JP5534576B2 - Thermally expansible microsphere and method for producing the same, additive and molded article - Google Patents

Description

  The present invention relates to a thermally expandable microsphere whose volume expands by heating, a method for producing the same, and an additive and a molded body using the thermally expandable microsphere. More specifically, the present invention relates to a technique for improving the heat resistance of a thermally expandable microsphere.

  The heat-expandable microsphere is obtained by microcapsulating a volatile foaming agent with an outer shell made of a polymer, and is also called a heat-expandable microcapsule. When producing this thermally expandable microsphere, for example, suspension polymerization of a polymerizable monomer and a polymerizable mixture containing a foaming agent is advanced in an aqueous dispersion medium to enclose the foaming agent. The outer shell (shell) is formed as follows.

  Generally, a thermoplastic resin that has good gas barrier properties and softens when heated is used as the polymer that forms the outer shell of the thermally expandable microsphere. Further, as the blowing agent, generally, a low-boiling point compound such as a hydrocarbon that becomes gaseous at a temperature below the softening point of the polymer forming the outer shell is used.

  When heat-expandable microspheres are heated, the foaming agent is vaporized, and the expansion force acts on the outer shell, and the elastic modulus of the polymer forming the outer shell decreases rapidly. Sudden expansion occurs. This temperature is referred to as “foaming start temperature”. When the heating temperature is equal to or higher than the foaming start temperature, hollow spherical particles (closed cells) are formed by the above-described expansion phenomenon. Thereafter, when the temperature is further increased, the thickness of the outer shell becomes thin and the foaming agent component permeates, so that the internal pressure decreases and the spherical particles contract (sag phenomenon).

  Thermally expandable microspheres are used in a wide range of fields such as designability-imparting agents, functionality-imparting agents, and weight-reducing agents, utilizing the property of expanding to form hollow spherical particles by heating. Yes. On the other hand, conventional heat-expandable microspheres have a narrow foaming start temperature region and start expanding at a relatively low temperature, so that improvement in processing characteristics such as heat resistance is required.

  For example, when used by adding to a synthetic resin such as a thermoplastic resin and a thermosetting resin, if the foaming start temperature is low, it is likely to expand early during processing such as kneading or pelletization before molding. The temperature must be lowered, which limits the types of synthetic resin and rubber that can be applied. For this reason, when applied to synthetic resins, particularly synthetic resins having a high processing temperature such as engineering plastics, the required level of heat-expandable microspheres for heat resistance is high, and there is a strong demand for improving their characteristics.

  Thus, conventionally, thermally expandable microspheres with improved heat resistance have been proposed (see Patent Documents 1 to 3). For example, in the microsphere described in Patent Document 1, the outer shell is composed of a copolymer that forms a polymethacrylimide structure by heating, thereby improving heat resistance and stabilizing foaming behavior.

  In addition, the thermally expandable microcapsules described in Patent Documents 2 and 3 contain a nitrile monomer, a non-nitrile monomer, a metal cation, and a crosslinking agent in order to be usable for calendar molding, extrusion molding, injection molding, and the like. The maximum foaming temperature is set to 200 ° C. or more by forming the outer shell with a vinyl monomer polymer.

International Publication No. 2007/072769 Pamphlet JP 2007-191690 A JP 2008-133366 A

  However, the conventional techniques described above have the following problems. That is, as in the technique described in Patent Document 1, when the outer shell is formed of a thermoplastic resin having excellent heat resistance, the maximum foaming temperature can be increased to about 280 ° C, but it is maintained at 260 to 270 ° C. Therefore, it is difficult to apply to synthetic resins that are processed at higher temperatures.

  Moreover, since the microcapsules described in Patent Documents 2 and 3 contain a metal cation in the outer shell, there are problems such as a decrease in thermal stability, coloring and corrosion. Furthermore, the molded body using the microcapsules containing such metal cations also has a problem that paint peeling is likely to occur.

  Therefore, the present invention is particularly excellent in heat resistance, has a small degree of shrinkage when held at high temperatures, and can be used for processing at high temperatures, and can suppress early foaming, and its production method, additive, and The main purpose is to provide a molded body.

