CN102850999A - Functional particle and manufacturing method thereof - Google Patents
Functional particle and manufacturing method thereof Download PDFInfo
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- CN102850999A CN102850999A CN2012102266392A CN201210226639A CN102850999A CN 102850999 A CN102850999 A CN 102850999A CN 2012102266392 A CN2012102266392 A CN 2012102266392A CN 201210226639 A CN201210226639 A CN 201210226639A CN 102850999 A CN102850999 A CN 102850999A
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Abstract
The invention provides a functional particle and a manufacturing method thereof. The functional particle can be manufactured through a simple method. Functional material can be sealed in pores of the multi-hole particle uniformly and stably. And the functional material does not permeate to the surface of the particle from the inner part of the pore. The functional particle provided by the invention is provided with a plurality of multi-hole particles penetrating from the surface to the inner part; the functional material filled in the pores of the multi-hole particles and performing functions in the pores; and capturing material filled in the pores of the multi-hole particles and capturing the functional material into the pores stably. And the capturing material is provided with a main chain part having affinity to the functional material and an tail end part having affinity to the functional material. And the tail end part is provided with mutually bonded reaction groups.
Description
Technical field
The inside that the present invention relates to the porousness particulate is filled with functional particle and the manufacture method thereof of functional substance.
Background technology
In the past, being used for the functional substance of various uses, many materials are arranged owing to purposes is difficult to directly process, such as the material of easy gasification, liquid etc. has mobile material or melts the material that demonstrates flowability etc. with temperature.For example, the materials such as paraffin are by undergoing phase transition and make the accumulation of heat of following the latent heat that phase transformation produces and heat radiation repeatedly to carry out the latent-heat storage material that plays a role between solid-liquid, owing between solid state and liquid state, repeatedly change, so its processing is very difficult.
Therefore, process easily in order to make these functional substance, proposed in the pore of porousness particulate, to be filled with the functional particle of functional substance.These functional particles can be made by fill the fairly simple like this method of functional substance in the pore of porousness particulate, so manufacturing cost is comparatively cheap.In addition, commercially available have a porousness particulate that much has uniform particle diameter, uses these porousness particulates according to purposes, the particle diameter of the functional particle of manufacturing can be controlled at uniform level thus.
But there are the following problems: the pore of porousness particulate penetrates into inside from the surface, and the functional substance that is filled in the pore oozes out (bleed out) easily to microparticle surfaces from pore inside.For example, for the functional particle that is filled with above-mentioned latent-heat storage material in the pore, the latent-heat storage material that is in solid state is kept stable in pore, but the latent-heat storage material that is transformed into liquid state by phase transformation is exuded to microparticle surfaces from pore inside, accumulation of heat and heat radiation can not be in the porousness particulate, repeatedly carried out, thereby the function as functional particle can not be repeated to demonstrate.
To this, taked following method: utilize resin layer etc. that the surface of the functional particle that is filled with functional substance in the pore is coated, thereby functional substance is sealing in the porousness particulate.For example, utilize the thermoplastic resins such as the various reaction resins such as melamine resin, acrylic resin, urethane resin or nylon resin, polyolefin resin that the surface of functional particle is covered.
But, in these methods, for the curing reaction that carries out reaction resin or the melting of thermoplastic resin, need to carry out the thermal treatment of high temperature.Therefore, under this hot conditions, ooze out after being filled in functional substance generating gasification in the pore or liquefaction, thereby functional substance can't be sealing in the porousness particulate.
For example, in pore, be filled with in the situation of functional particle of above-mentioned latent-heat storage material, if the fusing point of surface coated thermal treatment temp specific latent heat heat storage material is high, the latent-heat storage material that then is transformed into liquid state by phase transformation is exuded to microparticle surfaces from pore inside, mix with the resin layer that is coated on the surface, perhaps hinder the formation of resin layer, thereby can not successfully enclose the latent-heat storage material.
Therefore, in the following patent documentation 1, proposed will with the hole that is filled in the porousness particle in the scheme used as the surface coated resin layer of porousness particle of the immiscible liquid curing resin of latent-heat storage material.Particularly, following scheme has been proposed: adopt the immiscible liquid curing resin of Resins, epoxy conduct and latent-heat storage material, coat this Resins, epoxy on the surface of porousness particle and prepare accumulation of heat curable resin mixture, then, in the Resins, epoxy that is coated on this accumulation of heat curable resin mixture, add solidifying agent, then utilize process furnace etc. to form.
Patent documentation 1: TOHKEMY 2006-82427 communique
In the method for above-mentioned patent documentation 1, even the latent-heat storage material that is filled in the hole of porousness particle is phase-changed into liquid state when the curing reaction of Resins, epoxy, but because accumulation of heat composition and the Resins, epoxy of this liquid state are immiscible, thereby also be difficult for oozing out.But in the method, in order to form surface coated resin layer, need to carry out following numerous and diverse operation: at first, then coated epoxy resin mixes its solidifying agent, carries out heat treated again.Therefore, there are the following problems: be difficult to functional substance evenly and stably is sealing in the pore of porousness particulate, and cause producing rate variance because of the increase of process number.
Summary of the invention
The present invention can tackle above-mentioned situation, make by simple method, therefore, its purpose is, provides to make functional substance evenly and stably be sealing in the pore of porousness particulate and this functional substance can not be exuded to from pore inside the functional particle of microparticle surfaces.In addition, the object of the invention is to, be provided for making the manufacture method of the functional particle of above-mentioned functions particulate.
When addressing the above problem, the inventor has passed through further investigation, found that, for functional substance stably being sealing in the pore of porousness particulate, by also having the part of affinity and the predetermined substance that its end has the reactive group of bonding with possessing with functional substance, can achieve the above object, thereby finish the present invention.
That is, a first aspect of the present invention relates to:
[1] a kind of functional particle is characterized in that, has:
Have a plurality of porousness particulates that penetrate into inner pore from the surface;
Be filled in the pore of this porousness particulate and in this pore, demonstrate the functional substance of function; And
Be filled in the pore of above-mentioned porousness particulate and the above-mentioned functions material is stably captured scavenger in the above-mentioned pore, and,
Above-mentioned scavenger possesses with the above-mentioned functions material and has the main chain section of affinity and the terminal part that has affinity with above-mentioned porousness particulate, and this terminal part has the reactive group of mutual bonding.
According to above-mentioned formation, in the pore of porousness particulate, be filled with functional substance and scavenger, main chain section and the functional substance of this scavenger have affinity.Therefore, functional substance exists with scavenger jointly stabilizing ground in the pore of porousness particulate.In addition, the terminal part of this scavenger and porousness particulate have affinity, and this terminal part demonstrates the anchoring effect to the porousness particulate.And then the terminal part of this scavenger has the reactive group of mutual bonding, thereby at intermolecular mutual bonding its molecular weight is increased between the scavenger.
Thus, functional substance is stably captured the main chain section of the scavenger after molecular weight increases, and stably is sealing in the pore of porousness particulate by the terminal part of this scavenger.Therefore, in the invention of first aspect, can make by simple method, therefore, can provide to make functional substance evenly and stably be sealing in the pore of porousness particulate and this functional substance can not be exuded to from pore inside the functional particle of microparticle surfaces.
