CN108026435A

CN108026435A - Cold insulation apparatus

Info

Publication number: CN108026435A
Application number: CN201680052998.7A
Authority: CN
Inventors: 内野绫; 田中康弘
Original assignee: Toppan Forms Co Ltd
Current assignee: Toppan Edge Inc
Priority date: 2015-09-18
Filing date: 2016-09-14
Publication date: 2018-05-11
Also published as: WO2017047648A1; TW201720906A; SG11201801341YA; TWI697555B; HK1252676A1; JP2017057377A; MY186494A; JP6765897B2

Abstract

The cold insulation apparatus possesses containing water, inorganic salts, the cold insulation composition of tackifier and pH indicator, cold insulation composition contains the acid Acidic inorganic salts of its aqueous solution display and phosphate is used as the inorganic salts, in the cold insulation composition, the Acidic inorganic salts and phosphatic total content are by mass 5~100% to the ratio of the total content of the inorganic salts, the inorganic salts that cold insulation composition contains beyond dihydric phosphate and dihydric phosphate are used as the Acidic inorganic salts, the pKa of the pH indicator is 4.9~8.0, the cold insulation composition is by phosphate, the relation that pH (α 1) in the case of all being eliminated containing component beyond dihydric phosphate and water meets to be represented by following formula (i) relative to the pKa：PKa≤pH (pKa+1.8 ... (i) of the)≤pH indicator of α 1 of pH indicator.

Description

Cold insulation apparatus

Technical field domain

The present invention relates to it is a kind of possess can easily visual confirmation cool down when color change cold insulation composition guarantor Colod-application tool.

This application claims and based on the patent application in Japanese publication on the 18th of September in 2015 the 2015-185043rd it is excellent First weigh, be hereby incorporated its content.

Background technology

Cold insulation when cold insulation apparatus is widely used in the keeping of various fresh things or during transport, is usually recycled.This Kind cold insulation apparatus possesses the cold insulation composition with cold insulation effect, and being configured to enclose the cold insulation composition has heat biography In the container for the property led.

As cold insulation composition, it is known to it is a kind of containing colouring agent so as to can be true from the easy vision in the outside of cold insulation apparatus Recognize its existing cold insulation composition.Such as, it has been disclosed that there is a kind of cold insulation apparatus, its cold insulation for being sealed with by dyestuff coloring is used Composition, can easily confirm its enclosed volume from outside (with reference to patent document 1).

But even if the cold insulation apparatus cold insulation composition described in patent document 1 contains dyestuff, confirm by visual observation Whether there is freeze etc. the state of cooling be also it is highly difficult, there are cold insulation apparatus whether be sufficiently cooled to can cold insulation expectation temperature Degree etc. is difficult to the problem of visual confirmation state of cooling is such.

Citation

Patent document

Patent document 1：Japanese patent application discloses 2006-97984 publications.

The content of the invention

The subject that the invention solves

The present invention problem be, there is provided it is a kind of can easily the visual confirmation state of cooling whether be in dbjective state guarantor Colod-application tool.

Means for solving the problems

The first aspect of the present invention is a kind of cold insulation apparatus, it possesses containing water, inorganic salts, tackifier and pH indicator Cold insulation composition, wherein, as the inorganic salts, the cold insulation composition contains the acid acidity of its aqueous solution display Inorganic salts and phosphate, in the cold insulation composition, the Acidic inorganic salts and phosphatic total content are to described The ratio of the total content of inorganic salts is by mass 5~100%, and as the Acidic inorganic salts, the cold insulation is contained with composition There are the inorganic salts beyond dihydric phosphate and dihydric phosphate, the pKa of the pH indicator is 4.9~8.0, the cold insulation group PH (α 1) of the compound in the case of all being eliminated containing component beyond by phosphate, dihydric phosphate and water relative to The pKa meets the relation represented by following formula (i)：

PKa≤pH (pKa+1.8 ... (i) of the)≤pH indicator of α 1 of pH indicator

In the first aspect of the present invention, the pH of the cold insulation composition can be 4.6~8.8.

In the first aspect of the present invention, the cold insulation composition can be containing beyond by the tackifier and water Have component all substituted for water in the case of pH (α 3) become 6.0~8.5.

In addition, the second aspect of the present invention is a kind of cold insulation apparatus, it possesses containing water, inorganic salts, tackifier and pH The cold insulation composition of indicator, wherein, as the inorganic salts, it is acid that the cold insulation composition contains the display of its aqueous solution Acidic inorganic salts and dibasic alkaliine, in the cold insulation composition, the Acidic inorganic salts and dibasic alkaliine Total content is by mass 5~100% to the ratio of the total content of the inorganic salts, in the cold insulation composition, phosphorus The content of sour monohydric salt is by mass 0.2~5.0% to the ratio of the total content of water, the inorganic salts and tackifier, institute The pKa for stating pH indicator is 4.9~8.0.

In the second aspect of the present invention, the pH of the cold insulation composition can be 4.7~8.0.

In the second aspect of the present invention, the cold insulation composition can be containing beyond by the tackifier and water Have component all substituted for water in the case of pH (α 3) become 6.0~9.1.

In addition, the third aspect of the present invention is a kind of cold insulation apparatus, it possesses containing water, inorganic salts, tackifier and pH The cold insulation composition of indicator, wherein, as the inorganic salts, it is acid that the cold insulation composition contains the display of its aqueous solution Acidic inorganic salts, in the cold insulation composition, the contents of the Acidic inorganic salts is to the total contents of the inorganic salts Ratio is by mass 5~100%, the cold insulation composition all being used containing component beyond by the inorganic salts and water PH (α 2) in the case that water substituted for becomes less than 7, cold insulation composition the containing beyond by the tackifier and water Have component all substituted for water in the case of pH (α 3) become more than 7, pH (α 2) and pH (α 3) expression refer to less than the pH Show the pH of the color change interval of agent, the pH of color change interval and higher than the pH different from each other in tri- pH regions of pH of color change interval The value in region.

The effect of invention

Whether the cold insulation apparatus of the present invention easily the visual confirmation state of cooling can be in dbjective state.

Embodiment

The preferable example of the cold insulation apparatus of the present invention is being illustrated below.But the present invention is not only defined in These examples, for example, can without departing from the scope of spirit of the present invention be added, omitted, replaced and other changes (amount, number, position, size etc.).

In the present specification, the unit " ppm " of content (use level, concentration) is unless otherwise stated, be all based on matter Amount ratio.

《First embodiment》

The present invention first embodiment involved by cold insulation apparatus be one kind possess containing water, inorganic salts, tackifier with And the cold insulation apparatus of the cold insulation composition of pH indicator, wherein, as the inorganic salts, the cold insulation composition contains it Aqueous solution display acid Acidic inorganic salts and phosphate, in the cold insulation composition, the Acidic inorganic salts and phosphorus Total content of hydrochlorate is by mass 5~100% to the ratio of the total content of the inorganic salts, and the cold insulation is contained with composition There are the inorganic salts beyond dihydric phosphate and dihydric phosphate as the Acidic inorganic salts, the pKa of the pH indicator is 4.9 ~8.0, the cold insulation all being eliminated containing component beyond by phosphate, dihydric phosphate and water with composition In the case of pH (α 1) relative to the pKa meet by following formula (i) represent relation.

PKa≤pH (pKa+1.8 ... (i) of the)≤pH indicator of α 1 of pH indicator

It is very big that the color of the cold insulation composition of the cold insulation apparatus in cold insulation composition freezes front and rear change. This, cold insulation reflects pH indicator whether there is colour developing with the color of composition.Therefore, the cold insulation apparatus being capable of easy visual confirmation Whether the state of cooling is in dbjective state (state that can be sufficiently cool object).Moreover, cold insulation composition is freezing Front and rear color and the non-principal color containing component reflected beyond the pH indicator such as the inorganic salts, tackifier in itself.

Cold insulation in first embodiment composition contains inorganic salts and tackifier as exerting one's influence to its acidity Component.Moreover, in the cold insulation composition, the dihydric phosphate of Acidic inorganic salts is selected as, as Acidic inorganic salts Dihydric phosphate beyond inorganic salts and phosphate this particular combination as the inorganic salts, limit these inorganic salts Content, and these inorganic salts are applied in combination with the pH indicator that pKa is within a certain range.The guarantor with this composition Colod-application composition depends on the presence or absence of change or colour developing of the colour developing of pH indicator and significantly greatly carries out color change.

