CN103372409A - Hollow polymer particle and manufacturing method thereof - Google Patents
Hollow polymer particle and manufacturing method thereof Download PDFInfo
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- CN103372409A CN103372409A CN2013101298920A CN201310129892A CN103372409A CN 103372409 A CN103372409 A CN 103372409A CN 2013101298920 A CN2013101298920 A CN 2013101298920A CN 201310129892 A CN201310129892 A CN 201310129892A CN 103372409 A CN103372409 A CN 103372409A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08F2/00—Processes of polymerisation
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- C08F2/18—Suspension polymerisation
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/12—Powdering or granulating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
Abstract
Disclosed are a hollow polymer particle and a manufacturing method thereof. The invention provides a method for producing hollow polymer particles, capable of reducing generation of recessed particles low in hollow rate and increasing the particles high in hollow rate. The method is characterized in that, in water medium, a mixture of polymer monomers for forming housings of the polymer particles and organic solution is emulsified and scattered, the polymer monomers are floated and polymerized under the presence of a polymerization initiator to form polymer particles containing organic solution, and the organic solution in the polymer particles is gasified and removed through the housings of the particles so as to produce hollow polymer particles. In the method, the organic solution in the polymer particles is gasified and removed through the housings of the particles, when the polymer particles are scattered in the water medium, so as to produce hollow polymer particles.
Description
Technical field
The present invention relates to the manufacture method of hollow polymer particulate, it can make non-expansion type and the high hollow polymer particulate of hollow rate; And the non-expansion type and the high hollow polymer particulate of hollow rate that obtain by this manufacture method.Hollow polymer particulate of the present invention can as such as light material, improve the material of light scattering and the intermediate layer that between supporter and heat-sensitive color layer, forms for the recording sensitivity that improves thermosensitive recording body in contained heat-barrier material etc.The manufacture method of hollow polymer particulate of the present invention is characterised in that, in the generation that increases the high particulate of non-expansion type and hollow rate, water dispersible is good and coating preparation is simple, do not disperse during processing, environmentally friendly.
Background technology
Up to now, as the manufacture method of hollow polymer particulate is known patent documentation 1 and patent documentation 2 arranged.The hollow polymer particulate that these documents are put down in writing is as object take the intumescent hollow particle.That is: form shell with thermoplastic polymer, microsphere that inside includes volatile foaming agent by suspension polymerization after, heat this microsphere and make blowing agent volatilization that inside comprises, improve the internal pressure of microsphere, thereby make shell expand (expansion).
It is different and do not concentrate such shortcoming to utilize the intumescent hollow polymer particulate of the method manufacturing that patent documentation 1 and patent documentation 2 put down in writing to have a particle diameter after the expansion.When particle diameter is not concentrated, has the shortcoming that lacks at the using adaptability in following field: require to have used the coating composition of hollow polymer particulate to have stable field; Perhaps seek the field (for example, seeking the thermosensitive recording body of the stability of recording sensitivity) of controlled particle diameter.
As the method for making the hollow polymer particulate that particle diameter concentrates, known have a patent documentation 3.The manufacture method of the hollow particle that the document is put down in writing is called as so-called seeding polymerization method.The basic fundamental of seeding polymerization method be from first water, make polymerizable monomer (for example: styrene) thus polymerization forms seed (nuclear) and begins after carrying out emulsification in the presence of the emulsifying agent to form particulate.Then, make other polymerizable monomer (for example: acrylate) be adsorbed in this seed, then around this seed, utilize other polymerizable monomer to form outer shell.Then, add in the system and see through this outer shell and (for example: ammonia spirit), make thus the seed dissolving, and make this dissolved matter and outside water displacement make inner seed swelling, the material of dissolving, and then heat drying removes inner water, thereby makes hollow method.
For the hollow polymer particulate that utilizes this seeding polymerization method, generally speaking, owing to emulsification in the presence of emulsifying agent forms particulate, only can obtain particle diameter little to 1 μ m or below the 1 μ m, hollow rate mostly is the particulate about 50% most.With this hollow particle during as thermal photography body and function heat-barrier material for example, have the effect of heat insulation inadequate shortcoming that becomes.Therefore, there is the problem that how to make particle diameter become several μ m and improve hollow rate in the seeding polymerization method.
Patent documentation 4 has been put down in writing a kind of average grain diameter that contains in the formed voided layer between supporter and heat-sensitive color layer be that 0.1～20 μ m (preferred 2～10 μ m), hollow rate are the thermosensitive recording body of the non-expansion type polymer hollow particle of 60 (preferred 90) more than the %.But, do not provide in the document about how making the technical open of the non-expansion type hollow polymer particulate that satisfies such condition.
Patent documentation 5 discloses a kind of manufacture method of hollow polymer particulate, wherein, the preparation volatile hydrocarbon, the suspension of hydrophilic monomer and cross-linkable monomer coexistence, in this suspension, make the polymerization of aforementioned monomer composition, thereby obtain the dispersion liquid that inside comprises the polymer particles of this volatile hydrocarbon, then isolating polymer particulate and carry out drying and process from this dispersion liquid, perhaps do not separate and in dispersion, be blown into air, nitrogen, steam etc., perhaps be used in combination these means, the volatile hydrocarbon of rising isolating polymer particulate inside thus, thus the method for hollow bead made.
