CN118119445A - Hollow particle, method for producing hollow particle, resin composition, and molded article - Google Patents
Hollow particle, method for producing hollow particle, resin composition, and molded article Download PDFInfo
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- CN118119445A CN118119445A CN202280069995.XA CN202280069995A CN118119445A CN 118119445 A CN118119445 A CN 118119445A CN 202280069995 A CN202280069995 A CN 202280069995A CN 118119445 A CN118119445 A CN 118119445A
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- Prior art keywords
- hollow particles
- mass
- hollow
- resin
- shell
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Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides hollow particles which have excellent dielectric properties and solvent resistance and can reduce the dielectric constant and the dielectric loss tangent of a resin molded article, and a method for producing the hollow particles. The hollow particles of the present invention have a shell containing a resin and a hollow portion surrounded by the shell, the porosity of the shell being 50% or more, the shell containing a polymer containing 70 mass% or more of a crosslinkable hydrocarbon monomer unit as the resin, 0.1mg of the hollow particles being added to 4mL of toluene at 25 ℃, and the hollow particles being allowed to stand for 48 hours after shaking for 10 minutes at a shaking speed of 100rpm, and the hollow particles being precipitated in toluene being less than 5 mass% in a dipping test of the hollow particles.
Description
Technical Field
The present invention relates to hollow particles, a method for producing hollow particles, a resin composition, and a molded article.
Background
Hollow particles (hollow resin particles) are used for adding to resins, paints, various molded articles, and the like for the purpose of weight reduction, heat insulation, low dielectric constant, and the like because of the voids in the interior of the particles, and the use thereof relates to a wide range of fields such as automobiles, bicycles, aviation, electric, electronic, construction, home appliances, containers, stationery, tools, shoes, and the like.
In the fields of electric and electronic devices, it has been attempted to add hollow particles to an insulating material in order to reduce the dielectric constant and the dielectric loss tangent of the insulating material. Patent document 1 discloses hollow particles produced by emulsion polymerization using an acrylic resin, but hollow particles having a shell of an acrylic resin have a relatively high relative permittivity and dielectric loss tangent, and therefore have a problem that the effects of lowering the permittivity and lowering the dielectric loss tangent cannot be sufficiently obtained.
Therefore, in order to achieve low dielectric constant and low dielectric loss tangent of the hollow particles, hollow particles using a styrene resin were produced. For example, patent document 2 discloses a hollow particle in which the shell portion of the hollow particle includes an aromatic polymer (P1), and the aromatic polymer (P1) is obtained by polymerizing a monomer composition including an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth) acrylate monomer (c) having a specific structure.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-14944;
Patent document 2: international publication No. 2021/085189.
Disclosure of Invention
Problems to be solved by the invention
In addition, as an insulating resin having a low relative dielectric constant and low dielectric loss tangent, attention has been paid to a thermosetting modified polyphenylene ether (PPE) in recent years. However, even if the resin film formed using the heat-curable modified polyphenylene ether contains hollow particles described in patent document 2, as shown in comparative example 4 described below, the effects of lowering the dielectric constant and lowering the dielectric loss tangent by the hollow particles cannot be sufficiently obtained. Since a resin film formed using a thermosetting resin is generally obtained by heating a coating film of a resin composition in which the thermosetting resin is dissolved in a solvent, it is estimated that an organic solvent in the resin composition penetrates the shell of hollow particles and enters the inside of the particles, and remains after thermosetting, whereby the proportion of gas in the hollow portion is reduced, and as a result, the effects of lowering the dielectric constant and lowering the dielectric loss tangent become insufficient.
The subject of the invention is: provided are hollow particles which have excellent dielectric properties and solvent resistance and which enable a resin molded article to have a low dielectric constant and a low dielectric loss tangent; to provide a method for producing hollow particles having excellent dielectric properties and solvent resistance; and a molded article comprising the hollow particles and a resin composition comprising the hollow particles.
Solution for solving the problem
The present inventors focused on the resin composition of the shell and the permeability to toluene in the hollow particles, and found that the hollow particles having a shell which is hardly permeable to toluene and has excellent dielectric properties and solvent resistance can be produced by further adjusting the method of forming the shell by containing a large amount of crosslinkable hydrocarbon monomer units in the shell, and that the hollow particles have excellent effects of making the resin molded article low in dielectric constant and low in dielectric loss tangent when added to a resin composition containing an organic solvent to produce a resin molded article.
The present invention provides a hollow particle having a shell containing a resin and a hollow portion surrounded by the shell, the hollow particle having a porosity of 50% or more,
The shell contains, as the resin, a polymer containing 70 mass% or more of a crosslinkable hydrocarbon monomer unit,
0.1Mg of the hollow particles was added to 4mL of toluene at 25℃and the mixture was shaken at a shaking speed of 100rpm for 10 minutes, followed by standing for 48 hours, whereby the hollow particles precipitated in toluene were less than 5% by mass in the impregnation test of the hollow particles.
In the hollow particles of the present invention, the dielectric loss tangent at a frequency of 1GHz is preferably 0.0010 or less.
In the hollow particles of the present invention, the porosity is preferably 60% or more.
In the hollow particles of the present invention, the volume average particle diameter is preferably 1.0 μm or more and 10.0 μm or less.
Further, the present inventors have found that when hollow particles are produced by a suspension polymerization method using a crosslinkable hydrocarbon monomer, a specific reaction-promoting additive liquid is added during the polymerization reaction, thereby obtaining hollow particles having good dielectric characteristics and solvent resistance.
The present invention provides a method for producing hollow particles having a shell containing a resin and a hollow portion surrounded by the shell, the hollow particles having a porosity of 50% or more,
The method for producing the hollow particles comprises the following steps:
a step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium;
A step of preparing a suspension in which droplets of a monomer composition containing the polymerizable monomer, the hydrophobic solvent, and the polymerization initiator are dispersed in the aqueous medium by suspending the mixed solution; and
A step of preparing a precursor composition containing precursor particles having a hollow portion surrounded by a shell containing a resin and containing the hydrophobic solvent in the hollow portion by supplying the suspension to a polymerization reaction,
The content of the crosslinkable hydrocarbon monomer in 100 mass% of the polymerizable monomer contained in the mixed solution is 70 mass% or more,
In the step of preparing the precursor composition, after adding a reaction promoting additive solution during the polymerization reaction, the polymerization reaction is further carried out, and as the reaction promoting additive solution, a low molecular compound having a solubility in water of 20 ℃ greater than that of the hydrophobic solvent and 0.5g/L to 1000g/L is used.
In the method for producing hollow particles of the present invention, when a non-reactive low-molecular compound is added as the reaction-promoting additive liquid, the amount of the non-reactive low-molecular compound added is preferably 1 to 20 parts by mass relative to 100 parts by mass of the total of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid, and when a reactive low-molecular compound is added as the reaction-promoting additive liquid, the amount of the reactive low-molecular compound added is preferably 1 to 3 parts by mass relative to 100 parts by mass of the total of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid.
In the method for producing hollow particles of the present invention, it is preferable that in the step of preparing the precursor composition, the reaction promoting additive solution is added when the polymerization conversion rate of the polymerizable monomer contained in the mixed solution is 40 to 90%.
In the method for producing hollow particles of the present invention, the hydrophobic solvent is preferably a chain hydrocarbon solvent.
In the method for producing hollow particles of the present invention, the polymerization initiator is preferably an organic peroxide.
The present invention further provides a resin composition comprising the hollow particles of the present invention and a matrix resin.
The present invention further provides a molded article of a resin composition comprising the hollow particles of the present invention and a matrix resin.
Effects of the invention
As described above, according to the present invention, there is provided hollow particles which have excellent dielectric properties and solvent resistance and can reduce the dielectric constant and the dielectric loss tangent of a resin molded article, and a method for producing hollow particles having excellent dielectric properties and solvent resistance.
Further, as described above, according to the present invention, there are provided a resin composition containing the hollow particles and a molded article of the resin composition containing the hollow particles.
Drawings
Fig. 1 is a view illustrating an example of a method for producing hollow particles according to the present invention.
Detailed Description
In the present invention, "to" in the numerical range means that the numerical values described before and after "are included as the lower limit value and the upper limit value.
Further, in the present invention, (meth) acrylic acid ester means acrylic acid ester and methacrylic acid ester, (meth) acrylic acid means acrylic acid and methacrylic acid, and (meth) acryl group means acryl group and methacryl group.
In the present invention, the polymerizable monomer means a compound having a functional group capable of addition polymerization (in the present invention, may be simply referred to as a polymerizable functional group). In the present invention, as the polymerizable monomer, a compound having an ethylenically unsaturated bond as a functional group capable of addition polymerization is generally used.
In the present invention, a polymerizable monomer having only one polymerizable functional group is referred to as a non-crosslinkable monomer, and a polymerizable monomer having two or more polymerizable functional groups is referred to as a crosslinkable monomer. The crosslinkable monomer is a polymerizable monomer that forms a crosslink in the resin by polymerization.
In the present invention, the hydrocarbon monomer means a polymerizable monomer composed of carbon and hydrogen. The crosslinkable hydrocarbon monomer is a polymerizable monomer having two or more polymerizable functional groups and composed of carbon and hydrogen.
In the present invention, the term "good dielectric characteristics" means that the dielectric constant and the dielectric loss tangent are low, and the dielectric characteristics are good as the dielectric constant and the dielectric loss tangent are low.
The method for producing the hollow particles of the present invention and the hollow particles of the present invention will be described in detail in order, and further, the resin composition and the molded article containing the hollow particles of the present invention will be described.
1. Method for producing hollow particles
The method for producing hollow particles of the present invention is characterized in that the hollow particles have a shell containing a resin and a hollow portion surrounded by the shell, the porosity is 50% or more,
The method for producing the hollow particles comprises the following steps:
a step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium;
A step of preparing a suspension in which droplets of a monomer composition containing the polymerizable monomer, the hydrophobic solvent, and the polymerization initiator are dispersed in the aqueous medium by suspending the mixed solution; and
A step of preparing a precursor composition containing precursor particles having a hollow portion surrounded by a shell containing a resin and containing the hydrophobic solvent in the hollow portion by supplying the suspension to a polymerization reaction,
The content of the crosslinkable hydrocarbon monomer in 100 mass% of the polymerizable monomer contained in the mixed solution is 70 mass% or more,
In the step of preparing the precursor composition, after adding a reaction promoting additive solution during the polymerization reaction, the polymerization reaction is further carried out, and as the reaction promoting additive solution, a low molecular compound having a solubility in water of 20 ℃ greater than that of the hydrophobic solvent and 0.5g/L to 1000g/L is used.
The above-described manufacturing method of the present invention follows the following basic technique: the method comprises suspending a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium to prepare a suspension in which droplets having a distribution structure in which the polymerizable monomer and the hydrophobic solvent are phase-separated, the polymerizable monomer being biased to a distribution structure in which the polymerizable monomer is present on the surface side and the hydrophobic solvent is biased to the center, and supplying the suspension to a polymerization reaction to solidify the surfaces of the droplets and form hollow particles having hollow portions filled with the hydrophobic solvent.
In the production method of the present invention, in the above-described basic technique, the ratio of the crosslinkable hydrocarbon monomer in the polymerizable monomer is increased, and the above-described specific reaction-promoting additive liquid is added during the polymerization reaction, whereby hollow particles having good dielectric characteristics and solvent resistance can be obtained.
First, in the production method of the present invention, the content of the crosslinkable hydrocarbon monomer such as divinylbenzene is 70 mass% or more in 100 mass% of the polymerizable monomer contained in the suspension, and thus a shell having a high hydrocarbon content is formed, and therefore a shell having a resin composition with a low relative dielectric constant and low dielectric loss tangent can be formed as compared with hollow particles or the like having an acrylic resin as a main component of the shell.
In the conventional production method, even when a shell is formed using a crosslinkable hydrocarbon monomer, when hollow particles are added to a resin composition containing an organic solvent to produce a resin molded article, the resin molded article may not be sufficiently reduced in dielectric constant and dielectric loss tangent. In the conventional production method, it is assumed that even if the proportion of the crosslinkable monomer in the polymerizable monomer is increased, the polymerization reaction does not proceed sufficiently, and therefore the crosslinking density of the shell is not sufficiently high. Therefore, it is presumed that the solvent resistance of the hollow particles obtained by the conventional production method is insufficient, the organic solvent easily permeates the shell, and when the hollow particles are added to a resin composition containing the organic solvent to produce a resin molded article, the organic solvent permeates into the hollow particles, and the organic solvent remains in the hollow particles in the resin molded article, and the proportion of gas in the hollow portion is reduced, so that the resin molded article cannot be sufficiently reduced in dielectric constant and dielectric loss tangent.
In contrast, in the production method of the present invention, the shell is formed by polymerizing the polymerizable monomer containing a large amount of the crosslinkable hydrocarbon monomer, and the specific reaction-promoting additive liquid is added during the polymerization reaction for forming the shell, whereby the polymerization reaction is promoted and the polymerization reaction proceeds sufficiently. As a result, it is presumed that the shell formed has a resin composition having good dielectric properties and a high crosslinking density, and thus hollow particles excellent in dielectric properties and solvent resistance can be obtained. In the production method of the present invention, it is presumed that the above-mentioned specific reaction-promoting additive liquid added during the polymerization reaction enters into the shell to swell the shell, thereby promoting the thermal movement of the shell and promoting the polymerization reaction.
The method for producing hollow particles of the present invention may include a step of preparing a mixed solution, a step of preparing a suspension, and a step of supplying the suspension to a polymerization reaction, and may include steps other than these. In addition, two or more of the above steps and other additional steps may be performed simultaneously as one step, or the order may be changed, as long as the steps are technically feasible. For example, the preparation and suspension of the mixed solution may be performed simultaneously in one step, as if the suspension is performed simultaneously while the material for preparing the mixed solution is being put in.
As a preferred example of the method for producing hollow particles of the present invention, a production method including the following steps can be given.