＜ inorganic salts ＞

The inorganic salts in first embodiment play a role as a component of cold-retaining agent, cold insulation composition Solidification point mainly by its species and amount determine.

In addition, the inorganic salts are not equivalent to the component of the pH indicator, when cold insulation composition freezes, as Crystal or amorphous body (noncrystalline) and separate out, whether there is by it separate out participate in cold insulation composition color change.

The cold insulation composition in first embodiment contain the acid Acidic inorganic salts of its aqueous solution display and Phosphate contains the inorganic salts beyond dihydric phosphate and dihydric phosphate as the acidity as the inorganic salts Inorganic salts.

[Acidic inorganic salts]

(dihydric phosphate)

In the first embodiment, the dihydric phosphate as the Acidic inorganic salts is phosphoric acid (H₃PO₄) in a hydrogen The inorganic salts that ion is substituted by cation, either non-hydrate or hydrate.

As the dihydric phosphate in first embodiment, for example, can include：Sodium dihydrogen phosphate (NaH₂PO₄), phosphoric acid Potassium dihydrogen (KH₂PO₄), calcium dihydrogen phosphate (Ca (H₂PO₄)₂) etc. biphosphate metal salt；Ammonium dihydrogen phosphate (NH₄H₂PO₄) etc. phosphoric acid Dihydro non-metal salt etc..

Dihydric phosphate that cold insulation composition in first embodiment contains either it is only a kind of or It is two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

(inorganic salts beyond dihydric phosphate)

In the first embodiment, as long as the inorganic salts beyond the Acidic inorganic salts, dihydric phosphate its The acid inorganic salts of aqueous solution display are then just not particularly limited, either non-hydrate or hydrate.

As the inorganic salts beyond the dihydric phosphate in first embodiment, for example, can include：Ammonium chloride (NH₄Cl), magnesium chloride (MgCl₂), ammonium sulfate ((NH₄)₂SO₄), ammonium nitrate (NH₄NO₃), aluminum sulfate (Al₂(SO₄)₃), alum (AlK(SO₄)₂), ammonia-alum (Al (NH₄)(SO₄)₂), calcium nitrate tetrahydrate (Ca (NO₃)₂·4H₂O), calcium nitrate (Ca (NO₃)₂) etc., preferably ammonium chloride, ammonium nitrate.

Inorganic salts beyond the dihydric phosphate that cold insulation composition in first embodiment contains are either only It is a kind of or two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

[phosphate]

The phosphate in first embodiment is phosphoric acid (H₃PO₄) in three hydrogen ions substituted by cation and form Salt, either non-hydrate or hydrate.

The phosphate is typically the basic salt of its aqueous solution display alkalescence.

As the phosphate in first embodiment, for example, can include：Tertiary sodium phosphate (Na₃PO₄), tertiary sodium phosphate 12 Hydrate (Na₃PO₄·12H₂O), tripotassium phosphate (K₃PO₄) etc. tricresyl phosphate metal salt；Triammonium phosphate ((NH₄)₃PO₄) etc. tricresyl phosphate Non-metal salt etc., preferably tertiary sodium phosphate (Na₃PO₄), Trisodium phosphate dodecahydrate, tripotassium phosphate (K₃PO₄)。

The phosphate that cold insulation composition in first embodiment contains is either there was only one kind or two kinds More than, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

[other inorganic salts]

Cold insulation composition in first embodiment can be removed containing the Acidic inorganic salts (dihydric phosphate and phosphoric acid Inorganic salts beyond dihydric salt) and phosphate beyond also contain not equivalent to other inorganic salts conducts of any one in these salt The inorganic salts.

Other inorganic salts are either non-hydrate or hydrate.

As long as other inorganic salts in first embodiment are not particularly limited without damaging effect of the invention then, For example, it can include：The nothing in addition to phosphate of the neutral neutral inorganic of its aqueous solution display, its aqueous solution display alkalescence Machine salt etc..

As the neutral inorganic, for example, can include：Sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl₂), sodium sulphate (Na₂SO₄), potassium sulfate (K₂SO₄), magnesium sulfate (MgSO₄), sodium nitrate (NaNO₃), potassium nitrate (KNO₃), bromine Change potassium (KBr), sodium bromide (NaBr), potassium iodide (KI), sodium iodide (NaI), potassium chlorate (KClO₃), sodium perchlorate (NaClO₄)、 Sodium thiosulfate (Na₂S₂O₃) etc..

Among those, the neutral inorganic is preferably sodium chloride or potassium chloride.

Alkaline, inorganic salts beyond the phosphate are preferably the inorganic salts beyond dibasic alkaliine, for example, can include： Sodium carbonate (Na₂CO₃), potassium carbonate (K₂CO₃), sodium acid carbonate (NaHCO₃), saleratus (KHCO₃), sodium sulfite (Na₂SO₃)、 Borax (Na₂B₄O₇) etc..

Among those, the alkaline, inorganic salts beyond the phosphate are preferably sodium carbonate or potassium carbonate.

Other inorganic salts that cold insulation composition in first embodiment contains also may be used either only one kind To be two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

In cold insulation composition under first embodiment, the Acidic inorganic salts and phosphatic total content are to institute The ratio for stating the total content of inorganic salts is by mass 5~100%, preferably by mass 5.5~100%.Pass through the ratio Example is more than the lower limit, so that cold insulation composition is freezing front and rear color change increase.

Among such number range, as the lower limit of the ratio, for example, can select by mass 10%, 20%th, 30%, 40%, 45% etc., but be not limited to these.In addition, among such number range, as the ratio Upper limit value, for example, by mass 90%, 80%, 70%, 60%, 55% etc. can be selected, but is not limited to these.

Before the freezing of first embodiment in preferably more than 0 DEG C of cold insulation composition, the meltage of the inorganic salts More how the more preferred, the amount dissolved in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by matter Gauge more than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

In addition, in the cold insulation composition after the freezing of first embodiment, the amount of precipitation of the inorganic salts it is more more more It is preferred that the amount separated out in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by mass More than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

The total content of the inorganic salts of cold insulation composition in first embodiment is preferably by mass 5~35%, more Preferably by mass 10~30%, particularly preferably by mass 15~25%.

＜ tackifier ＞

The tackifier in first embodiment are that the viscosity for making cold insulation composition increases, do not refer to equivalent to the pH Show the component of agent.The tackifier in first embodiment are not preferably separated out when cold insulation is freezed with composition.In this explanation In book, so-called " tackifier are not separated out when cold insulation is freezed with composition ", it is meant that the tackifier when cold insulation composition freezes Holding is dissolved in the state cured of water, thus it is speculated that is surrounded by water molecules all the time to be a kind of little duration set of the molecule of tackifier Cured state, thus it is speculated that for the not substantial amounts of cured state of tackifier elements collection.

As the tackifier in first embodiment, it is not particularly limited, for example, can include：Polyacrylic acid, gather The acrylic acid series polymeric compounds such as sodium acrylate (compound with polyacrylic acid skeleton)；The carboxyalkyls such as carboxymethyl cellulose (CMC) Cellulose；Guar gum；The guars such as hydroxypropyl guar gum；Pectin；Xanthans；Tamarind gum；Carragheen；Propane diols etc. Alkylene glycol etc..

The tackifier in first embodiment are preferably selected from by acrylic acid series polymeric compounds, carboxyl alkyl cellulose, Huang Virgin rubber, guar gum, guar, pectin, tamarind gum, carragheen and alkylene glycol composition group more than one.

Moreover, the tackifier are more preferably selected from by acrylic acid series polymeric compounds, carboxyl alkyl cellulose, xanthans, Guar Glue and guar composition group more than one.

By using such tackifier, discoloration of the cold insulation composition before and after freezing is big and operability is more excellent.

The tackifier that cold insulation composition in first embodiment contains are either there was only one kind or two kinds More than, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

In cold insulation composition before the freezing of first embodiment and after freezing, the amount of precipitation of tackifier is more few more excellent To select, the amount separated out in the total amount of tackifier is preferably by mass less than 10%, more preferably by mass less than 5%, More preferably by mass less than 2%, particularly preferably by mass 0% (whole amount does not all separate out).

The content of the tackifier of cold insulation composition in first embodiment is preferably by mass 0.1~10%, more Preferably by mass 0.3~6%, particularly preferably by mass 0.6~3%.

＜ pH indicator ＞

The pH indicator (acid-base indicator) in first embodiment is to reflect the presence or absence of its colour developing to determine cold insulation With the component of the color of composition.Cold insulation composition containing pH indicator by freezing front and rear color change.