But, utilize the hollow polymer particulate of the method manufacturing that patent documentation 5 puts down in writing to have the part of polymer wall (shell) or the shortcoming that the concavity particulate of depression is seriously caved in, forms at a few place.This is to separate along with the gasification of the volatile hydrocarbon that comprises is rising, granule interior pressure reduces, the polymeric membrane (shell) that namely consists of spherical particle can't be resisted inner pressure relief and be inhaled inwards the phenomenon that produces, and can think that its reason is hardness, the undercapacity of this polymeric membrane.The hollow rate of the spill polymer particles of depression reduces, even also can't give full play to desirable effect of heat insulation as the insulation agent in the intermediate layer that is used for thermosensitive recording body.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 42-26524 communique
Patent documentation 2: Japanese JP 5-86746 communique
Patent documentation 3: Japanese kokai publication sho 56-32513 communique
Patent documentation 4: Japanese kokai publication hei 5-169818 communique
Patent documentation 5: Japanese kokai publication sho 61-87734 communique
Summary of the invention
The problem that invention will solve
As mentioned above, the particle diameter of the hollow polymer particulate of existing known, intumescent is uneven, is difficult to form uniform particulate.The particle diameter that utilizes the hollow polymer particulate that the seeding polymerization method forms is for several μ m and be not suitable for expecting the situation of high hollow rate particulate.Non-expansion type hollow polymer particulate can have the part of particulate or a few place depression and become depression the concavity particulate, form the low problems such as particulate of hollow rate.Need to prove that the hollow rate of this place record refers to the volume of hollow bead hollow core part and the ratio of the volume of hollow bead, represents with following formula (1).
Hollow rate (%)=[(radius of hollow parts)
3/ (radius of hollow bead)
3] * 100... (1)
Major subjects of the present invention is, thereby provide in a kind of non-expansion type polymer particles that comprises internally organic solvent the organic solvent gasification and remove particulate is made when hollow, reduce the generation of the concavity particulate of the low depression of hollow rate, increase the manufacture method of the hollow polymer particulate of the high particulate of hollow rate.Problem of the present invention also is, on the basis of described problem, provide a kind of when consisting of water-based paint compositions, simple to the compatibility of water and favorable dispersibility and coating preparation, do not disperse when processing, the manufacture method of environment amenable non-expansion type hollow polymer particulate.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research repeatedly for the solution that solves foregoing problems, result's design, studied a kind of new method, its do not adopt existing method (from thermoplastic resin as isolated by filtration polymer particles the polymer particles dispersion of shell, for example when thereby the drying device that uses taper drying machine and so on carries out the heat drying powdered, thereby the rising organic solvent of removing of gasification is made hollow method), but in being dispersed with the aqueous dispersions of this polymer particles, be included in gasification and the removal of the organic solvent of non-expansion type polymer particles inside, make hollow (desolventizing in the solution), thereby finished the present invention.
The invention is characterized in, in the manufacturing of non-expansion type polymer particles, increase the high hollow polymer particulate of hollow rate by introducing described new method, from aqueous dispersions, temporarily take out, be dried from the existing methodical polymer particles that inside is comprised organic solvent and make hollow existing method when making powder and have the different of essence in scheme, effect.
The invention provides a kind of manufacture method of hollow polymer particulate, it is characterized in that, in aqueous medium, the emulsifying mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent is disperseed, and in the presence of polymerization initiator, make aforementioned polymerizable monomer suspension polymerisation, thereby form the inner polymer particles that comprises organic solvent, make the organic solvent gasification that is included in this polymer particles inside and see through the shell of this particulate and remove, thereby make the hollow polymer particulate, in the method, thus being dispersed in state in the aqueous medium with polymer particles makes the organic solvent gasification that is included in aforementioned polymer particulate inside and removes particulate is made hollow operation.
For the manufacture method of hollow polymer particulate of the present invention, preferably, when making aforementioned polymerizable monomer suspension polymerisation, in aqueous medium, add one or more additives that are selected from the group that is formed by crosslinking agent, dispersant, dispersing aid.
Manufacture method for hollow polymer particulate of the present invention, preferably, when making the organic solvent gasification that is included in aforementioned polymer particulate inside and removing, the volumetric concentration that is dispersed with this polymer particles in the aqueous dispersions of aforementioned polymer particulate is in 20～65% the scope.
Manufacture method for hollow polymer particulate of the present invention, preferably, when making the organic solvent gasification that is included in aforementioned polymer particulate inside and removing, be set as at the fluid temperature of the aqueous dispersions that will be dispersed with the aforementioned polymer particulate under the condition of the temperature higher than the azeotropic point of aqueous medium and organic solvent and carry out.
Manufacture method for hollow polymer particulate of the present invention, preferably, thereby with making the organic solvent gasification that is included in aforementioned polymer particulate inside and removing the water that particulate is made in the aqueous dispersions of the hollow and hollow polymer particulate that obtains and separate, so that solid component concentration is in the scope of 12～70 quality %.
Manufacture method for hollow polymer particulate of the present invention, preferably, in aqueous medium, when the emulsifying mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent is disperseed, make the mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent carry out emulsion dispersion with the volumetric concentration of 20～65% scope.
For the manufacture method of hollow polymer particulate of the present invention, preferably, form inner comprise the polymer particles of organic solvent after, add dilution and dilute, so that the volumetric concentration of the aqueous dispersions of this polymer particles is in 20～65% the scope.
Manufacture method for hollow polymer particulate of the present invention, preferably, with normal-temperature water as aforementioned dilution and add after this normal-temperature water dilutes aforementioned aqueous dispersions, fluid temperature is warming up to the temperature higher than the azeotropic point of aqueous medium and organic solvent, thereby makes organic solvent gasification and the removal that is included in polymer particles inside.
