportion by weight from 1:1 to 1:15 and a porous moisture absorbent as the balance, wherein the pyoktanin blue is 0.0005-0.5 wt.%, and the quinaldine red is 0.0005-7.5 wt.%. Provided is a method of high efficiency preparing the moisture absorbent. The moisture absorbent has non harm to a human body and does destroy the environment, a colour intensity is changed from deep blue to purple and then to light purple with little pink, peachblow, shallow red and ultimately incarnadine based on a hygroscopic degree, such that the moisture absorbent can exhibit the stable indicating ability for sure by multi-level obvious variation.
Description
Technical field
The present invention relates to have the hygroscopic agent of multistage self-deixis and the correlation technique of manufacture method thereof, in more detail, relate to such porous hygroscopic agent and manufacture method thereof, on moisture-proof deodorants such as silica gel, smear or flood acid solution as the specific organic dyestuff mixed liquor of multistage self-indicator, make it dry afterwards, thereby hygroscopic agent has the multistage self-deixis that can change the moisture absorption degree that judge hygroscopic agent more exactly according to multistage colourity, parches and/or damping being used to.
Background technology
Hygroscopic agent is generally deposited in food container and the drug packaging container, it is below the mark to make product moisture content in processes such as preservation, circulation, use stably remain on the moisture content of regulation by the moisture that absorbs the internal tank gas medium, therefore be widely used in and prevent that food from becoming damp and rotten, keeping the freshness, local flavor, mouthfeel of food etc. to be in good original state, the protection against the tide that perhaps is used for semi-conductor chip, printed circuit board (PCB) and contains these parts the accurate electrical and electronic product of humidity sensitive.
As typical hygroscopic agent, use silica gel (silica gel:SiO
2H
2O), the clay of aluminium silicate salt pearl (alumino-silicate beads), smectite (montmorillonite) and so on and as the zeolite (zeolite:Na of molecular sieve
12AlO
3SiO
212XH
2O), activated charcoal, calcium oxide (CaO), calcium sulphate (CaSO
4) etc.
Silica gel has significant adsorbance and nontoxic, non-corrosiveness, deliquescence, water insoluble not, and processing ease, cheap need not be considered the pollution problem of its initiation, so used the most widely.
Porcelain earth becomes that the adsorbent of pearl form of Almasilate is more common, and low price but easily pollutes when Powdered, and its water-intake capacity is compared inferior to some extent with silica gel, and this is kaolinic shortcoming, but its advantage is that price is minimum comparatively speaking.
Zeolite has netted microspheroidal structure, and non-surface area is at 700～800m
2About/g, so its advantage is also as silica gel and clay: can be along with the rising of temperature in packing product release steam, its shortcoming is that price is higher relatively.
Activated charcoal has very large 200～1200m
2Non-surface area about/g, absorption affinity is superpower, but has contamination of products, so do not use as general purpose hygroscopic agent substantially.
Calcium oxide is as the calcining with absorption 28.5wt% following steam ability, calcine the lime of type again, and the adsorbed moisture of still having the ability under low-down relative humidity refrigerates or the moisture absorption packaging for foodstuff of frozen food so be mainly used in.
The commercial calcium sulphate of extensively knowing as drierite, its chemical property is stable and do not have non-disintegrative, toxicity and corrosivity, also can not discharge the steam that has absorbed along with the rising of temperature.But only about 10wt%, this is its shortcoming to its steam adsorptive power, so mainly use in limited scope.
In the above-mentioned multiple hygroscopic agent, particularly silica gel is more outstanding than other hygroscopic agent aspect performance and expense, so not only use in the packing of food, medical supplies and various electronic products, also extensively applies to the industry of all spectra.Do not have the silica gel that the silicon dioxide molecules of crystallization constitutes by high-purity, it is characterized by: according to the process structure that particle inside is expanded significantly, its non-surface area is very big, chemical change can not take place, no dissolubility is difficult for being corroded, water insoluble, during body spherical in shape, particle is transparent and hard, no color or smell, harmless, moisture and gas there are significant absorption affinity, no change after the moisture absorption, water tolerance is strong in commercial Application, and percentage of damage is low when contacting with water, and is safe.
On the other hand, just began to propose steam is adsorbed the hygroscopic agent that deixis is given the various ways of above-mentioned hygroscopic agent in the past.This hygroscopic agent with steam absorption deixis can be removed the moisture in the packing containers such as food, medical supplies and precise electronic product, and make it remain on drying regime.Meanwhile; along with its colourity of increase of moisture that hygroscopic agent absorbs will change; so with the naked eye can easily grasp the degree of absorption of moisture; the humidity change indicator that perhaps can be used as the dry post of gas is used; perhaps be used for transformer air-vent, circuit air-vent and motor electronic telecommunication system are dehumidified, protect, repair, safeguard and provide moistureproof indicator to use; perhaps use as the damp proof indicator in the breadboard exsiccator; by inference; along with the variation of living and advanced, its demand will further increase.
The typical hygroscopic agent that in the past had the water vapor absorption deixis is extensive use of the hygroscopic agent that contains the cobalt indicator, for example, USP2,460,071 (hygroscopic agent that contains cobalt chloride), USP 2,460,069 (hygroscopic agent (Block ロ one system コ バ Le ト contains body moisture absorption drug) that contains the Bu Luomuization cobalt), USP2,460,073 (hygroscopic agents that contain cobaltous iodide), USP 2,460,074 (hygroscopic agent that contains the thiocyanic acid cobalt), USP2,460,065 (hygroscopic agent of sulfur acid cobalt) and USP2,460,070 (hygroscopic agents of phosphoric acid cobalt) etc.