(1) Preparation of the Mixed solution
A step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium;
(2) Suspension step
A step of preparing a suspension in which droplets of a monomer composition containing a polymerizable monomer, a hydrophobic solvent, and a polymerization initiator are dispersed in an aqueous medium by suspending the mixed solution;
(3) Polymerization step
A step of preparing a precursor composition containing precursor particles having a hollow portion surrounded by a shell containing a resin and containing a hydrophobic solvent therein by supplying the suspension to a polymerization reaction;
(4) Solid-liquid separation step
A step of obtaining precursor particles having a hollow portion filled with a hydrophobic solvent by solid-liquid separation of the precursor composition; and
(5) Solvent removal step
And a step of removing the hydrophobic solvent contained in the precursor particles obtained in the solid-liquid separation step to obtain hollow particles.
In the present invention, the hollow particles having the hollow portion filled with the hydrophobic solvent are regarded as intermediates of the hollow particles having the hollow portion filled with the gas, and are sometimes referred to as "precursor particles". In the present invention, "precursor composition" refers to a composition comprising precursor particles.
Fig. 1 is a schematic diagram showing an example of a manufacturing method of the present invention. In fig. 1, (1) to (5) correspond to the respective steps (1) to (5). White arrows between the figures indicate the order of the steps. Fig. 1 is a schematic diagram for illustration only, and the manufacturing method of the present invention is not limited to the manufacturing method shown in the drawings. The structure, size, and shape of the material used in the manufacturing method of the present invention are not limited to those of the various materials in these figures.
Fig. 1 (1) is a schematic cross-sectional view showing an embodiment of the mixed solution in the mixed solution preparation step. As shown in the figure, the mixed solution includes an aqueous medium 1 and a low-polarity material 2 dispersed in the aqueous medium 1. The low polarity material 2 is a material having low polarity and being not easily mixed with the aqueous medium 1. In the present invention, the low polarity material 2 includes a polymerizable monomer, a hydrophobic solvent, and a polymerization initiator.
Fig. 1 (2) is a schematic cross-sectional view showing an embodiment of a suspension in a suspension process. The suspension includes an aqueous medium 1 and droplets 8 of the monomer composition dispersed in the aqueous medium 1. The droplets 8 of the monomer composition contain a polymerizable monomer, a hydrophobic solvent, and a polymerization initiator, but the distribution within the droplets is uneven. The droplets 8 of the monomer composition have the following structure: the hydrophobic solvent 4a is phase-separated from the material 4b containing the polymerizable monomer other than the hydrophobic solvent, the hydrophobic solvent 4a is biased to exist in the center portion, the material 4b other than the hydrophobic solvent is biased to exist on the surface side, and a dispersion stabilizer (not shown) is attached to the surface.
Fig. 1 (3) is a schematic cross-sectional view showing an embodiment of a precursor composition obtained by the polymerization step and including a precursor particle having a hydrophobic solvent enclosed in a hollow portion. The precursor composition comprises an aqueous medium 1 and precursor particles 9 dispersed in the aqueous medium 1, wherein the hollow portion is filled with a hydrophobic solvent 4 a. The shell 6 forming the outer surface of the precursor particle 9 is formed by polymerizing the polymerizable monomer in the droplet 8 of the monomer composition described above, and a polymer containing the polymerizable monomer is used as a resin.
Fig. 1 (4) is a schematic cross-sectional view showing an embodiment of the precursor particles after the solid-liquid separation step. Fig. 1 (4) shows a state in which the aqueous medium 1 is removed from the state in fig. 1 (3).
Fig. 1 (5) is a schematic cross-sectional view of one embodiment of the hollow particles after the solvent removal step. Fig. 1 (5) shows a state in which the hydrophobic solvent 4a is removed from the state in fig. 1 (4). By removing the hydrophobic solvent from the precursor particles, hollow particles 10 having the hollow portion 7 filled with gas inside the shell 6 can be obtained.
The five steps and the other steps are described in order below.
(1) Preparation of the Mixed solution
The present step is a step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium. The mixed solution may further contain other materials within a range not impairing the effects of the present invention.
The materials of the mixed solution will be described in the order of (a) polymerizable monomer, (B) hydrophobic solvent, (C) polymerization initiator, (D) dispersion stabilizer, (E) aqueous medium, and (F) other materials.
(A) Polymerizable monomer
The polymerizable monomer in the mixed solution may contain at least a crosslinkable hydrocarbon monomer, and may contain a non-crosslinkable hydrocarbon monomer and a polymerizable monomer different from the hydrocarbon monomer within a range that does not impair the effects of the present invention.
[ Crosslinkable hydrocarbon monomer ]
Examples of the crosslinkable hydrocarbon monomer include: aromatic divinyl monomers such as divinylbenzene, divinylbiphenyl, divinylnaphthalene, and the like; linear or branched dienes such as butadiene, isoprene, 2, 3-dimethylbutadiene, pentadiene and hexadiene, and alicyclic dienes such as dicyclopentadiene, cyclopentadiene and ethylene tetracyclododecene. In addition, crosslinkable macromers such as polybutadiene, polyisoprene, a block copolymer of Styrene and Butadiene (SBS), a block copolymer of Styrene and Isoprene (SIS), and the like can be used. These crosslinkable hydrocarbon monomers may be used singly or in combination of two or more. Among them, aromatic divinyl monomers are preferred, and divinylbenzene is more preferred, from the viewpoint of obtaining hollow particles which are easily stabilized in polymerization reaction and are excellent in dielectric characteristics, solvent resistance, strength, heat resistance, and the like.
In the production method of the present invention, by setting the content of the crosslinkable hydrocarbon monomer to 70 mass% or more in 100 mass% of the polymerizable monomer contained in the mixed solution, a shell having a high crosslinking density and excellent solvent resistance can be formed, and hollow particles having good dielectric characteristics can be obtained. Hollow particles having a shell with a high crosslink density also have the advantages of excellent strength, less breakage, less deformation even with heat applied from the outside, and the like. When the content of the crosslinkable hydrocarbon monomer is 70 mass% or more, the component constituting the shell and the hydrophobic solvent are likely to be phase-separated in the droplets of the monomer composition, and thus hollow portions are likely to be formed.
The content of the crosslinkable hydrocarbon monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The upper limit of the content of the crosslinkable hydrocarbon monomer is not particularly limited, and may be 98 mass% or less or 96 mass% or less, for example.
[ Non-crosslinkable hydrocarbon monomer ]
Examples of the non-crosslinkable hydrocarbon monomer include: aromatic monovinyl monomers such as styrene, vinyl toluene, α -methylstyrene, p-methylstyrene, ethylvinylbenzene, ethylvinylbiphenyl, and ethylvinylnaphthalene; linear or branched mono-olefins such as ethylene, propylene, and butene; alicyclic monoolefins such as vinylcyclohexane, norbornene, tricyclododecene and 1, 4-methyl-1, 4a,9 a-tetrahydrofluorene. In addition, non-crosslinkable macromers can also be used. These non-crosslinkable hydrocarbon monomers can be used singly or in combination of two or more kinds. Among them, aromatic monovinyl monomers are preferable, and ethyl vinyl benzene is particularly preferable, from the viewpoint of improving the dielectric properties of the hollow particles.
The content of the non-crosslinkable hydrocarbon monomer in 100 mass% of the polymerizable monomer contained in the mixed solution is not particularly limited, but from the viewpoint of suppressing a decrease in solvent resistance of the hollow particles, the upper limit is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, still more preferably 5 mass% or less, and the lower limit is not particularly limited, and may be, for example, 2 mass% or more or 4 mass% or more.
Further, from the viewpoint of improving the dielectric properties of the hollow particles, the content of the hydrocarbon monomer as the sum of the crosslinkable hydrocarbon monomer and the non-crosslinkable hydrocarbon monomer is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 98 mass% or more, and still more preferably 100 mass% of the polymerizable monomer contained in the mixed solution in 100 mass%. The higher the ratio of polymerizable monomer such as acrylic monomer to hydrocarbon monomer, the higher the relative permittivity and dielectric loss tangent tend to be in the hollow particles obtained, so that the content of hydrocarbon monomer is preferably large from the viewpoint of dielectric characteristics.
[ Polymerizable monomer different from hydrocarbon monomer ]
The polymerizable monomer in the mixed solution may further contain a polymerizable monomer different from the hydrocarbon monomer within a range that does not impair the effects of the present invention. The polymerizable monomer different from the hydrocarbon monomer may be a crosslinkable monomer or a non-crosslinkable monomer.
Examples of the crosslinkable monomer different from the hydrocarbon monomer include: crosslinkable acrylic monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 3- (meth) acryloxy-2-hydroxypropyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, and the like; and crosslinkable allyl monomers such as diallyl phthalate. In addition to these, crosslinkable macromers such as polyphenylene ether having both ends modified with vinyl groups and polyphenylene ether having both ends modified with methacrylic acid can be used.
Examples of the non-crosslinkable monomer other than the hydrocarbon monomer include: non-crosslinkable acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, t-butylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid; acrylamide monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide, and derivatives thereof; vinyl carboxylate monomers such as vinyl acetate; vinyl chloride and other vinyl halide monomers; vinylidene chloride and other vinylidene halide monomers; vinyl pyridine monomers, and the like. In addition, a non-crosslinkable macromonomer such as polystyrene modified at the end with (meth) acrylic acid and polymethyl methacrylate modified at the end with (meth) acrylic acid can be used.
The content of the polymerizable monomer as the sum of the crosslinkable hydrocarbon monomer and the crosslinkable monomer different from the hydrocarbon monomer is preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and still more preferably 95 mass% or more, based on 100 mass% of the polymerizable monomer contained in the mixed solution, from the viewpoint of improving the solvent resistance of the hollow particles. The more the content of the crosslinkable monomer is, the more easily the crosslinking density of the shell becomes, and therefore the solvent resistance of the hollow particles can be improved. The upper limit of the content of the crosslinkable monomer is not particularly limited, and may be 98 mass% or less or 96 mass% or less, for example.
The content of the polymerizable monomer in the mixed solution is not particularly limited, but is preferably 15 to 50 mass%, more preferably 20 to 40 mass% with respect to 100 mass% of the total mass of the components in the mixed solution other than the aqueous medium, from the viewpoint of balance of the porosity, particle diameter and mechanical strength of the hollow particles.
From the viewpoint of improving the mechanical strength of the hollow particles, the content of the polymerizable monomer is preferably 90 mass% or more, more preferably 95 mass% or more, relative to 100 mass% of the total mass of solid components other than the hydrophobic solvent in the material that becomes the oil phase in the mixed liquid.
In the present invention, the solid component means all components except the solvent, and the liquid polymerizable monomer and the like are contained in the solid component.
(B) Hydrophobic solvent
The hydrophobic solvent used in the production method of the present invention is a non-polymerizable and poorly water-soluble organic solvent.
The hydrophobic solvent functions as a spacer material that forms a hollow inside the particle. In the suspension step described later, a suspension in which droplets of the monomer composition containing the hydrophobic solvent are dispersed in an aqueous medium can be obtained. In the suspension step, as a result of phase separation occurring within the droplets of the monomer composition, the hydrophobic solvent having low polarity is easily concentrated inside the droplets of the monomer composition. Finally, in the droplets of the monomer composition, the hydrophobic solvent is distributed inside thereof and the other materials than the hydrophobic solvent are distributed at the edges thereof according to the respective polarities.
Then, in a polymerization step described later, an aqueous dispersion containing hollow particles in which a hydrophobic solvent is contained can be obtained. That is, the hydrophobic solvent is concentrated in the interior of the particles, whereby hollow portions filled with the hydrophobic solvent are formed in the interior of the obtained precursor particles.
As the hydrophobic solvent, an organic solvent having a solubility in water of 20 ℃ smaller than that of the crosslinkable hydrocarbon monomer contained in the mixed solution is preferably selected. Here, when two or more kinds of crosslinkable hydrocarbon monomers or hydrophobic solvents are contained in combination, the hydrophobic solvent is preferably selected so that the solubility of the most soluble hydrophobic solvent is smaller than the solubility of the least soluble crosslinkable hydrocarbon monomer, depending on the type of crosslinkable hydrocarbon monomer.
The organic solvent having a solubility in water of 20℃lower than that of the crosslinkable hydrocarbon monomer can be appropriately selected from known organic solvents, and is not particularly limited, and for example, a hydrocarbon solvent can be preferably used. Hydrocarbon solvents are also preferred in terms of their solubility in water at 20 ℃ being less than the divinylbenzene as the crosslinkable hydrocarbon monomer preferably used in the present invention.
Examples of the hydrocarbon solvent include: a chain hydrocarbon solvent such as pentane, hexane, heptane, octane, 2-methylbutane and 2-methylpentane; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and cycloheptane; aromatic hydrocarbon solvents such as benzene, toluene and xylene.
Among them, from the viewpoint of easy formation of hollow portions, easy obtainment of hollow particles excellent in dielectric characteristics and solvent resistance, easy removal, and easy reduction of residual amount of hydrophobic solvent in the hollow particles, a chain hydrocarbon solvent is preferred, a chain hydrocarbon solvent having 5 to 8 carbon atoms is more preferred, and at least one selected from pentane, hexane, heptane, and octane is still more preferred.
In addition, the hydrophobic solvent may be used singly or in combination of two or more kinds.
The boiling point of the hydrophobic solvent is not particularly limited, but is preferably 130 ℃ or lower, more preferably 100 ℃ or lower, from the viewpoint of easy removal in a solvent removal step described later, and is preferably 50 ℃ or higher, more preferably 60 ℃ or higher, from the viewpoint of easy inclusion in the precursor particles.
In the case where the hydrophobic solvent is a mixed solvent containing a plurality of hydrophobic solvents and having a plurality of boiling points, the boiling point of the solvent having the highest boiling point among the solvents contained in the mixed solvent is preferably not less than the upper limit, and the boiling point of the solvent having the lowest boiling point among the solvents contained in the mixed solvent is preferably not less than the lower limit.