In addition, another aspect of the present invention relates to:
Such as above-mentioned [1] described functional particle, it is characterized in that [2] above-mentioned porousness particulate is porous silica.
According to above-mentioned formation, can adopt porous silica as the porousness particulate.Thus, for above-mentioned [2] described functional particle, also can more specifically reach the action effect identical with above-mentioned [1] described invention.
In addition, another aspect of the present invention relates to:
Such as above-mentioned [1] or [2] described functional particle, it is characterized in that [3] above-mentioned scavenger has reactive silyl as above-mentioned end section.
According to above-mentioned formation, can adopt terminal part to have the scavenger of reactive silyl.Such scavenger utilizes the silyl of terminal part and the porousness particulates such as porous silica is had more affinity.Therefore, for above-mentioned [3] described functional particle, also can more specifically reach the action effect identical with above-mentioned [1] or [2] described invention.
In addition, another aspect of the present invention relates to:
Such as above-mentioned [3] described functional particle, it is characterized in that [4] above-mentioned reactive silyl has at least one alkoxyl group as above-mentioned reactive group.
According to above-mentioned formation, can adopt to have alkoxyl group as the scavenger of the reactive group of reactive silyl.Such reactive group is mutual bonding at normal temperatures, therefore do not need pyroprocessing when the manufacturing function particulate, thereby further the inhibit feature material oozes out.Therefore, for above-mentioned [4] described functional particle, also can more specifically reach the action effect identical with above-mentioned [3] described invention.
In addition, another aspect of the present invention relates to:
[5] such as each described functional particle in above-mentioned [1] ~ [4], it is characterized in that above-mentioned scavenger has at least a oligopolymer in the group that is selected from polyisobutene, polyoxypropylene, polyacrylic ester, polyether glycol and polymethacrylate or polymkeric substance as above-mentioned main chain section.
According to above-mentioned formation, can adopt to have at least a oligopolymer that is selected from above-mentioned group or polymkeric substance as the scavenger of main chain section.Such scavenger utilizes the structure of main chain section and functional substance is particularly had more affinity to the functional substance that is made of organic substance.Therefore, for above-mentioned [5] described functional particle, also can more specifically reach the action effect identical with each described invention in above-mentioned [1] ~ [4].
In addition, another aspect of the present invention relates to:
Such as each described functional particle in above-mentioned [1] ~ [5], it is characterized in that [6] the above-mentioned functions material is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce demonstrates heat accumulation function in above-mentioned pore.
According to above-mentioned formation, for example can adopt by between solid-liquid, undergoing phase transition and make the accumulation of heat of following the latent heat that phase transformation produces and the latent-heat storage material that heat radiation is carried out playing a role repeatedly as functional substance.Such latent-heat storage material has following character: be transformed into liquid state by phase transformation, thereby ooze out from the pore of porousness particulate easily.Therefore, for above-mentioned [6] described functional particle, even for this functional substance that easily oozes out, also can reach particularly the action effect identical with each described invention in above-mentioned [1] ~ [5].
In addition, another aspect of the present invention relates to:
Such as above-mentioned [6] described functional particle, it is characterized in that [7] above-mentioned latent-heat storage material contains the organic substances such as paraffin, wax, lipid acid, polyalkylene glycol, and its transformation temperature is-30 ℃ ~ 200 ℃.
According to above-mentioned formation, can adopt the latent-heat storage material that contains above-mentioned organic substance.The transformation temperature of preferred such latent-heat storage material is-30 ℃ ~ 200 ℃.Thus, for above-mentioned [7] described functional particle, also can more specifically reach the action effect identical with above-mentioned [6] described invention.
In addition, another aspect of the present invention relates to:
[8] such as above-mentioned [6] or [7] described functional particle, it is characterized in that, contain the above-mentioned latent-heat storage material of 30 % by weight ~ 90 % by weight, and the latent heat amount is more than the 50J/g.
According to above-mentioned formation, the containing ratio of the latent-heat storage material in the preferred function particulate in the scope of 30 % by weight ~ 90 % by weight and the latent heat amount of functional particle be more than the 50J/g.Thus, for above-mentioned [8] described functional particle, also can more specifically reach the action effect identical with above-mentioned [6] or [7] described invention.
In addition, another aspect of the present invention relates to:
[9] a kind of manufacture method of functional particle for the manufacture of each described functional particle in above-mentioned [1] ~ [8], is characterized in that having:
Filling work procedure, the composition that will contain above-mentioned functions material and above-mentioned scavenger mixes with above-mentioned porousness particulate, fills above-mentioned composition in the pore of this porousness particulate; And
The bonding reaction operation, the mutual bonding of above-mentioned reactive group that the above-mentioned scavenger in the above-mentioned composition is had.
According to above-mentioned formation, the manufacture method of functional particle has filling work procedure and bonding reaction operation.In filling work procedure, at first make the composition that contains functional substance and scavenger.In the said composition, as mentioned above, the main chain section of functional substance and scavenger has affinity, therefore forms stable composition.Then, the porousness particulate is mixed filled compositions in the pore of porousness particulate with said composition.
On the other hand, in the bonding reaction operation, as mentioned above, consist of between the scavenger of the composition in the pore be filled in the porousness particulate, the reactive group that its terminal part has is at intermolecular mutual bonding, thereby its molecular weight is increased.In addition, this terminal part and porousness particulate have affinity, and this terminal part demonstrates the anchoring effect to the porousness particulate.Thus, functional substance is stably captured the main chain section of the scavenger after molecular weight increases, and stably is sealing in the pore of porousness particulate by the terminal part of this scavenger.
Need to prove that this bonding reaction operation can be carried out after above-mentioned filling work procedure finishes, perhaps, filling work procedure and bonding reaction operation can be carried out simultaneously.That is, can proceed to a certain degree at filling work procedure but still under the unclosed state, gently carry out the bonding reaction operation.
Therefore, in above-mentioned [9] described invention, can make by simple method, therefore a kind of manufacture method of functional particle can be provided, and it is for the manufacture of making functional substance evenly and stably being sealing in the pore of porousness particulate and this functional substance can not be exuded to from pore inside the functional particle of microparticle surfaces.
In addition, another aspect of the present invention relates to:
[10] such as the manufacture method of above-mentioned [9] described functional particle, it is characterized in that,
The above-mentioned functions material is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce in above-mentioned pore demonstrates heat accumulation function;
In above-mentioned filling work procedure, make above-mentioned composition maintain liquid state by the phase transformation of above-mentioned functions material, said composition is filled in the pore of above-mentioned porousness particulate;
In above-mentioned bonding reaction operation, make the phase transformation of above-mentioned composition by the above-mentioned functions material in the pore that is filled in above-mentioned porousness particulate maintain solid state, make the mutual bonding of above-mentioned reactive group.
According to above-mentioned formation, adopt above-mentioned latent-heat storage material as functional substance, in filling work procedure, make the latent-heat storage material maintain liquid state by phase transformation, composition is filled in the pore of porousness particulate.Like this, be in liquid state by making the latent-heat storage material, the flowability of composition improves, thereby easily is filled in the pore of porousness particulate.