The thermally expandable microsphere according to the present invention is a microsphere in which a volatile foaming agent is encapsulated in an outer shell made of a polymer, and the foaming agent has a 50% distillation temperature of 180 ° C. or higher. use of light iso paraffinic hydrocarbons, in which the foaming start temperature _{(T start)} higher than 230 ° C..
In the present invention, since the foaming agent is a light paraffinic hydrocarbon having a 50% distillation temperature of 180 ° C. or higher, the foaming start temperature and the maximum foaming temperature are higher than before. For this reason, even if it uses for the application processed at high temperature, there is little sag and it is hard to generate | occur | produce early foaming.
This microspheres, for example, the maximum foaming temperature _{(T max)} can the be Turkey and 290 ° C. or higher.
Further, the displacement amount _{d 1} of when held 25 minutes at maximum foaming temperature 50 ° C. lower temperature than _(T max -50 ℃), the ratio of the displacement amount _{d 2} at a maximum foaming temperature _{(T max) (d 1} / D ₂ ) can be 0.7 or more.
Furthermore, the light paraffinic hydrocarbon may be composed of two or more hydrocarbons selected from the group consisting of hydrocarbons having 6 to 13 carbon atoms and hydrocarbons having 15 to 30 carbon atoms.
On the other hand, the polymer constituting the outer shell is, for example, a copolymer having a nitrile group and a carboxyl group, and at least a part of which forms a polymethacrylimide structure by heating, or an acrylonitrile-based polymer.
In that case, the polymer constituting the outer shell may be a copolymer of methacrylonitrile and methacrylic acid.

Method for producing heat-expandable microspheres according to the present invention, in an aqueous dispersion medium containing a dispersion stabilizer, in the presence of 50% distillation temperature is from light iso paraffinic hydrocarbons over 180 ° C. blowing agent Then, by subjecting the polymerizable monomer to suspension polymerization, the foaming agent is enclosed in an outer shell made of a polymer to obtain a thermally expandable microsphere having a foaming start temperature (T _start ) higher than 230 ° C. .
In the present invention, since a light paraffinic hydrocarbon having a 50% distillation temperature of 180 ° C. or higher is used as a foaming agent, a microsphere having both a high foaming start temperature and a maximum foaming temperature can be obtained.
In the manufacturing method of the heat-expandable microsphere, before Symbol light paraffinic hydrocarbons, one or carbons hydrocarbons and carbon number of 6 to 13 is selected from the group consisting of hydrocarbons 15-30 It is desirable that it is composed of two or more hydrocarbons.
Furthermore, as the polymerizable monomer, for example, a nitrile monomer or a mixture of a nitrile monomer and a monomer having a carboxyl group can be used.
In that case, acrylonitrile or methacrylonitrile may be used as the nitrile monomer, and methacrylic acid may be used as the monomer having a carboxyl group.

The additive according to the present invention contains the above-described thermally expanded microsphere.
In the present invention, since it includes a thermally expandable microsphere having a foaming start temperature and a maximum foaming temperature higher than those of conventional ones, even if used for applications processed at high temperatures, there is less sag and early foaming occurs. Hateful.

The molded body according to the present invention contains the above-described thermally expandable microsphere.
In the present invention, a thermally expandable microsphere having a higher foaming start temperature and a maximum foaming temperature than conventional ones is used. Therefore, a molded article stably containing closed cells even when processed at a temperature exceeding 230 ° C. Can be obtained. As a result, it is also possible to produce a foam molded article using engineering plastics such as polyamide, which has been difficult with conventional microspheres.

  According to the present invention, a light paraffinic hydrocarbon having a 50% distillation temperature of 180 ° C. or higher is used as a foaming agent, so that the heat resistance is improved, the degree of shrinkage when kept at a high temperature is reduced, and the high temperature It is possible to suppress the occurrence of early foaming when it is applied to the purpose of processing with the above.