The hydrophobic solvent used in the production method of the present invention preferably has a relative dielectric constant of 2.0 or less at 20 ℃. The relative dielectric constant is one of the indicators indicating the magnitude of the polarity of the compound. When the relative dielectric constant of the hydrophobic solvent is sufficiently small to 2.0 or less, it is considered that phase separation in the polymerizable monomer droplets proceeds rapidly and hollowness is easily formed.
Examples of the hydrophobic solvent having a relative dielectric constant of 2.0 or less at 20℃are as follows. The values of the relative dielectric constants are in brackets.
Pentane (1.8), hexane (1.9), heptane (1.9), octane (1.9).
The relative dielectric constant at 20℃can be obtained by referring to values and other technical information described in known documents (for example, japanese chemical society, revised edition, chart of chemical review, 4 th edition, chart of Wan-Shang Co., ltd., release at 9 months and 30 days, pages II-498 to II-503). As a method for measuring the relative permittivity at 20℃there may be mentioned, for example, a relative permittivity test conducted in accordance with JIS C2101:1999 at 23 and a measurement temperature of 20 ℃.
By varying the amount of hydrophobic solvent in the mixed liquid, the porosity of the hollow particles can be adjusted. In the suspension step described later, since the oil droplets containing the crosslinkable monomer or the like are polymerized in a state of being encapsulated with the hydrophobic solvent, the porosity of the obtained hollow particles tends to be higher as the content of the hydrophobic solvent is larger.
In the present invention, the content of the hydrophobic solvent in the mixed solution is preferably 50 parts by mass to 500 parts by mass in relation to 100 parts by mass of the polymerizable monomer, from the viewpoints of easy control of the particle diameter of the hollow particles, easy improvement of the porosity while maintaining the strength of the hollow particles, and easy reduction of the amount of the residual hydrophobic solvent in the particles. The content of the hydrophobic solvent in the mixed solution is more preferably 60 parts by mass or more and 400 parts by mass or less, and still more preferably 70 parts by mass or more and 300 parts by mass or less, with respect to 100 parts by mass of the polymerizable monomer.
(C) Polymerization initiator
In the production method of the present invention, the mixed solution preferably contains an oil-soluble polymerization initiator as a polymerization initiator. As a method of polymerizing droplets of the monomer composition after suspending the mixed solution, there are an emulsion polymerization method using a water-soluble polymerization initiator and a suspension polymerization method using an oil-soluble polymerization initiator, and suspension polymerization can be performed by using an oil-soluble polymerization initiator.
The oil-soluble polymerization initiator is not particularly limited as long as it is a lipophilic polymerization initiator having a solubility in water of 0.2 mass% or less, and examples thereof include: organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxydiethylacetate, and t-butyl peroxypivalate; azo compounds such as 2,2 '-azobis (2, 4-dimethylvaleronitrile), azobisisobutyronitrile, and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile). In the production method of the present invention, it is particularly preferable to use an organic peroxide as the polymerizable initiator. The organic peroxide can easily promote the polymerization reaction, so that the solvent resistance of the hollow particles can be improved, and decomposition products are less likely to remain after the polymerization reaction, so that deterioration of the dielectric characteristics of the hollow particles can be suppressed. Since the decomposed product of the polymerization initiator remaining in the shell increases the molecular motion of the shell, if the remaining amount of the decomposed product is large, the dielectric loss tangent of the hollow particles may be increased. Since the decomposed product of the organic peroxide is easily removed and hardly remains, the increase in molecular movement of the shell is suppressed by using the organic peroxide, and as a result, the increase in dielectric loss tangent can be suppressed.
The content of the oil-soluble polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polymerizable monomer in the mixed solution. When the content of the oil-soluble polymerization initiator is not less than the above-mentioned lower limit, the polymerization reaction can be sufficiently conducted, and when the content of the oil-soluble polymerization initiator is not more than the above-mentioned upper limit, the possibility of the oil-soluble polymerization initiator remaining after the completion of the polymerization reaction is small, and the possibility of unexpected side reactions is also small.
(D) Dispersion stabilizer
The dispersion stabilizer is a reagent for dispersing droplets of the monomer composition in an aqueous medium in the suspension step. Examples of the dispersion stabilizer include inorganic dispersion stabilizers, organic or inorganic water-soluble polymer stabilizers, and surfactants. In the present invention, an inorganic dispersion stabilizer is preferably used as the dispersion stabilizer in terms of easy control of the particle diameter of the droplets in the suspension and narrowing of the particle diameter distribution of the hollow particles to be obtained, and suppression of the decrease in the strength of the hollow particles by the shell becoming too thin.
Examples of the inorganic dispersion stabilizer include: sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as aluminum oxide and titanium oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and iron hydroxide; inorganic compounds such as silica. These inorganic dispersion stabilizers can be used singly or in combination of two or more.
Among the above inorganic dispersion stabilizers, the poorly water-soluble inorganic dispersion stabilizers are preferable, the poorly water-soluble metal salts such as the above sulfate, carbonate, phosphate, metal hydroxide and the like are more preferable, the metal hydroxide is further preferable, and magnesium hydroxide is particularly preferable.
In the present invention, the poorly water-soluble inorganic dispersion stabilizer is preferably an inorganic compound having a solubility of 0.5g or less in 100g of water. The metal salt which is hardly soluble in water is preferably an inorganic metal salt having a solubility of 0.5g or less in 100g of water.
In the present invention, it is particularly preferable to use the poorly water-soluble inorganic dispersion stabilizer in a state of being dispersed in an aqueous medium in the form of colloidal particles, that is, in a state of being contained in a colloidal dispersion of poorly water-soluble inorganic dispersion stabilizer colloidal particles. By using the poorly water-soluble inorganic dispersion stabilizer in the state of the colloidal dispersion containing the poorly water-soluble inorganic dispersion stabilizer colloidal particles, the particle size distribution of the droplets of the monomer composition can be narrowed, and the residual amount of the inorganic dispersion stabilizer in the obtained hollow particles can be easily suppressed to be low by washing.
The colloidal dispersion containing the poorly water-soluble inorganic dispersion stabilizer colloidal particles can be prepared, for example, by reacting at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides with a water-soluble polyvalent metal salt (excluding alkaline earth metal hydroxides) in an aqueous medium.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the alkaline earth metal hydroxide include barium hydroxide and calcium hydroxide.
The water-soluble polyvalent metal salt may be any water-soluble polyvalent metal salt other than the compound belonging to the alkaline earth metal hydroxide, and examples thereof include: magnesium metal salts such as magnesium chloride, magnesium phosphate, and magnesium sulfate; calcium metal salts such as calcium chloride, calcium nitrate, calcium acetate, and calcium sulfate; aluminum metal salts such as aluminum chloride and aluminum sulfate; barium salts such as barium chloride, barium nitrate, and barium acetate; zinc salts such as zinc chloride, zinc nitrate and zinc acetate. Among these, magnesium metal salts, calcium metal salts and aluminum metal salts are preferable, magnesium metal salts are more preferable, and magnesium chloride is particularly preferable. In addition, the water-soluble polyvalent metal salts may be used singly or in combination of two or more kinds.
The method of reacting at least one selected from the alkali metal hydroxide and the alkaline earth metal hydroxide with the water-soluble polyvalent metal salt in the aqueous medium is not particularly limited, and there is a method of mixing an aqueous solution of at least one selected from the alkali metal hydroxide and the alkaline earth metal hydroxide with an aqueous solution of the water-soluble polyvalent metal salt. In this case, from the viewpoint of being able to properly control the particle diameter of the poorly water-soluble metal hydroxide colloidal particles, the following method is preferable: the aqueous solution of at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides is gradually added to the aqueous solution while stirring the aqueous solution of the water-soluble polyvalent metal salt, thereby mixing the aqueous solution.
Colloidal silica can be used as a colloidal dispersion containing colloidal particles of an inorganic dispersion stabilizer which is hardly water-soluble.
Examples of the organic water-soluble polymer stabilizer include polyvinyl alcohol, polycarboxylic acid (polyacrylic acid, etc.), cellulose (hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, etc.), polyvinylpyrrolidone, polyacrylic imide, polyethylene oxide, poly (hydroxystearic acid-g-methyl methacrylate-co-methacrylic acid), and the like.
Examples of the inorganic water-soluble polymer compound include sodium tripolyphosphate.
The surfactant is a compound having both a hydrophilic group and a hydrophobic group in one molecule, and examples thereof include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
The content of the dispersion stabilizer is not particularly limited, but is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent. By setting the content of the dispersion stabilizer to the above lower limit or more, the droplets of the monomer composition can be sufficiently dispersed in the suspension without aggregation. On the other hand, by setting the content of the dispersion stabilizer to the above upper limit value or less, it is possible to prevent the viscosity of the suspension from rising during granulation and to avoid the problem of clogging of the granulator with the suspension.
The content of the dispersion stabilizer is usually 2 parts by mass or more and 15 parts by mass or less, preferably 3 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the aqueous medium.
(E) Aqueous medium
In the present invention, the aqueous medium means a medium selected from water, a hydrophilic solvent, and a mixture of water and a hydrophilic solvent. In the production method of the present invention, water is preferably used as the aqueous medium in order to obtain the effect of promoting the polymerization reaction by the reaction-promoting additive liquid.
In the case of using a mixture of water and a hydrophilic solvent, it is important that the polarity of the mixture as a whole is not too low from the viewpoint of forming droplets of the monomer composition. In this case, the mass ratio of water to hydrophilic solvent (water: hydrophilic solvent) may be, for example, 99:1 to 50:50.
The hydrophilic solvent in the present invention is not particularly limited as long as it is a solvent that is sufficiently mixed with water without undergoing phase separation. Examples of the hydrophilic solvent include: alcohols such as methanol and ethanol; tetrahydrofuran (THF); dimethyl sulfoxide (DMSO), and the like. In the polymerization step described later, the hydrophilic solvent contained in the aqueous medium is preferably different from the reaction-promoting additive from the viewpoint of sufficiently obtaining the effect of promoting the polymerization reaction by the reaction-promoting additive.
(F) Other materials
The mixed solution may contain other materials than the materials (a) to (E) described above within a range that does not impair the effects of the present invention.
The mixed solution may contain a polar component as another material. By including the polar component in the mixed liquid, the thickness of the shell of the hollow particles obtained can be appropriately adjusted.
As the polar component, for example, an organic acid or a metal salt thereof can be used.
The organic acid may be abietic acid or higher fatty acid. Examples of the higher fatty acid include higher fatty acids having 10 to 25 carbon atoms, which do not include the carbon atoms in the carboxyl group.
Examples of the metal used for the metal salt of the organic acid include alkali metals such as Li, na, and K, alkaline earth metals such as Mg and Ca, and among them, alkali metals are preferable, and at least one selected from Li, na, and K is more preferable.
When the organic acid or the metal salt thereof is used as the polar component, the total content of the organic acid or the metal salt thereof is preferably 0.001 part by mass or more, more preferably 0.0015 part by mass or more, and on the other hand, preferably 0.1 part by mass or less, more preferably 0.05 part by mass or less, relative to 100 parts by mass of the total of the polymerizable monomer and the hydrophobic solvent in the mixed solution. When the content is not less than the lower limit, the particle diameter of the hollow particles and the thickness of the shell can be easily controlled, and particularly the volume average particle diameter of the hollow particles can easily be in a preferable range described later. On the other hand, when the content is not more than the upper limit, the decrease in the content ratio of the polymerizable monomer can be suppressed, and therefore, the decrease in the strength and solvent resistance of the shell can be suppressed.
The above-described materials are mixed with other materials as needed, and stirred appropriately to obtain a mixed solution. In this mixed solution, an oil phase containing the above-mentioned (a) polymerizable monomer, (B) hydrophobic solvent, and (C) lipophilic material such as polymerization initiator is dispersed in an aqueous phase containing (D) dispersion stabilizer, and (E) aqueous medium, etc., in a size of about several mm in particle diameter. The dispersion state of these materials in the mixed solution can also be observed by naked eyes according to the kind of the materials.
In the mixed solution preparation step, the above-described materials and other materials as needed may be mixed and appropriately stirred to obtain a mixed solution, but from the viewpoint of easy uniformity of the shell, it is preferable to prepare an oil phase containing a polymerizable monomer, a hydrophobic solvent and a polymerization initiator and an aqueous phase containing a dispersion stabilizer and an aqueous medium separately in advance, and mix them to prepare a mixed solution. In the present invention, a colloidal dispersion in which an inorganic dispersion stabilizer that is poorly water-soluble is dispersed in an aqueous medium in the form of colloidal particles can be preferably used as the aqueous phase.
By mixing the oil phase and the water phase after preparing them separately in advance in this manner, hollow particles having a uniform composition in the shell portion can be produced, and the particle diameter of the hollow particles can be easily controlled.
(2) Suspension step
The suspension step is a step of preparing a suspension in which droplets of the monomer composition containing the hydrophobic solvent are dispersed in an aqueous medium by suspending the above-described mixed solution.
The suspension method for forming the droplets of the monomer composition is not particularly limited, and a known suspension method can be employed. As a dispersing machine used in preparing a suspension, for example, can be used: a horizontal multistage pipeline disperser such as a miller (trade name) manufactured by pacific corporation (PACIFIC MACHINERY & Engineering co., ltd.), a Cavitron (trade name) manufactured by the corporation Eurotec, and a vertical multistage pipeline disperser such as a pipeline disperser manufactured by IKA (for example, a DISPAX-REACTOR (registered trademark) DRS (trade name); commercially available stirring devices such as HOMOMIXER MARK II series emulsifying and dispersing machines manufactured by Shimeji corporation.
In the suspension prepared in the suspension step, droplets of the monomer composition containing the lipophilic material and having a particle diameter of about 1 to 10 μm are uniformly dispersed in an aqueous medium. The droplets of the monomer composition are not easily observed by naked eyes, and can be observed by a known observation device such as an optical microscope.