Then, in the bonding reaction operation, make the latent-heat storage material maintain solid state by phase transformation, make reactive group that the terminal part of scavenger has at intermolecular mutual bonding.Like this, be in solid state by making the latent-heat storage material, the flowability of composition is suppressed, thereby carries out the bonding of reactive group under the state in the latent-heat storage material is stably captured the pore of porousness particulate.
Therefore, for the manufacture method of above-mentioned [10] described functional particle, also can more specifically reach the action effect identical with above-mentioned [9] described invention.
In addition, another aspect of the present invention relates to:
[11] a kind of manufacture method of functional particle for the manufacture of each described functional particle in above-mentioned [1] ~ [8], is characterized in that having:
Filling work procedure mixes the above-mentioned functions material with above-mentioned porousness particulate, fill the above-mentioned functions material in the pore of this porousness particulate;
Scavenger adds operation, behind this filling work procedure, mixes the above-mentioned porousness particulate that is filled with the above-mentioned functions material in containing the treatment solution of above-mentioned scavenger, adds above-mentioned scavenger to the pore section on the surface that is present in this porousness particulate; And
The bonding reaction operation, in the pore section on the surface that is present in above-mentioned porousness particulate, the mutual bonding of above-mentioned reactive group that above-mentioned scavenger is had.
According to above-mentioned formation, the manufacture method of functional particle has filling work procedure, scavenger adds operation and bonding reaction operation.In filling work procedure, the porousness particulate is mixed with functional substance, in the pore of porousness particulate, fill functional substance.
Add in the operation at ensuing scavenger, at first make the treatment solution that contains scavenger.Then, the scavenger that this treatment solution is contained adds the pore section on the surface that is present in the porousness particulate to.At this moment, (be not only the pore section that is present in the surface) in all pores of porousness particulate and all be filled with functional substance, scavenger can not arrive the inside of pore.But as mentioned above, because the main chain section of functional substance and scavenger has affinity, thereby scavenger is added to the pore section on the surface that is present in the porousness particulate.
At this moment, be filled in the functional substance in the pore, be filled in the main chain section that is present in the scavenger that contains near the functional substance of surperficial pore section and the treatment solution and have affinity and carry out bonding, thereby make scavenger stably add the pore section on the surface that is present in the porousness particulate to.Think that namely scavenger concentrates on the near surface in the pore section, functional substance is filled in pore inside.
Then, in the bonding reaction operation, as mentioned above, make reactive group that the terminal part of the scavenger of the pore section that is filled in the surface that is present in the porousness particulate has at intermolecular mutual bonding, thereby its molecular weight is increased.In addition, this terminal part and porousness particulate have affinity, and this terminal part demonstrates the anchoring effect to the porousness particulate.Thus, functional substance is stably captured the main chain section of the scavenger after molecular weight increases.At this, scavenger is concentrated the near surface that is present in the pore section, therefore, stably maintain the pore section that is present in the surface in the pore of porousness particulate by its terminal part, the functional substance that is filled in the inside of this pore section stably is sealing in the pore.
Therefore, in above-mentioned [11] described invention, can make by simple method, therefore a kind of manufacture method of functional particle can be provided, and it is for the manufacture of making functional substance evenly and stably being sealing in the pore of porousness particulate and this functional substance can not be exuded to from pore inside the functional particle of microparticle surfaces.
In addition, another aspect of the present invention relates to:
[12] such as the manufacture method of above-mentioned [11] described functional particle, it is characterized in that,
The above-mentioned functions material is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce in above-mentioned pore demonstrates heat accumulation function;
In above-mentioned filling work procedure, make the above-mentioned functions material maintain liquid state by phase transformation, this functional substance is filled in the pore of above-mentioned porousness particulate;
Add in the operation at above-mentioned scavenger, make the above-mentioned functions material in the pore that is filled in above-mentioned porousness particulate maintain solid state by phase transformation, add above-mentioned treatment solution to the pore section on the surface that is present in above-mentioned porousness particulate;
In above-mentioned bonding reaction operation, make the above-mentioned functions material maintain solid state by phase transformation, make the mutual bonding of above-mentioned reactive group.
According to above-mentioned formation, adopt above-mentioned latent-heat storage material as functional substance, in filling work procedure, make the latent-heat storage material maintain liquid state by phase transformation, fill it in the pore of porousness particulate.Like this, because the latent-heat storage material is in liquid state, therefore, the flowability of latent-heat storage material improves, thereby easily is filled in the pore of porousness particulate.
Add in the operation at ensuing scavenger, make the latent-heat storage material maintain solid state by phase transformation, ooze out from the pore of porousness particulate thereby suppress the latent-heat storage material, the scavenger that treatment solution is contained adds the pore section on the surface that is present in the porousness particulate to.At this moment, be filled in the pore and maintain in the functional substance of solid state, be filled in be present in the surface pore section near functional substance and the main chain section of the scavenger in the treatment solution have affinity and carry out bonding, thereby make scavenger stably add the pore section on the surface that is present in the porousness particulate to.
Then, in the bonding reaction operation, when making the latent-heat storage material maintain solid state, make reactive group that the terminal part of scavenger has at intermolecular mutual bonding.Like this, because the latent-heat storage material is in solid state, therefore, the flowability of composition is suppressed, and carries out the bonding of reactive group under the state in the latent-heat storage material is stably captured the pore of porousness particulate.
Thus, for the manufacture method of above-mentioned [12] described functional particle, also can more specifically reach the action effect identical with above-mentioned [11] described invention.
Embodiment
The below describes the present invention in detail.Functional particle of the present invention is filled with functional substance and scavenger in the pore of porousness particulate.In addition, main chain section and the functional substance of scavenger have affinity, and functional substance and scavenger together stably are sealing in the pore of porousness particulate.And the terminal part of this scavenger and porousness particulate have affinity, and scavenger utilizes the anchoring effect of its terminal part and remains in the pore of porousness particulate.
In the present invention, the porousness particulate refers to have the particulate that is made of inorganic substance or organic substance that penetrates into inner pore from its surface, can be the hollow minute particle that its inside has cavity, perhaps can be the particulate with cavity.For example, as the porousness particulate that is consisted of by inorganic substance, can enumerate the porousness particulate that is consisted of by phosphoric acid salt such as the carbonate such as the silicate such as the metal oxides such as silicon-dioxide, aluminum oxide, Calucium Silicate powder, Magnesium Silicate q-agent, calcium carbonate, magnesiumcarbonate, trimagnesium phosphate, phosphatic rock etc.In addition, as the porousness particulate that is consisted of by organic substance, can enumerate foam that is consisted of by the various resins such as polyethylene, polyurethane(s) etc.
But, in the present invention, owing to work as functional particle, therefore physical strength, chemical stability etc. is had requirement.Therefore, the preferred porousness particulate that is made of inorganic substance that uses in addition, owing to commercially available the particulate that much has uniform particle diameter etc. arranged, therefore more preferably uses porous silica.
At this, the particle diameter of porousness particulate is not particularly limited, and is general preferred in the scope of 1 μ m ~ 500 μ m, further preferably in the scope of about 5 μ m ~ about 300 μ m.