As long as the indicator that the pH indicator pKa in first embodiment is 4.9~8.0 does not just limit especially then It is fixed.

The pKa of pH indicator in present embodiment unless otherwise stated, mean solvent be water, temperature be Value in the case of 25 DEG C.

PH indicator has the pH scopes, that is, color change interval for observing its discoloration.PH indicator be divided into the solution dissociation shape and Not dissociating shape and exist, dissociation equilibrium is set up between them, does not dissociate in dissociation shape and the color difference presented between shape, but Outside color change interval, the obvious relatively dissociation shape of balance or do not dissociate shape either one, only see the color of a side.Moreover, in transformation region In domain, the dissociation shape of pH indicator and shape is not dissociated mixed with the amount of comparable degree, it can be seen that both colors Mix (" chemical voluminous dictionary minimo the 39th prints, on September 15th, 2006 ", vertical altogether to publish Co., Ltd. ").

The example of main pH indicator is shown in table 1.Record its discoloration in the lump together with pH indicator in table 1 Region and color change." color change (low pH → high pH) " in so-called table 1 means in the liquid containing pH indicator The color change that pH indicator is shown in color change interval when pH has changed from being specifically worth to the value higher than the value, for example, institute It is yellow that meaning " red → yellow ", which means that pH indicator makes the liquid change colour from red during the pH of the liquid becomes higher,.

Table 1

For example preferably its color change interval (pH) is in the range of 3.0~10.5 pH indicator in first embodiment, It is more preferably in the range of 4.0~9.5, particularly preferably in the range of 4.5~9.0.

The pH indicator that cold insulation composition in first embodiment contains is either there was only one kind or two More than kind, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.However, it is often preferred to comprise only one Kind pH indicator.

As long as the content of the pH indicator of the cold insulation composition in first embodiment may achieve cold insulation composition Target discoloration is then just not particularly limited, but preferably 1~30ppm, more preferably 5~20ppm.

The other component ＞ of ＜

Cold insulation composition in first embodiment can remove water, inorganic salts, tackifier and pH indicator are with external Do not damage in the range of the effect of the present invention containing not equivalent to other components of these components., can as other components Include：Solvent beyond water；Well-known various additives such as preservative, surfactant etc..

Other components that cold insulation composition in first embodiment contains, can also either only one kind It is two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

(solvent)

The solvent in first embodiment is preferably able to dissolve the inorganic salts, tackifier and pH indicator, makees For such solvent, for example, ethanol etc. can be included.

Water and the solvent are the components to play a role as a component of cold-retaining agent, together with the inorganic salts, The solidification point of cold insulation composition is mainly determined by their species and amount.

In cold insulation composition under first embodiment, the total content of the content of the solvent to water and the solvent Ratio be preferably by mass less than 10%, more preferably by mass less than 5%, particularly preferably by mass 2% with Under.

(preservative)

As the preservative in first embodiment, for example, can include：Food preservative, antioxidant etc., more Specifically, can include：It is Pyrithione Sodium, p-hydroxybenzoate (para-hydroxybenzonate), nucleoprotamine, organic Nitrogen chalcogenide compound etc..

Cold insulation in first embodiment is not particularly limited with the content of the preservative of composition, but is preferably to press quality Meter 0.02~0.5%, more preferably by mass 0.04~0.2%.

(surfactant)

As the surfactant in first embodiment, well-known surfactant can be included, for example, It can include：The alkyl sulfates such as lauryl sodium sulfate；The alkyl carboxylates such as sodium caprate；The N- alkane such as n-isopropyl acrylamide Base acrylamide；The polyoxyethylene dialkyl ether such as polyoxethylene octylphenyl lauryl ether；The polyoxyethylene such as polyoxyethylene laurel ether Monoalky lether；Polyoxyethylene mono alkenyl ether such as polyoxyethylene oleyl ether etc..

For the cold insulation composition in first embodiment, the inorganic salts, tackifier and pH indicator always contain Measure to beyond water and the solvent component (beyond the inorganic salts, tackifier, pH indicator and the solvent it is other into Point) total content ratio be preferably by mass more than 90%, more preferably by mass more than 93%, more preferably By mass more than 96%, particularly preferably by mass more than 98%, or by mass 100%.By described total The ratio of content is more than the lower limit, so that cold insulation composition is freezing front and rear color change bigger.

Cold insulation composition in first embodiment contains component beyond by phosphate, dihydric phosphate and water The relation that pH (α 1) in the case of all eliminating meets to be represented by following formula (i) relative to the pKa of the pH indicator：

PKa≤pH (pKa+1.8 ... (i) of the)≤pH indicator of α 1 of pH indicator

PH (α 1) is equivalent to only by phosphate, the phosphorus of the amount same amount contained with the cold insulation composition in first embodiment The pH for the mixed liquor (such as aqueous solution containing phosphate and dihydric phosphate) that acid dihydride salt and water are obtained by mixing.pH(α 1) become in the cold insulation with the phosphate used in composition and the index of the acidity of the mixture of dihydric phosphate.

PH (α 1) is preferably the PH at the temperature that pH indicator has been dissolved in the cold insulation composition, more preferably institute The pH when temperature for stating mixed liquor is 25 DEG C.

PH (α 1) is further 5.0~10.6 preferably on the basis of the relation of the formula (i) is met, more preferably 5.3~10.3, particularly preferably 5.6~10.0.

Cold insulation in first embodiment is preferably 4.6~8.8 with the pH of composition, and more preferably 4.9~8.5, especially Preferably 5.1~8.3.

Cold insulation in first embodiment has preferably been dissolved in the cold insulation composition with composition in pH indicator At a temperature of show the PH of the number range, more preferably show the number when it is 25 DEG C that the cold insulation is with the temperature of composition It is worth the PH of scope.

In the present embodiment, it is unless otherwise indicated, no on description as simple " pH " of cold insulation composition Then mean the pH of cold insulation composition in itself.

Cold insulation in first embodiment all uses water beyond by the inorganic salts and water with composition containing component PH (α 2) in the case of substituted for is preferably 4.4~8.7, and more preferably 4.9~8.2.

PH (α 2) is equivalent to the content (quality identical with the content (mass percent) in the cold insulation composition Percentage) comprise only the pH containing inorganic brine (such as inorganic salt solution) of the inorganic salts.PH (α 2) becomes in the guarantor The index of the acidity of the inorganic salts used in colod-application composition.

PH (α 2) is preferably the PH at the temperature that pH indicator has been dissolved in the cold insulation composition, more preferably institute State containing inorganic brine be 25 DEG C when pH.

Cold insulation in first embodiment all uses water beyond by the tackifier and water with composition containing component PH (α 3) in the case of substituted for is preferably 6.0~8.5, and more preferably 6.0~8.3, for example, both can be 6.0~8.0, Can also be 6.5~7.5.

PH (α 3) is equivalent to the content (quality identical with the content (mass percent) in the cold insulation composition Percentage) comprise only the tackifier water containing tackifier (such as tackifier water solution) pH.PH (α 3) becomes in the guarantor The index of the acidity of the tackifier used in colod-application composition.

PH (α 3) is preferably the PH at the temperature that pH indicator has been dissolved in the cold insulation composition, more preferably exists The pH when water containing tackifier is 25 DEG C.

Cold insulation composition in first embodiment by hydrous water, the inorganic salts, tackifier, pH indicator and As needed other components and obtain.

The fitting method of each component is not particularly limited, and can be appointed at the temperature higher than the solidification point of cold insulation composition Meaning is adjusted so that each component is equably dissolved or disperseed.

For example, when coordinating each component, they can both be mixed again after it with the addition of whole components, can also side according to Secondary a part of component side of addition is mixed, and can also be mixed when adding whole components successively.

Mixed method is not particularly limited, and can suitably be selected from following well-known methods：Make stirring parts or stir The method for mixing the rotations such as blade to be mixed；Using blender, three-roller, kneader or ball mill etc. come the side that is mixed Method；Method for applying ultrasonic wave to be mixed etc..

Cold insulation apparatus involved by the first embodiment of the present invention is that possess the apparatus for having the cold insulation composition, is led to Cross using such as can enclose liquid material it is container-like, bag-shaped holding meanss formed to keep cold insulation composition.

The color change for the cold insulation composition that the material of the holding meanss is kept as long as there is energy visual confirmation (becomes Color) degree the transparency, then be just not particularly limited.