In the suspension step, phase separation occurs in the droplets of the monomer composition, and therefore, the hydrophobic solvent having low polarity tends to concentrate inside the droplets. As a result, in the obtained droplets, the hydrophobic solvent is distributed inside, and the material other than the hydrophobic solvent is distributed at the edges thereof.
The droplets of the monomer composition dispersed in the aqueous medium are formed by surrounding the periphery of the oil-soluble monomer composition with a dispersion stabilizer. The droplets of the monomer composition contain an oil-soluble polymerization initiator, a polymerizable monomer, and a hydrophobic solvent.
The droplets of the monomer composition are minute oil droplets, and the oil-soluble polymerization initiator generates polymerization initiating radicals inside the minute oil droplets. Therefore, the precursor particles having the desired particle diameter can be produced without excessive growth of the fine oil droplets.
In the suspension polymerization method using such an oil-soluble polymerization initiator, there is no chance that the polymerization initiator will come into contact with the polymerizable monomer dispersed in the aqueous medium. Therefore, by using the oil-soluble polymerization initiator, it is possible to suppress the generation of excessive resin particles such as compact particles having a relatively small particle diameter other than the targeted resin particles having the hollow portion as a by-product.
(3) Polymerization step
The present step is a step of preparing a precursor composition containing precursor particles having a hollow portion surrounded by a shell containing a resin and containing a hydrophobic solvent in the hollow portion by supplying the suspension obtained in the suspension step to a polymerization reaction.
In the production method of the present invention, the polymerization reaction is further carried out after the reaction promoting additive liquid is added during the polymerization reaction. As the reaction-promoting additive solution, a low-molecular compound having a solubility in water of 20℃greater than that of the hydrophobic solvent and 0.5g/L to 1000g/L is used.
Here, when two or more hydrophobic solvents are contained in combination, the reaction-promoting additive solution is preferably selected so that the solubility is greater than that of the hydrophobic solvent having the greatest solubility.
The low-molecular compound used as the reaction-promoting additive is liquid at 0 to 30 ℃, and the upper limit of the molecular weight is preferably 200 or less, more preferably 100 or less, and the lower limit of the molecular weight is not particularly limited, but is usually 50 or more.
The low-molecular compound may be a non-reactive low-molecular compound or a reactive low-molecular compound, and the non-reactive low-molecular compound is preferable in that the dielectric characteristics of the hollow particles are not adversely affected even if the amount of the low-molecular compound is increased. Here, reactive means reacting with the polymerizable monomer in the mixed solution, and nonreactive means not reacting with the polymerizable monomer in the mixed solution. That is, reactivity means that covalent bonds are formed by chemical reaction with polymerizable monomers in the mixed solution.
The solubility of the non-reactive low-molecular compound used as the reaction promoting additive liquid in water at 20℃is preferably 0.5g/L to 1000g/L, more preferably 10g/L or more, still more preferably 30g/L or more, still more preferably 40g/L or more, still more preferably 50g/L or more, and on the other hand preferably 700g/L or less, still more preferably 500g/L or less, still more preferably 300g/L or less, in terms of improving the solvent resistance of the hollow particles.
As the non-reactive low molecular compound used as the reaction-promoting additive liquid, an organic solvent is preferably used in view of easy entry into the shell and easy promotion of the crosslinking reaction.
The organic solvent is not particularly limited, and may be appropriately selected from known organic solvents to satisfy the above solubility. Specific examples of the organic solvent used as the reaction-promoting additive solution include, for example: ketone solvents such as methyl ethyl ketone, acetone, and 3-pentanone; ester solvents such as methyl acetate and ethyl acetate; ether solvents such as dimethyl ether and diethyl ether; alcohol solvents such as propanol, isopropanol and butanol. These organic solvents can be used singly or in combination of two or more kinds.
Among these organic solvents, at least one selected from ketone solvents and ester solvents is preferable, and at least one selected from methyl ethyl ketone, 3-pentanone, methyl acetate and ethyl acetate is more preferable from the viewpoint of improving solvent resistance of the hollow particles.
The solubility of the reactive low-molecular compound used as the reaction promoting additive liquid in water at 20℃is only 0.5g/L to 1000g/L, which is greater than the hydrophobic solvent in the mixed liquid, and is preferably 100g/L or less, more preferably 80g/L or less, still more preferably 70g/L or less, still more preferably 30g/L or less, and particularly preferably 20g/L or less, from the viewpoint of suppressing deterioration of dielectric characteristics of the hollow particles. The lower limit of the solubility of the low-molecular compound is not particularly limited, but is preferably 1.0g/L or more, more preferably 2.0g/L or more, from the viewpoint of improving the solvent resistance of the hollow particles.
As the reactive low-molecular compound used as the reaction-promoting additive liquid, a polymerizable monomer containing a hetero atom is preferably used in view of easy entry into the shell and easy promotion of the crosslinking reaction. The polymerizable monomer used as the reaction promoting additive may be a crosslinkable monomer or a non-crosslinkable monomer, and is preferably a crosslinkable monomer in that the decrease in solvent resistance of the hollow particles can be suppressed by suppressing the decrease in crosslinking density of the shell.
As the polymerizable monomer containing a heteroatom, for example, a (meth) acrylic monomer having a (meth) acryloyl group as a polymerizable functional group and a polar group-containing monomer can be preferably used.
Examples of the (meth) acrylic monomer include: alkyl (meth) acrylates having an alkyl group having 1 to 5 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and derivatives thereof; (meth) acrylonitrile, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, and the like.
The polar group-containing monomer may preferably be a polymerizable monomer containing a polar group selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, a polyoxyethylene group, and an epoxy group. More specifically, there can be mentioned: carboxyl group-containing monomers such as ethylenically unsaturated carboxylic acid monomers including (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, and butenetricarboxylic acid; hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate; sulfonic acid group-containing monomers such as styrenesulfonic acid; amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; polyoxyethylene group-containing monomers such as methoxypolyethylene glycol (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate, allyl glycidyl ether, and glycidyl 4-hydroxybutyl acrylate.
These polymerizable monomers containing a heteroatom may be used singly or in combination of two or more kinds.
Among the above polymerizable monomers containing a heteroatom, at least one type of (meth) acrylic monomer having two or more polymerizable functional groups and a polar group-containing monomer having two or more polymerizable functional groups is preferable, and a (meth) acrylic monomer having two or more polymerizable functional groups is more preferable, and allyl (meth) acrylate is particularly preferable, in terms of facilitating the crosslinking reaction of the shell and suppressing the decrease in solvent resistance of the hollow particles by suppressing the decrease in the crosslinking density of the shell due to the introduction of the polymerizable monomers. Among the polymerizable monomers containing a heteroatom having only one polymerizable functional group, alkyl (meth) acrylates having an alkyl group having 1 to 5 carbon atoms and (meth) acrylic monomers containing the polar group are preferable, and alkyl (meth) acrylates having an alkyl group having 1 to 3 carbon atoms and (meth) acrylic monomers containing a hydroxyl group or an amino group are more preferable. As the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms, methyl (meth) acrylate is particularly preferred. As the (meth) acrylic monomer containing a hydroxyl group or an amino group, t-butylaminoethyl (meth) acrylate is particularly preferable.
The reaction-promoting additive may be a mixture of the non-reactive low-molecular compound and the reactive low-molecular compound, or may be either the non-reactive low-molecular compound or the reactive low-molecular compound alone. As the reaction promoting additive liquid, for example, at least one selected from a ketone-based solvent, an ester-based solvent, a (meth) acrylic monomer having two or more polymerizable functional groups, an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms, and a (meth) acrylic monomer containing a hydroxyl group or an amino group can be preferably used, and at least one selected from methyl ethyl ketone, 3-pentanone, methyl acetate, ethyl acetate, allyl (meth) acrylate, methyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate can be more preferably used.
When a non-reactive low-molecular compound is added as the reaction-promoting additive liquid, the amount of the non-reactive low-molecular compound to be added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid.
When the addition amount of the non-reactive low-molecular compound as the reaction promoting additive liquid is not less than the above lower limit, the effect of promoting the crosslinking reaction of the shell is improved, and the solvent resistance of the hollow particles can be improved. On the other hand, when the addition amount of the non-reactive low-molecular compound as the reaction promoting additive liquid is not more than the above upper limit value, deformation of the hollow particles due to swelling of the shell can be suppressed.
When the reactive low-molecular compound is added as the reaction-promoting additive liquid, the amount of the reactive low-molecular compound to be added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 3 parts by mass or less, relative to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid.
When the addition amount of the reactive low-molecular compound as the reaction promoting additive liquid is not less than the above lower limit, the effect of promoting the crosslinking reaction of the shell is improved, and the solvent resistance of the hollow particles can be improved. On the other hand, when the amount of the reactive low-molecular compound to be added as the reaction promoting additive is not more than the upper limit, deterioration of the dielectric characteristics of the hollow particles can be suppressed. Since the reactive low-molecular compound generally contains a heteroatom and reacts with the polymerizable monomer in the shell to form a constituent of the shell, the addition amount of the reactive low-molecular compound is not more than the upper limit, and the increase in the amount of the heteroatom in the shell is suppressed, whereby deterioration of dielectric characteristics can be suppressed. In addition, the reactive low-molecular compound is preferably a non-crosslinkable monomer, since the decrease in the crosslinking density of the shell and the deterioration in solvent resistance can be suppressed by setting the addition amount of the reactive low-molecular compound to the above upper limit or less.
In the polymerization step, the reaction-promoting additive is preferably added when the polymerization conversion rate of the polymerizable monomer contained in the mixed solution is preferably 40 to 90%, more preferably 45 to 85%, from the viewpoint of promoting the crosslinking reaction of the shell and improving the solvent resistance of the hollow particles.
In the present invention, the polymerization conversion is obtained from the mass of the solid component of the particles produced when the reaction-promoting additive liquid is added and the mass of the unreacted polymerizable monomer when the reaction-promoting additive liquid is added by the following formula (B). The mass of the unreacted polymerizable monomer can be measured by Gas Chromatography (GC).
Formula (B):
Polymerization conversion (mass%) =100- { mass of unreacted polymerizable monomer/(mass of solid component of particles produced when the reaction-promoting additive liquid was added+mass of unreacted polymerizable monomer) } ×100
When a non-reactive low-molecular compound is added as a reaction-promoting additive liquid, the precursor particles are formed by polymerizing polymerizable monomers contained in droplets of the monomer composition, and the shell of the precursor particles contains a polymer of the polymerizable monomers as a resin. On the other hand, when a reactive low-molecular compound is added as the reaction-promoting additive liquid, the precursor particles are formed by polymerizing a polymerizable monomer and a reactive low-molecular compound contained in droplets of the monomer composition, and the shell of the precursor particles contains a polymer of the polymerizable monomer and the reactive low-molecular compound as a resin.
In the present invention, the content of the hydrocarbon monomer is preferably 90 mass% or more, more preferably 91 mass% or more, and still more preferably 94 mass% or more, based on 100 mass% of the total amount of the polymerizable monomer and the reactive low-molecular compound forming the shell, in terms of improving the dielectric properties of the hollow particles.
In the polymerization step, the polymerization method is not particularly limited, and for example, batch type (batch type), semi-continuous type, and the like can be used.
The polymerization temperature is preferably 40 to 90℃and more preferably 50 to 80 ℃.
The heating rate at the time of heating to the polymerization temperature is preferably 10 to 60℃C/hr, more preferably 15 to 55℃C/hr.
The reaction time for the polymerization is preferably 1 to 48 hours, more preferably 4 to 36 hours.
The timing of adding the reaction-promoting additive liquid is preferably adjusted so that the polymerization conversion rate of the polymerizable monomer in the mixed liquid falls within the above-described preferable range, and for example, after the temperature is raised to the polymerization temperature, the reaction-promoting additive liquid is preferably added over 20 minutes to 2 hours, more preferably over 30 minutes to 1.5 hours, and then the polymerization reaction is preferably performed for about 1 to 30 hours, more preferably about 2 to 25 hours.
In the polymerization step, the shell portion of the droplet of the monomer composition containing the hydrophobic solvent therein is polymerized, and thus, as described above, hollow portions filled with the hydrophobic solvent are formed inside the obtained precursor particles.
(4) Solid-liquid separation step
The present step is a step of obtaining a solid component containing precursor particles by solid-liquid separation of the precursor composition containing precursor particles obtained in the above-described polymerization step.
The method for solid-liquid separation of the precursor composition is not particularly limited, and a known method can be used. Examples of the solid-liquid separation method include a centrifugal separation method, a filtration method, and a stationary separation method, and among these, a centrifugal separation method or a filtration method can be used, and from the viewpoint of simplicity of operation, a centrifugal separation method can be used.
After the solid-liquid separation step and before the solvent removal step described later, any step such as a pre-drying step may be performed. Examples of the preliminary drying step include a step of preliminary drying the solid component obtained after the solid-liquid separation step by a drying device such as a dryer or a dryer.
(5) Solvent removal step
The present step is a step of removing the hydrophobic solvent contained in the precursor particles obtained in the solid-liquid separation step.
For example, by removing the hydrophobic solvent entrapped in the precursor particles in a gas, the hydrophobic solvent inside the precursor particles is replaced with air, resulting in hollow particles filled with gas.
The term "in gas" in this step strictly means that the liquid component is not present at all outside the precursor particles, and that the liquid component is present only in an extremely small amount outside the precursor particles to such an extent that the removal of the hydrophobic solvent is not affected. The "in gas" can change not only the state expressed as that the precursor particles are not present in the slurry but also the state expressed as that the precursor particles are present in the dry powder. That is, in this step, it is important to remove the hydrophobic solvent in an environment where the precursor particles are in direct contact with the external gas.
The method for removing the hydrophobic solvent in the precursor particles in the gas is not particularly limited, and a known method can be used. Examples of the method include a reduced pressure drying method, a heat drying method, a pneumatic drying method, and a combination of these methods.