In the present invention, functional substance is so long as can be filled in the porousness particulate and can show in the porousness particulate that the material of its function then is not particularly limited.Particularly, the present invention has given play to effect when the functional substance that is difficult to directly process owing to character such as volatility, flowabilities is processed.For example, can enumerate: repeatedly carry out the latent-heat storage material that plays a role by between solid-liquid, undergoing phase transition and make the accumulation of heat of following the latent heat that phase transformation produces and heat radiation.In order to demonstrate heat accumulation function, these latent-heat storage materials change between solid state and liquid state repeatedly, under solid state, process easily, if but be transformed into liquid state by phase transformation, then produce mobile and become and be difficult to process.
As long as these latent-heat storage materials use can undergo phase transition under its fusing point (transformation temperature) and repeatedly carry out accumulation of heat and heat radiation and its fusing point and utilizing latent-heat storage material in the temperature range.Generally speaking, as the large material of latent heat, can enumerate such as the ethers of paraffin, wax, lipid acid, polyalkylene glycol or polyalkylene glycol etc.Wherein, with regard to paraffin, wax etc., commercially available have a different material of a large amount of fusing points, controls to easily arbitrarily exothermic temperature, therefore as the latent-heat storage material and preferred.
In addition, the fusing point of these latent-heat storage materials (transformation temperature) is as long as in the target temperature range of functional particle, and is general many-30 ℃ ~ 200 ℃ lower uses, and more-10 ℃ ~ 100 ℃ lower uses.As these materials, for example have: n-tetradecane (C
14H
30), fusing point is 5.9 ℃, the latent heat amount is 333.9J/g; Octadecane (C
18H
38), fusing point is 28.2 ℃, the latent heat amount is 243.6J/g; NSC 62789 (C
20H
42), fusing point is 36.8 ℃, the latent heat amount is 247.3J/g.
Need to prove that the heat storage capacity that is filled with the functional particle of latent-heat storage material is regulated by the pore volume of the porousness particulate of usefulness and the latent-heat storage amount of substance that is filled in the porousness particulate.Generally speaking, the latent-heat storage amount of substance that is filled in the porousness particulate is being in the scope of 30 % by weight ~ 90 % by weight with respect to functional particle preferably, further preferably in the scope of 50 % by weight ~ 80 % by weight.Therefore by making the latent-heat storage amount of substance that is filled in the porousness particulate in the scope of 30 % by weight ~ 90 % by weight, the latent heat amount of functional particle is maintained more than the 50J/g, as heat-storing material and preferred.
In addition, in the present invention, scavenger is to have and be filled in functional substance in the porousness particulate and have the main chain section of affinity and have the material of the terminal part of affinity with the porousness particulate.As such scavenger, according to the kind of functional substance and the kind of porousness particulate, a lot of materials are eligible, but in the present invention, and in the situation of the different in kind of functional substance and porousness particulate, it is large especially that the effect of scavenger becomes.That is, scavenger refers to bring into play the material of the effect in the pore that the functional substance that character is different from the material that consists of the porousness particulate stably is filled into this porousness particulate.
At this, carry out Appraising Methods as the nature difference to functional substance and porousness particulate, can estimate by the intermiscibility when both are mixed, also can estimate by the different moistening difficulties that cause of surface tension because of both.Perhaps, can estimate by both solubility parameter (SP value) or the measured values such as organic value and inorganic value.
For example, consider with latent-heat storage materials such as above-mentioned paraffin as functional substance, with the situation of porous silica as the porousness particulate.At this, paraffin is organic substance, and porous silica is inorganic substance, and therefore, their character differs widely.Therefore, even fill paraffin in the pore of porous silica, affinity is also low each other, thereby oozes out easily.Therefore, in the present invention, make scavenger between between them.At this moment, because paraffin is organic substance, therefore, the main chain section of scavenger is for having the structure of affinity to organic substance.On the other hand, because porous silica is inorganic substance, therefore, the terminal part of scavenger is for having the structure of affinity to inorganic substance.
At this, the molecular structure of scavenger is made of with the terminal part that is positioned at the end of this main chain section main chain section as mentioned above.The main chain section of this scavenger has affinity to functional substance, can be the straight chain shape or also can be chain.In addition, the molecular weight of main chain section can be arbitrary extent, be not particularly limited, but as described below, in the pore of porousness particulate, utilize its terminal part mutually to carry out intermolecular bonding between the scavenger, thereby increase its molecular weight.Therefore, scavenger is preferably lower molecular weight and is filled into easily in the pore of porousness particulate and by utilizing subsequently intermolecular bonding that molecular weight is increased to become the material that rests on easily in the pore.
At this, as an example, consider with latent-heat storage materials such as above-mentioned paraffin as functional substance, with the situation of porous silica as the porousness particulate.At this moment, the material of the main chain section of scavenger for the organic substances such as paraffin are had affinity can be enumerated such as oligopolymer or polymkeric substance such as polyisobutene, polyoxypropylene, polyacrylic ester, polyether glycol and polymethacrylate.These oligopolymer or polymkeric substance are organic substance, and the latent-heat storage materials such as paraffin are had strong affinity.In addition, for the foregoing reasons, with regard to its molecular weight, compare more preferably oligopolymer with polymer phase.
On the other hand, the terminal part of scavenger has affinity to the porousness particulate, and this affinity demonstrates scavenger to the anchoring effect of porousness particulate, and scavenger is firmly held in the pore of porousness particulate.In addition, for the terminal part of this scavenger, all there is the terminal part that the porousness particulate is had affinity in all positions of a plurality of ends that can be not do not have in main chain section, and preferably there is the terminal part that the porousness particulate is had affinity in the most of position in a plurality of ends.
For example, be in the situation of straight chain shape in the main chain section of scavenger, all have the terminal part that the porousness particulate is had affinity by making its both ends, intermolecular bonding occurs in a large number, and the molecular weight of scavenger becomes larger, thereby rests in the pore easily.In addition, in the situation of main chain section for a chain of scavenger, have the terminal part that the porousness particulate is had affinity by making its most of end, form reticulated structure by intermolecular bonding between the scavenger, it is larger that molecular weight becomes, thereby rest in the pore easily.
In addition, scavenger has and makes the reactive group that the porousness particulate is had the mutual bonding of terminal part of affinity.At this, as an example, consider with latent-heat storage materials such as above-mentioned paraffin as functional substance, with the situation of porous silica as the porousness particulate.At this moment, the terminal part of scavenger has affinity to porous silica and has the reactive group of mutual bonding.In this case, as the terminal part of scavenger, can enumerate for example reactive silyl.
Reactive silyl refers to that the hydroxyl and/or the hydrolization group that contain with silicon atom bonding carry out condensation reaction, form siloxane bond and the silyl of mutual bonding as reactive group, in the presence of moisture or catalyzer.At this, hydrolization group refers to the group that passes through hydrolysis formation reactive hydroxyl that alkoxyl groups such as methoxyl group, oxyethyl group is such.Therefore, in above-mentioned example, the terminal part that preferably makes scavenger is to have alkoxyl group as the reactive silyl (hereinafter referred to as " alkoxysilyl ") of reactive group.The quantity of the alkoxyl group of the reactive group that has as this alkoxysilyl can be any one in, two, three.