The described hygroscopic agent that contains the cobalt indicator generally is to be made for anhydrous granular blue gel, make it contain the cobalt halogenide of 0.5wt% at least in the cobalt halide solution by moistening silica gel or silicon gel are immersed in, tone is by blue pulverize redness when absorbing steam.
But, cobalt halogenide, particularly cobalt chloride, European Union classifies it as II class carcinogen (ECC bulletin, 15/12/98), for adapting to new EU policy on July 1st, 2000 (Directive 98/98/EC regulation), production and the circulation that all comprise the cobalt halogenide that is defined as potential carcinogen matter of cobalt chloride and contain this product almost forbidden in European Union inside, and this trend is just expanded to the whole world.
Particularly, consider that the silica gel as hygroscopic agent mainly uses object to be food, medical supplies etc., so can infer in the near future, relevant therewith, the halid use of cobalt will be completely forbidden in worldwide.Therefore, require us to research and develop and substitute the moisture absorption indicator, replace original cobalt halogenide hygroscopic agent that uses.
According to this requirement, proposed to replace the multiple prior art that contains the halid hygroscopic agent of cobalt.
USP2,460,072 and USP2,460,067 is expressed as cupric chloride (II) and Bu Luomuization copper (び Block ロ one system Copper) (II), these compounds have environment and human body as potential toxicant can not compatibility, so be not suitable for the food of commercial use and the hygroscopic agent of medical supplies packing container.
In addition, in file " Indicator properties of vanadium-modified silicas and zeolites " (the indicator character of the silica of alum modification and zeolite: people such as Belotserkovskaya, Zh.Prikl.Khim. (Leningrad), 63 (8), 1674-9), " Synthesis and study of physicochemical properties of vanadium-containing silica-a humidity indicator " (synthetic and research: Malygin of the physicochemical property of the silicon of aluminiferous-a humidity indicator, A.A., Sb.Nauch.Tr. VNII Lyuminoforov I Osobo Chist.Veshchestv, 23,24-8) with " Study of properties of vanadium-containing silica gel " (property research of aluminiferous silica gel: Malygin, A.A. wait the people, Zh.Prikl.Khim. (Leningrad), 52 (9), reported the situation of change of this colourity in 2094-6): vfanadium compound VOCl
3In the time of in being impregnated into gel,,, become orangely again, gradually become red afterwards, finally become dark brown by the colourless yellow that becomes along with the increase of humidity.But above-mentioned VOCl
3Its corrosivity and toxicity are very strong, and its manufacturing and use difficulty become serious problem.
In addition; korean registered patent the 676th; hygroscopic agent as protection semi-conductor chip and tellite has been proposed for No. 777; employing is selected indicator and it is dissolved in ethanol from bromothymol blue, methyl red, methyl orange, neutralizer aniline blue, adds the metal chloride of sodium hydroxide solution, hygroscopy and the no cobalt humidity indication solution of organic high molecular compound then.But because it contains NaOH and metal chloride, so be not suitable in the food and medicine articles for use container.
In addition,, in test in the past, present variation, propose to use the method for various organic dyestuff and other mineral compounds for reaching according to its colourity of moisture absorption degree for replacing cobalt halogenide, especially cobalt chloride.But the problem of these hygroscopic agents is, is that the hygroscopic agent that comprises cobalt chloride that blue system, dangerous indication look are red colour system is compared with generally needing person and trader that impressive safety indication look was not arranged, and can not show similar colourity variation in the past.
Specifically, contain the hygroscopic agent cobalt chloride hygroscopic agent, that have humidity indicating function as being used to replace, for example, use the hygroscopic agent of phenolphthalein (value of discoloration is pH 8.3～10.0), along with its colourity of increase of humidity can be become colorless by yellow, for example, used the hygroscopic agent of methyl orange (value of discoloration is pH 6.0～7.6) or phenol red (value of discoloration is pH 6.8～8.4), present by the colourity variation of redness, so as the hygroscopic agent with the humidity indicating function that can not cause conflict and improper to the birch look.
In order to solve the variety of problems of conventional art, according to the applicant's requirement, propose to use that Korean Patent in the past announces for the 894th, No. 629 is harmless, good, the hygroscopic agent that contains methyl violet of damage to the environment, moisture absorption sensitivity not with safe deixis.But become purple by blueness according to its colourity of the humidity that is absorbed, the deep cognitive danger indication look of person and trader is red theory so do not meet the primary demand, add that relative humidity one surpasses 30%, himself just present purple and the variation of colourity no longer takes place, so still can as parching agent, but use has certain difficulty as conditioning agent, only take place to change to this single weight of purple according to its colourity of moisture absorption degree by blueness, and can not show clearly that large-scale multistage colourity changes, so be not suitable for and the corresponding colourity indicating card of moisture absorption degree.
Summary of the invention
Therefore, first purpose of the present invention provides hygroscopic agent harmless, that do not destroy environment, have multistage self-deixis.