In addition, also can be serviceability temperature than the high warm water of the azeotropic point of aqueous medium and organic solvent as aforementioned dilution, aforementioned aqueous dispersions is warming up to the temperature higher than aforementioned azeotropic point, thereby makes the organic solvent gasification that is included in polymer particles inside and the technical scheme of removing.
In addition, the invention provides a kind of hollow polymer particulate that obtains by the manufacture method of aforesaid hollow polymer particulate.
The effect of invention
The manufacture method of hollow polymer particulate of the present invention is by making the emulsifying mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent disperse in aqueous medium, and in the presence of polymerization initiator, make aforementioned polymerizable monomer suspension polymerisation, thereby form the inner polymer particles that comprises organic solvent, make the organic solvent gasification that is included in this polymer particles inside and see through the shell of this particulate and remove, thereby make the hollow polymer particulate, in the method, the state that is dispersed in the aqueous medium with polymer particles makes organic solvent gasification and the removal that is included in aforementioned polymer particulate inside, thereby particulate is made hollow operation, thereby have the generation of the concavity particulate that reduces depression, increase the effect of the generation of the high hollow polymer particulate of non-foaminess and hollow rate.
In addition, manufacture method according to hollow polymer particulate of the present invention, except the generation of the concavity particulate that can reduce depression, increase the generation of the high moistening hollow polymer particulate of hollow rate, also have the moistening hollow polymer particulate of gained to the compatibility of water and excellent dispersion thus coating preparation is simple, can not disperse so not worry when processing by breathing to operation task personnel's health cause damage, environment amenable effect.
The hollow polymer particulate of gained comprises the high polymer particles of a large amount of hollow rates according to the present invention, it is contained sometimes as the heat-barrier material in the intermediate layer of thermosensitive recording body for example, have and when record, to intercept the Joule heat that the heat head gives and the effect that improves effect of heat insulation, recording sensitivity is improved tremendously.
Description of drawings
Fig. 1 is the electron microscope enlarged image of the polymer particles group of manufacturing in comparative example 1, comparative example 1 is made into hollow existing method based on separating this polymer particles in the aqueous dispersions of the polymer particles that comprises internally organic solvent when making it dry.
Fig. 2 is based on the present invention's (using normal-temperature water as dilution) electron microscope enlarged image of the hollow polymer Particle Swarm of manufacturing in embodiment 1.
Fig. 3 is based on the electron microscope enlarged image of the non-expansion type hollow polymer Particle Swarm that the present invention's (use can be warming up to temperature than the high warm water of the azeotropic point of aqueous medium and this organic solvent as dilution) makes in embodiment 2.
The specific embodiment
As the polymerizable monomer that is used to form the polymer particles shell used among the present invention, from vinylpyridine, glycidyl acrylate, GMA, (methyl) acrylate, (methyl) acrylic acid, acrylonitrile, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, the N-methylol methacrylamide, itaconic acid, fumaric acid, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, select in the styrene, wherein, (methyl) acrylic acid, (methyl) acrylate or (methyl) acrylonitrile are high with the dissolubility that the inner organic solvent that comprises compares water, and the periphery of the solvent that comprises in inside forms polymeric membrane excellently, and is therefore more suitable.
These polymerizable monomers can use separately, also for example (methyl) acrylic acid and (methyl) acrylate, (methyl) acrylic acid and acrylonitrile can be used in combination.
For forming for the polymer particles that inside comprises organic solvent by aforementioned polymerizable monomer is used alone or in combination, preferably with other crosslinking agent, polymerization initiator, dispersant, dispersing aid and use.
Employed organic solvent is characterised in that among the present invention, be selected from Anaesthetie Ether, neohexane, pentane, hexane, heptane, isooctane, octane, cyclohexane, the hexahydrotoluene any, thereby can preferably use in the polymerization of polymerizable monomer and polymerization is being included in after finishing and can not gasifies under the state of particulate inside and can be heated to by the dispersion liquid with this particulate 60～130 ℃ of hexanes of successfully removing from the polymeric membrane (shell) of particulate of gasifying, heptane, octane etc.
The consumption of organic solvent uses 400 mass parts～2000 mass parts with respect to 100 mass parts polymerizable monomers, preferably uses 800 mass parts～1700 mass parts, further preferred 1200 mass parts～1400 mass parts of using.Along band, during usefulness quantity not sufficient 400 mass parts of organic solvent, the thickness of the shell of formed particulate increases and hollow rate decline relatively, can't form the high polymer particles of hollow rate.On the other hand, even use more than 2000 mass parts, being difficult to expect the technique effect corresponding with the amount that surpasses, is not very wise move economically yet.
The aforementioned polymerizable monomer of polymer particles shell and the mixture emulsion dispersion in aqueous medium of aforementioned organic solvent of being used to form.
In aforementioned aqueous medium, except aforementioned polymerizable monomer and organic solvent, can also add various additives.As this additive, preferred one or more additives that are selected from the group that is formed by crosslinking agent, dispersant, dispersing aid that add.In addition, when aforementioned polymerizable monomer is carried out suspension polymerisation, add the polymerization initiator of aforementioned polymerizable monomer.
Aforementioned crosslinking agent also can affect hardness, the intensity of polymeric membrane, thereby is associated to select with polymerizable monomer.Particularly, can list divinylbenzene, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid triglycol ester, trimethyl acrylic acid trimethylolpropane, two (methyl) acrylic acid 1,3-butanediol ester and (methyl) allyl acrylate etc., when selecting (methyl) acrylic acid, (methyl) acrylate, acrylonitrile or their combination as polymerizable monomer, two (methyl) acrylic acid glycol ester or three (methyl) acrylic acid trimethylolpropane are fit to as crosslinking agent.