Shown in this example, terminal part at scavenger is in the situation of alkoxysilyl, and as mentioned above, the terminal part at them between the scavenger forms siloxane bond and mutual bonding, a plurality of scavengers are bonded to linearity or netted, thereby form the scavenger of high molecular.This is bonded in the pore of porousness particulate and carries out, and therefore, scavenger is utilizing its main chain section to keep increasing the molecular weight of self under the state of functional substance, thereby rests on securely in the pore of porousness particulate.Therefore, functional substance is sealing in the pore of porousness particulate more firmly by scavenger.
In addition, in above-mentioned example, the siloxane bond section that the alkoxysilyl of scavenger or their bondings form has very strong affinity with Siliciumatom as skeleton and with the porous silica that is made of silicon-dioxide.In addition, exist on the surface of porous silica in the situation of hydroxyl, alkoxysilyl also with this hydroxyl reaction, the result, scavenger itself can be bonded in securely with porous silica the surface of porous silica by siloxane bond.
At this, describe by the manufacture method of following each embodiment to functional particle of the present invention.In these embodiments, in order to be described more specifically manufacture method, use porous silica as the porousness particulate, use the latent-heat storage material that is consisted of by paraffin as the functional substance that is filled in its pore.In addition, as the scavenger in the pore that paraffin is captured porous silica, use the two terminal-reactive hydrocarbon oligomers that have alkoxysilyl with hydrocarbon oligomer as main chain section, at its two end.
(the first embodiment)
The manufacture method of the functional particle of this first embodiment has filling work procedure and bonding reaction operation.Below, each operation is described.
A1: filling work procedure
In filling work procedure, at first, make the composition that contains functional substance and scavenger.In this first embodiment, functional substance is paraffin, and the main chain section of scavenger is hydrocarbon oligomer, and therefore, their affinity demonstrates by force intermiscibility.At first, make employed paraffin be in the above temperature of its fusing point and form liquid state, to wherein mixing scavenger.The ratio of the scavenger that mixes in the paraffin as functional substance is as long as capture paraffin as the amount in the pore of the porous silica of porousness particulate for being enough to, in this first embodiment, preferably the amount with respect to the paraffin in the pore that is filled into porous silica is the scope of 1 % by weight ~ 20 % by weight, more preferably the scope of 2 % by weight ~ 10 % by weight.Ratio by making the scavenger that mixes in the paraffin can capture paraffin the pore section of porous silica the most efficiently in the scope of 1 % by weight ~ 20 % by weight.
At this, except functional substance and scavenger, can be to mixed solvent, linking agent, catalyzer etc. in the composition.But solvent need to be removed in the pore that composition is filled into the porousness particulate afterwards, therefore, does not preferably use as far as possible, also wants inferior limit ground to use even perhaps use.On the other hand, the contrast reactive group that has of scavenger and use as required linking agent and catalyzer.In this first embodiment, the reactive group of scavenger is alkoxyl group, therefore, and can be to the required moisture of the hydrolysis of mixed oxyalkyl in the composition.In addition, also can mix the organic titanic compounds such as the organo-tin compound such as lauric acid dioctyltin (ジ オ Network チ ル Tin ラ ウ レ one ト) or tetraisopropoxy titanium in the composition as the catalysts of alkoxyl group.
Then, make the composition of as above making under the temperature more than the melting point of paraffin wax, maintain liquid state, and be filled in the pore of porous silica.At this moment, in order to improve the flowability of composition, preferably be made as the temperature that fully is higher than fusing point.By in the composition of such formation liquid state, mixing porous silica and stirring, said composition can be filled in the pore of porous silica.Need to prove, by reducing pressure or pressurize or reduce pressure and pressurize when this filling, can composition be filled in the pore of porous silica more completely.
Behind filled compositions, the temperature of porous silica is reduced to below the melting point of paraffin wax.Thus, paraffin undergoes phase transition, and composition is transformed into solid state, thereby stably remains in the pore.Therefore, composition can not ooze out in pore.
B1: bonding reaction operation
In the bonding reaction operation, as mentioned above, consist of between the scavenger of the composition in the pore be filled in the porousness particulate, the reactive group that its terminal part has is at intermolecular mutual bonding, thereby its molecular weight is increased.In this first embodiment, the alkoxyl group of alkoxysilyl that is arranged in two ends of scavenger utilizes the moisture of composition or the moisture of environment hydrolysis to occur and form hydroxyl, and terminal part becomes reactive high hydroxyl silyl.This hydroxyl silyl and the hydroxyl silyl of adjacent scavenger between condensation reaction occurs, form siloxane bond, thereby form the scavenger of high molecular.
In addition, as mentioned above, exist in the situation of hydroxyl on the surface as the porous silica of porousness particulate, be formed on scavenger terminal part the reactive hydroxyl silyl also with this hydroxyl reaction, as a result, scavenger self and porous silica form siloxane bond.
These bonding reactions do not need to carry out especially pyroprocessing, can occur under the temperature below the melting point of paraffin wax or room temperature yet.Therefore think, carry out above-mentioned filling work procedure during in also carry out bonding reaction operation in this first embodiment of a part.Think in addition, behind above-mentioned filling work procedure, make porous silica maintain temperature below the melting point of paraffin wax during in also carry out, finish afterwards.
Like this, the bonding reaction operation is finished, make thus functional particle of the present invention.In this first embodiment, for this functional particle, paraffin as functional substance is stably captured the main chain section that makes the scavenger after molecular weight increases by siloxane bond, and stably is sealing in the pore of porousness particulate by the terminal part of this scavenger.
(the second embodiment)
The manufacture method of the functional particle of this second embodiment is different from above-mentioned the first embodiment, has scavenger interpolation operation between filling work procedure and bonding reaction operation, with the interpolation of the filling of functional substance and scavenger as the operation of separating.That is, in this second embodiment, have filling work procedure, scavenger interpolation operation, bonding reaction operation.Below, each operation is described.
A2: filling work procedure
In filling work procedure, in the pore of porousness particulate, fill functional substance.At first, make paraffin as functional substance maintain its more than fusing point temperature and form liquid state.At this moment, in order to improve the flowability of paraffin, preferably be made as the temperature that fully is higher than fusing point.By in the paraffin of such formation liquid state, mixing porous silica and the stirring as the porousness particulate, this paraffin can be filled in the pore of porous silica.Need to prove, by reducing pressure or pressurize or reduce pressure and pressurize when this filling, can paraffin be filled in the pore of porous silica more completely.
After filling paraffin, the temperature of porous silica is reduced to below the melting point of paraffin wax.Thus, paraffin undergoes phase transition and is transformed into solid state, thereby stably remains in the pore of porous silica.Therefore, the paraffin as functional substance can not ooze out in the pore of porous silica.