Second purpose of the present invention provide a kind of according to humidity change its colourity can significantly present by mazarine become purple, again become slightly pinkish lilac, pink, light red, finally become wine-colored multi-level variation, and be consistent for red theory with the deep cognitive hazard level indication look of primary demand person and trader, moisture absorption susceptibility height, hygroscopic agent with stable multistage self-deixis.
The 3rd purpose of the present invention provides pulp based paper, the resin plate of the card form that is applicable to the hygroscopic agent that has multistage self-deixis in above-mentioned first and second purposes and the colourity indicating card that changes according to the moisture absorption degree.
The 4th purpose of the present invention provides the effective preparation method about the hygroscopic agent with multistage self-deixis described in above-mentioned first to the 3rd purpose.
In order to realize first and second purposes of the present invention, hygroscopic agent with multistage self-deixis is provided, preferred a kind of mode according to the present invention, hygroscopic agent comprises multistage self-indicator and as the porous hygroscopic agent of remainder, the weight ratio that multistage self-indicator is methyl violet and quinaldine red is 1: 1～1: 15, optimum value is 1: 7.5～1: 12.5 formed mixture, simultaneously, with the general assembly (TW) of hygroscopic agent with multistage self-deixis as benchmark, the content of methyl violet is 0.0005～0.5wt%, optimum value is 0.01～0.2wt%, under the particular case 0.01～0.1wt%, the content of quinaldine red is 0.0005～7.5wt%, optimum value is 0.01～5.0wt%, be 0.1～3wt% under the particular case, multistage self-indicator is uniformly distributed in porous hygroscopic agent surface.
In order to realize the present invention's first and second purposes, preferred other forms provide the hygroscopic agent with multistage self-deixis according to the present invention, and porous hygroscopic agent wherein is a silica gel.
In order to realize the present invention's the 3rd purpose, a kind of hygroscopic agent with multistage self-deixis is provided, the preferred form according to the present invention, hygroscopic agent with multistage self-deixis is to be 35～55wt% under 20～70wt%, the particular case with 10～80wt%, optimum value, with 20～90wt%, optimum value is to be that the paper pulp of 45～65wt% or synthetic resin constitute and contains the resin plate that hygroscopic agent pulp based paper or moulding contain hygroscopic agent under 30～80wt%, the particular case, and the hygroscopic agent that perhaps has multistage self-deixis is in pulp based paper or resin plate surface lamination.
In order to realize the present invention's the 4th purpose, the preparation method of the hygroscopic agent with multistage self-deixis is provided, according to form preferred for this invention, this preparation method may further comprise the steps:
(A) step of preparation coating fluid: with the general assembly (TW) of hygroscopic agent with multistage self-deixis as benchmark, the content of methyl violet is 0.0005～0.5wt%, optimum value is 0.01～0.2wt%, under the particular case 0.01～0.1wt%, the content of quinaldine red is 0.0005～7.5wt%, optimum value is 0.01～5.0wt%, under the particular case 0.1～3wt%, and the weight ratio of methyl violet and quinaldine red is 1: 1～1: 15, optimum value is 1: 7.5～1: 12.5, forming potpourri is multistage self-indicator, it is dissolved in the acid solution, regulate its pH3.5～4.5, optimum value is 3.8～4.2, forms coating fluid;
(B) application step: the porous hygroscopic agent be impregnated in the described coating fluid or with the coating fluid spraying, so that coating fluid is uniformly distributed in porous hygroscopic agent surface; With
(C) drying steps: with described acid solution evaporative removal.
In order to realize the present invention's the 4th purpose, the preparation method of the hygroscopic agent with multistage self-deixis is provided, preferred other modes according to the present invention, is to be 35～55wt% under 20～70wt%, the particular case with described hygroscopic agent with multistage self-deixis with 10～80wt%, optimum value, with 20～90wt%, optimum value is to be that paper pulp or the synthetic resin of 45～65wt% mixes under 30～80wt%, the particular case, copy paper and dry, with the form preparation of pulp based paper; Perhaps with the resin fusion and be fixed to the form of resin plate or with lamination in the preparation of its surperficial form.
Description of drawings
Fig. 1 has the photo that the colourity of each relative humidity of the hygroscopic agent of multistage self-deixis changes for prepared of the present invention of embodiment 1.
Fig. 2 when only using methyl violet in the past, the photo synoptic diagram that changes of the separately colourity of relative humidity under 3% and 30% condition.
Embodiment
Above-mentioned purpose of the present invention and other feature and advantage will by with reference to following content to the explanation of the preferred embodiment of the present invention and clearer and more definite.
Hygroscopic agent with multistage self-deixis according to the present invention comprises multistage self-indicator and as the porous hygroscopic agent of surplus portion.Multistage self-indicator is the potpourri of the following stated: with the general assembly (TW) of hygroscopic agent with multistage self-deixis as benchmark, the content of methyl violet is that 0.0005～0.5wt%, optimum value are to be 0.01～0.1wt% under 0.01～0.2wt%, the particular case, the content of quinaldine red is that 0.0005～7.5wt%, optimum value are to be 0.1～3wt% under 0.01～5.0wt%, the particular case, and the weight ratio of methyl violet and quinaldine red is that 1: 1～1: 15, optimum value are 1: 7.5～1: 12.5.Described multistage self-indicator is uniformly distributed in porous hygroscopic agent surface by dipping or spraying.