In particular, when the heat drying method is used, the heating temperature needs to be not lower than the boiling point of the hydrophobic solvent and not higher than the highest temperature at which the shell structure of the precursor particles does not collapse. Therefore, depending on the composition of the shell in the precursor particles and the kind of the hydrophobic solvent, the heating temperature may be, for example, 50 to 200 ℃, or 70 to 200 ℃, or 100 to 200 ℃.
By the drying operation in the gas, the hydrophobic solvent inside the precursor particles is replaced with the external gas, with the result that hollow particles in which the gas occupies the hollow portion are obtained.
The drying atmosphere is not particularly limited, and may be appropriately selected according to the use of the hollow particles. As the dry atmosphere, for example, air, oxygen, nitrogen, argon, and the like can be considered. Further, once the hollow particles are filled with a gas, the hollow particles can be obtained by drying under reduced pressure while the inside is temporarily evacuated.
As another method, the hydrophobic solvent may be removed from the slurry containing the precursor particles and the aqueous medium without solid-liquid separation of the slurry-like precursor composition obtained in the polymerization step.
In this method, the inert gas is blown into the precursor composition at a temperature of, for example, 35 ℃ or higher after subtracting the boiling point of the hydrophobic solvent, whereby the hydrophobic solvent contained in the precursor particles can be removed.
Here, in the case where the hydrophobic solvent is a mixed solvent containing a plurality of hydrophobic solvents and has a plurality of boiling points, the boiling point of the hydrophobic solvent in the solvent removal step means the boiling point of the solvent having the highest boiling point among the solvents contained in the mixed solvent, that is, the boiling point having the highest boiling point among the plurality of boiling points.
In terms of reducing the residual amount of the hydrophobic solvent in the hollow particles, the temperature at which the inert gas is blown into the precursor composition is preferably a temperature of 30 ℃ or higher subtracted from the boiling point of the hydrophobic solvent, and more preferably a temperature of 20 ℃ or higher subtracted from the boiling point of the hydrophobic solvent. The temperature at the time of bubbling is usually not lower than the polymerization temperature in the polymerization step. The temperature at the time of air blowing is not particularly limited, but may be 50 ℃ or higher and 100 ℃ or lower.
The inert gas to be blown in is not particularly limited, and examples thereof include nitrogen, argon, and the like.
The conditions of the aeration may be appropriately adjusted according to the kind and amount of the hydrophobic solvent so that the hydrophobic solvent contained in the precursor particles can be removed, and are not particularly limited, and for example, the inert gas may be introduced in an amount of 1 to 3L/min for 1 to 10 hours.
In this method, an aqueous slurry in which the precursor particles are encapsulated with an inert gas can be obtained. The hollow particles obtained by solid-liquid separation of the slurry are dried, and the aqueous medium remaining in the hollow particles is removed, thereby obtaining hollow particles in which the gas occupies the hollow portion.
When comparing a method of removing a hydrophobic solvent in a precursor particle in a slurry form in a gas after solid-liquid separation of the precursor composition to obtain hollow particles having a hollow portion filled with the gas, the former method has an advantage of hardly breaking the hollow particles in a step of removing the hydrophobic solvent, and a method of removing an aqueous medium in a precursor particle in a gas by solid-liquid separation after removing the hydrophobic solvent enclosed in the precursor particle in a slurry containing the precursor particle and the aqueous medium to obtain hollow particles having a hollow portion filled with the gas, the latter method has an advantage of reducing the residual hydrophobic solvent by performing a bubbling using an inactive gas.
In addition, as a method for removing the hydrophobic solvent contained in the precursor particles without solid-liquid separation of the slurry-like precursor composition obtained in the polymerization step after the polymerization step and before the solid-liquid separation step, for example, the following method may be used: a method of distilling off the hydrophobic solvent entrapped in the precursor particles from the precursor composition under a prescribed pressure (high pressure, normal pressure, or reduced pressure); and a method in which an inert gas such as nitrogen, argon, helium, or the like or steam is introduced into the precursor composition under a predetermined pressure (high pressure, normal pressure, or reduced pressure) and distilled off.
(6) Others
As the steps other than the steps (1) to (5), for example, the following (6-a) washing step and the following (6-b) intra-particle replacement step may be added.
(6-A) cleaning step
The cleaning step is a step of cleaning by adding an acid or a base to remove the dispersion stabilizer remaining in the precursor composition containing the precursor particles before the solvent removal step. In the case where the dispersion stabilizer used is an inorganic dispersion stabilizer soluble in an acid, it is preferable to add an acid to the precursor composition containing the precursor particles for cleaning, and in the case where the dispersion stabilizer used is an inorganic compound soluble in an alkali, it is preferable to add an alkali to the precursor composition containing the precursor particles for cleaning.
In the case of using an inorganic dispersion stabilizer soluble in an acid as the dispersion stabilizer, the acid is added to the precursor composition containing the precursor particles, preferably to adjust the pH to 6.5 or less, and more preferably to adjust the pH to 6 or less. As the acid to be added, an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, or the like, and an organic acid such as formic acid, acetic acid, or the like can be used, and sulfuric acid is particularly preferable because the removal efficiency of the dispersion stabilizer is high and the burden on the production facility is small.
(6-B) Process for replacing the interior of the particles
The step of replacing the inside of the hollow particles refers to a step of replacing the gas or liquid inside the hollow particles with another gas or liquid. By such substitution, the chemical structure inside the hollow particle can be modified by changing the environment inside the hollow particle, selectively encapsulating molecules inside the hollow particle, or by fitting the use.
2. Hollow particles
The hollow particles of the present invention have a shell containing a resin and a hollow portion surrounded by the shell, and the hollow particles have a porosity of 50% or more,
The shell contains, as the resin, a polymer containing 70 mass% or more of a crosslinkable hydrocarbon monomer unit,
0.1Mg of the hollow particles was added to 4mL of toluene at 25℃and the mixture was shaken at a shaking speed of 100rpm for 10 minutes, followed by standing for 48 hours, whereby the hollow particles precipitated in toluene were less than 5% by mass in the impregnation test of the hollow particles.
In the above impregnation test, it is considered that the smaller the hollow particles precipitated in toluene, the more excellent the solvent resistance of the hollow particles.
The hollow particles of the present invention have less than 5 mass% of hollow particles precipitated in toluene in the above impregnation test, and thus have excellent solvent resistance. The hollow particles precipitated in toluene in the above impregnation test may be less than 5 mass%, preferably less than 3 mass%, and more preferably less than 1 mass%.
The hollow particles of the present invention are particles having a shell (outer shell) containing a resin and a hollow portion surrounded by the shell.
In the present invention, the hollow portion is a hollow space clearly distinguished from the shell of the hollow particle formed of the resin material. The shell of the hollow particles may have a porous structure, in which case the hollow portion has a size clearly distinguishable from a plurality of minute spaces uniformly dispersed within the porous structure. From the standpoint of dielectric properties and solvent resistance, the hollow particles of the present invention preferably have a dense shell.
The hollow portion of the hollow particle can be confirmed by SEM observation of a particle cross section or the like, or by directly subjecting the particle to TEM observation or the like, for example.
In addition, the hollow particles of the present invention preferably have hollow portions filled with a gas such as air, in order to exhibit excellent dielectric characteristics.
Hollow particles obtained by using a hydrocarbon resin such as a styrene resin are expected to be an additive for lowering the dielectric constant and the dielectric loss tangent of various materials because the relative dielectric constant and the dielectric loss tangent of the resin itself constituting the shell are low. However, when a resin molded article is produced by adding conventional hollow particles obtained using a hydrocarbon resin to a resin composition containing an organic solvent, there is a problem that the effects of lowering the dielectric constant and lowering the dielectric loss tangent are insufficient. This is presumably because the organic solvent in the resin composition permeates into the hollow particles, and the organic solvent remains in the hollow particles in the resin molded article, so that the proportion of the gas in the hollow portion is reduced.
In contrast, the hollow particles of the present invention have a resin composition having a low relative permittivity and low dielectric loss tangent and are excellent in solvent resistance, and therefore, even when the hollow particles are added to a resin composition containing an organic solvent to produce a resin molded article, the resin molded article can be sufficiently reduced in permittivity and low in dielectric loss tangent. The shell of the hollow particle of the present invention contains a polymer containing 70 mass% or more of a structural unit derived from a crosslinkable hydrocarbon monomer such as divinylbenzene, and has a resin composition having a lower relative permittivity and dielectric loss tangent than those of hollow particles containing an acrylic resin as a main component of the shell because the proportion of hydrocarbon in the shell is high. Further, the shell of the hollow particle of the present invention contains a large number of crosslinkable monomer units, and therefore, the covalent bond network is densely packed, and in the impregnation test described above, the hollow particle precipitated in toluene is less than 5 mass%, and it is estimated that the shell has a structure with a high crosslinking density that is less likely to permeate toluene, and thus, the solvent resistance is estimated to be excellent. As described above, the hollow particles of the present invention are excellent in dielectric characteristics and solvent resistance, and therefore, when the hollow particles of the present invention are added to a resin composition containing an organic solvent to produce a resin molded article, the hollow particles themselves are excellent in dielectric characteristics, and the organic solvent in the resin composition is less likely to penetrate into the hollow particles, and the proportion of gas in the hollow particles is maintained in the resin molded article, so that the effects of lowering the dielectric constant and lowering the dielectric loss tangent of the resin molded article are excellent.
In addition, the hollow particles of the present invention preferably have 5 or less hollow particles having a communication hole or a shell defect among 100 hollow particles in SEM observation.
Typically, there are in the hollow particles: the shell does not have hollow particles having a communication hole for communicating the hollow portion with an outer space of the particles; and a shell having one or more communication holes, hollow particles in which the hollow portion communicates with the outside of the particles via the communication holes. The diameter of the communication hole is usually about 10 to 500nm, although it depends on the size of the hollow particle. Although the communication holes may impart a beneficial function to the hollow particles, the communication holes are portions where the shell is defective, and therefore the strength of the hollow particles is reduced, and breakage is likely to occur.
In addition, hollow particles sometimes have extremely large crack-like shell defects compared to the size of the particles. Although also depending on the size of the hollow particles, cracks having a length of 1 μm or more often significantly deteriorate the strength of the hollow particles, and are thus considered as shell defects.
In the above-described impregnation test of hollow particles, when the hollow particles precipitated in toluene are less than 5 mass%, it can be considered that 100 hollow particles having a communication hole or a shell defect among the hollow particles are 5 or less.
In the hollow particles of the present invention, the content of the crosslinkable hydrocarbon monomer unit in the polymer contained in the shell is not less than 70% by mass, and is preferably not less than 80% by mass, more preferably not less than 90% by mass, and still more preferably not less than 95% by mass, from the viewpoint of improving the dielectric characteristics and solvent resistance of the hollow particles. The upper limit of the content of the crosslinkable hydrocarbon monomer unit is not particularly limited, and may be, for example, 98 mass% or less or 96 mass% or less.
In the hollow particles of the present invention, the content of the hydrocarbon monomer unit in the polymer contained in the shell is preferably 90 mass% or more, more preferably 91 mass% or more, and still more preferably 94 mass% or more, from the viewpoint of improving the dielectric properties of the hollow particles. The upper limit of the content of the hydrocarbon monomer unit is not particularly limited, and may be 98 mass% or less or 96 mass% or less, for example.
In the hollow particles of the present invention, the content of the crosslinkable monomer unit in the polymer contained in the shell is preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and still more preferably 95 mass% or more, from the viewpoint of improving the solvent resistance of the hollow particles. The upper limit of the content of the crosslinkable monomer unit is not particularly limited, and may be 98 mass% or less or 96 mass% or less, for example.
The hollow particles of the present invention preferably have a relative dielectric constant of 1.50 or less, more preferably 1.45 or less, and still more preferably 1.40 or less at a frequency of 1 GHz. The lower limit of the relative dielectric constant of the hollow particles of the present invention is not particularly limited, but is usually 1.00 or more when the frequency is 1 GHz.
The hollow particles of the present invention preferably have a dielectric loss tangent of 0.0010 (1.0X10 -3) or less, more preferably 9.5X10 -4 or less, still more preferably 9.0X10 -4 or less, and still more preferably 8.5X10 -4 or less at a frequency of 1 GHz. The lower limit of the dielectric loss tangent of the hollow particles of the present invention at a frequency of 1GHz is not particularly limited, and may be, for example, 1.0X10 -5 or more.
In the present invention, the relative permittivity and dielectric loss tangent of the hollow particles are measured using a disturbance type measuring device under the condition that the measurement frequency is 1 GHz.
The hollow particles of the present invention have a porosity of 50% or more, preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more. By setting the porosity to the above lower limit value or more, the hollow particles are excellent in dielectric characteristics, and further excellent in lightweight properties, heat insulation properties, and the like. The upper limit of the porosity of the hollow particles is not particularly limited, but is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, and still more preferably 75% or less, from the viewpoint of suppressing the decrease in strength, the difficulty in breakage, and the decrease in solvent resistance of the hollow particles.
The porosity of the hollow particles was calculated from the apparent density D 1 and the true density D 0 of the hollow particles.
The determination of the apparent density D 1 of the hollow particles is as follows. First, hollow particles of about 30cm 3 were filled in a volumetric flask having a capacity of 100cm 3, and the mass of the filled hollow particles was precisely weighed. Next, the volumetric flask filled with the hollow particles was filled with isopropyl alcohol to the scale mark accurately while taking care not to mix with air bubbles. The mass of isopropyl alcohol added to the volumetric flask was precisely weighed, and the apparent density D 1(g/cm3 of the hollow particles was calculated based on the following formula (I).
Formula (I)
Apparent density D 1 = [ mass of hollow particles ]/(100- [ mass of isopropyl alcohol ]/[ specific gravity of isopropyl alcohol at measurement temperature ])
The apparent density D 1 corresponds to the specific gravity of the whole hollow particle in the case where the hollow portion is regarded as a part of the hollow particle.