(A) is a side view which shows the structure of the thermally expansible microsphere of this embodiment, (b) is a partial cross section perspective view which shows the internal structure. It is a graph which shows the expansion behavior of a thermally expansible microsphere by taking temperature on a horizontal axis and taking an expansion ratio on a vertical axis. It is a graph which shows the expansion behavior of the microsphere of Example 1, taking temperature on the horizontal axis and taking the amount of displacement on the vertical axis. It is a graph which shows the change of a foaming state when taking a retention time on a horizontal axis | shaft and taking a displacement amount on a vertical axis | shaft and hold | maintaining the microsphere of Example 1 at 270 degreeC.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited to each embodiment shown below.

  As a result of earnest experimental research to solve the above-described problems, the present inventor configures a shell (outer shell) at the processing temperature in order to make the microsphere applicable to processing at a high temperature. It has been found that the elastic modulus of the resin, the expansion pressure of the foaming agent, and the balance thereof are important. On the other hand, in the conventional microspheres (microcapsules) described in Patent Documents 1 to 3 described above, the balance between the elastic modulus of the resin constituting the shell and the expansion pressure of the foaming agent is appropriate within a high temperature range. Therefore, it seems that high-temperature foaming microspheres having a maximum foaming temperature of 290 ° C. or higher could not be realized.

  Therefore, the present inventor examines the balance between the elastic modulus of the resin constituting the shell at a high temperature, particularly higher than 230 ° C., and the expansion pressure of the foaming agent, and by using a specific foaming agent, The present inventors have found that the balance between the elastic modulus of the resin constituting the shell at a high temperature and the expansion pressure of the foaming agent is improved, and the present invention has been achieved. That is, the heat-expandable microsphere according to the present invention is characterized in that a light paraffinic hydrocarbon having a 50% distillation temperature of 180 ° C. or higher is included as a foaming agent in a shell made of a polymer. Thereby, compared with the conventional microsphere, while being able to improve heat resistance, the shrinkage degree at the time of hold | maintaining at high temperature can be made small.

  First, the thermally expandable microsphere according to the first embodiment of the present invention will be described. FIG. 1A is a side view showing the structure of the thermally expandable microsphere of this embodiment, and FIG. 1B is a partially sectional perspective view showing the internal structure. As shown in FIGS. 1A and 1B, the thermally expandable microsphere 1 of this embodiment has a structure in which a foaming agent 3 is enclosed in a shell (outer shell) 2 made of a polymer. ing. And this microsphere 1 expands in volume by heating, and forms a hollow spherical particle.

<Foaming agent 3>
In the microsphere 1 of the present embodiment, a light paraffinic hydrocarbon is used as the foaming agent 3. Since the light paraffinic hydrocarbon is a mixture composed of a plurality of hydrocarbon compounds, the increase in vapor pressure at the time of temperature increase due to heating is slower than that of a single compound. By using this light paraffinic hydrocarbon for the foaming agent 3, rapid gas permeation from the shell 2 can be suppressed, and the degree of contraction during expansion can be reduced.

  The 50% distillation temperature of the light paraffinic hydrocarbon used as the blowing agent 3 is 180 ° C or higher, preferably 230 ° C or higher, more preferably 250 ° C or higher, and particularly preferably 300 ° C or higher. If light paraffinic hydrocarbon having a 50% distillation temperature of less than 180 ° C. is used, the gas resulting from the foaming agent 3 easily passes through the shell 2 and the degree of shrinkage increases. Further, the “50% distillation temperature” here is a value measured based on the atmospheric pressure distillation test method defined in JIS K 2254.

  The light paraffinic hydrocarbon used as the foaming agent 3 is preferably a light isoparaffinic hydrocarbon. Since the isoparaffinic hydrocarbon is branched, the dissipation from the shell 2 is smaller than that of the linear paraffinic hydrocarbon. For this reason, by using light isoparaffinic hydrocarbons, it is possible to further reduce the degree of shrinkage when the microsphere 1 is held at a high temperature.