B2: scavenger adds operation
In scavenger adds operation, add scavenger in the porous silica behind the filling work procedure.At first, make the treatment solution that contains scavenger.Treatment solution can be scavenger itself, preferably utilizes solvent that scavenger is diluted to suitable concentration and is used as treatment solution.Particularly when scavenger itself is not liquid state, utilizes solvent to dilute and make the treatment solution of liquid state.In this second embodiment, scavenger is two terminal-reactive hydrocarbon oligomers, even but owing to the molecular weight of the hydrocarbon oligomer of main chain section is liquid state, its viscosity is also different, thereby in full-bodied situation, be difficult to add in the porous silica equably.Therefore, in the situation that molecular weight is large and viscosity is high of scavenger, preferably utilize solvent to dilute.
At this, except scavenger and solvent, can be to mixed cross-linker, catalyzer etc. in the treatment solution.The contrast reactive group that has of scavenger and use as required linking agent and catalyzer.In this second embodiment, the reactive group of scavenger is alkoxyl group, therefore, and can be to the needed moisture of the hydrolysis of mixed oxyalkyl in the treatment solution.In addition, also can mix the organic titanic compounds such as the organo-tin compound such as lauric acid dioctyltin or tetraisopropoxy titanium in the treatment solution as the catalysts of alkoxyl group.
Then, the treatment solution of as above making is added in the porous silica.At this moment, under its temperature below fusing point, maintain solid state as the paraffin that is filled in the functional mass in the pore.Treatment solution with respect to the addition of porous silica take the amount of contained scavenger as long as being enough to that paraffin is captured amount in the pore of porous silica, in this second embodiment, preferably the amount with respect to the paraffin in the pore that is filled in porous silica is the scope of 1 % by weight ~ 20 % by weight, more preferably the scope of 2 % by weight ~ 10 % by weight.By make add the scavenger in the porous silica to amount with respect to the amount that is filled in the paraffin in the pore in the scope of 1 % by weight ~ 20 % by weight, can will capture in the pore of porous silica as the paraffin of functional substance the most efficiently.
At this, in all pores of porous silica, be filled with paraffin by above-mentioned filling work procedure, thereby treatment solution can not arrive the inside of pore.But in this second embodiment, the functional substance that is filled in first in the pore is paraffin, and the main chain section of the scavenger that adds take the form for the treatment of solution afterwards is as hydrocarbon oligomer, and therefore, their affinity is strong and demonstrate intermiscibility.Thus, be filled in the paraffin in the pore of porous silica, be filled near the pore section that is present in the surface paraffin and the main chain section of the scavenger in the treatment solution is had affinity and be captured.Then, by removing the solvent in the treatment solution, make scavenger stably add the pore section (part that is present in silica sphere in the pore) on the surface that is present in porous silica to.
C2: bonding reaction operation
In the bonding reaction operation, add between the scavenger of pore section on the surface that is present in porous silica, the reactive group that its terminal part has is at intermolecular mutual bonding, thereby its molecular weight is increased.In this second embodiment, identical with above-mentioned the first embodiment, the alkoxyl group of alkoxysilyl that is arranged in two ends of scavenger utilizes the moisture for the treatment of solution or the moisture of environment hydrolysis to occur and form hydroxyl, and terminal part becomes reactive high hydroxyl silyl.This hydroxyl silyl and the hydroxyl silyl of adjacent scavenger between condensation reaction occurs, form siloxane bond, thereby form the scavenger of high molecular in the pore section on the surface that is present in porous silica.
In addition, as mentioned above, exist in the situation of hydroxyl on the surface as the porous silica of porousness particulate, be formed on scavenger terminal part the reactive hydroxyl silyl also with this hydroxyl reaction, as a result, scavenger self and porous silica form siloxane bond.
These bonding reactions do not need to carry out especially pyroprocessing, can occur under the temperature below the melting point of paraffin wax or room temperature yet.Therefore think, carry out above-mentioned scavenger add operation during in also carry out bonding reaction operation in this second embodiment of a part.Think in addition, after above-mentioned scavenger adds operation, also carry out, finish afterwards.
Like this, the bonding reaction operation is finished, make thus functional particle of the present invention.In this second embodiment, for this functional particle, paraffin as functional substance is stably captured the main chain section that makes the scavenger after molecular weight increases by siloxane bond, and stably is sealing in the pore of porousness particulate by the terminal part of this scavenger.
Particularly in this second embodiment, the internal main in the pore of porousness particulate will be filled with the paraffin as functional substance, and the pore section that is present in the surface of porous silica in pore mainly is filled with scavenger.Thus, block the mode of the outlet of pore by scavenger, can prevent highly that functional substance from oozing out in pore.
Embodiment
At this, utilize the manufacture method of the functional particle of above-mentioned first and second embodiment to carry out following each embodiment.
Embodiment 1
Present embodiment 1 is made with the functional particle 1 of latent-heat storage material as functional substance according to the manufacture method of above-mentioned the first embodiment.In present embodiment 1, as the porousness particulate, using median size is the porous silica (manufacturing of デ グ サ ジ ヤ パ Application Co., Ltd.) of 100 μ m.In addition, as the latent-heat storage material in the pore that is filled in porous silica, to use fusing point (transformation temperature) be 66 ℃, latent heat amount is the paraffin of 210J/g (Paraffin Wax-150, Japanese smart wax Co., Ltd. makes).In addition, as the scavenger in the pore that this paraffin is captured porous silica, use the two terminal-reactive polyisobutylene oligomer (エ ピ オ Application 100S, the カ ネ カ of Co., Ltd. makes) that have methyl dimethoxy oxygen base silyl with polyisobutylene oligomer as main chain section, at its two end.
A1: filling work procedure
The 700g heating paraffin is arrived 80 ℃ of the temperature of its fusing point more than 66 ℃, make it form liquid state, mix 30g two terminal-reactive polyisobutylene oligomer and 0.1g in the paraffin of this liquid state as the lauric acid dioctyltin of catalysts, make composition 1.
Then, in omnipotent mixing and blending machine (manufacturing of the ダ of Co., Ltd. Le ト Application), drop into the 500g porous silica, make above-mentioned composition 1 maintain the required water 3g of hydrolysis that further mixes methoxyl group under 80 ℃ the state, then, be injected into immediately in the porous silica, in that omnipotent mixing and blending machine is maintained under 80 ℃ the state, mix 30 minutes, above-mentioned composition 1 is filled in the pore of porous silica.Mix that porous silica after 30 minutes shows that the composition 1 of sening as an envoy to is filled in its pore fully and the pulverulence of surface dry.
B1: bonding reaction operation
Then, Yi Bian the porous silica that is filled with composition 1 in the pore is stirred, Yi Bian omnipotent mixing and blending machine is cooled to the temperature 60 C of melting point of paraffin wax below 66 ℃.Under this state, the interior composition 1 of pore that is filled in porous silica is transformed into solid state, thereby can not ooze out in this pore.Further mix 120 minutes, then, finish the bonding reaction between the two terminal-reactive polyisobutylene oligomer in that omnipotent mixing and blending machine is maintained under 60 ℃ the state.Then, will take out the functional particle 1 of making after the omnipotent mixing and blending machine cooling.