The determination of the true density D 0 of the hollow particles is as follows. After the hollow particles were pulverized in advance, a volumetric flask having a capacity of 100cm 3 was filled with about 10g of fragments of the hollow particles, and the mass of the filled fragments was precisely weighed. Then, isopropyl alcohol was added to a volumetric flask in the same manner as in the measurement of the apparent density described above, and the mass of isopropyl alcohol was precisely weighed, and the true density D 0(g/cm3 of the hollow particles was calculated based on the following formula (II).
Formula (II)
True density D 0 = [ mass of fragments of hollow particles ]/(100- [ mass of isopropyl alcohol ]/[ specific gravity of isopropyl alcohol at measurement temperature ])
The true density D 0 corresponds to the specific gravity of only the shell portion of the hollow particles. As is apparent from the above measurement method, the hollow portion is not regarded as a part of the hollow particles when the true density D 0 is calculated.
The porosity (%) of the hollow particles is calculated from the apparent density D 1 and the true density D 0 of the hollow particles by the following formula (III).
Formula (III)
Porosity (%) =100- (apparent density D 1/true density D 0) ×100
The lower limit of the volume average particle diameter of the hollow particles of the present invention is preferably 1.0 μm or more, more preferably 1.5 μm or more, and still more preferably 2.0 μm or more. On the other hand, the upper limit of the volume average particle diameter of the hollow particles is preferably 10.0 μm or less, more preferably 8.0 μm or less, and still more preferably 6.0 μm or less. When the volume average particle diameter of the hollow particles is equal to or larger than the lower limit, the hollow particles have a smaller cohesiveness to each other, and therefore excellent dispersibility can be exhibited. When the volume average particle diameter of the hollow particles is not more than the upper limit, the variation in the shell thickness is suppressed, a uniform shell is easily formed, and the hollow particles are not easily broken, so that the hollow particles have high mechanical strength. The hollow particles having a volume average particle diameter in the above range have a sufficiently small particle diameter, and therefore, are preferably used as a substrate material for electronic circuit boards and the like, and can be added to small-sized substrates having a small thickness.
The shape of the hollow particles of the present invention is not particularly limited as long as the hollow portion is formed inside, and examples thereof include spherical, ellipsoidal, irregular shapes, and the like. Among these, a spherical shape is preferable from the viewpoint of ease of production.
The hollow particles of the present invention may have one or two or more hollow portions, and preferably have only one hollow portion in order to maintain a good balance between high porosity and mechanical strength and to improve dielectric characteristics. In addition, the shell of the hollow particles of the present invention and the partition wall that separates adjacent hollow portions in the case of having two or more hollow portions may be porous, and are preferably dense in terms of improving dielectric characteristics and solvent resistance.
The hollow particles of the present invention may have an average roundness of 0.950 to 0.995.
An example of the shape of the hollow particle of the present invention is a bag formed of a thin film and inflated with a gas, and the cross-sectional view thereof is shown as hollow particle 10 in fig. 1 (5). In this example, a thin film is provided on the outside, and the inside thereof is filled with gas.
The particle shape can be confirmed by SEM or TEM, for example.
The particle size distribution (volume average particle diameter (Dv)/number average particle diameter (Dn)) of the hollow particles may be, for example, 1.1 to 2.5. By setting the particle size distribution to 2.5 or less, particles having small variation in compressive strength characteristics and heat resistance among particles can be obtained. Further, by setting the particle size distribution to 2.5 or less, for example, when a sheet-like resin molded article is produced, a product having a uniform thickness can be produced.
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the hollow particles can be measured, for example, by a particle size distribution measuring apparatus, and the number average and the volume average thereof can be calculated, respectively, and the obtained values are used as the number average particle diameter (Dn) and the volume average particle diameter (Dv) of the particles. The particle size distribution is a value obtained by dividing the volume average particle diameter by the number average particle diameter.
Examples of the use of the hollow particles of the present invention include use as an additive in low dielectric materials, heat insulating materials, soundproof materials, light reflecting materials, and other members used in various fields such as automobiles, electric, electronic, construction, aviation, and aerospace, food containers, sports shoes, shoes such as sandals, household electrical appliance parts, bicycle parts, stationery, tools, and filaments (filaments) of 3D printers. The hollow particles of the present invention are particularly preferably used as an additive for achieving a low dielectric constant or a low transmission loss in the field of electric or electronic because of excellent dielectric characteristics and solvent resistance. For example, the hollow particles of the present invention are preferably used as a material for an electronic circuit board, and specifically, by containing the hollow particles of the present invention in an insulating resin layer of an electronic circuit board, the relative dielectric constant of the insulating resin layer can be reduced, and the transmission loss of the electronic circuit board can be reduced.
The hollow particles of the present invention are preferably used as additives in semiconductor materials such as interlayer insulating materials, dry film resists, solder resists, bonding wires, magnet wires (MAGNET WIRE), semiconductor sealing materials, epoxy sealing materials, molding underfills, underfills (undershoots), die bond paste (die bond paste), buffer coating materials, copper clad laminates, flexible substrates, high frequency device modules, antenna modules, and vehicle radar. Among these, particularly preferred are interlayer insulating materials, solder resists, magnet wires, epoxy sealing materials, underfill materials, buffer coating materials, copper clad laminates, flexible substrates, high frequency device modules, antenna modules, vehicle-mounted radars, and other semiconductor materials.
In addition, the hollow particles of the present invention have high porosity, are not easily broken, and are excellent in heat resistance, and therefore satisfy the heat insulation property and cushioning property (cushiony property) required for the primer material, and also satisfy heat resistance suitable for use in thermal paper. The hollow particles of the present invention are also useful as plastic pigments excellent in gloss, hiding power, and the like.
Further, the hollow particles of the present invention can be used for various applications depending on the components contained therein, because useful components such as fragrances, chemicals, agricultural chemicals, ink components, and the like can be enclosed therein by a method such as impregnation treatment, reduced pressure, or pressurized impregnation treatment.
3. Resin composition
The resin composition of the present invention contains the hollow particles of the present invention described above and a matrix resin.
The hollow particles of the present invention are excellent in solvent resistance, and therefore, if the resin composition of the present invention further contains an organic solvent, the hollow particles of the present invention are excellent in the effects of lowering the dielectric constant and lowering the dielectric loss tangent when the resin composition of the present invention is formed into a molded article, and are therefore preferable.
The matrix resin used in the liquid resin composition of the present invention is not particularly limited, and examples thereof include curable resins such as thermosetting resins, photocurable resins, and ambient temperature curable resins, and thermoplastic resins. The matrix resin used by dispersing or dissolving in an organic solvent is preferable, and the thermosetting resin is particularly preferable, in view of the ease of exhibiting the effects of lowering the dielectric constant and lowering the dielectric loss tangent due to the hollow particles of the present invention.
The matrix resin contained in the resin composition of the present invention may be an unreacted monomer, a prepolymer or a macromer, may be a polymer, or may be a precursor of a cured resin such as polyamide acid. The matrix resin contained in the resin composition of the present invention functions as a binder (adhesive) by curing with heat, light, a curing agent, a polymerization initiator, a catalyst, or the like, for example.
The thermosetting resin may be any known thermosetting resin, and examples thereof include, but are not particularly limited to, phenol resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, polyurethane resins, silicone resins, alkyd resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, and benzonitrile resinsOxazine-based resins, allyl-based resins, aniline-based resins, maleimide-based resins, bismaleimide-triazine-based resins, liquid-crystalline polyester-based resins, vinyl ester-based resins, unsaturated polyester-based resins, cyanate-based resins, polyether-imide resins, and precursors of these resins before curing. These thermosetting resins may be used singly or in combination of two or more.
The thermosetting resin is preferably used together with a curing agent or a curing catalyst such as an amine, an acid anhydride, or an imidazole, depending on the type of the resin. As the curing agent (radical initiator) for the heat-curable modified polyphenylene ether, for example, organic peroxides such as 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane, di-t-butylperoxy, dicumyl peroxide, benzoyl peroxide, 1, 3-bis (2-t-butylperoxy isopropyl) benzene and 2, 5-dimethyl-2, 5-di-t-butylperoxy hexyne can be preferably used.
Examples of the room temperature curable resin include epoxy adhesives, silicone adhesives, acrylic adhesives, and adhesives that can be cured at room temperature by adding a catalyst.
Examples of the thermoplastic resin include polyolefin resins, polyamide resins, polycarbonate resins, polyphenylene sulfide resins, polyether ether ketone resins, polystyrene resins, polyphenylene oxide resins, and Liquid Crystal Polymers (LCP).
These matrix resins can be used singly or in combination of two or more.
In applications requiring low dielectric constant and low dielectric loss tangent, epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, silicone resin, and benzo resin are particularly preferably used as the base resinInsulating resins such as oxazine-based resins, melamine-based resins, urea-based resins, allyl-based resins, phenol-based resins, unsaturated polyester-based resins, polyurethane-based resins, and aniline-based resins, and epoxy-based resins, thermosetting polyimide-based resins, modified polyphenylene ether-based resins, silicone-based resins, and benzo/>And oxazine-based resins and melamine-based resins. These insulating resins may be used singly or in combination of two or more.
In addition, from the viewpoint of easily exhibiting the effects of low dielectric constant and low dielectric loss tangent by the hollow particles of the present invention, the resin composition of the present invention is preferably a toluene-soluble matrix resin and a resin composition containing toluene as an organic solvent. Examples of the toluene-soluble base resin include a thermosetting modified polyphenylene ether resin and a thermosetting epoxy resin.
The content of the matrix resin in 100 mass% of the total solid content of the resin composition of the present invention is not particularly limited, and is preferably 50 to 95 mass%. When the content of the matrix resin is not less than the above lower limit, the moldability of the resin composition in the production of a resin molded article is excellent, and the obtained resin molded article has excellent mechanical strength. On the other hand, by setting the content of the matrix resin to the above upper limit or less, the hollow particles of the present invention can be sufficiently contained, and therefore, the effects such as low dielectric constant and low dielectric loss tangent due to the hollow particles of the present invention can be sufficiently exhibited.
In the present invention, when the matrix resin is a resin or the like used together with an additive for curing a resin such as a curing agent and a curing catalyst, the content of the additive is also included in the content of the matrix resin.
The content of the hollow particles of the present invention is not particularly limited, but is preferably 5 to 50 mass% based on 100 mass% of the total solid content of the resin composition of the present invention. By setting the content of the hollow particles to the above lower limit or more, the effects of the hollow particles of the present invention such as low dielectric constant and low dielectric loss tangent can be sufficiently exhibited. On the other hand, when the content of the hollow particles is not more than the above-mentioned upper limit, the matrix resin can be sufficiently contained, and thus moldability and mechanical strength can be improved.
The resin composition of the present invention preferably contains an organic solvent, more preferably at least toluene as an organic solvent, in a state before the production of a molded article, from the viewpoint of easily exhibiting the effects of low dielectric constant and low dielectric loss tangent due to the hollow particles of the present invention.
The resin composition of the present invention may contain an organic solvent other than toluene, and may contain an organic solvent appropriately selected according to the type of the matrix resin. Among these, the organic solvent contained in the resin composition of the present invention preferably contains at least toluene and is composed of an aromatic hydrocarbon solvent, particularly preferably toluene, from the viewpoint of easily exhibiting the effects of lowering the dielectric constant and lowering the dielectric loss tangent by the hollow particles of the present invention.
When the resin composition of the present invention contains an organic solvent, the content of the organic solvent is not particularly limited, and may be, for example, 10 to 100 parts by mass or 20 to 50 parts by mass relative to 100 parts by mass of the base resin.
The resin composition of the present invention may contain additives such as ultraviolet absorbers, colorants, heat stabilizers, fillers, and flame retardants, as necessary, in addition to the hollow particles of the present invention and the matrix resin, within a range that does not impair the effects of the present invention.
The resin composition of the present invention may contain organic or inorganic fibers such as carbon fibers, glass fibers, aramid fibers, and polyethylene fibers when a molded article is produced.
As a method for producing the resin composition of the present invention, there is a method comprising a step of mixing the hollow particles obtained by the production method of the present invention described above with a matrix resin.
The liquid resin composition of the present invention is obtained by, for example, mixing the hollow particles of the present invention, the matrix resin, and further optionally added organic solvents, additives, and the like.
The resin composition of the present invention can be used as a molded body.
The molded article of the resin composition of the present invention may be produced into a molded article by curing a liquid resin composition into a desired shape, or a molded article may be produced by heating a resin composition containing the hollow particles of the present invention and a thermoplastic resin, melting the thermoplastic resin, and melt-kneading and molding the same.
In addition, in the molded article of the resin composition, the matrix resin is a cured product. The matrix resin of the cured product is a resin cured by a chemical reaction or not, and examples thereof include a resin cured by a curing reaction, a resin cured by drying, a resin cured by cooling a thermoplastic resin, and the like. The molded article obtained using the above resin composition contains, as a base resin, a cured product of a resin cured with a curing agent, a polymerization initiator, a catalyst, or the like as necessary. In this case, the matrix resin may contain a curing agent or the like. The molded article obtained by melt-kneading and molding the hollow particles of the present invention with a thermoplastic resin contains a cured product of the thermoplastic resin which is cured by cooling, as a matrix resin.
The thermoplastic resin used for melt kneading and molding the resin composition containing the hollow particles of the present invention and the thermoplastic resin can be any known thermoplastic resin, and examples thereof include: polyolefins such as polypropylene and polyethylene; polyamides such as PA6, PA66, PA12, and the like; polyimide, polyamideimide, polyetherimide, polyetherketoneketone, polyvinylchloride, polystyrene, poly (meth) acrylate, polycarbonate, polyvinylidene fluoride, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polyphenylene oxide, polyphenylene sulfide, polyester, polytetrafluoroethylene, thermoplastic elastomer, and the like. These thermoplastic resins can be used singly or in combination of two or more kinds.
The resin molded article as a molded article of the resin composition of the present invention is excellent in dielectric characteristics by containing the hollow particles of the present invention.