  Furthermore, the blowing agent 3 is a light paraffinic hydrocarbon composed of two or more hydrocarbons selected from the group consisting of hydrocarbons having 6 to 13 carbon atoms and hydrocarbons having 15 to 30 carbon atoms. It is desirable. In this way, as one of the causative substances of sick house, by using one that does not contain tetradecane, which the Ministry of Health, Labor and Welfare has set the indoor concentration guideline value, as a highly safe material, it can also be used for interior materials, etc. It can be preferably used.

  The light paraffinic hydrocarbon used as the foaming agent 3 is desirably liquid at room temperature from the viewpoint of industrial handling, and is liquid even at 0 ° C. or lower, and further at −20 ° C. or lower. Is more desirable. Light paraffinic hydrocarbons only need to have a 50% distillation temperature of 180 ° C. or higher, can be appropriately selected according to the purpose and application, and can be used in combination of two or more. is there. Furthermore, a light paraffinic hydrocarbon and a chemical foaming agent can be used in combination.

  On the other hand, when the amount of the foaming agent 3 enclosed in the shell 2 is less than 5% by mass with respect to the total mass of the microsphere 1, a sufficient expansion ratio may not be obtained, and 50% by mass. If it exceeds, the thickness of the shell becomes thin, and it becomes easy to loosen. For this reason, it is preferable that the quantity of the foaming agent 3 is 5-50 mass% with respect to the total mass of the microsphere 1, More preferably, it is 7-40 mass%. Thereby, it is possible to obtain a microsphere that is difficult to sag while securing a sufficient expansion ratio. In order to make the amount of the foaming agent 3 within this range, when the microsphere 1 is produced, the blending ratio of the polymerizable monomer constituting the shell 2 and the foaming agent 3 may be adjusted.

<Outer shell>
The shell 2 is preferably formed of a polymer having excellent heat resistance. Examples of such a polymer include a copolymer having a nitrile group and a carboxyl group, and at least a part of these functional groups are cyclized by heating or the like to form a polymethacrylimide structure, and an acrylonitrile-based polymer. Is mentioned.

  The “copolymer in which a polymethacrylimide structure is formed by heating or the like” is obtained by copolymerizing a nitrile monomer and a monomer having a carboxyl group. Examples of the nitrile monomer used at that time include acrylonitrile and methacrylonitrile. If necessary, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, and the like can be used in combination. Examples of the monomer having a carboxyl group include methacrylic acid. If necessary, acrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, etc. may be used in combination. You can also.

  In this copolymer, the molar ratio of acrylonitrile and / or methacrylonitrile and methacrylic acid is preferably 1: 9 to 9: 1, more preferably 1: 7 to 7: 1, more preferably 1: 5 to 5: 1. In addition, when the ratio of acrylonitrile and / or methacrylonitrile is small and the molar ratio to methacrylic acid is less than 1: 9, the granulation property is deteriorated and may be agglomerated during polymerization. On the other hand, when the ratio of acrylonitrile and / or methacrylonitrile is large and the molar ratio with respect to methacrylic acid exceeds 9: 1, the heat resistance is lowered, and thermal yellowing may become remarkable.

  Furthermore, a vinyl monomer may be copolymerized with this copolymer together with a nitrile monomer and a monomer having a carboxyl group. By adding a vinyl monomer, the foaming characteristics of the shell 2 can be adjusted. However, when the proportion of the vinyl monomer exceeds 30% by mass with respect to the total mass of the monomers to be copolymerized, the heat resistance of the shell 2 is lowered, so the blending amount of the vinyl monomer is 0-30. It is desirable to set it as the mass%.

  Examples of the vinyl monomer copolymerizable with a nitrile monomer and a monomer having a carboxyl group include, for example, vinylidene chloride, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid ester such as β-carboxyethyl acrylate, styrene Styrene sulfonic acid or its sodium salt, styrene monomers such as α-methylstyrene and chlorostyrene, monomers that undergo polymerization reaction with radical initiators such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide and the like. These mixtures can be mentioned.