According to the hygroscopic agent with multistage self-deixis of the present invention, its moisture absorption indicator applicatory selects methyl violet (Methyl Violet) as initial moisture absorption indicator of the present invention, the reasons are as follows: all present the variation that is tied to red colour system by blueness according to colourity, though can consider methyl violet, mauve (Mauveine), Tetrabromophenol Blue (Tetrabromo Phenol Blue), bromthymol blue (bromothymol blue), reindeer moss etc., but except methyl violet, the color change interval of other indicator all arrives between the faintly acid scope or within the moderate acid scope at neutral range, so, its variable color degree is insensitive when absorbing aqueous vapor, and according to test findings to the hygroscopic agent applicability, can judge mauve, Tetrabromophenol Blue, bromthymol blue, reindeer moss can not present the significant colourity variation that is tied to red colour system by blueness fully on colourity changes, methyl violet then can become purple from blueness, presents distinct colourity and changes.
On the other hand, continue and become purple from blueness, present after the distinct colourity variation, select quinaldine red as second kind of moisture absorption indicator, specify as follows: according to colourity is changed to red inducing action from purple, though can consider benzopurpurin (benzopurpurin), Congo red (congo red), methyl orange, quinaldine red etc., but, benzopurpurin and Congo red be 0.005～0.5wt% at addition, when being 0.005～0.05wt% under the particular case, not painted to silica gel, or colored state is not good, so whether be difficult to conclude it is suitable for, though methyl orange is painted within above-mentioned addition scope, but it is not obvious that its colourity changes, and quinaldine red is between 30% to 90% relative humidity, presents a kind of so multi-level, the significant variation: the purple by methyl violet becomes slightly pinkish lilac, become pink again, light red, finally become peony.Thereby person and trader have impressive safety to indicate look for blue, dangerous indication look is red theory to meet the primary demand, have clear and definite, stable deixis.
At this, is that 1: 7.5～1: 12.5 weight ratio is mixed when using with methyl violet and quinaldine red by 1: 1～1: 15, optimum value, quinaldine red can not influence methyl violet can become purple when the relative humidity that reaches about 30% colourity to be changed, and this effect with its as to become red indicator also uncorrelated by colourless.In addition, surpass at 30% o'clock still can keep its color in relative humidity to methyl violet is also not influence of purple, and is 30% to present the dark red to light red of level between 90% the time in relative humidity.
Above-mentioned quinaldine red does not reach at 1 o'clock with respect to the weight ratio of methyl violet, influenced by methyl violet, reach in relative humidity and still to present purple and colourity more than 30% and change not obviously, surpass at 15 o'clock in weight ratio on the contrary, even relative humidity changes not obvious also can presenting redness and colourity below 30%.Therefore all be undesirable.
On the other hand, even the weight ratio of methyl violet and quinaldine red satisfied described 1: 1～1: 15, if its addition not reach then tone can be thin out, thereby it is undesirable, on the contrary, if its addition surpasses above-mentioned scope, then extremely heavy, whole dark and its colourity that cause of tone changes and is difficult to identification, thereby also undesirable.
According to the hygroscopic agent with multistage self-deixis of the present invention, its porous hygroscopic agent is silica (silica), alumina silicate (alumino-silicate), zeolite (zeolite), smectite (montmorillonite), activated charcoal (activated carbon), calcium oxide (CaO), calcium sulphate (CaSo
4), the potpourri of lime chloride or these materials.Though the present invention does not get rid of these materials, preferably use silica gel (silica gel), silico-aluminate pearl (aluminosilicate bead) and zeolite.Not only as parching agent but also, and consider security and cost issues, use silica gel to be optimal selection as conditioning agent.
According to the hygroscopic agent with multistage self-deixis of the present invention, comprise that in the following manner the potpourri that forms is as multistage self-indicator: with the general assembly (TW) of hygroscopic agent with multistage self-deixis as benchmark, the content of methyl violet is 0.0005～0.5wt%, optimum value is 0.01～0.2wt%, under the particular case 0.01～0.1wt%, the content of quinaldine red is 0.0005～7.5wt%, optimum value is 0.01～5.0wt%, be 0.1～3wt% under the particular case, and the weight ratio of methyl violet and quinaldine red it is 1: 1～1: 15, optimum value is 1: 7.5～1: 12.5.Multistage self-indicator is dissolved in the aqueous solution of ethanol and so on, is adjusted to pH3.5～4.5, optimum value and is 3.8～4.2 acid solution, carry out carrying out drying behind surface spraying or the dipping, thereby finish preparation.Demonstrating the colourity that can clearly discern in its entire scope with respect to humidity changes.
On the other hand, the form that contains the hygroscopic agent of moisture absorption indicator according to the present invention can adopt powder morphology, also it can be fixed to the common bead-like body that mean diameter is 20～3000 μ m, and be accommodated under the packing with gas penetration potential, perhaps optionally the mean diameter of described hygroscopic agent is limited within the scope of 0.5～200 μ m, and it is mixed with paper pulp or synthetic resin, forming the form of pulp based paper or resin plate then, perhaps also can be the form that it is laminated to pulp based paper or resin plate surface.
In this case, above-mentioned use amount with hygroscopic agent of multistage self-deixis is that 10～80wt%, optimum value are to be 35～55wt% under 20～70wt%, the particular case, and the use amount of paper pulp or synthetic resin is that 20～90wt%, optimum value are to be 45～65wt% under 30～80wt%, the particular case.
According to the hygroscopic agent with multistage self-deixis of the present invention, prepare by following steps.