Embodiment 2
Present embodiment 2 is made with the functional particle 2 of the latent-heat storage material identical with above-described embodiment 1 as functional substance according to the manufacture method of above-mentioned the second embodiment.Particularly, be that to fill fusing point (transformation temperature) in the porous silica (manufacturing of デ グ サ ジ ヤ パ Application Co., Ltd.) of 100 μ m be that 66 ℃, latent heat amount are the paraffin (Paraffin Wax-150, Japanese smart wax Co., Ltd. makes) of 210J/g to the median size identical with above-described embodiment 1 as the porousness particulate.In addition, as scavenger, use the two terminal-reactive polyisobutylene oligomer (エ ピ オ Application 100S, Co., Ltd. カ ネ カ manufacturing) identical with above-described embodiment 1.
A2: filling work procedure
To 80 ℃ of the temperature of its fusing point more than 66 ℃, make it form liquid state the 700g heating paraffin.Then, in omnipotent mixing and blending machine (manufacturing of the ダ of Co., Ltd. Le ト Application), drop into the 500g porous silica, to the paraffin that wherein injects the aforesaid liquid state, mix 30 minutes, above-mentioned paraffin is filled in the pore of porous silica in that omnipotent mixing and blending machine is maintained under 80 ℃ the state.Mix that porous silica after 30 minutes shows that the paraffin of sening as an envoy to is filled in its pore fully and the pulverulence of surface dry.
B2: scavenger adds operation
Then, 30g two terminal-reactive polyisobutylene oligomer are dissolved in the 70g solvent xylene, in this solution, mix 0.1g as the lauric acid dioctyltin of catalysts, make treatment solution 2.The temperature of this treatment solution 2 is 50 ℃.
Then, Yi Bian the porous silica that is filled with paraffin in the pore is stirred, Yi Bian omnipotent mixing and blending machine is cooled to the temperature 60 C of melting point of paraffin wax below 66 ℃.Under this state, the interior paraffin of pore that is filled in porous silica is transformed into solid state, thereby can not ooze out in this pore.
At this, omnipotent mixing and blending machine is maintained under 60 ℃ the state, the required water 3g of hydrolysis that mixes methoxyl group in the above-mentioned treatment solution 2, then, be injected into immediately in the porous silica, make again omnipotent mixing and blending machine mix 30 minutes, the surface of adding above-mentioned treatment solution 2 to porous silica.
C2: bonding reaction operation
Then, the porous silica that its surface is coated with treatment solution 2 further mixes 120 minutes in that omnipotent mixing and blending machine is maintained under 60 ℃ the state.At this moment, the solvent evaporates for the treatment of solution 2 is fallen, thereby two terminal-reactive polyisobutylene oligomer are added to the pore section on the surface that is present in porous silica.In addition, during this period, finish the bonding reaction between the two terminal-reactive polyisobutylene oligomer.Then, will take out the functional particle 2 of making after the omnipotent mixing and blending machine cooling.
Comparative example 1
This comparative example 1 is made with the functional particle 3 of the latent-heat storage material identical with above-described embodiment 1 as functional substance according to existing manufacture method.Particularly, be that to fill fusing point (transformation temperature) in the porous silica (manufacturing of デ グ サ ジ ヤ パ Application Co., Ltd.) of 100 μ m be that 66 ℃, latent heat amount are the paraffin (Paraffin Wax-150, Japanese smart wax Co., Ltd. makes) of 210J/g to the median size identical with above-described embodiment 1 as the porousness particulate.But, different from above-described embodiment 1 and 2, do not use the scavengers such as two terminal-reactive polyisobutylene oligomer.
A2: filling work procedure
To 80 ℃ of the temperature of its fusing point more than 66 ℃, make it form liquid state the 700g heating paraffin.Then, in omnipotent mixing and blending machine (manufacturing of the ダ of Co., Ltd. Le ト Application), drop into the 500g porous silica, to the paraffin that wherein injects the aforesaid liquid state, mix 30 minutes, above-mentioned paraffin is filled in the pore of porous silica in that omnipotent mixing and blending machine is maintained under 80 ℃ the state.Mix that porous silica after 30 minutes shows that the paraffin of sening as an envoy to is filled in its pore fully and the pulverulence of surface dry.In this comparative example 1, do not implement scavenger and add operation and bonding reaction operation, will take out the functional particle 3 of making after the omnipotent mixing and blending machine cooling.
Then, the performance of the functional particle 1 ~ 3 of making in above-described embodiment 1, embodiment 2 and the comparative example 1 is estimated.As assessment item, carry out heat storage capacity mensuration and ooze out evaluation.
Below, each test subject and evaluation result are described.
A. heat storage capacity is measured
The DSC figure that the heat storage capacity of functional particle obtains by using differential scanning calorimeter (DSC) EXSTAR6000 (manufacturing of Seiko Electronics Co., Ltd) to measure calculates.
B. ooze out evaluation
(1) oozes out evaluation 1
Get the 10g functional particle and put into beaker, add 90g water.This beaker was heated 30 minutes in 80 ℃ water-bath.Then, be cooled to below 30 ℃.(in the intensification, after the intensification) and cooled state were judged according to following metewand when visual observation should be heated.
Zero: in intensification, heat up after, all unconfirmedly after the cooling ooze out from silicon-dioxide to paraffin.
*: under the temperature more than the fusing point in intensification, after heating up, paraffin floats on water layer top, confirms to have paraffin mass (cured article) after the cooling.
(2) ooze out evaluation 2
Get the 5g functional particle and put into the aluminium dish.This aluminium dish heated 10 hours in 100 ℃ drying machine after, measure its weight, judge according to following metewand.In addition, similarly, heating was measured its weight after 5 hours in 150 ℃ drying machine, judged according to same metewand.
Zero: the weight to functional particle unconfirmed reduces.
*: the weight of functional particle obviously reduces.
(3) ooze out evaluation 3
After oozing out evaluation 2 end, the condition of surface of visual observation functional particle is judged according to following metewand after the cooling.
Zero: the condition of surface of functional particle is unchanged, is dry and comfortable white powder state.
*: functional particle bonds and is not pulverulence, and color also variable color becomes Sandy.
Each evaluation result of the functional particle of making for above-described embodiment 1, embodiment 2 and comparative example 1 is shown in Table 1.
Table 1
As shown in Table 1, in heat storage capacity is measured, in embodiment 1, embodiment 2 and comparative example 1, do not observe larger difference.Therefore as can be known, the paraffin as the latent-heat storage material all is filled into the inside of silicon-dioxide and forms functional particle.
On the other hand, in oozing out evaluation 1, the functional particle 1 and 2 of making among embodiment 1 and the embodiment 2, even in the situation that is heated to the temperature higher than melting point of paraffin wax, paraffin all is not exuded to silica sphere yet and is stably filled.Relative therewith, as to make in the comparative example 1 functional particle 3, in the situation that is heated to the temperature higher than melting point of paraffin wax, paraffin is exuded to the outside of silicon-dioxide.
Then, estimate in 2 oozing out, in embodiment 1, embodiment 2 and the comparative example 1, under the temperature of 100 ℃ or 150 ℃, all do not observe weight and reduce.