Consumption for crosslinking agent, study with the related of employed polymerizable monomer by it, use 10 mass parts～200 mass parts with respect to 100 mass parts polymerizable monomers, preferably use 40 mass parts～150 mass parts, further preferred 60 mass parts～100 mass parts of using.Along band, during usefulness quantity not sufficient 10 mass parts of crosslinking agent, be difficult to form the hollow property of the non-expansion type polymer particles of hard and excellent strength, even and use more than 200 mass parts, being difficult to expect the technique effect corresponding with the amount that surpasses, is not very wise move economically yet.
Dispersant is necessary in order to keep the stable dispersiveness of particulate after the dispersion that forms the inner particulate that comprises organic solvent.Just can be used as dispersant and use so long as have the material of such function, the inventor etc. are that dispersant, water soluble polymer are that the effect of dispersant, cataloid etc. is investigated for phosphorus, results verification arrives: wherein, himself has positive charge cataloid, be attached to the polymeric membrane periphery of particulate and each particulate is repelled mutually, stop that assemble, excellent dispersion effect thereby can bring into play.
Among the present invention, the reason of the dispersion effect that cataloid performance is excellent is: by under acid condition, making the polymerizable monomer polymerization reaction take place, cataloid himself with positive charge.Positively charged silica embeds the polymeric membrane of particulate and makes each particulate become the particle with positive charge.Can think that thereby mutually exclusive the preventing of each particulate of positively charged assemble.
When dispersant was cataloid, the consumption of dispersant preferably used 40 mass parts～80 mass parts for to use 30 mass parts～100 mass parts with respect to 100 mass parts polymerizable monomers, further preferred 50 mass parts～70 mass parts of using.Along band, during usefulness quantity not sufficient 30 mass parts of dispersant, can't obtain dispersion effect.In addition, even use more than 100 mass parts, being difficult to expect the technique effect corresponding with the amount that surpasses, is not very wise move economically yet.
Dispersing aid is by also using with dispersant, to forming/keep more stable dispersion liquid performance cooperative effect, therefore be suitable such as the condensation product of condensation product, adipic acid and the MEA of condensation product, adipic acid and the AMPD of adipic acid and diethanol amine etc.
When dispersing aid was the condensation product of adipic acid and diethanol amine, the consumption of dispersing aid preferably used 2 mass parts～7 mass parts for to use 1 mass parts～10 mass parts with respect to 100 mass parts polymerizable monomers, more preferably uses 3 mass parts～5 mass parts.Along band, during usefulness quantity not sufficient 1 mass parts of dispersing aid, can't obtain the effect of dispersing aid.In addition, even use more than 10 mass parts, being difficult to expect the technique effect corresponding with the amount that surpasses, is not very wise move economically yet.
Polymerization initiator so long as oil-soluble and the material that can produce free radical just can use, the organic solvent that comprises in inside is not under the temperature range of generating gasification, it is excellent making polymerizable monomer finish polymerisation in Best Times, for example can use 2,2 '-azobis isobutyronitrile, hydrogen phosphide cumene, TBHP, cumyl peroxide, di-tert-butyl hydrogen peroxide, benzoyl peroxide, lauroyl peroxide etc.When using normal heptane as organic solvent, the half-life under 60 ℃ be 10 hours 2,2 '-azobis isobutyronitrile is excellent.
For obtain the hollow polymer particulate according to the present invention for, thereby make the emulsifying mixture dispersion, the suspension polymerisation that comprise aforementioned each material form the inner polymer particles that comprises organic solvent, the compounding ratio of each material decides with the related of hollow polymer particulate that obtains having which kind of feature according to it, is not particularly limited.
Aforesaid emulsion dispersion method is at first used the emulsification mixer of homogeneous mixer and so on.Suspension polymerisation is to carry out in that emulsified dispersed liquid is warming up in the process of proceeding to stir by other mixer under the state of set point of temperature.
Advance and the polymer particles of formation for suspension polymerisation, thereby then make the organic solvent gasification and the removal that are included in particulate inside make hollow, the invention is characterized in, thereby the gasification of organic solvent and removal are made and hollowly are in being dispersed with the aqueous dispersions of this polymer particles and the fluid temperature of this dispersion liquid are set as under the condition of the temperature higher than the azeotropic point of aqueous medium and this organic solvent and carry out (desolventizing in the solution).
The volumetric concentration of the aqueous dispersions that is dispersed with this polymer particles of this moment is in 20～65%, preferably is in 30～50%, further preferably is in 40～45% the scope.Along band, this is because volumetric concentration is in the situation 20% below, is accompanied by low concentration, manufacturing efficient extremely descends; On the other hand, be in the situation more than 65%, the viscosity of dispersion liquid uprises, and the organic solvent that has gasified is removed in the dispersion liquid and causes easily when distillating outside system and foams, and removes deterioration of efficiency, makes efficient and extremely descend thereby make.
Be 20～65% polymer particles aqueous dispersions in order to make volumetric concentration, following methods is arranged: make the mixture of the polymerizable monomer, crosslinking agent, organic solvent, dispersant and the dispersing aid that comprise aqueous medium, be used to form polymer particles become the method for carrying out emulsion dispersion under 20～65% the compounding condition in its volumetric concentration; And the adding dilution is regulated after forming polymer particles, becomes 20～65% method so that be dispersed with the volumetric concentration of the aqueous dispersions of this polymer particles.Can also adopt any method, if but the emulsion dispersion efficient of consideration mixture, the latter's method is favourable.