(A) step of preparation coating fluid: with the potpourri of following composition as multistage self-indicator: with the general assembly (TW) of hygroscopic agent with multistage self-deixis as benchmark, the content of methyl violet is that 0.0005～0.5wt%, optimum value are to be 0.01～0.1wt% under 0.01～0.2wt%, the particular case, the content of quinaldine red is that 0.0005～7.5wt%, optimum value are to be 0.1～3wt% under 0.01～5.0wt%, the particular case, and the weight ratio of methyl violet and quinaldine red is that 1: 1～1: 15, optimum value are 1: 7.5～1: 12.5.Multistage self-indicator is dissolved in the acid solution, is adjusted to pH3.5～4.5, is preferably 3.8～4.2, make coating fluid;
(B) application step: impregnated in the porous hygroscopic agent in the coating fluid or spray, coating fluid is uniformly distributed in porous hygroscopic agent surface; With
(C) drying steps: with the acid solution evaporative removal.
In above-mentioned steps (A), be 3.5～4.5 by in the aqueous solution of the organic dyestuff indicator of methyl violet and quinaldine red, adding acid, regulating its pH value, optimum value is 3.8～4.2, preparation acidic aqueous solution (following all titles " coating fluid ").
As the used acid of the above-mentioned acid solution of preparation, so long as the acid that can use and prepare aqueous solution together with selected organic dyestuff indicator, just there is not any restriction, but the mixed solvent of preferred single use ethanol, acetic acid, phosphoric acid, tartrate, succinic acid (succinic acid), citric acid (citric acid), maleic acid (malein acid), fumaroyl (fumaric acid) or these acid.
At this, the acidic aqueous solution of above-mentioned organic dyestuff indicator preferably comprises the coating assistant so that the porous hygroscopic agent is evenly soaked.This coating assistant can comprise for example alcohol type, particularly ethanol, but the present invention is not limited to this, if can improve coating dispersiveness, with the corresponding polar solvent of moisture absorption indicator, it is added and without particular limitation.
In above-mentioned steps (B), in the above in Zhi Bei the acid solution dipping or with its applying porous hygroscopic agent, make the moistening porous hygroscopic agent of coating fluid surface.This dipping or coating process generally carry out at normal temperatures.
In addition, in the dipping of above-mentioned steps (B) or the process,, can utilize vapour-saturated porous hygroscopic agent for avoiding producing splash phenomena to the coating of porous hygroscopic agent.Like this, when being coated with the coating fluid direct impregnation or to the porous hygroscopic agent, granularity will reduce.
In the above-mentioned steps (C), with hygroscopic agent with coating fluid moistening after, when its drying stage, under 200 ℃ of conditions, carry out 1～10 hour drying.
On the other hand, in use, hygroscopic agent is owing to absorbing moisture and colourity takes place change, if dryly once more then can return to original state to it, so still can keep the wettability deixis when reusing.
Above, in the organic dyestuff indicator aqueous solution of methyl violet and quinaldine red, add acid, and to regulate its pH value be 3.5～4.5, be preferably 3.8～4.2.It is very important that the pH value of acidic aqueous solution is adjusted in the above-mentioned scope.Because the scope of above-mentioned pH value helps hygroscopic agent when absorbing moisture, its methyl violet susceptibility reduces and the susceptibility rising of quinaldine red slightly, and change not relation with colourity, and be in the moderate acid range when following at silica gel, its packing material and packed article might be corroded, so preferably silica gel is in more than the moderate acid range.
As mentioned above, porous hygroscopic agent with multistage self-deixis involved in the present invention, owing to more than the moderate acid range, still have the wettability deixis, so according to the variation of hygroscopic capacity, to neutral range this multi-level colourity can take place by acid range and change: by blueness become purple, more progressively become slightly pinkish lilac, pink, light red, become peony at last.
As silica gel, when hygroscopic agent is produced with variform and character, accurately regulate the pH value of organic dyestuff indicator aqueous solution (aqueous solution of methyl violet and quinaldine red) and the use amount of indicator according to its character, can the most suitably regulate the colourity change point thus.
The hygroscopic agent that has multistage self-deixis among the present invention, relative humidity shows that 10% the discernible colourity of naked eyes changes when above, relative humidity shows that at 20%～60% o'clock the complete colourity that can clearly distinguish changes, and the difference according to the depth within 60%～90% scope also can fully be distinguished.Under the situation that the potpourri with methyl violet and quinaldine red uses as the organic dyestuff indicator, be blue color states when dry, after moisture absorption, then can be changed to purple with having levels, be changed to redness again, so be particularly suitable as the colourity indicating card.
On the other hand, can the hygroscopic agent of multistage self-deixis such as the Korean Patent the 894th as prior art that the applicant proposes will be had among the present invention, put down in writing for No. 629 like that, can adopt the form of paper pulp or resin plate or at an upper portion thereof the form of lamination prepare.In such cases, though the content of hygroscopic agent is unrestricted, but should be 0～80wt%, be preferably 20～70wt%, be 35～55wt% under the particular case, though the content of paper pulp or synthetic resin is unrestricted equally, with the dry weight is that benchmark should be 20～90wt%, is preferably 30～80wt%, is 45～65wt% under the particular case.
With the form of pulp based paper or when the form of lamination prepares at an upper portion thereof, can use level and smooth paper or paper mould shaping thing as the pulp based paper of underlay substrate.