But, in oozing out evaluation 3, the functional particle 1 and 2 of making among embodiment 1 and the embodiment 2 is dry and comfortable white powder state, relative therewith, in the functional particle 3 of making in the comparative example 1, the paraffin that is exuded to the surface of silicon-dioxide occur to solidify and makes between the particle of silicon-dioxide hot stickyly, and this paraffin becomes Sandy at the silica sphere thermo-color.
Based on the above results, the functional particle 1 and 2 of making among embodiment 1 and the embodiment 2, even under the condition of high temperature of oozing out evaluation 2, paraffin can not be exuded to silica sphere yet and stably be filled.
Relative therewith, the functional particle 3 of making in the comparative example 1 is under the condition of high temperature of oozing out evaluation 2, and the paraffin that is filled in the inside of silicon-dioxide liquefies, and is exuded to silica sphere.But the vapour pressure of the paraffin that oozes out is high, therefore, does not evaporate even heat also for a long time under 100 ℃ or 150 ℃, thereby do not produce changes in weight in oozing out evaluation 2.
But, it is evident that even do not produce changes in weight, in the functional particle 3 of making in the comparative example 1, paraffin is exuded to the surface of silicon-dioxide, does not reach the state of standing Reusability as functional particle.
Relative therewith, the functional particle 1 and 2 of making among embodiment 1 and the embodiment 2 is constructed as follows functional particle: even heat for a long time under 100 ℃ or 150 ℃, weight can not reduce yet, and paraffin stably remains on silicon-dioxide inside, thereby can Reusability.
Therefore, in the present invention, can make by simple method, therefore, can provide to make functional substance evenly and stably be sealing in the pore of porousness particulate and this functional substance can not be exuded to from pore inside functional particle and the manufacture method thereof of microparticle surfaces.
Need to prove, when enforcement is of the present invention, be not limited to the respective embodiments described above, can enumerate following various variation.
(1) in the respective embodiments described above, make the functional particle take the latent-heat storage material as functional substance, but be not limited to this, can make various functional particles.Particularly, for being filled in inner functional substance, the material, liquid etc. that can make easy gasification have mobile material or melt with temperature and demonstrate mobile material etc.
(2) in the respective embodiments described above; use porous silica as the porousness particulate; but be not limited to this, can contrast and be filled in inner functional substance and use the organic fine particles such as the inorganic particles such as aluminum oxide, Calucium Silicate powder, calcium carbonate, phosphatic rock or foamed resin.
(3) in the respective embodiments described above, use two terminal-reactive polyisobutylene oligomer as scavenger, but be not limited to this, can contrast the porousness particulate of functional substance that the main chain section of scavenger catches or terminal part performance anchoring effect and use the scavenger of various structures.In addition, the functional substance of the main chain section that catches above-mentioned two terminal-reactive polyisobutylene oligomer be can contrast and the higher polyoxypropylene of polarity or polyacrylic ester etc. changed to.
(4) in the respective embodiments described above, the terminal part that has as scavenger, use alkoxysilyl, particularly, use methyl dimethoxy oxygen base silyl, but be not limited to this, can contrast the porousness particulate and use other reactive groups, so that terminal part performance anchoring effect.In addition, also may be used the compound of silane coupling agent etc. and silanol group and the reaction of other reactive groups and bonding.
Claims (12)
1. functional particle is characterized in that having:
Have a plurality of porousness particulates that penetrate into inner pore from the surface;
Be filled in the pore of this porousness particulate and in this pore, demonstrate the functional substance of function; And
Be filled in the pore of described porousness particulate and described functional substance is stably captured scavenger in the described pore, and,
Described scavenger possesses with described functional substance and has the main chain section of affinity and the terminal part that has affinity with described porousness particulate, and this terminal part has the reactive group of mutual bonding.
2. functional particle as claimed in claim 1 is characterized in that, described porousness particulate is porous silica.
3. functional particle as claimed in claim 1 or 2 is characterized in that, described scavenger has reactive silyl as described terminal part.
4. functional particle as claimed in claim 3 is characterized in that, described reactive silyl has at least one alkoxyl group as described reactive group.
5. such as each described functional particle in the claim 1 ~ 4, it is characterized in that described scavenger has at least a oligopolymer in the group that is selected from polyisobutene, polyoxypropylene, polyacrylic ester, polyether glycol and polymethacrylate or polymkeric substance as described main chain section.
6. such as each described functional particle in the claim 1 ~ 5, it is characterized in that described functional substance is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce demonstrates heat accumulation function in described pore.
7. functional particle as claimed in claim 6 is characterized in that, described latent-heat storage material contains the organic substances such as paraffin, wax, lipid acid, polyalkylene glycol, and its transformation temperature is-30 ℃ ~ 200 ℃.
8. such as claim 6 or 7 described functional particles, it is characterized in that, contain the described latent-heat storage material of 30 % by weight ~ 90 % by weight, and the latent heat amount is more than the 50J/g.
9. the manufacture method of a functional particle for the manufacture of each described functional particle in the claim 1 ~ 8, is characterized in that having:
Filling work procedure, the composition that will contain described functional substance and described scavenger mixes with described porousness particulate, fills described composition in the pore of this porousness particulate; And
The bonding reaction operation, the mutual bonding of described reactive group that the described scavenger in the described composition is had.
10. the manufacture method of functional particle as claimed in claim 9 is characterized in that,
Described functional substance is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce in described pore demonstrates heat accumulation function;
In described filling work procedure, make described composition maintain liquid state by the phase transformation of described functional substance, said composition is filled in the pore of described porousness particulate;
In described bonding reaction operation, make the phase transformation of described composition by described functional substance in the pore that is filled in described porousness particulate maintain solid state, make the mutual bonding of described reactive group.
11. the manufacture method of a functional particle for the manufacture of each described functional particle in the claim 1 ~ 8, is characterized in that having:
Filling work procedure mixes described functional substance with described porousness particulate, fill described functional substance in the pore of this porousness particulate;
Scavenger adds operation, after this filling work procedure, mixes the described porousness particulate that is filled with described functional substance in containing the treatment solution of described scavenger, adds described scavenger to the pore section on the surface that is present in this porousness particulate; And
The bonding reaction operation, in the pore section on the surface that is present in described porousness particulate, the mutual bonding of described reactive group that described scavenger is had.
12. the manufacture method of functional particle as claimed in claim 11 is characterized in that,
Described functional substance is the latent-heat storage material that the latent heat that utilizes the phase transformation caused by temperature variation to produce in described pore demonstrates heat accumulation function;
In described filling work procedure, make described functional substance maintain liquid state by phase transformation, this functional substance is filled in the pore of described porousness particulate;
Add in the operation at described scavenger, make the described functional substance in the pore that is filled in described porousness particulate maintain solid state by phase transformation, add described treatment solution to the pore section on the surface that is present in described porousness particulate;
In described bonding reaction operation, make described functional substance maintain solid state by phase transformation, make the mutual bonding of described reactive group.
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| JP2016079351A (en) * | 2014-10-22 | 2016-05-16 | 株式会社デンソー | Composite heat-storing material |
| JP6604721B2 (en) * | 2014-12-26 | 2019-11-13 | 永大産業株式会社 | Thermal storage material impregnated with latent heat storage material with excellent heat resistance |
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Application publication date: 20130102 |