When adding the method for dilution after forming polymer particles as previously mentioned, this dilution for the generation that reduces the low concavity particulate of hollow rate, the generation that increases the high particulate of hollow rate, uses warm water to have more effect take normal-temperature water and warm water as object.
Along band, the organic solvent that the temperature when making inside comprise the particle suspension polymerization of organic solvent comprises take inside is set as benchmark.For example use in the situation of normal heptane as this organic solvent, be set as below 79 ℃.
If use normal-temperature water as dilution herein, do not arrive the periostracum of the state that finishes crosslinked zone because hardness and intensity are insufficient, under quick-frozen, shrink.And, thereby to make hollowly by making the organic solvent gasification that inside comprises and removing, the internal pressure of particulate further reduces.The overlapping shell that causes of these factors is attracted to inside, and particulate presents the state of the concavity particulate that is easy to form depression.
But, about increasing this problem of the present invention of generation of the high particulate of hollow rate, thereby gasification and the removal of the organic solvent by being included in polymer particles inside in being dispersed with the aqueous dispersions of polymer particles are made hollow, its effect is compared with the hollow polymer particulate (Fig. 1) of making based on existing method, and it is apparent seeing improvement from (Fig. 2).
On the other hand, use can be set as the fluid temperature of this suspension polymerisation liquid in the situation of warm water as dilution of the temperature higher than the azeotropic point of aqueous medium and this organic solvent, the crosslinked of polymeric membrane (shell) that forms particulate carries out continuously, its hardness, intensity further improve, the internal pressure that formation can tolerate particulate descends and shell is attracted the particulate of such power to inside, the concavity particulate of depression reduces, and the particulate that hollow rate is high further increases.(Fig. 3) compared with the hollow polymer particulate (Fig. 2) that the hollow polymer particulate (Fig. 1) of making based on existing method and use normal-temperature water are made, and this also is apparent.
So, the polymer particles group who makes based on existing method almost all presents the concavity micronize of depression, substantially can't observe the high spheroidal particle of hollow rate.On the other hand, if compare with (Fig. 1), it is apparent that the hollow polymer Particle Swarm (Fig. 2) of making based on the present invention, (Fig. 3) generate the high particulate of a large amount of hollow rates.
Along band, about accessing the reason of aforementioned effect, the inventor etc. consider as follows.This reason and following operation are closely related: for hollow polymer particulate of the present invention, thereby in being dispersed with the aqueous dispersions of this particulate volumetric concentration be 20～65% and the fluid temperature of this dispersion liquid be set as the gasification and the removal that are included in the organic solvent of polymer particles inside under the condition of the temperature higher than the azeotropic point of aqueous medium and this organic solvent and make hollow.
Thereby carrying out the gasification of organic solvent and removal subject to the foregoing makes when hollow, be included in the organic solvent generating gasification of particulate inside and see through the shell of particulate and break away to the outside, thereby this disengaging mode is owing to cover the hydraulic pressure of the aqueous dispersions of outside and be suppressed slowly.Therefore, particulate is owing to the delay of the organic solvent that has gasified is risen internal pressure, and its pressure puts on the inwall of particulate.At this moment, compare with the internal pressure that disengaging because of the organic solvent that gasified reduces, the rising of the internal pressure that is caused by the delay of the organic solvent that has gasified is more obvious.And, because the organic solvent time dependent ground that has gasified disengaging causes internal pressure to reduce gradually.But during this period, the shell of particulate is still carrying out crosslinkedly, can think that the particulate that the tolerance internal pressure reduces, can keep spherical hardness, intensity increases.
On the other hand, existing method is the polymer particles temporarily taking-up from aqueous dispersions that inside is comprised organic solvent, makes hollow when being heated drying.At this moment, do not exist the organic solvent that has gasified to see through the shell of particulate and the factor that is suppressed when breaking away to the outside.Therefore, can think: the limit breaks away from successively and makes internal pressure descend, shell is attracted to inside thereby gasify in the organic solvent limit in the particulate, and its result causes particulate basically to become the concavity particulate of depression.
Then, thus be important with making the organic solvent gasification that is included in polymer particles inside and removing the high temperature of azeotropic point that the fluid temperature of making the dispersion liquid when hollow is set as than aqueous medium and this organic solvent.Particularly, the kind according to the organic solvent that uses decides.
With the following setting of the fluid temperature of dispersion: for example use in the situation of octane to be more than 89.6 ℃, to use in the situation of heptane to be more than 79.2 ℃, to use in the situation of cyclohexane to be more than 69.5 ℃, to use in the situation of hexane to be more than 61.6 ℃ as organic solvent.
Set as described above the inner fluid temperature that comprises the polymer particles dispersion liquid of organic solvent, be included in the organic solvent generating gasification of polymer particles inside, extremely outside by the shell disengaging of polymer particles, thus form the hollow polymer particulate.
The hollow polymer particle dispersion liquid that the spherical particle that the gained hollow rate is high increases can be adjusted into the form that is suitable for purposes.For example, thereby can make powder hollow polymer particulate in the laggard row drying of separation moisture, perhaps also can make moistening hollow polymer particulate.For example, if make the form of moistening hollow polymer particulate, can not disperse to the outside when then operating thus environmentally friendly, to compatibility and the excellent dispersion of water, so coating preparation becomes simple.Along band, in order to make moistening hollow polymer particulate, take solid component concentration as 12～70%, be preferably 20～50%, more preferably 30～40% mode is separated and is removed water and get final product.Along band, if below 12%, then do not become moisture state for the aqueous dispersion state.On the other hand, if more than 70%, thereby then exist the hollow polymer particulate to become to disperse easily and by breathing health to the operation task personnel unworkable worry that becomes that causes damage.