When pulp based paper is used common level and smooth paper, can further implement following steps.
(D1) hygroscopic agent that will be coated with the moisture absorption indicator through above-mentioned steps (B) is spread on the level and smooth paper of smearing or be attached with adhesive linkage or double-sided adhesive tape at least one surperficial at least a portion zone (being sprayed at the step of adhesive linkage).Then, at (D2), transfer in the hothouse, the drying means that for example uses warm-air pipe, infrared heater and so on below 200 ℃, be preferably between 70～80 ℃, made the adhesive linkage sclerosis in dry 0.5～4 hour, by making the hygroscopic agent drying, hygroscopic agent can be permanently secured to (sclerosis and drying stage) on the level and smooth paper simultaneously.Alternatively, at (D3),, remove the mask means if when forming specific pattern and implement mask process.Afterwards, at (D4), the remaining hygroscopic agent that does not adhere on the level and smooth paper is cleared away by round brush and air blast (for example, carrying out 30～50 seconds air purge under the air pressure of 5～7kbar), reclaims (cleaning stage) by recycle bin then.
Kind as adhesive linkage, in order fully to play the effect of permanent fixation, though there is not particular restriction, but can use aqueous acrylamide acid copolymer or polyether polyols with reduced unsaturation any thing, the material of using always in the cementing agent field that contains cationic, anionic property or nonionic pigment and pertroleum wax as principal ingredient.In addition, though the sclerosis thickness of described adhesive linkage is arbitrarily in the present invention, its general thickness is that 30～300 μ m, preferred thickness are 50～150 μ m, 90～120 μ m more preferably.
When pulp based paper is used paper mould, can further implement following steps.
(E1) hygroscopic agent that has been coated with the moisture absorption indicator in the above-mentioned steps (B) is mixed in the pulp liquor of beating and separation, the paper stage is copied in enforcement, afterwards at (E2), transfer in the exsiccator, use dry means as described above, below 200 ℃, be preferably between 70～80 ℃ dry 0.5～4 hour, perhaps air drying is 1～2 day, can obtain being fixed with in level and smooth paper or the paper mould shaping thing with the given shape moulding paper mould shaping thing of hygroscopic agent in view of the above.
In addition, alternatively, in the form of using synthetic resin board or when the form of lamination is made at an upper portion thereof, can carry out following steps: (F1) behind the melted synthetic resin with tygon, polypropylene, polyurethane and so on, extrusion modling is on sheet material, simultaneously, be spread in applied the hygroscopic agent of moisture absorption indicator (hygroscopic agent spreading stage) in the above-mentioned steps (B); (F2) make the hygroscopic agent sclerosis, thereby hygroscopic agent is fixed at least one surperficial going up (sclerosis is the stage fixedly) of sheet material.Perhaps alternatively at (G1), the synthetic resin (hygroscopic agent mix stages) of the tygon after the hygroscopic agent that will be coated with the moisture absorption indicator in above-mentioned steps (B) is mixed in fusion, polypropylene, polyurethane and so on; (G2) extrusion modling and sclerosis (formative stage) on sheet material.
Though it is the thickness of above-mentioned pulp based paper or resin plate can be arbitrarily in the present invention, general big between 0.1～0.5mm.
In addition, when the hygroscopic agent that has multistage self-deixis among the present invention is used for multistage colourity indicating card, variable color colourity photochrome under each rank relative humidity is printed on the banded card paper as standard, hygroscopic agent on other regional parts among spraying or bonding the present invention, its colourity is changed and above-mentioned standard contrast, in view of the above can be comparatively correctly the relative humidity that is held under the specific gas environment.
The hygroscopic agent that has multistage self-deixis among the present invention, can be used as relative humidity about 10%, when particularly not reaching 10% drying regime, the necessary hygroscopic agent of packing of product environment uses, also can be when relative humidity be 50% left and right sides, particularly under the necessary wet environment more than 50% of succulence packaging for foodstuff, use as conditioning agent.
Though following examples, comparative example and test do not limit the scope of the invention the effect that the present invention has actual illustration.
Embodiment 1: the preparation with hygroscopic agent of multistage self-deixis
At average particle diameter is in the porasil of 1800 μ m, and methyl violet and quinaldine red are used as the moisture absorption indicator.With the silica gel normal temperature dipping in the solution that is constituted by methyl violet 0.1wt%, quinaldine red 1wt% and alcohol 5wt% wetting after, under 150 ℃ of conditions dry 2 hours 30 minutes.
Prepared silica gel is when drying, and moisture absorption under navy blue state can present by purple and becomes slightly pinkish lilac, becomes pink, light red, final multi-level variation for dark (secretly) redness again.
Its result as a comparison, does not add situation that quinaldine red only uses methyl violet as shown in Figure 2 as shown in Figure 1.
Comparative example 1: contain the preparation of the hygroscopic agent of methyl violet and benzophenone
((benzopurpurin: the solution state blueness of serving as reasons becomes redness to benzophenone for methyl violet that preparation mixes and benzophenone; Flex point is pH1.3～5) the moisture absorption indicator, it is used for the porasil that average particle diameter is 1800 μ m.With the silica gel normal temperature dipping in the solution that constitutes by methyl violet 0.05wt%, benzophenone 0.05wt%, alcohol 5wt% wetting after, under 150 ℃ of conditions dry 2 hours 30 minutes.