The resin molded article of the present invention preferably has a relative dielectric constant of 2.50 or less, more preferably 2.40 or less, and still more preferably 2.30 or less at a frequency of 1 GHz. The lower limit of the relative dielectric constant of the resin molded body of the present invention is not particularly limited, but is usually 1.00 or more when the frequency is 1 GHz.
The dielectric loss tangent of the resin molded article of the present invention at a frequency of 1GHz is preferably 0.010 (1.0X10 -2) or less, more preferably 5.0X10- -3 or less, and still more preferably 4.5X10- -3 or less. The lower limit of the dielectric loss tangent of the resin molded article of the present invention at a frequency of 1GHz is not particularly limited, and may be, for example, 1.0X10 -5 or more.
In the present invention, the relative permittivity and dielectric loss tangent of the resin molded article were measured in accordance with JIS C2565 using a disturbance type measuring device under the condition that the measurement frequency was 1 GHz.
As a method for producing a molded article from the liquid resin composition of the present invention, for example, the following methods can be mentioned: the liquid resin composition of the present invention is applied to a support, dried as necessary, and then cured by heating.
Examples of the material of the support include: resins such as polyethylene terephthalate and polyethylene naphthalate; copper, aluminum, nickel, chromium, gold, silver, and the like.
As a method of applying the liquid resin composition, known methods can be used, and examples thereof include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.
In the case where the resin composition contains an organic solvent, it is preferable to dry the resin composition after the above-mentioned application. The drying temperature is preferably a temperature to the extent that the resin composition is not cured, usually 20 ℃ to 200 ℃, preferably 30 ℃ to 150 ℃ from the viewpoint of removing the organic solvent in an uncured or semi-cured state of the resin composition. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.
The temperature of heating for curing the resin composition is not particularly limited, and is usually 30℃or higher and 400℃or lower, preferably 70℃or higher and 300℃or lower, more preferably 100℃or higher and 200℃or lower, in the case where the resin composition contains a thermosetting resin. The curing time is 5 minutes to 5 hours, preferably 30 minutes to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven or the like.
As a method for melt-kneading a resin composition comprising the hollow particles of the present invention and a thermoplastic resin to obtain a molded article, for example, the following method can be mentioned: after melt-kneading the particulate resin composition, the resultant is molded into a desired shape by a known molding method such as extrusion molding, injection molding, compression molding, or compression molding. The temperature at the time of melt kneading is not particularly limited as long as it is a temperature at which the thermoplastic resin used can be melted. The kneading can be performed by a known method, but is not particularly limited, and can be performed using a kneading apparatus such as a single-shaft kneader or a twin-shaft kneader.
The shape of the resin molded article of the present invention is not particularly limited, and may be any of various shapes that can be molded using the resin composition of the present invention, and may be, for example, any of a sheet-like shape, a film-like shape, a plate-like shape, a tubular shape, and other various three-dimensional shapes. In addition, when the resin molded body contains fibers, the fibers in the resin molded body may be nonwoven fabric-like. In the case where the resin molded article contains fibers, the hollow particle resin composition of the present invention may be added to a fiber-reinforced plastic containing the above-mentioned resin and fibers.
Examples of the use of the resin composition and the molded article of the present invention include the use in which the resin composition can be used in the use of the hollow particles of the present invention.
Examples
The present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and% are based on mass.
Example 1
(1) Preparation of the Mixed solution
First, the following materials were mixed to prepare an oil phase.
DVB960 (trade name, manufactured by Nitro Chemicals Co., ltd., 96% divinylbenzene, 4% ethylvinylbenzene) 38.7 parts
0.89 Part of t-butyl peroxydiethylacetate (oil-soluble polymerization initiator, trade name: trigonox27, manufactured by Nouo chemical Co., ltd.)
0.05 Part of abietic acid (softening point is above 150 ℃, acid value is 150-160 mgKOH/g)
Hydrophobic solvent: 61.3 parts of heptane (solubility in water at 20 ℃ C.: 2.2 mg/L)
Next, an aqueous solution of magnesium hydroxide colloid (water-insoluble metal hydroxide colloid) (10 parts of magnesium hydroxide) was prepared by adding slowly, with stirring, an aqueous solution of 13.72 parts of sodium hydroxide (alkali metal hydroxide) dissolved in 55 parts of ion-exchanged water to an aqueous solution of 19.59 parts of magnesium chloride (water-soluble polyvalent metal salt) dissolved in 225 parts of ion-exchanged water in a stirring tank.
The resulting aqueous phase was mixed with the oil phase to prepare a mixed solution.
(2) Suspension step
A suspension in which droplets of the monomer composition containing heptane were dispersed in water was prepared by suspending the mixture obtained in the above-described mixture preparation step using a pipeline emulsifying disperser (trade name: cavitron, manufactured by Kyowa Kagaku Co., ltd.) at a rotor peripheral speed of 40 m/s.
(3) Polymerization step
The suspension obtained in the above-mentioned suspension step was heated to 80℃in a nitrogen atmosphere, and after 1 hour from the time when the temperature reached 80℃was reached, 5 parts of Methyl Ethyl Ketone (MEK) (solubility in water at 20℃:275 g/L) as a reaction-promoting additive solution was added to the suspension, followed by stirring at 80℃for 24 hours, and then polymerization was carried out. By this polymerization reaction, a precursor composition of a slurry liquid in which the precursor particles containing the hydrophobic solvent are dispersed in water is obtained.
(4) Cleaning step and solid-liquid separation step
The precursor composition obtained in the polymerization step was washed with dilute sulfuric acid (25 ℃ C., 10 minutes) to a pH of 5.5 or less. Next, after separating the water by filtration, 200 parts of ion-exchanged water was newly added to make the slurry again, and water washing treatment (washing, filtration, dehydration) was repeated several times at room temperature (25 ℃) to obtain a solid component by filtration and separation. The obtained solid component was dried at a temperature of 40 ℃ by a dryer to obtain precursor particles having a hydrophobic solvent enclosed therein.
(5) Solvent removal step
The precursor particles obtained in the above-mentioned solid-liquid separation step were subjected to a heating treatment for 6 hours under vacuum conditions of 200 ℃ by a vacuum dryer, whereby the hydrophobic solvent entrapped in the particles was removed, to obtain hollow particles of example 1. The obtained hollow particles were confirmed to be spherical and have a hollow portion based on the observation result of a scanning electron microscope and the value of porosity.
Example 2
In example 1, hollow particles of example 2 were produced in the same manner as in example 1, except that 5 parts of ethyl acetate (solubility in water at 20 ℃ C.: 83 g/L) was added as a reaction-promoting additive solution in the above-mentioned "(3) polymerization step" instead of 5 parts of MEK.
Example 3
In example 1, hollow particles of example 3 were produced in the same manner as in example 1, except that the amount of MEK added was changed from 5 parts to 2 parts as a reaction promoting additive in the above "(3) polymerization step".
Example 4
In example 1, hollow particles of example 4 were produced in the same manner as in example 1, except that the timing of adding the reaction-promoting additive liquid was changed from when the reaction time had elapsed after the reaction time had reached 80 ℃ to when the reaction time had elapsed after the reaction time had reached 80 ℃ and 8 hours had elapsed in the polymerization step "(3).
Example 5
In example 1, hollow particles of example 5 were produced in the same manner as in example 1, except that the amount of DVB960 added was changed from 38.7 parts to 36.7 parts in the "(1) mixed solution preparation step", and 2 parts of Allyl Methacrylate (AMA) (solubility in water at 20 ℃ c.: 2.2 g/L) was further added in the "(3) polymerization step" instead of 5 parts of MEK.
Example 6
In example 1, hollow particles of example 6 were produced in the same manner as in example 1 except that the amount of MEK added was changed from 5 parts to 10 parts in the above "(3) polymerization step".
Example 7
In example 1, hollow particles of example 7 were produced in the same manner as in example 1 except that the amount of DVB960 added was changed from 38.7 parts to 49.6 parts in the above-described "(1) mixed solution preparation step", and the amount of polymerization initiator added and the amount of heptane added were changed according to table 2.
Example 8
In example 1, hollow particles of example 8 were produced in the same manner as in example 1 except that the amount of DVB960 added was changed from 38.7 parts to 33.0 parts in the above-mentioned "(1) mixed solution preparation step", and the amount of polymerization initiator added and the amount of heptane added were changed according to table 2.
Example 9
In example 1, hollow particles of example 9 were produced in the same manner as in example 1 except that the amount of DVB960 added in the "step of preparing a mixed solution of" (1) was changed from 38.7 parts to 37.7 parts, and 1.0 part of styrene was further added.
Example 10
In example 1, hollow particles of example 10 were produced in the same manner as in example 1, except that the amount of DVB960 added in the mixed solution preparation step "in the above" (1) was changed from 38.7 parts to 32.7 parts, and 6.0 parts of styrene was further added.
Example 11
In example 1, hollow particles of example 11 were produced in the same manner as in example 1 except that the amount of DVB960 added in the mixed solution preparation step "in the above" (1) was changed from 38.7 parts to 28.7 parts, and 10.0 parts of styrene was further added.
Example 12
In example 1, hollow particles of example 12 were produced in the same manner as in example 1, except that 5 parts of 3-pentanone (solubility in water at 20 ℃ C.: 47 g/L) was added as a reaction promoting additive solution in the above-mentioned "(3) polymerization step" instead of 5 parts of MEK.
Example 13
In example 1, hollow particles of example 13 were produced in the same manner as in example 1 except that 5 parts of methyl acetate (solubility in water at 20 ℃ C.: 250 g/L) was added as a reaction-promoting additive solution in the above-mentioned "(3) polymerization step" instead of 5 parts of MEK.
Example 14
In example 1, hollow particles of example 14 were produced in the same manner as in example 1, except that the amount of DVB960 added was changed from 38.7 parts to 36.7 parts in the above "(1) mixed solution preparation step", and 2 parts of methyl methacrylate (solubility in water at 20 ℃ C.: 15.9 g/L) was added as a reaction-promoting additive solution in the above "(3) polymerization step", instead of 5 parts of MEK.
Example 15
In example 1, hollow particles of example 15 were produced in the same manner as in example 1, except that in the above-mentioned "(1) mixed solution preparation step", the addition amount of DVB960 was changed from 38.7 parts to 36.7 parts, and in the above-mentioned "(3) polymerization step", 2 parts of t-butylaminoethyl methacrylate (solubility in water at 20 ℃ C.: 18 g/L) was added as a reaction-promoting additive solution in place of 5 parts of MEK.
Comparative example 1
In example 1, hollow particles of comparative example 1 were produced in the same manner as in example 1 except that the reaction promoting additive liquid was not added in the above "(3) polymerization step".
Comparative example 2
In example 1, hollow particles of comparative example 2 were produced in the same manner as in example 1 except that the timing of adding the reaction-promoting additive liquid was changed from the timing when the temperature had reached 80℃and the timing had elapsed from the time when the temperature had increased in the polymerization step "(3)".
Comparative example 3
In example 1, hollow particles of comparative example 3 were produced in the same manner as in example 1, except that the amount of DVB960 added was changed from 38.7 parts to 33.7 parts in the "(1) mixed solution preparation step", the amount of polymerization initiator added was changed according to table 3, and 5 parts of styrene (St) (solubility in water at 20 ℃ c.: 0.3 g/L) was further added in the "(3) polymerization step" instead of 5 parts of MEK.
Comparative example 4
Hollow particles of comparative example 4 were produced in the same manner as in example 1 of patent document 2.
That is, 1.15 parts of styrene, 1.85 parts of DVB810 (trade name, manufactured by Nitro chemical Co., ltd., 81% of divinylbenzene, 19% of ethylvinylbenzene), 2.4 parts of heptane, 0.3 part of HS CRYSTA 4100 (trade name, side chain crystalline polyolefin, manufactured by Feng Guo oil Co., ltd.), 0.3 part of BLEMER-50 PEP-300 (trade name, polyethylene glycol propylene glycol monomethacrylate, manufactured by Nitro oil Co., ltd.), and 0.099 part of PEROYL L (trade name, polymerization initiator, manufactured by Nitro oil Co., ltd.) were mixed to prepare an oil phase.
Then, 34 parts of ion-exchanged water and 0.017 parts of RAPISOL A-80 (surfactant, daily oil Co., ltd.) were mixed to prepare an aqueous phase.
The oil phase was added to the aqueous phase and the suspension was prepared using an ultrasonic homogenizer. The resulting suspension was heated at 70℃for 4 hours, whereby polymerization was carried out to obtain a slurry. The resulting slurry was heated at 100℃for 24 hours, thereby obtaining hollow particles of comparative example 4.
< Determination of polymerization conversion >
In the polymerization steps of examples and comparative examples, 50g of a suspension of the reaction-promoting additive liquid was collected and subjected to pressure filtration to obtain particles (including moisture and a hydrophobic solvent) contained in the suspension.
About 3g of the above particles obtained by pressure filtration were collected, 27g of ethyl acetate was added, and after stirring for 15 minutes, 13g of methanol was added and further stirred for 10 minutes. The obtained solution was allowed to stand to precipitate insoluble components, and a supernatant of the solution was collected as a sample for measurement. 2. Mu.L of the measurement sample was injected into a gas chromatograph, and the amount of the polymerizable monomer in the measurement sample was quantified by Gas Chromatography (GC) under the following conditions, and the amount was taken as the mass of the unreacted polymerizable monomer when the reaction-promoting additive was added.
The particles obtained by the pressure filtration were dried at 200℃for 2 hours, whereby the water and the hydrophobic solvent were removed, and the mass of the solid content of the particles produced when the reaction-promoting additive liquid was added was determined.
Then, the polymerization conversion was calculated by the following formula (B).
Formula (B):
Polymerization conversion (mass%) =100- { mass of unreacted polymerizable monomer/(mass of solid component of particles produced when the reaction-promoting additive liquid was added+mass of unreacted polymerizable monomer) } ×100
Condition of GC
Chromatographic column: TC-WAX (0.25 mm. Times.30 m)
Chromatographic column temperature: 80 DEG C
Injection temperature: 200 DEG C
FID detection side temperature: 200 DEG C
[ Evaluation ]
The hollow particles obtained in each example and each comparative example were subjected to the following measurement and evaluation. The results are shown in tables 1 to 3.