  In the above-described copolymer, the nitrile group and the carboxyl group are cyclized by heating or the like to form a polymethacrylimide structure, so the use of the crosslinkable monomer is not essential, but the crosslinkable monomer is used. In this case, a polyfunctional monomer having two or more polymerizable carbon-carbon double bonds (—C═C—) is preferable. Examples of the polymerizable carbon-carbon double bond include a vinyl group, a methacryl group, an acrylic group, and an allyl group. Moreover, each polymerizable carbon-carbon double bond may be the same or different from each other.

  Examples of the crosslinkable monomer used in the copolymer constituting the shell 2 include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; ethylene glycol diacrylate, diethylene glycol diacrylate, ethylene glycol di Diethylenically unsaturated carboxylic acid esters such as methacrylate and diethylene glycol dimethacrylate, polyethylenically unsaturated carboxylic acid esters such as triethylene glycol diacrylate and triethylene glycol dimethacrylate, 1,4-butanediol, 1,9-nonanediol, etc. And bifunctional cross-linkable monomers such as divinyl compounds such as acrylates or methacrylates derived from both aliphatic terminal alcohols, N, N-divinylaniline, and divinyl ether.

  Examples of other crosslinkable monomers include trifunctional crosslinkable monomers such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and triacryl formal, Examples thereof include tetrafunctional or more cross-linkable monomers such as erythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, triallyl cyanurate or triallyl isocyanurate.

  In addition, when adding a crosslinkable monomer, you may mix and use two or more monomers which are mutually different. However, if the amount of the crosslinkable monomer exceeds 1 mol% per total monomer amount, the foaming ratio of the microsphere 1 is remarkably lowered, so the addition amount of the crosslinkable monomer is 0 to 1 mol%. More preferably, it is 0.4 mol% or less, and particularly preferably 0.3 mol% or less.

  On the other hand, examples of the acrylonitrile-based polymer include a polymer of (meth) acrylonitrile or a copolymer of (meth) acrylonitrile and a vinyl monomer. Here, examples of the vinyl monomer copolymerizable with (meth) acrylonitrile include vinylidene chloride, acrylic acid ester, methacrylic acid ester, styrene, and vinyl acetate.

  Examples of such acrylonitrile-based polymers include (a) at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile: 30 to 100% by mass, and (b) vinylidene chloride and acrylate ester. It is desirable to use a (co) polymer obtained by polymerizing at least one monomer selected from the group consisting of methacrylate ester, styrene and vinyl acetate: 0 to 70% by mass. In addition, when the acrylonitrile-type polymer whose ratio of (meth) acrylonitrile is less than 30 mass% is used, solvent resistance and heat resistance may become inadequate.

  Or, as the acrylonitrile-based polymer, (a-1) at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile: 51 to 100% by mass; and (b-2) vinylidene chloride: 0 (Co) polymer obtained by polymerizing ˜40 mass% and (b-2) at least one monomer selected from the group consisting of acrylic acid ester and methacrylic acid ester: 0 to 48 mass% Can also be used.

  Or, as the acrylonitrile-based polymer, (a-2) at least one monomer selected from the group consisting of acrylonitrile and methacrylonitrile: 80 to 100% by mass, and (b-3) vinylidene chloride, acrylic A (co) polymer obtained by polymerizing at least one monomer selected from the group consisting of acid ester, methacrylate ester, styrene and vinyl acetate: 0 to 20% by mass may be used.

  Next, a method for manufacturing the microsphere 1 having the above-described configuration will be described. The thermally expandable microsphere 1 of the present embodiment is polymerizable in an aqueous dispersion medium containing a dispersion stabilizer in the presence of a foaming agent composed of light paraffinic hydrocarbons having a 50% distillation temperature of 180 ° C. or higher. It can be produced by subjecting the monomer to suspension polymerization.

  Specifically, first, an oily polymerizable monomer mixture containing at least a polymerizable monomer and a light paraffinic hydrocarbon (foaming agent 3) having a 50% distillation temperature of 180 ° C. or higher, an aqueous dispersion medium, And the polymerizable monomer mixture is dispersed in the aqueous dispersion medium to form droplets of the polymerizable monomer mixture. Hereinafter, this process is referred to as “granulation process”.