As the material of preferable holding meanss, for example, can include：The polyolefin such as polyethylene, polypropylene；Polyamide； Synthetic resin such as polyester etc..As polyethylene, for example, can include：Low density polyethylene (LDPE) (LDPE), straight-chain low density polyethylene (LLDPE), high density polyethylene (HDPE) (HDPE) etc..

The holding of the form of such as holding meanss, cold insulation composition can be contemplated in the material and size of the holding meanss Amount or cold insulation are selected with composition freezing front and rear method of color change etc..

For example, in the case of for bag-shaped holding meanss, can as an example of the material of preferable holding meanss Include low density polyethylene (LDPE).In addition, in the case of for container-like holding meanss, the material as preferable holding meanss An example, high density polyethylene (HDPE) can be included.

For example, bag-shaped holding meanss are being used as the situation i.e. maintenance dose of cold insulation composition of small holding meanss In the case of fewer preferably.In addition, container-like holding meanss are used in the situation i.e. cold insulation for being used as big holding meanss In the case that the maintenance dose of composition is relatively more preferably.

But the system of selection of the material and size of a holding meanss shown here only example.

The material of the holding meanss in terms of low temperature resistant brittleness, water resistance and resistance to chemical reagents etc. are excellent on be preferably Polyolefin, further, shaping easily, have high intensity in terms of on more preferably high density polyethylene (HDPE).

The thickness at the flat position such as the membranaceous or sheet in the holding meanss is not particularly limited, but preferably 5~200 μm。

The flat position is either the position being made of individual layer or the portion being made of more than two layers of multilayer Position.In the case of being made of at the flat position multilayer, these multilayers are mutually the same and different.That is, either institute The all identical or all layer of some layers is all different or only part layer is identical.Moreover, in multiple layers each other In the case of difference, these multiple layers combinations are not particularly limited.Here, so-called multiple layers are different from each other to mean each layer Material and thickness at least one party it is different from each other.

In the case of being made of at the flat position multilayer, the aggregate thickness of each layer can be made become above-mentioned preferable The thickness at flat position.

Cold insulation composition in first embodiment is due to freeze front and rear color change very big, can easily regard Feel confirmation whether there is to freeze.Moreover, this color change of cold insulation composition can be from the outside visual confirmation of cold insulation apparatus.By This, whether cold insulation apparatus easily can be sufficiently cooled to preferred temperature by visual confirmation.

In addition, even if the cold insulation composition freezes and thaw repeatedly etc. that cooling and heating is repeated, will not damage Evil effect.Therefore, possessing has the cold insulation to be also suitable for recycling with the cold insulation apparatus of composition.

《Second embodiment》

Cold insulation apparatus involved by second embodiment of the present invention be one kind possess containing water, inorganic salts, tackifier with And the cold insulation apparatus of the cold insulation composition of pH indicator, wherein, it is acid that the cold insulation composition contains the display of its aqueous solution Acidic inorganic salts and dibasic alkaliine as the inorganic salts, in the cold insulation composition, the Acidic inorganic salts Total content with dibasic alkaliine is by mass 5~100% to the ratio of the total content of the inorganic salts, in the cold insulation With in composition, the content of dibasic alkaliine is by mass to the ratio of the total content of water, the inorganic salts and tackifier 0.2~5.0%, the pKa of the pH indicator is 4.9~8.0.

It is very big that the color of the cold insulation composition of the cold insulation apparatus in cold insulation composition freezes front and rear change. This, cold insulation reflects pH indicator whether there is colour developing with the color of composition.Therefore, the cold insulation apparatus being capable of easy visual confirmation Whether the state of cooling is in dbjective state (state that can be sufficiently cool object).Moreover, cold insulation composition is before freezing Color and the non-principal color containing component reflected beyond the pH indicator such as the inorganic salts, tackifier in itself afterwards.

Cold insulation in second embodiment composition contains inorganic salts and tackifier as exerting one's influence to its acidity Component.Moreover, in the cold insulation composition, particular combination as Acidic inorganic salts and dibasic alkaliine is selected as institute Inorganic salts are stated, define the content of these inorganic salts, to dibasic alkaliine, also define its content to water, inorganic salts and increasing The ratio of the total content of stick, and these inorganic salts and tackifier have been applied in combination with the pH that pKa is within a certain range and has been referred to Show agent.The cold insulation with this composition is shown with the presence or absence of the change or colour developing of composition dependent on the colour developing of pH indicator Write ground and greatly carry out color change.

＜ inorganic salts ＞

The inorganic salts in second embodiment play a role as a component of cold-retaining agent, cold insulation composition Solidification point mainly by its species and amount determine.

The cold insulation composition in second embodiment contains the acid Acidic inorganic salts and phosphorus of its aqueous solution display Sour monohydric salt is as the inorganic salts.

[Acidic inorganic salts]

The Acidic inorganic salts in second embodiment are not particularly limited, and can suitably be selected according to purpose, both may be used To be non-hydrate or hydrate.

As the Acidic inorganic salts in second embodiment, for example, can include and the acid in first embodiment Property inorganic salts identical i.e. dihydric phosphate and dihydric phosphate beyond inorganic salts.

Acidic inorganic salts that cold insulation composition in second embodiment contains also may be used either only one kind To be two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

[dibasic alkaliine]

The dibasic alkaliine in second embodiment is phosphoric acid (H₃PO₄) in two hydrogen ions substituted by cation The salt formed, either non-hydrate or hydrate.

The dibasic alkaliine is typically the basic salt of its aqueous solution display alkalescence.

As the dibasic alkaliine in second embodiment, for example, can include：Disodium hydrogen phosphate (Na₂HPO₄), phosphoric acid Hydrogen dipotassium (K₂HPO₄), calcium monohydrogen phosphate (CaHPO₄) etc. one hydrogen metal salt of phosphoric acid；Diammonium hydrogen phosphate ((NH₄)₂HPO₄) etc. phosphoric acid one Hydrogen non-metal salt etc..

Dibasic alkaliine that cold insulation composition in second embodiment contains either it is only a kind of or It is two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

[other inorganic salts]

Cold insulation composition in second embodiment can be in addition to containing the Acidic inorganic salts and dibasic alkaliine Also contain not equivalent to any one in these salt other inorganic salts as the inorganic salts.

Other inorganic salts are either non-hydrate or hydrate.

As long as other inorganic salts in second embodiment are not particularly limited without damaging effect of the invention then, For example, it can include：Beyond the alkaline dibasic alkaliine of the neutral neutral inorganic of its aqueous solution display, the display of its aqueous solution Inorganic salts etc..

As the neutral inorganic, for example, can include identical with the neutral inorganic in first embodiment Inorganic salts, be preferably sodium chloride, potassium chloride or sodium sulphate.

Alkaline, inorganic salts beyond the dibasic alkaliine are preferably the inorganic salts beyond phosphate, for example, can include The inorganic salts identical with the alkaline, inorganic salts beyond the phosphate in first embodiment, are preferably sodium carbonate or carbonic acid Potassium.

Other inorganic salts that cold insulation composition in second embodiment contains also may be used either only one kind To be two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

As the preferable composition in the cold insulation composition of second embodiment, can include containing the conduct acid The property dihydric phosphate of inorganic salts and the composition of neutral inorganic.Such cold insulation composition is freezing front and rear color change Completion needed for time it is shorter, there is more preferably character.

It is described in the case that cold insulation composition in this second embodiment contains dihydric phosphate and neutral inorganic Neutral inorganic is preferably sodium chloride or potassium chloride.By and with such neutral inorganic, so that in second embodiment Cold insulation composition completes color change before and after freezing with the shorter time.

It is neutral in the case that cold insulation composition in this second embodiment contains dihydric phosphate and neutral inorganic The content of inorganic salts is preferably by mass 40~60%, more preferably by mass 43 to the ratio of the total content of inorganic salts~ 57%, particularly preferably by mass 46~54%.It is such scope by the ratio, so that in second embodiment Cold insulation composition completes color change and color change bigger before and after freezing with the shorter time.

In the case that cold insulation composition in this second embodiment contains dihydric phosphate and neutral inorganic, phosphoric acid The content (quality) of dihydric salt to the ratio of the content (quality) of dibasic alkaliine ([dihydric phosphate of cold insulation composition Content (quality)]/content (quality) of the dibasic alkaliine of composition [cold insulation with]) and it is preferably 0.04~2, more preferably 0.04 ~1.6, particularly preferably 0.04~1.4.It is such scope by the ratio, so that the cold insulation in second embodiment is used Composition completes color change before and after freezing with the shorter time.