Benzophenone is not painted in silica gel.
Comparative example 2: contain the preparation of methyl violet and Congo red hygroscopic agent
The methyl violet that preparation mixes and Congo red (Congo red: solution state is for to become redness by purple; Flex point is pH 3.0～5.2) the moisture absorption indicator, it is used for the porasil that average particle diameter is 1800 μ m.With the silica gel normal temperature dipping in the solution that constitutes by methyl violet 0.05wt%, Congo red 0.05wt%, alcohol 5wt% moistening after, under 150 ℃ of conditions dry 2 hours 30 minutes.
Congo red not painted in silica gel.
Comparative example 3: contain the preparation of the hygroscopic agent of methyl violet and methyl orange
Methyl violet and methyl orange (methyl orange: become yellow that preparation mixes by redness; Flex point is pH3.0～4.4) the moisture absorption indicator, it is used for the porasil that average particle diameter is 1800 μ m.With the silica gel normal temperature dipping in the solution that constitutes by methyl violet 0.05wt%, methyl orange 0.05wt%, alcohol 5wt%, make its moistening after, under 150 ℃ of conditions dry 2 hours 30 minutes.
Methyl orange is painted in silica gel, but is subjected to the influence of the darkviolet of methyl violet, and the colourity of methyl orange self changes not obvious.
Embodiment 2: the preparation of hygroscopic agent pulp based paper
The hygroscopic agent with multistage self-deixis of embodiment 1 preparation is coated on a part of zone on a surface and has smeared on the pulp based paper of adhering with epoxy resin layer, dry 2 hours 30 minutes and the adhesive linkage that hardens under 150 ℃ of conditions, the hygroscopic agent bead-like body is permanently secured on the pulp based paper with specific model, simultaneously abundant dry hygroscopic agent.At this, the weight of hygroscopic agent is that the weight of 51wt%, pulp based paper is 49wt%.
The pattern of prepared pulp based paper along with the increase of hygroscopic capacity, takes place to become purple by blueness when drying, becomes slightly pinkish lilac, pink, light red again, finally becomes wine-colored significantly multi-level variation.
Embodiment 3: the preparation of hygroscopic agent pulp based paper (paper mould)
The hygroscopic agent with multistage self-deixis (is the 50wt% of benchmark with the dry weight) of embodiment 1 preparation is mixed in kraft (kraf) the slurry beating liquid (is the 50wt% of benchmark with the dry weight), copy paper and prepare the level and smooth paper mould that thickness is 2mm, drying is 2 hours 30 minutes under 150 ℃ condition, to form the paper of plate-like form, and above-mentioned hygroscopic agent is fixed in the paper mould, meanwhile, abundant dry hygroscopic agent.
Prepared paper mould begins moisture absorption under blue color states when drying, become purple, slightly pinkish lilac, pink, light red again, finally become dark (secretly) redness, changes at many levels.
Embodiment 4: the preparation of hydroscopicity synthetic resin board
With the hygroscopic agent spreading with multistage self-deixis of embodiment 1 preparation in scribbling on the synthetic resin board of adhering with epoxy resin layer in a lip-deep a part of zone, under 110 ℃ of conditions, adhesive linkage was hardened in dry 2 hours 30 minutes, and the bead-like body of hygroscopic agent permanently is fixed on the pulp based paper with specific pattern, make hygroscopic agent fully dry simultaneously.At this, the weight of hygroscopic agent is that the weight of 38wt%, synthetic resin is 62wt%.
Model on the prepared synthetic resin board when drying, moisture absorption under blue color states, and gradually become purple, slightly pinkish lilac, pink, light red, finally become dark (secretly) redness, thus the variation of distinctness takes place at many levels.
Embodiment 5: the preparation of hydroscopicity synthetic resin board
With the coating of embodiment 1 preparation the hygroscopic agent and the mixed also fusion of polyvinyl resin (is that standard is 80wt% with the dry weight) of moisture absorption indicator, extrusion molding afterwards, prepare the synthetic resin board that thickness is 1.5mm, under 80 ℃ condition dry 2 hours 30 minutes and hygroscopic agent is fixed in the polyvinyl resin plate, make hygroscopic agent fully dry simultaneously.
Prepared polyvinyl resin plate when drying, moisture absorption under blue color states, and gradually become purple, slightly pinkish lilac, pink, light red, finally become dark (secretly) redness, thus the variation of distinctness takes place at many levels.
Embodiment 6: the preparation of colourity indicating card
Be that the colourity that is changed under 0%, 20%, 40%, 50%, 60%, 90% the condition takes color photographs with the hygroscopic agent with multistage self-deixis of embodiment 1 preparation in relative humidity, after standard print is on copy paper, duplicate again on a lip-deep copy paper of banded pulp based paper.Then, smear the adhering with epoxy resin layer not adhering on a part of zone of copy paper, with above-mentioned hygroscopic agent spreading, bonding after under 150 ℃ condition dry 2 hours 30 minutes, thereby make the adhesive linkage sclerosis, and a part of zone that the pearl hygroscopic agent is permanently secured to the pulp based paper surface gone up as measurement section, make hygroscopic agent fully dry simultaneously.
The colourity of the measurement section of prepared colourity indicating card and the photochrome under above-mentioned each level relative humidity are done contrast, can measure the relative humidity in the atmosphere in the specific region.