1. Density and porosity of hollow particles
1-1 Measurement of apparent Density of hollow particles
First, hollow particles of about 30cm 3 were filled in a volumetric flask having a capacity of 100cm 3, and the mass of the filled hollow particles was precisely weighed. Next, the volumetric flask filled with the hollow particles was filled with isopropyl alcohol to the scale mark accurately while taking care not to mix with air bubbles. The mass of isopropyl alcohol added to the volumetric flask was precisely weighed, and the apparent density D 1(g/cm3 of the hollow particles was calculated based on the following formula (I).
Formula (I)
Apparent density D 1 = [ mass of hollow particles ]/(100- [ mass of isopropyl alcohol ]/[ specific gravity of isopropyl alcohol at measurement temperature ])
1-2 Measurement of the true Density of hollow particles
After the hollow particles were pulverized in advance, a volumetric flask having a capacity of 100cm 3 was filled with about 10g of fragments of the hollow particles, and the mass of the filled fragments was precisely weighed.
Then, isopropyl alcohol was added to a volumetric flask in the same manner as in the measurement of the apparent density described above, and the mass of isopropyl alcohol was precisely weighed, and the true density D 0(g/cm3 of the hollow particles was calculated based on the following formula (II).
Formula (II)
True density D 0 = [ mass of fragments of hollow particles ]/(100- [ mass of isopropyl alcohol ]/[ specific gravity of isopropyl alcohol at measurement temperature ])
1-3 Calculation of porosity
The porosity of the hollow particles is calculated based on the following formula (III) from the apparent density D 1 and the true density D 0 of the hollow particles.
Formula (III)
Porosity (%) =100- (apparent density D 1/true density D 0) ×100
2. Measurement of volume average particle diameter (Dv) and number average particle diameter (Dn) and calculation of particle diameter distribution (Dv/Dn)
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the hollow particles were measured by a particle size distribution measuring machine (trade name: multisizer 4e, manufactured by Beckmann coulter Co., ltd.) to calculate a particle size distribution (Dv/Dn). The measurement conditions were pore diameter: 50 μm, dispersion medium: ISOTON II (trade name), concentration 10%, number of particles measured: 100000.
Specifically, 0.2g of a particle sample was taken in a beaker, and an aqueous surfactant solution (trade name: DRIHEL, manufactured by Fuji film Co., ltd.) was added thereto as a dispersant. Further, 2ml of a dispersion medium was added thereto to wet the particles, 10ml of the dispersion medium was added thereto, and after dispersing for 1 minute by an ultrasonic disperser, the measurement was performed by the particle size distribution measuring machine.
3. Determination of the relative permittivity (Dk) and dielectric loss tangent (Df) of hollow particles
The relative permittivity and dielectric loss tangent of the hollow particles were measured at a frequency of 1GHz and at room temperature (25 ℃) using a disturbance type measuring device (model number ADMS N.C. manufactured by AET Co., ltd.).
4. Impregnation test (toluene solvent resistance)
0.1Mg of the hollow particles was added to 4mL of toluene at 25℃and the mixture was shaken for 10 minutes at a shaking speed of 100rpm using a shaker, and the mixture was allowed to stand for 48 hours to determine the proportion of the precipitated hollow particles, and the mixture was evaluated on the basis of the following evaluation. The hollow particles precipitated in toluene were separated by a centrifuge, dried, and the mass of the hollow particles precipitated in toluene was measured. The proportion of the mass of the hollow particles precipitated in toluene to the mass of the whole hollow particles immersed in toluene was calculated, and the proportion of the precipitated hollow particles was obtained.
(Evaluation criterion of immersion test)
AA: the precipitated hollow particles are less than 1 mass%
A: the precipitated hollow particles are 1 mass% or more and less than 3 mass%
B: the precipitated hollow particles are 3 mass% or more and less than 5 mass%
C: the precipitated hollow particles are 5 mass% or more
5. Determination of the relative permittivity (Dk) and dielectric loss tangent (Df) of PPE films comprising hollow particles
5-1 Preparation of PPE film comprising hollow particles
To a cup of a 65% toluene solution of 20g of polyphenylene ether (PPE) (product name: OPE-2200, manufactured by Mitsubishi gas chemical Co., ltd.) were added 1.50g of hollow particles and 0.15g of PERCUMYL (registered trademark) D (manufactured by Nikko Co., ltd.) and uniformly dispersed in a planetary stirring and deaeration device (product name: MAZERUSTAR, manufactured by Cangfu textile Co., ltd.) to obtain a resin composition. An aluminum foil was adhered to a glass plate without wrinkles, and the obtained resin composition was coated on the aluminum foil using a bar coater No.75 to form a coating film. The coating film was heated at 80℃for 1 hour, 120℃for 30 minutes, and 160℃for 1 hour in this order in a nitrogen atmosphere, and cured to form a PPE film containing hollow particles on an aluminum foil. The laminate of the film and aluminum foil was immersed in a 1N predetermined aqueous hydrochloric acid solution to remove the aluminum foil, thereby obtaining only the film. The obtained film was washed with ion-exchanged water and dried, thereby obtaining a PPE film containing hollow particles.
5-2 Measurement of relative permittivity (Dk) and dielectric loss tangent (Df) of film
The PPE film containing hollow particles obtained in the above was cut to a width of 3mm and a length of 80mm to obtain a measurement sample. The relative permittivity and dielectric loss tangent of the hollow particle-containing PPE film were measured under conditions of a frequency of 1GHz and room temperature (25 ℃) using a disturbance type measuring device (model: ADMS N.C. manufactured by AET Co., ltd.) in accordance with JIS C2565.
Further, as reference example 1, the relative permittivity and dielectric loss tangent were measured similarly for PPE films containing no hollow particles.
TABLE 1
TABLE 2
TABLE 3
In tables 1 to 3, for simplicity, the values of dielectric loss tangent (Df) are marked with an index prescribed in JIS X0210. For example, "7.7X10 -4" is labeled "7.7E-04".
Discussion of the related art
The hollow particles obtained in comparative examples 1 to 3 had a porosity of 50% or more, and the shell contained a polymer containing 70 mass% or more of a crosslinkable hydrocarbon monomer unit, and in the impregnation test described above, the hollow particles precipitated in toluene were 5 mass% or more. Therefore, the hollow particles obtained in comparative examples 1 to 3 have low relative permittivity and low dielectric loss tangent, but have poor effect of lowering the permittivity and low dielectric loss tangent of the PPE film. In comparative examples 1 to 3, toluene in the resin composition permeated into the hollow particles during the production of the PPE film, and toluene remained in the hollow particles in the PPE film obtained, and therefore it was estimated that the PPE film could not be sufficiently reduced in dielectric constant and dielectric loss tangent. In comparative example 1, since the reaction-promoting additive liquid was not added in the polymerization step and the crosslinking reaction of the shell was not promoted, it was estimated that a shell excellent in solvent resistance was not formed. In comparative example 2, since the reaction promoting additive solution was added before the polymerization reaction, the effect of promoting the crosslinking reaction of the shell by the reaction promoting additive solution was not exerted, and therefore, it was assumed that a shell excellent in solvent resistance was not formed. In comparative example 3, styrene was added in place of the reaction promoting additive in the polymerization step, but the solubility of styrene in water was low and it was not able to enter the shell, so that the effect of promoting the crosslinking reaction of the shell was not obtained, and it was estimated that a shell excellent in solvent resistance was not formed.
Comparative example 4 corresponds to example 1 of patent document 2, the porosity of the obtained hollow particles is less than 50%, the crosslinkable hydrocarbon monomer unit in the polymer contained in the shell is less than 70% by mass, and in the impregnation test described above, the hollow particles precipitated in toluene are 5% by mass or more. Therefore, the hollow particles obtained in comparative example 4 had a high relative permittivity and dielectric loss tangent and poor solvent resistance, and the PPE film had poor effects of lowering the permittivity and low dielectric loss tangent. The hollow particles obtained in comparative example 4 were low in porosity, high in relative permittivity and dielectric loss tangent, and poor in solvent resistance due to insufficient crosslinking density of the shell. In comparative example 4, since the hollow particles themselves had poor dielectric characteristics and the solvent resistance of the hollow particles was insufficient, toluene in the resin composition permeated into the hollow particles during the production of the PPE film, and toluene remained in the hollow particles in the PPE film obtained, it was estimated that the PPE film was not sufficiently reduced in dielectric constant and low in dielectric loss tangent.
In contrast, the hollow particles obtained in each example had a porosity of 50% or more, and the shell contained a polymer containing 70 mass% or more of crosslinkable hydrocarbon monomer units, and in the immersion test described above, the hollow particles precipitated in toluene were less than 5 mass%, and the relative permittivity and dielectric loss tangent were low, so that the PPE film was excellent in the effect of lowering the permittivity and lowering the dielectric loss tangent. In each example, the content of the crosslinkable hydrocarbon monomer was 70 mass% or more in 100 mass% of the polymerizable monomer contained in the mixed solution, and the reaction-promoting additive solution was added during the polymerization reaction, whereby hollow particles excellent in dielectric characteristics and solvent resistance were obtained. In each example, since the content of the hydrocarbon monomer in the polymerizable monomer is sufficiently large, the shell formed has a resin composition excellent in dielectric characteristics, and since the content of the crosslinkable monomer in the polymerizable monomer is sufficiently large and the crosslinking reaction of the shell is promoted by adding the reaction-promoting additive liquid, a shell having a high crosslinking density is formed, it is inferred that the obtained hollow particle is excellent in dielectric characteristics and solvent resistance.
In addition, in each example, since the hollow particles themselves are excellent in dielectric characteristics and the hollow particles are excellent in solvent resistance, toluene in the resin composition is less likely to penetrate into the hollow particles during the production of the PPE film, and toluene is hardly or not at all left in the hollow particles in the PPE film obtained, and therefore, it is estimated that the effect of making the PPE film low in dielectric constant and low in dielectric loss tangent is excellent.
Description of the reference numerals
1: An aqueous medium;
2: a low polarity material;
4a: a hydrophobic solvent;
4b: materials other than hydrophobic solvents;
6: a shell;
7: a hollow portion;
8: a droplet;
9: precursor particles;
10: hollow particles having hollow portions filled with a gas.
Claims (11)
1. A hollow particle having a shell containing a resin and a hollow portion surrounded by the shell, the hollow particle having a porosity of 50% or more,
The shell contains, as the resin, a polymer containing 70 mass% or more of a crosslinkable hydrocarbon monomer unit,
In the impregnation test, the hollow particles precipitated in toluene are less than 5 mass%,
The impregnation test is as follows: 0.1mg of the hollow particles was added to 4mL of toluene at 25℃and the mixture was allowed to stand for 48 hours after shaking at a shaking speed of 100rpm for 10 minutes.
2. The hollow particle according to claim 1, wherein the dielectric loss tangent at a frequency of 1GHz is 0.0010 or less.
3. The hollow particle of claim 1 or 2, wherein the porosity is 60% or more.
4. The hollow particle according to any one of claims 1 to 3, wherein a volume average particle diameter is 1.0 μm or more and 10.0 μm or less.
5. A method for producing hollow particles having a shell containing a resin and a hollow portion surrounded by the shell, the hollow particles having a porosity of 50% or more,
The method for producing the hollow particles comprises the following steps:
a step of preparing a mixed solution containing a polymerizable monomer, a hydrophobic solvent, a polymerization initiator, a dispersion stabilizer, and an aqueous medium;
A step of preparing a suspension in which droplets of a monomer composition containing the polymerizable monomer, the hydrophobic solvent, and the polymerization initiator are dispersed in the aqueous medium by suspending the mixed solution; and
A step of preparing a precursor composition containing precursor particles having a hollow portion surrounded by a shell containing a resin and enclosing the hydrophobic solvent in the hollow portion by supplying the suspension to a polymerization reaction,
The content of the crosslinkable hydrocarbon monomer in 100 mass% of the polymerizable monomer contained in the mixed solution is 70 mass% or more,
In the step of preparing the precursor composition, after adding a reaction promoting additive solution during the polymerization reaction, the polymerization reaction is further carried out, and as the reaction promoting additive solution, a low molecular compound having a solubility in water of 20 ℃ greater than that of the hydrophobic solvent and 0.5g/L to 1000g/L is used.
6. The method for producing hollow particles according to claim 5, wherein,
When a non-reactive low-molecular compound is added as the reaction promoting additive liquid, the amount of the non-reactive low-molecular compound added is 1 to 20 parts by mass relative to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid,
When a reactive low-molecular compound is added as the reaction promoting additive liquid, the amount of the reactive low-molecular compound added is 1 to 3 parts by mass relative to 100 parts by mass of the total mass of the polymerizable monomer and the hydrophobic solvent contained in the mixed liquid.
7. The method for producing hollow particles according to claim 5 or 6, wherein the reaction-promoting additive solution is added when the polymerization conversion rate of the polymerizable monomer contained in the mixed solution is 40 to 90% in the step of producing the precursor composition.
8. The method for producing hollow particles according to any one of claims 5 to 7, wherein the hydrophobic solvent is a chain hydrocarbon solvent.
9. The method for producing hollow particles according to any one of claims 5 to 8, wherein the polymerization initiator is an organic peroxide.
10. A resin composition comprising the hollow particles according to any one of claims 1 to 4 and a matrix resin.
11. A molded article of a resin composition comprising the hollow particles according to any one of claims 1 to 4 and a matrix resin.
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| JP2021-177264 | 2021-10-29 | ||
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| JP2021177265 | 2021-10-29 | ||
| PCT/JP2022/039609 WO2023074651A1 (en) | 2021-10-29 | 2022-10-25 | Hollow particle, method for producing hollow particle, resin composition, and molded body |
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