Also, because the cold insulation composition in second embodiment is freezing front and rear color change bigger, institute It is preferably 0.04~1.2 to state ratio, more preferably 0.07~0.8, particularly preferably 0.1~0.6.

In cold insulation composition under second embodiment, total content of the Acidic inorganic salts and dibasic alkaliine Ratio to the total content of the inorganic salts is by mass 5~100%, preferably by mass 5.5~100%, more preferably For by mass 6~100%.By the ratio to be more than the lower limit, thus cold insulation composition freeze it is front and rear Color change increases.

Among such number range, as the lower limit of the ratio, for example, can select by mass 10%, 20%th, 30%, 40%, 45% etc., but be not limited to these.In addition, among such number range, as the ratio Upper limit value, for example, by mass 90%, 80%, 75%, 70%, 65% etc. can be selected, but is not limited to these.

Before the freezing of second embodiment in preferably more than 0 DEG C of cold insulation composition, the meltage of the inorganic salts More how the more preferred, the amount dissolved in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by matter Gauge more than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

In addition, in the cold insulation composition after the freezing of second embodiment, the amount of precipitation of the inorganic salts it is more more more It is preferred that the amount separated out in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by mass More than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

The total content of the inorganic salts of cold insulation composition in second embodiment is preferably by mass 5~35%, more Preferably by mass 5~30%, more preferably by mass 10~30%, for example, can be by mass 15~ 25%.

＜ tackifier ＞

The tackifier in second embodiment are that the viscosity for making cold insulation composition increases, do not refer to equivalent to the pH Show the component of agent.The tackifier in second embodiment are not preferably separated out when cold insulation is freezed with composition.In this explanation In book, so-called " tackifier are not separated out when cold insulation is freezed with composition ", as that first illustrated in the first embodiment Sample.

As the tackifier in second embodiment, for example, can include and the tackifier in first embodiment Identical tackifier.

Same with the situation of first embodiment, the tackifier in second embodiment are preferably selected from by acrylic acid Based polymer, carboxyl alkyl cellulose, xanthans, guar gum, guar, pectin, tamarind gum, carragheen and alkylene Glycol composition group more than one.

By using such tackifier, color change of the cold insulation composition before and after freezing is big and operability is more excellent It is different.

The tackifier that cold insulation composition in second embodiment contains are either there was only one kind or two kinds More than, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

In cold insulation composition before the freezing of second embodiment and after freezing, the amount of precipitation of tackifier is more few more excellent To select, the amount separated out in the total amount of tackifier is preferably by mass less than 10%, more preferably by mass less than 5%, More preferably by mass less than 2%, particularly preferably by mass 0% (whole amount does not all separate out).

The content of the tackifier of cold insulation composition in second embodiment is preferably by mass 0.1~10%, more Preferably by mass 0.3~6%, particularly preferably by mass 0.6~3%.

In cold insulation composition under second embodiment, the content of the dibasic alkaliine is to water, the inorganic salts And the ratio of the total content of tackifier is by mass 0.2~5.0%, preferably by mass 0.23~4.9%, more preferably For by mass 0.26~4.8%.It is such scope by the ratio, so that cold insulation composition is freezing front and rear face Color change increases.

＜ pH indicator ＞

The pH indicator (acid-base indicator) in second embodiment is to reflect the presence or absence of its colour developing to determine cold insulation With the component of the color of composition.Cold insulation composition containing pH indicator by freezing front and rear color change.

As long as the indicator that the pH indicator pKa in second embodiment is 4.9~8.0 does not just limit especially then It is fixed.

As the pH indicator in second embodiment, refer to for example, can include with the pH in first embodiment Show the identical indicator of agent.

For example preferably its color change interval (pH) is in the range of 3.0~9.0 pH indicator in second embodiment, more It is preferably in the range of 4.0~8.5, particularly preferably in the range of 4.5~8.0.

The pH indicator that cold insulation composition in second embodiment contains is either there was only one kind or two More than kind, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.However, it is often preferred to comprise only one Kind pH indicator.

As long as the content of the pH indicator of the cold insulation composition in second embodiment may achieve cold insulation composition Target discoloration is then just not particularly limited, but preferably 1~30ppm, more preferably 5~20ppm.

The other component ＞ of ＜

Cold insulation composition in second embodiment can remove water, inorganic salts, tackifier and pH indicator are with external Do not damage in the range of the effect of the present invention and also contain not equivalent to other components of these components.As other components, It can include：Solvent beyond, water same with the situation of first embodiment；Preservative, surfactant etc. are well-known Various additives etc..

Other components that cold insulation composition in second embodiment contains, can also either only one kind It is two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

Cold insulation in second embodiment with the content of other components of composition be with first embodiment The content of other components of cold insulation composition is identical.

For example, in cold insulation composition under second embodiment, the content of the solvent is to water and the solvent The ratio of total content is preferably by mass less than 10%, more preferably by mass less than 5%, particularly preferably by mass Less than 2%.

In addition, the cold insulation in second embodiment is not particularly limited with the content of the preservative of composition, but it is preferably By mass 0.02~0.5%, more preferably by mass 0.04~0.2%.

For the cold insulation composition in second embodiment, the inorganic salts, tackifier and pH indicator always contain Measure to beyond water and the solvent component (beyond the inorganic salts, tackifier, pH indicator and the solvent it is other into Point) total content ratio be preferably by mass more than 90%, more preferably by mass more than 93%, more preferably By mass more than 96%, particularly preferably by mass more than 98%, or by mass 100%.By described total The ratio of content is more than the lower limit, so that cold insulation composition is freezing front and rear color change bigger.

Cold insulation in second embodiment is preferably 4.7~8.0 with the pH of composition, and more preferably 5.0~7.7, especially Preferably 5.2~7.5.

Cold insulation in second embodiment has preferably been dissolved in the cold insulation composition with composition in pH indicator At a temperature of show the PH of the number range, more preferably show the number when it is 25 DEG C that the cold insulation is with the temperature of composition It is worth the PH of scope.

Cold insulation in second embodiment all uses water beyond by the inorganic salts and water with composition containing component PH (α 2) in the case of substituted for is preferably 4.7~8.0, and more preferably 5.2~7.5.

PH (α 2) is preferably the PH at the temperature that pH indicator has been dissolved in the cold insulation composition, more preferably exists It is described containing inorganic brine be 25 DEG C when pH.

Cold insulation in second embodiment all uses water beyond by the tackifier and water with composition containing component PH (α 3) in the case of substituted for is preferably 6.0~9.1, and more preferably 6.5~8.6.

Cold insulation in second embodiment is used and above-mentioned first with composition in addition to this different point of gradation composition The identical method of cold insulation composition in embodiment and obtain.

Cold insulation apparatus involved by second embodiment of the present invention is that possess the apparatus for having the cold insulation composition, is removed Cold insulation can be set to the knot same with the cold insulation apparatus involved by above-mentioned first embodiment with beyond this different point of composition Structure.

Cold insulation apparatus involved by second embodiment of the present invention is in addition to using the cold insulation, with composition, this puts, Obtained using the method same with the cold insulation apparatus involved by above-mentioned first embodiment.

Cold insulation composition in second embodiment is due to freeze front and rear color change very big, can easily regard Feel confirmation whether there is to freeze.Moreover, this color change of cold insulation composition can be from the outside visual confirmation of cold insulation apparatus.By This, whether cold insulation apparatus easily can be sufficiently cooled to preferred temperature by visual confirmation.

《3rd embodiment》

Cold insulation apparatus involved by third embodiment of the present invention be one kind possess containing water, inorganic salts, tackifier with And the cold insulation apparatus of the cold insulation composition of pH indicator, wherein, it is acid that the cold insulation composition contains the display of its aqueous solution Acidic inorganic salts as the inorganic salts, in the cold insulation composition, the content of the Acidic inorganic salts is to the nothing The ratio of the total content of machine salt is by mass 5~100%, and the cold insulation composition is beyond by the inorganic salts and water PH (α 2) in the case of all substituted for containing component with water becomes less than 7, and the cold insulation composition is by the thickening PH (α 3) in the case of all substituted for containing component with water beyond agent and water becomes more than 7, pH (α 2) and pH (α 3) table Show less than the pH of color change interval, the pH of color change interval of the pH indicator and higher than in tri- pH regions of pH of color change interval PH regions different from each other value.