Embodiment
Below, be described more specifically the present invention by embodiment and comparative example, but the present invention is not subjected to any restriction of these embodiment.
[embodiment 1]
The condensation product 0.6g of dissolving adipic acid and diethanol amine adds the 8.5g colloidal silica as dispersant as dispersing aid in the four-hole boiling flask of the 1000ml that has added the 201.2g deionized water.With 3% dilute sulfuric acid aqueous solution 4.5g the pH of this aqueous solution is adjusted into 3.0 and is used as water.
As polymerizable monomer, 12.5g trimethyl acrylic acid trimethylolpropane is as crosslinking agent with 11.2g methyl methacrylate, 1.3g acrylonitrile, and the 150.0g normal heptane mixes as organic solvent and is used as oil phase.
Mix water and oil phase, stirred 6 minutes with rotating speed 12000rpm with the automatic homogeneous mixer M of T.K type (Tokushu Kika Kogyo K.K's manufacturing), after particle diameter is adjusted into 1～10 μ m, add 2,2 '-azobis isobutyronitrile 0.1g is as polymerization initiator, carry out nitrogen replacement, the limit is stirred the limit and was carried out polymerization in 4 hours under 78 ℃ of reaction temperatures, rotating speed 180rpm.
Add the 385.0g normal-temperature water in the water system polymer dispersion after finishing to polymerization, while stirring dispersion is heated to 79～100 ℃ under condition of normal pressure, be included in gasification and the removal of the normal heptane of polymer particles inside through 8 hours, thereby polymer particles is made hollow (desolventizing in the solution).At this moment, by adding normal-temperature water, the temperature when making dispersion carry out polymerisation temporarily is cooled to 40 ℃ by 78 ℃.
The amount of the normal heptane of having removed from polymer particles is 141g, can confirm with input amount normal heptane about equally to gasify and removed by shell at the micro polymer intragranular.
After normal heptane gasification and removing, be that polymer dispersion carries out suction filtration to this water-based, obtain the 155.3g solid constituent and be the polymer particles of 18.7% moisture state.The particle diameter of resulting polymers particulate is 4.0 μ m.(particle diameter refers to use laser diffraction formula particle size distribution device " SALD-2000 (Shimadzu Seisakusho Ltd.'s manufacturing) " to measure, and volumetric particle size distribution is accumulated as 50% particle diameter.)
With electron microscope the hollow polymer particulate of gained non-expansion type is photographed and enlarged image be shown in Fig. 2.Can be confirmed by this image, the resulting polymers particulate is compared with the hollow polymer particulate (Fig. 1) of making based on existing method, and the particulate that the concavity particulate of depression reduces, hollow rate is high increases.
Because gained non-expansion type hollow polymer particulate is moisture state, therefore for simple to the compatibility of water and favorable dispersibility and coating preparation, can not disperse when processing, environment amenable particulate.
The visual shape of the particulate of gained is recorded in table 1 among the embodiment 1, and the recording sensitivity of the thermosensitive recording body when using this particulate as heat-barrier material is recorded in table 2.
[embodiment 2]
Comprise normal heptane, finish the dilution of the microparticle dispersion be polymerized as inside, the azeotropic point that adds normal heptane and water is warm water (85 ℃) 385.0g more than 79 ℃, in addition, similarly to Example 1 operation, thereby the high polymer particles of hollow rate of manufacturing moisture state.
Keep from polymerisation begin to the gasification of organic solvent and the temperature of the dispersion till removing from the state without cooling, similarly to Example 1 operation, be included in gasification and the removal of the normal heptane of particulate inside, thereby obtain making the particulate of hollow moisture state.
With electron microscope the resulting polymers particulate is photographed and enlarged image be shown in Fig. 3.Can be confirmed by this Fig. 3, the resulting polymers particulate is compared with the hollow polymer particulate (Fig. 1) of making based on existing method, perhaps compare with the hollow polymer particulate (Fig. 2) of the embodiment 1 that uses normal-temperature water to make as dilution, the hollow polymer particulate that the concavity particulate of depression reduces, hollow rate is high further increases.
In addition, when the gained particle is also used the electron microscope observation sectional view with epoxy resin embedding, the shape of particle is compared with the concavity particulate of the depression that adopts existing method to obtain, spheroidal particle generates in a large number, average grain diameter is that the thickness of 4.0 μ m and periostracum is about 0.05 μ m, has hollow rate and surpasses 90% high hollow rate.The bulk density of gained hollow polymer particulate is 0.1g/ml.
Can think, the reason of this effect is as follows: by using warm water, begin to make the temperature of the dispersion till hollow from the state without cooling to the gasification of organic solvent and removal thereby can keep from polymerisation, thereby it is crosslinked that the polymeric membrane that forms particulate is not carried out with not shrinking continuously, and the hardness of this polymer particles, intensity are improved.
The visual shape of the particulate of gained is recorded in table 1 among the embodiment 2, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[embodiment 3]
Employed deionized water is made as 586.2g in the time of will preparing water, after emulsion dispersion, suspension polymerisation, do not use dilution, in addition, similarly to Example 2 operation, thereby be included in gasification and the removal of the normal heptane of particulate inside, thereby obtain making the particulate of hollow moisture state.
Can confirm, the hollow polymer particulate that the concavity particulate of the depression in the polymer particles reduces, hollow rate is high further increases, and this degree and embodiment 2 are roughly same degree.