Test example 1: the hydroscopicity and the colourity that are caused by relative humidity change
The moisture content that has the corresponding hygroscopic agent that is caused by relative humidity variations of hygroscopic agent of multistage self-deixis in measurement and observation and the foregoing description 1 changes and colourity changes, its result as shown in the following Table 1, concrete colourity changes with reference to Fig. 1.
[table 1]
In addition, among the embodiment 1 to embodiment 5, will cause that hygroscopic agent that colourity changes under 150 ℃ of conditions dry about 2 hours 30 minutes once again, can be reduced to initial mazarine once again.
The effect of invention
The hygroscopic agent that has multistage self-deixis among the present invention is in middle acidity good moisture absorption deixis of display sensitivity in the faintly acid scope, so change irrelevant with colourity, needn't worry the packaged thing corrosion that is caused by hygroscopic agent, harmless, without detriment to environment, and its colourity becomes purple according to the moisture absorption degree by navy blue, become again slightly pinkish lilac, pink, light red, finally become peony, multi-level significant change takes place, thereby the primary demand person and the trader that meet in the past have impressive safety indication look for blue, dangerous indication look is red theory, shows stable deixis. Therefore, be to parch agent for the necessary environment of the drying regime of relative humidity about 10%, play the effect of conditioning agent for the necessary environment of the drying regime of relative humidity about 50%. And, can effectively replace the harmful cobalt chloride of existing use is the silica gel of indicator, optionally with the form moulding of paper pulp paper or the resin plate of card form, perhaps with lamination when the form on surface is used, needn't worry fully because eating by mistake of infant also do not worried in user's carelessness or the food pollution that the infant causes.
Claims (8)
1. the hygroscopic agent that has multistage self-deixis, comprise multistage self-indicator, surplus is the porous hygroscopic agent, the described multistage self-indicator potpourri that to be methyl violet and quinaldine red form with 1: 1～1: 15 weight ratio, general assembly (TW) with hygroscopic agent with multistage self-deixis is a benchmark, methyl violet is that 0.0005～0.5wt%, quinaldine red are 0.0005～7.5wt%
Described multistage self-indicator is uniformly distributed in the porous hygroscopic agent.
2. the hygroscopic agent with multistage self-deixis according to claim 1, the described multistage self-indicator potpourri that to be methyl violet and quinaldine red form with 1: 1～1: 15 weight ratio.
3. the hygroscopic agent with multistage self-deixis according to claim 1 and 2, described porous hygroscopic agent is a silica gel.
4. the hygroscopic agent with multistage self-deixis according to claim 1 is the form of pulp based paper, synthetic resin board or colourity indicating card.
5. the hygroscopic agent with multistage self-deixis according to claim 4, the weight of slurry paper or synthetic resin board accounts for 20～90wt%.
6. have the preparation method of the hygroscopic agent of multistage self-deixis, may further comprise the steps:
(A) step of preparation coating fluid, be dissolved in multistage self-indicator in the acidic aqueous solution and be adjusted to coating fluid, the weight ratio that described multistage self-indicator is methyl violet and quinaldine red is 1: 1～1: 15 a potpourri, general assembly (TW) with hygroscopic agent with multistage self-deixis is a benchmark, and methyl violet is that 0.0005～0.5wt%, quinaldine red are 0.0005～7.5wt%;
(B) application step, thus make it be uniformly distributed in porous hygroscopic agent surface with described coating fluid dipping or spraying porous hygroscopic agent; With
(C) drying steps is with described acidic aqueous solution evaporative removal.
7. the preparation method with hygroscopic agent of multistage self-deixis according to claim 6, the solvent that utilizes when preparing described acidic aqueous solution is an ethanol.
8. the preparation method with hygroscopic agent of multistage self-deixis according to claim 6, described porous hygroscopic agent is a silica gel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090074183A KR101046774B1 (en) | 2009-08-12 | 2009-08-12 | Hygroscopic agent with multi-stage self-indicating ability and manufacturing method |
| KR10-2009-0074183 | 2009-08-12 |
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| CN101995447A true CN101995447A (en) | 2011-03-30 |
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| CN (1) | CN101995447A (en) |
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| CN102527228A (en) * | 2011-12-31 | 2012-07-04 | 南京亿谱环境服务有限公司 | Novel visible color change formaldehyde scavenger |
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| KR100390726B1 (en) * | 2000-12-18 | 2003-07-10 | 극동화학 주식회사 | Absorbents having moisture indicator using organic dyes and their method of preparation |
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2009
- 2009-08-12 KR KR1020090074183A patent/KR101046774B1/en not_active IP Right Cessation
- 2009-09-21 CN CN2009101761206A patent/CN101995447A/en active Pending
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| CN102527228A (en) * | 2011-12-31 | 2012-07-04 | 南京亿谱环境服务有限公司 | Novel visible color change formaldehyde scavenger |
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| CN109173627B (en) * | 2018-10-25 | 2021-04-09 | 青岛美高集团有限公司 | Preparation method of allochroic silica gel drying agent and allochroic silica gel prepared by same |
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| CN115320196A (en) * | 2022-08-16 | 2022-11-11 | 苏州海顺包装材料有限公司 | High-barrier moisture absorption film capable of intelligently changing color and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101046774B1 (en) | 2011-07-05 |
| KR20110016594A (en) | 2011-02-18 |
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Application publication date: 20110330 |