Cold insulation in 3rd embodiment composition contains inorganic salts and tackifier as exerting one's influence to its acidity Component.Moreover, in the cold insulation composition, Acidic inorganic salts are selected to define its content as the inorganic salts, limit The acidity of inorganic salts and tackifier, and these inorganic salts and tackifier have been applied in combination with suitable color change interval PH indicator.The presence or absence of the change or colour developing of composition dependent on the colour developing of pH indicator of the cold insulation with this composition And significantly greatly carry out color change.

＜ inorganic salts ＞

The inorganic salts in 3rd embodiment play a role as a component of cold-retaining agent, cold insulation composition Solidification point mainly by its species and amount determine.

The cold insulation in 3rd embodiment composition contain the acid Acidic inorganic salts of its aqueous solution display as The inorganic salts.

[Acidic inorganic salts]

The Acidic inorganic salts in 3rd embodiment are not particularly limited, and can suitably be selected according to purpose, both may be used To be non-hydrate or hydrate.

As the preferable inorganic salts in the Acidic inorganic salts of the 3rd embodiment, implement for example, can include with first The identical inorganic salts of inorganic salts beyond dihydric phosphate in mode are：Ammonium chloride (NH₄Cl), magnesium chloride (MgCl₂), sulfuric acid Ammonium ((NH₄)₂SO₄), ammonium nitrate (NH₄NO₃), aluminum sulfate (Al₂(SO₄)₃), alum (AlK (SO₄)₂), ammonia-alum (Al (NH₄) (SO₄)₂), calcium nitrate tetrahydrate (Ca (NO₃)₂·4H₂O), calcium nitrate (Ca (NO₃)₂) etc., preferred ammonium chloride.

Acidic inorganic salts that cold insulation composition in 3rd embodiment contains also may be used either only one kind To be two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

[other inorganic salts]

As the inorganic salts, the cold insulation composition in the 3rd embodiment can be gone back in addition to the Acidic inorganic salts Contain other inorganic salts.

Other inorganic salts are either non-hydrate or hydrate.

As long as other inorganic salts in the 3rd embodiment are not particularly limited without damaging effect of the invention then, For example, it can include：The neutral neutral inorganic of its aqueous solution display, alkaline, inorganic salts of its aqueous solution display alkalescence etc..

As the neutral inorganic, for example, can include identical with the neutral inorganic in first embodiment Inorganic salts, be preferably sodium chloride or potassium chloride.

The alkaline, inorganic salts are preferably the inorganic salts beyond phosphate and dibasic alkaliine, for example, can include and the The identical inorganic salts of alkaline, inorganic salts beyond the phosphate in one embodiment, are preferably sodium carbonate or potassium carbonate.

Other inorganic salts that cold insulation composition in 3rd embodiment contains also may be used either only one kind To be two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

In cold insulation composition under the 3rd embodiment, the content of the Acidic inorganic salts is to the total of the inorganic salts The ratio of content is by mass 5~100%, for example, by mass 20~80%, by mass 40~60% can be set to Deng, but it is not limited to these.

Among such number range, as the lower limit of the ratio, except above-mentioned by mass 20%, 40% with Outside, also alternative such as by mass 10%, 30%, 45%, but be not limited to these.In addition, in such number range Among, as the upper limit value of the ratio, in addition to above-mentioned by mass 80%, 60%, also alternative is as by mass 90%th, 70%, 55% etc., but be not limited to these.

Before the freezing of the 3rd embodiment in preferably more than 0 DEG C of cold insulation composition, the meltage of the inorganic salts More how the more preferred, the amount dissolved in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by matter Gauge more than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

In addition, in the cold insulation composition after the freezing of the 3rd embodiment, the amount of precipitation of the inorganic salts it is more more more It is preferred that the amount separated out in the total amount of the inorganic salts is preferably by mass more than 90%, more preferably by mass More than 95%, more preferably by mass more than 98%, can be by mass 100% (full doses).

The total content of the inorganic salts of cold insulation composition in 3rd embodiment is preferably by mass 5~35%, more Preferably by mass 10~30%, particularly preferably by mass 15~25%.

＜ tackifier ＞

The tackifier in 3rd embodiment are that the viscosity for making cold insulation composition increases, do not refer to equivalent to the pH Show the component of agent.The tackifier in 3rd embodiment are not preferably separated out when cold insulation is freezed with composition.In this explanation In book, so-called " tackifier are not separated out when cold insulation is freezed with composition ", as that first illustrated in the first embodiment Sample.

As the tackifier in the 3rd embodiment, for example, can include and the tackifier in first embodiment Identical tackifier.

Same with the situation of first embodiment, the tackifier in the 3rd embodiment are preferably selected from by acrylic acid Based polymer, carboxyl alkyl cellulose, xanthans, guar gum, guar, pectin, tamarind gum, carragheen and alkylene Glycol composition group more than one.

The tackifier that cold insulation composition in 3rd embodiment contains are either there was only one kind or two kinds More than, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

In cold insulation composition before the freezing of the 3rd embodiment and after freezing, the amount of precipitation of tackifier is more few more excellent To select, the amount separated out in the total amount of tackifier is preferably by mass less than 10%, more preferably by mass less than 5%, More preferably by mass less than 2%, particularly preferably by mass 0% (whole amount does not all separate out).

The content of the tackifier of cold insulation composition in 3rd embodiment is preferably by mass 0.1~10%, more Preferably by mass 0.3~6%, particularly preferably by mass 0.6~3%.

＜ pH indicator ＞

The pH indicator (acid-base indicator) in 3rd embodiment is to reflect the presence or absence of its colour developing to determine cold insulation With the component of the color of composition.Cold insulation composition containing pH indicator by freezing front and rear color change.

The pH indicator in 3rd embodiment is not particularly limited, but the pH that preferably pKa is 4.0~7.5 is indicated Agent.

As the pH indicator in the 3rd embodiment, refer to for example, can include with the pH in first embodiment Show the identical pH indicator of agent.

For example preferably its color change interval (pH) is in the range of 3.0~10.5 pH indicator in 3rd embodiment, It is more preferably in the range of 3.3~9.5, particularly preferably in the range of 3.5~9.0.

The pH indicator that cold insulation composition in 3rd embodiment contains is either there was only one kind or two More than kind, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.However, it is often preferred to comprise only one Kind pH indicator.

As long as the content of the pH indicator of the cold insulation composition in the 3rd embodiment may achieve cold insulation composition Target discoloration is then just not particularly limited, but preferably 1~30ppm, more preferably 5~20ppm.

The other component ＞ of ＜

Cold insulation composition in 3rd embodiment can remove water, inorganic salts, tackifier and pH indicator are with external Do not damage in the range of the effect of the present invention and also contain not equivalent to other components of these components.As other components, It can include：Solvent beyond, water same with the situation of first embodiment；Preservative, surfactant etc. are well-known Various additives etc..

Other components that cold insulation composition in 3rd embodiment contains, can also either only one kind It is two or more, in the case of two or more, combinations thereof and ratio can be selected arbitrarily.

Cold insulation in 3rd embodiment with the content of other components of composition be with first embodiment The content of other components of cold insulation composition is identical.

For example, in cold insulation composition under the 3rd embodiment, the content of the solvent is to water and the solvent The ratio of total content is preferably by mass less than 10%, more preferably by mass less than 5%, particularly preferably by mass Less than 2%.

In addition, the cold insulation in the 3rd embodiment is not particularly limited with the content of the preservative of composition, but it is preferably By mass 0.02~0.5%, more preferably by mass 0.04~0.2%.

For the cold insulation composition in the 3rd embodiment, the inorganic salts, tackifier and pH indicator always contain Measure to beyond water and the solvent component (beyond the inorganic salts, tackifier, pH indicator and the solvent it is other into Point) total content ratio be preferably by mass more than 90%, more preferably by mass more than 93%, more preferably By mass more than 96%, particularly preferably by mass more than 98%, or by mass 100%.By described total The ratio of content is more than the lower limit, so that cold insulation composition is freezing front and rear color change bigger.

Cold insulation in 3rd embodiment all uses water beyond by the inorganic salts and water with composition containing component PH (α 2) in the case of substituted for becomes less than 7.

PH (α 2) is preferably 3.5~7.0, more preferably 4.0~6.6, particularly preferably 4.5~6.3.