The visual shape of the particulate of gained is recorded in table 1 among the embodiment 3, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[comparative example 1]
Mix water and the oil phase identical with embodiment 1, stirred 6 minutes with rotating speed 12000rpm with the automatic homogeneous mixer M of T.K type (Tokushu Kika Kogyo K.K's manufacturing), after particle diameter is adjusted into 1～10 μ m, add 2,2 '-azobis isobutyronitrile 0.1g is as polymerization initiator, carry out nitrogen replacement, the limit is stirred the limit and was carried out polymerization in 4 hours under 78 ℃ of reaction temperatures, rotating speed 180rpm.
From the polymer particles aqueous dispersion that comprises normal heptane that polymerization is through with, utilize suction filtration that this polymer particles is carried out Separation of Solid and Liquid, thereby obtain comprising the polymer particles of normal heptane.
This polymer particles was being gasified to the normal heptane that is included in particulate inside through 24 hours under the condition of normal pressure, under 40 ℃ and removing, thereby obtaining the polymer particles of drying regime.
With electron microscope the resulting polymers particulate is photographed and enlarged image be shown in Fig. 1.As can be clear and definite by this image, this polymer particles group's particle almost all be the concavity particulate of depression.
The visual shape of the particulate of gained is recorded in table 1 in the comparative example 1, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[comparative example 2]
Employed deionized water is made as the 72.6g except will prepare water the time, carries out similarly to Example 2 emulsion dispersion, suspension polymerisation, thereby to obtain volumetric concentration be 70% and comprise the dispersion of the polymer particles of normal heptane.
Thereby the trial limit is stirred this dispersion limit and is heated to 79～100 ℃ of gasifications and removes the normal heptane that is included in polymer particles inside under condition of normal pressure, but the concentration of dispersing aid uprises, ability as surfactant rises, the normal heptane that comprises in inside is removed in the dispersion liquid, is foamed in flask when distillating to system seriously by the shell of polymer particles, is difficult to gasification and removes normal heptane.
[comparative example 3]
Similarly to Example 1 operation, thus obtain comprising the polymer particles of normal heptane.The azeotropic point that adds normal heptane and water is warm water (85 ℃) 385.0g more than 79 ℃, trial makes the normal heptane gasification that is included in polymer particles inside with this dispersion and removes under the reduced pressure of 300mmHg, but the temperature in the flask does not rise to more than 79 ℃, only there is the water in the dispersion to be vaporized and to remove, therefore is difficult to gasification and removes normal heptane.
Its reason is: because dispersion is placed under the reduced pressure of 300mmHg, the vapour pressure of water descends, and the temperature in the flask is lower than 79 ℃.This forms in the formed particulate, for normal heptane is removed by the shell of polymer particles, need to make the normal heptane gasification.At this moment, because normal heptane is included in the inside of polymer particles, becoming is difficult to reduce vapour pressure by decompression.Can think, if even if under reduced pressure, be heated near just can't gasifying and remove near the boiling point of normal heptane in not with flask, thereby the vapour pressure of water reduces under reduced pressure, temperature in the flask significantly descends than the boiling point of the inner normal heptane that comprises, and therefore is difficult to gasification and removes normal heptane.
[table 1]
[hollow rate and effect of heat insulation]
Respectively with the dry particles that obtains in the moistening particulate that obtains among the embodiment 1～3, the comparative example 1 and utilize hollow particle that the seeding polymerization method obtains as heat-barrier material and blending in the intermediate layer of thermosensitive recording body, the developing sensitivity of investigation thermosensitive recording body.
For the structure of thermosensitive recording body, prepare priming coat with coating and heat sensitive recording layer coating according to following prescription.
(the priming coat preparation of coating)
For the hollow polymer particulate that obtains in the hollow polymer particulate that obtains among the embodiment 1～3, the comparative example 1 and the commercially available synthetic hollow particle of seeding polymerization method (Rohm and Haas company make " trade name: Ropaque SN-1055: particle diameter 1 μ m, hollow rate about 50%) that utilizes, form preparation priming coat coating according to following prescription respectively.
(the recording layer preparation of coating)
Form preparation coating with coating according to following prescription as recording layer.
(making of thermosensitive recording body)
At basic weight 64g/m
2High-quality neutralized paper single face on each priming coat with coating take dry weight as 4g/m
2Mode be coated with and dry, and on this priming coat with recording layer with coating take dry weight as 3g/m
2Mode be coated with and dry, thereby obtain thermosensitive recording body.In addition, form each layer after, carry out supercalender and process.
(colour rendering test)
For each thermosensitive recording body of gained, carry out colour rendering test as follows.
Use Ohkura Electric Co., Ltd. the trade name " TH-PMD (thermal head 1653 Ω) " of making, under 24V, 0.6 millisecond, 0.8 millisecond and 1.6 milliseconds, make the thermosensitive recording body colour developing, use Macbeth (Macbeth) densimeter " RD-914 " to measure record concentration.Its result is recorded in table 2.
[table 2]
(evaluation)
All can clearly be gone out with data by table 2: compare with the hollow particle that the seeding polymerization method of utilizing " Ropaque " and so on is made, the effect of heat insulation of the hollow polymer particulate of the non-foaminess that obtains according to the present invention is high, effectively help the raising of the developing sensitivity of thermosensitive recording body, in addition, hollow polymer particulate for non-foaminess, increase along with the high hollow polymer particulate of minimizing, the hollow rate of the concavity particulate that caves in, effect of heat insulation uprises, and more effectively helps the raising of the developing sensitivity of thermosensitive recording body.
Utilizability on the industry
The manufacture method of the hollow polymer particulate that the high particle of non-expansion type of the present invention and hollow rate increases does one's utmost to reduce the generation of the concavity particulate of the low depression of hollow rate as manufacturing, the method of the non-expansion type hollow polymer particulate of the generation of the hollow polymer particulate that the increase hollow rate is high is useful, the non-expansion type hollow polymer particulate that obtains according to the present invention is as light material, the material or the liquid component that improve light scattering contain retention agent, and then the heat-barrier material that contains of the intermediate layer that forms between supporter and heat-sensitive color layer as the recording sensitivity that be used for to improve thermosensitive recording body etc. is useful, and then, the moistening non-expansion type hollow polymer particulate that obtains according to the present invention is to the compatibility of water and water dispersible is good and coating preparation is simple, also can not disperse during processing and also friendly to environment, thereby can effectively utilize.
Claims (10)
1. the manufacture method of a hollow polymer particulate, it is characterized in that, in aqueous medium, the emulsifying mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent is disperseed, and in the presence of polymerization initiator, make described polymerizable monomer suspension polymerisation, thus form the inner polymer particles that comprises organic solvent, make the organic solvent gasification that is included in this polymer particles inside and see through the shell of this particulate and remove, thereby make the hollow polymer particulate
In the method, thus being dispersed in state in the aqueous medium with polymer particles makes the organic solvent gasification that is included in described polymer particles inside and removes particulate is made hollow operation.
2. the manufacture method of hollow polymer particulate according to claim 1, it is characterized in that, when making described polymerizable monomer suspension polymerisation, in aqueous medium, add one or more additives that are selected from the group that is formed by crosslinking agent, dispersant, dispersing aid.
3. the manufacture method of hollow polymer particulate according to claim 1 and 2, it is characterized in that, when making the organic solvent gasification that is included in described polymer particles inside and removing, the volumetric concentration that is dispersed with this polymer particles in the aqueous dispersions of described polymer particles is in 20～65% the scope.
4. the manufacture method of the described hollow polymer particulate of each according to claim 1～3, it is characterized in that, when making the organic solvent gasification that is included in described polymer particles inside and removing, be set as at the fluid temperature of the aqueous dispersions that will be dispersed with described polymer particles under the condition of the temperature higher than the azeotropic point of aqueous medium and organic solvent and carry out.
5. the manufacture method of the described hollow polymer particulate of each according to claim 1～4, it is characterized in that, thereby with making the organic solvent gasification that is included in described polymer particles inside and removing the water that particulate is made in the aqueous dispersions of the hollow and hollow polymer particulate that obtains and separate, so that solid component concentration is in the scope of 12～70 quality %.
6. the manufacture method of the described hollow polymer particulate of each according to claim 1～5, it is characterized in that, in aqueous medium, when the emulsifying mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent is disperseed, make the mixture that comprises the polymerizable monomer that is used to form the polymer particles shell and organic solvent carry out emulsion dispersion with the volumetric concentration of 20～65% scope.
7. the manufacture method of the described hollow polymer particulate of each according to claim 1～6, it is characterized in that, after formation inside comprises the polymer particles of organic solvent, add dilution and dilute, so that the volumetric concentration of the aqueous dispersions of this polymer particles is in 20～65% the scope.
8. the manufacture method of hollow polymer particulate according to claim 7, it is characterized in that, with normal-temperature water as described dilution and add after this normal-temperature water dilutes described aqueous dispersions, fluid temperature is warming up to the temperature higher than the azeotropic point of aqueous medium and organic solvent, thereby makes organic solvent gasification and the removal that is included in polymer particles inside.
9. the manufacture method of hollow polymer particulate according to claim 7, it is characterized in that, serviceability temperature than the high warm water of the azeotropic point of aqueous medium and organic solvent as described dilution, described aqueous dispersions is warming up to the temperature higher than described azeotropic point, thereby makes organic solvent gasification and the removal that is included in polymer particles inside.
10. hollow polymer particulate, it is that manufacture method by each the described hollow polymer particulate in the claim 1～9 obtains.
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| CN111741808A (en) * | 2018-02-22 | 2020-10-02 | 阿科玛股份有限公司 | Water void resistant polymeric particles |
| CN111978441A (en) * | 2020-08-07 | 2020-11-24 | 华东师范大学 | Hollow polystyrene nano-particles and preparation method and application thereof |
| CN112739455A (en) * | 2018-09-28 | 2021-04-30 | 日本瑞翁株式会社 | Hollow particles, process for producing the same, and aqueous dispersion containing the same |
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| US11760857B2 (en) | 2017-08-01 | 2023-09-19 | Zeon Corporation | Method for producing latex and method for producing hollow resin particles |
| JP7310797B2 (en) | 2018-03-30 | 2023-07-19 | 日本ゼオン株式会社 | Hollow resin particles and sheets |
| JP6513273B1 (en) * | 2018-08-31 | 2019-05-15 | 三井化学株式会社 | Resin particles |
| CN113302210B (en) * | 2019-02-06 | 2023-06-06 | 日本瑞翁株式会社 | Method for producing hollow resin particles |
| WO2020261926A1 (en) * | 2019-06-27 | 2020-12-30 | 日本ゼオン株式会社 | Production method for hollow resin particles |
| JPWO2022092076A1 (en) * | 2020-10-30 | 2022-05-05 |
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| KR20130116817A (en) | 2013-10-24 |
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| JP5727962B2 (en) | 2015-06-03 |
| JP2013221070A (en) | 2013-10-28 |
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