Cold insulation in 3rd embodiment all uses water beyond by the tackifier and water with composition containing component PH (α 3) in the case of substituted for becomes more than 7.

PH (α 3) is preferably 7.0~9.5, more preferably 7.0~9.0, particularly preferably 7.0~8.5.

For the cold insulation composition in the 3rd embodiment, pH (α 2) and pH (α 3) are represented less than the pH indicator The pH of color change interval, the pH of color change interval and higher than the pH regions different from each other in tri- pH regions of pH of color change interval Value.

Cold insulation in 3rd embodiment is preferably 4.1~7.4 with the pH of composition, and more preferably 4.4~7.1, especially Preferably 4.6~6.9.

Cold insulation in 3rd embodiment has preferably been dissolved in the cold insulation composition with composition in pH indicator At a temperature of show the PH of the number range, more preferably show the number when it is 25 DEG C that the cold insulation is with the temperature of composition It is worth the PH of scope.

Cold insulation in 3rd embodiment is used and above-mentioned first with composition in addition to this different point of gradation composition The identical method of cold insulation composition in embodiment and obtain.

Cold insulation apparatus involved by third embodiment of the present invention is that possess the apparatus for having the cold insulation composition, is removed Cold insulation can be set to same with the cold insulation apparatus involved by above-mentioned first embodiment with beyond this different point of composition Form.

Cold insulation apparatus involved by third embodiment of the present invention is in addition to using the cold insulation, with composition, this puts, Obtained using the method same with the cold insulation apparatus involved by above-mentioned first embodiment.

Cold insulation composition in 3rd embodiment is due to freeze front and rear color change very big, can easily regard Feel confirmation whether there is to freeze.Moreover, this color change of cold insulation composition can be from the outside visual confirmation of cold insulation apparatus.By This, whether cold insulation apparatus easily can be sufficiently cooled to preferred temperature by visual confirmation.

Embodiment

Hereinafter, the present invention is described in more detail by specific embodiment.But the present invention at all be not limited in Embodiment described below.

Raw material described below used in the present embodiment and comparative example.

(tackifier)

HPG1 (hydroxypropyl guar gum)：Three brilliant company system " Maypro HPG8111 "

CMC (carboxymethyl cellulose)：First industrial pharmaceutical company system " Cellogen "

CVP (carboxyl ethylene polymer)：East Asia Synesis Company system " Rheogic270 " (pH indicator)

·BCP：Bromocresol purple (and the pure medicine company system of light)

·PR：Phenol red (and the pure medicine company system of light)

·BTB：Bromthymol blue (and the pure medicine company system of light)

·MR：Methyl red (and the pure medicine company system of light)

·BCG：Bromocresol green (and the pure medicine company system of light)

(preservative)

Three love oil company's systems " Pyrithione Sodium (Sodium Omadine) "

[embodiment 1]

The manufacture ＞ of ＜ cold insulations composition and cold insulation apparatus (first embodiment)

BCP is made an addition in water (79.16 mass parts) under room temperature (20~25 DEG C) and makes its dissolving, then, then is added Ammonium chloride (9.72 mass parts), potassium chloride (9.72 mass parts), Trisodium phosphate dodecahydrate (0.15 mass parts) and phosphoric acid Ammonium dihydrogen (0.10 mass parts) simultaneously dissolves them, and then, addition HPG1 (1.10 mass parts), is stirred at room temperature one always Hour and make its dissolving, confirm obtained liquid material fully viscosify after, add preservative (0.05 mass parts) And be stirred at room temperature always 30 minutes, it resulting in cold insulation composition.At this time, the use level of BCP is adjusted to：In gained To cold insulation composition in content become 8ppm.By each gradation composition and its in cold insulation table is shown in the content in composition 2.In table 2, " basic salt " on gradation composition column means the basic salt beyond phosphate and dibasic alkaliine.In addition, tricresyl phosphate Sodium dodecahydrate omits the crystallization water (12H₂O) record.It is also same in these tables afterwards.

In addition, by pH (α 1), pH (α 2), pH (α 3), solvent are water and the pH indicator in the case that temperature is 25 DEG C PKa, cold insulation are shown in table 7 with physical property such as the pH of composition.PH (α 1), pH (α 2), pH (α 3) and the pH are by measurement object The temperature of thing is set to 25 DEG C and is measured.In obtained cold insulation composition, Acidic inorganic salts and phosphatic conjunction Content is counted to be also depicted in table 7 ratio (following, to represent the value with symbol " (X1) " sometimes) of the total content of inorganic salts.

Then, obtained cold insulation composition is enclosed in high density polyethylene (HDPE) container and has obtained the first embodiment party The cold insulation apparatus of formula.

The evaluation ＞ of ＜ cold insulation compositions

(color change)

Obtained cold insulation is cooled to -25 DEG C with composition (cold insulation apparatus).During this period, cold insulation composition is in height While -25 DEG C of temperature is freezed, changed freezing front and rear color.Then, lead to according to following benchmark Cross and visually have rated the color change for freezing front and rear cold insulation composition.Show the result in table 9.Also show in the lump in table 9 The color change interval and color change of pH indicator used in going out.

In table 9, " color change " described in evaluation result column represents that cold insulation composition is freezing front and rear color Change, such as " green → yellow " represent that the color of cold insulation composition is being green before freezing, after freezing is being yellow.

○：Color change before and after freezing is big, and the visual confirmation of the state of cooling is easy to.

△：It can identify and freeze front and rear color change, the visual confirmation of the state of cooling can be carried out.

×：It is unintelligible to freeze front and rear color change, it is difficult to or the visual confirmation of the state of cooling cannot be carried out.

In addition, in table 9, " low pH → high pH color changes " described in the color change interval column of pH indicator represent containing The face that pH indicator is shown in color change interval when the pH for having the liquid of pH indicator has changed from particular value to the value higher than its Color change, for example, so-called " yellow → purple " represents that pH indicator makes the liquid from Huang during the pH of the liquid becomes higher Discoloration color is purple.

The manufacture of ＜ cold insulations composition and cold insulation apparatus (first embodiment), the evaluation ＞ of cold insulation composition

[embodiment 2~13]

Except being set to by cold insulation with the gradation composition of composition and its in cold insulation with the content in composition such as table 2 and table Shown in 3 like that this point beyond, using method same as Example 1 come manufacture the cold insulation composition of first embodiment with Cold insulation apparatus, have rated cold insulation composition.Cold insulation is shown in table 7, table 9 with each physical property, the evaluation result of composition.

[embodiment 14]

The manufacture ＞ of ＜ cold insulations composition and cold insulation apparatus (second embodiment)

BCP is made an addition in water (78.90 mass parts) under room temperature (20~25 DEG C) and makes its dissolving, then, then is added Ammonium chloride (9.70 mass parts), potassium chloride (9.70 mass parts) and diammonium hydrogen phosphate (0.50 mass parts) simultaneously dissolve them, Then, add CMC (1.10 mass parts), a hour is stirred at room temperature always and makes its dissolving, confirm it is obtained After liquid material fully viscosifies, addition preservative (0.05 mass parts) is simultaneously stirred at room temperature 30 minutes always, thus obtains Cold insulation composition is arrived.At this time, the use level of BCP is adjusted to：Content in obtained cold insulation composition becomes 8ppm.By each gradation composition and its in cold insulation table 3 is shown in the content in composition.

In addition, by pH (α 1), pH (α 2), pH (α 3), solvent are water and the pH indicator in the case that temperature is 25 DEG C PKa, cold insulation are shown in table 7 with physical property such as the pH of composition.PH (α 1), pH (α 2), pH (α 3) and the pH are by measurement object The temperature of thing is set to 25 DEG C and is measured.In obtained cold insulation composition, Acidic inorganic salts and dibasic alkaliine Total content to the ratio (following, to represent the value with symbol " (X2) " sometimes) of the total contents of inorganic salts and dibasic alkaliine Content is also depicted in the ratio (following, to represent the value with symbol " (X3) " sometimes) of the total content of water, inorganic salts and tackifier In table 7.

Then, obtained cold insulation composition is enclosed in high density polyethylene (HDPE) container and has obtained the second embodiment party The cold insulation apparatus of formula.

The evaluation ＞ of ＜ cold insulation compositions

Obtained cold insulation composition have rated using method same as Example 1.Show the result in table 9.

The manufacture of ＜ cold insulations composition and cold insulation apparatus (second embodiment), the evaluation ＞ of cold insulation composition

[embodiment 15~33]

Except being set to by cold insulation with the gradation composition of composition and its in cold insulation with the content in composition such as table 3~5 It is shown like that this point beyond, using the method identical with embodiment 14 come manufacture the cold insulation composition of second embodiment and Cold insulation apparatus, have rated cold insulation composition.Cold insulation is shown in table 7~8, table with each physical property, the evaluation result of composition 9。

[embodiment 34]

The manufacture ＞ of ＜ cold insulations composition and cold insulation apparatus (the 3rd embodiment)

MR is made an addition in water (79.35 mass parts) under room temperature (20~25 DEG C) and makes its dissolving, then, then adds chlorine Change ammonium (9.75 mass parts) and potassium chloride (9.75 mass parts) and dissolve them, then, addition CMC (1.10 mass parts), one Directly a hour is stirred at room temperature and makes its dissolving, after confirming that obtained liquid material fully viscosifies, addition Preservative (0.05 mass parts) is simultaneously stirred at room temperature 30 minutes always, resulting in cold insulation composition.At this time, MR matches somebody with somebody Resultant is adjusted to：Content in obtained cold insulation composition becomes 8ppm.By each gradation composition and its in cold insulation group Content in compound is shown in table 5.

In addition, by pH (α 1), pH (α 2), pH (α 3), solvent are water and the pH indicator in the case that temperature is 25 DEG C PKa, cold insulation are shown in table 8 with physical property such as the pH of composition.PH (α 1), pH (α 2), pH (α 3) and the pH are by measurement object The temperature of thing is set to 25 DEG C and is measured.In obtained cold insulation composition, Acidic inorganic salts contents are to inorganic The ratio (following, to represent the value with symbol " (X4) " sometimes) of the total content of salt is also depicted in table 8.

Then, obtained cold insulation composition is enclosed in high density polyethylene (HDPE) container and has obtained the 3rd embodiment party The cold insulation apparatus of formula.

The evaluation ＞ of ＜ cold insulation compositions

The manufacture of ＜ cold insulations composition and cold insulation apparatus (the 3rd embodiment), the evaluation ＞ of cold insulation composition

[embodiment 35~37]

Except being set to as shown in table 5 with the content in composition by cold insulation with the gradation composition of composition and its in cold insulation Like that beyond this point, the cold insulation composition of the 3rd embodiment and cold insulation are manufactured using the method identical with embodiment 34 Apparatus, have rated cold insulation composition.Cold insulation is shown in table 8, table 9 with each physical property, the evaluation result of composition.

The manufacture of ＜ cold insulations composition and cold insulation apparatus, the evaluation ＞ of cold insulation composition

[comparative example 1~9]

Except being set to by cold insulation with the gradation composition of composition and its in cold insulation with the content in composition such as table 5 and table Beyond this puts like that shown in 6, cold insulation composition and cold insulation apparatus are manufactured using method same as Example 1, evaluated Cold insulation composition.Cold insulation is shown in table 8, table 9 with each physical property, the evaluation result of composition.

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

Table 9

As the above results it will be apparent that the present invention first embodiment involved by cold insulation apparatus (implement Example 1~13), the cold insulation apparatus (embodiment 14~33) involved by second embodiment, the cold insulation involved by the 3rd embodiment In apparatus (embodiment 34~37), the precipitation with inorganic salts when cold insulation composition freezes, reflection pH indicator is shown The change of color, being capable of the easy visual confirmation state of cooling so that at it to freeze front and rear color change clear for cold insulation composition.

The cold insulation apparatus of especially embodiment 1~3,8~11,13 in the cold insulation apparatus involved by first embodiment In, the time needed for the completion of the color change of cold insulation composition is short, shows particularly satisfactory character.

In the cold insulation apparatus of especially embodiment 22~27 in the cold insulation apparatus involved by second embodiment, cold insulation It is short with the time needed for the completion of the color change of composition, show particularly preferred character.This display, in cold insulation group Compound is in the trend for showing this gratifying character in the case of containing dihydric phosphate and neutral inorganic.

In contrast, in the cold insulation apparatus of comparative example 1~9, the cold insulation of cold insulation composition and the above embodiments is used Composition is different, unintelligible in the change for freezing front and rear color, it is difficult to or the visual confirmation of the state of cooling cannot be carried out.

[embodiment 38~40]

Except being set to by cold insulation with the gradation composition of composition and its in cold insulation with the content in composition such as the institute of table 10 Show beyond this point like that, the cold insulation composition of first embodiment and guarantor are manufactured using method same as Example 1 Colod-application tool, have rated cold insulation composition.Cold insulation is shown in table 11, table 12 with each physical property, the evaluation result of composition.

[embodiment 41~46]

Except being set to by cold insulation with the gradation composition of composition and its in cold insulation with the content in composition such as the institute of table 10 Show beyond this point like that, the cold insulation composition of second embodiment and guarantor are manufactured using the method identical with embodiment 14 Colod-application tool, have rated cold insulation composition.Cold insulation is shown in table 11, table 12 with each physical property, the evaluation result of composition.

[table 10]

[table 11]

Table 12

As described above, in the cold insulation apparatus (embodiment 38~40) involved by first embodiment of the invention, second in fact Apply in the cold insulation apparatus (embodiment 41~46) involved by mode, the analysis with inorganic salts when cold insulation composition freezes Go out, reflect the change of the colour developing of pH indicator, so that cold insulation composition at it freezes front and rear color change clear, Neng Gourong The easy visual confirmation state of cooling.

Industrial feasibility

The present invention can be utilized as the cold insulation apparatus of various fresh things.

Claims

1. a kind of cold insulation apparatus, possesses the cold insulation composition containing water, inorganic salts, tackifier and pH indicator,

Cold insulation composition contains the acid Acidic inorganic salts of its aqueous solution display and phosphate as the inorganic salts,

In the cold insulation composition, the Acidic inorganic salts and phosphatic total content always containing to the inorganic salts The ratio of amount is by mass 5~100%,

Cold insulation composition contains inorganic salts beyond dihydric phosphate and dihydric phosphate as the Acidic inorganic salts,

The pKa of the pH indicator is 4.9~8.0,

Situation about containing component all eliminating of the cold insulation with composition beyond by phosphate, dihydric phosphate and water Under pH (α 1) relative to the pKa meet by following formula (i) represent relation：

PKa≤pH (pKa+1.8 ... (i) of the)≤pH indicator of α 1 of pH indicator.

2. cold insulation apparatus according to claim 1, wherein,

The cold insulation is 4.6~8.8 with the pH of composition.

3. cold insulation apparatus according to claim 1 or 2, wherein,

The cold insulation is with composition in the case of all substituted for containing component with water beyond by the tackifier and water PH (α 3) becomes 6.0~8.5.

4. a kind of cold insulation apparatus, possesses the cold insulation composition containing water, inorganic salts, tackifier and pH indicator,

Cold insulation composition contains the acid Acidic inorganic salts of its aqueous solution display and dibasic alkaliine is used as the nothing Machine salt,

In the cold insulation composition, total content of the Acidic inorganic salts and dibasic alkaliine is to the total of the inorganic salts The ratio of content is by mass 5~100%,

In the cold insulation composition, the content of dibasic alkaliine is to the total content of water, the inorganic salts and tackifier Ratio is by mass 0.2~5.0%,

The pKa of the pH indicator is 4.9~8.0.

5. cold insulation apparatus according to claim 4, wherein,

The pH of the cold insulation composition is 4.7~8.0.

6. cold insulation apparatus according to claim 4 or 5, wherein,

The cold insulation is with composition in the case of all substituted for containing component with water beyond by the tackifier and water PH (α 3) becomes 6.0~9.1.

7. a kind of cold insulation apparatus, possesses the cold insulation composition containing water, inorganic salts, tackifier and pH indicator,

Cold insulation composition contains the acid Acidic inorganic salts of its aqueous solution display as the inorganic salts,

In the cold insulation composition, the content of the Acidic inorganic salts is by matter to the ratio of the total content of the inorganic salts Gauge 5~100%,

The cold insulation is with composition in the case of all substituted for containing component with water beyond by the inorganic salts and water PH (α 2) becomes less than 7,

The cold insulation is with composition in the case of all substituted for containing component with water beyond by the tackifier and water PH (α 3) becomes more than 7,

PH (α 2) and pH (α 3) is represented less than the pH of color change interval, the pH of color change interval of the pH indicator and higher than discoloration The value in the pH regions different from each other in tri- pH regions of pH in region.