  It is preferable that the average particle size of the droplets obtained by this granulation step is approximately the same as the average particle size of the target microsphere 1, usually 1 to 500 μm, preferably 3 to 300 μm, particularly preferably 5 ~ 200 μm.

  Further, in order to make the particle size distribution of the obtained microsphere 1 sharper, the aqueous dispersion medium and the polymerizable monomer mixture are supplied into a continuous high-speed rotation high shear type stirring and dispersing machine. It is desirable to continuously stir and disperse both of them, and then inject the resulting dispersion into a polymerization tank and perform suspension polymerization therein.

  On the other hand, the aqueous dispersion medium in which the polymerizable monomer mixture is dispersed is usually prepared by blending a dispersion stabilizer or auxiliary stabilizer with deionized water. Examples of the dispersion stabilizer used in this case include inorganic fine particles such as silica and magnesium hydroxide. Further, examples of the dispersion stabilizer include auxiliary stabilizers such as a condensation product of diethanolamine and an aliphatic dicarboxylic acid, polyvinylpyrrolidone, polyethylene oxide, and various emulsifiers.

  The blending amount of these dispersion stabilizer and dispersion aid is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. If the amount added is less than 0.1% by mass, the droplets may become unstable and granulation may not be possible. Moreover, when these addition amounts exceed 20 mass%, the particle size distribution of the obtained microsphere 1 will become broad, and the ratio of what foams at low temperature may increase.

  One preferred combination of dispersion stabilizers is a combination of colloidal silica and a condensation product. As the condensation product, a condensation product of diethanolamine and an aliphatic dicarboxylic acid is preferable, and a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid is particularly preferable. The acid value of the condensation product is preferably 60 or more and less than 95, and more preferably 65 to 90.

  In addition to these, inorganic salts such as sodium chloride and sodium sulfate may be added. Thereby, the particle shape of the microsphere 1 can be made more uniform. In general, sodium chloride is preferably used as the inorganic salt.

  The amount of colloidal silica added in this case varies depending on the particle diameter, but is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Moreover, a condensation product is normally used in the ratio of 0.05-2 mass parts with respect to 100 mass parts of polymerizable monomers. Furthermore, an inorganic salt is used in the ratio of 0-100 mass parts with respect to 100 mass parts of polymerizable monomers.

  Another preferred combination of the dispersion stabilizer is a combination of colloidal silica and a water-soluble nitrogen-containing material. Among these, a combination of colloidal silica and polyvinylpyrrolidone is preferable.

  Further, magnesium hydroxide and / or calcium phosphate and an emulsifier may be combined. In that case, a hardly water-soluble metal hydroxide obtained by a reaction in a water phase of a water-soluble polyvalent metal salt compound (for example, magnesium chloride) and an alkali metal hydroxide (for example, sodium hydroxide) as a dispersion stabilizer. Colloids of products (eg, magnesium hydroxide) can also be used. Moreover, as calcium phosphate, the reaction product in the aqueous phase of sodium phosphate and calcium chloride can be used. Furthermore, an anionic surfactant such as dialkylsulfosuccinate or polyoxyethylene alkyl (allyl) ether phosphate ester can be used as the emulsifier.

  Subsequently, suspension polymerization of the polymerizable monomer is performed using the polymerizable initiator. The suspension polymerization is carried out by degassing the inside of the reaction vessel or replacing it with an inert gas and raising the temperature to 30 to 100 ° C. Further, during suspension polymerization, the polymerization temperature may be controlled to a constant temperature, or may be raised stepwise. By this suspension polymerization step, the microsphere 1 having a structure in which the foaming agent 3 is enclosed in the shell 2 formed from the produced polymer is obtained.

  The pH of the aqueous phase at the time of polymerization can be appropriately set depending on the type of dispersion stabilizer and auxiliary stabilizer used. For example, when silica such as colloidal silica is used as a dispersion stabilizer, polymerization is performed in an acidic environment. In order to make the aqueous dispersion medium acidic, an acid is added as necessary to adjust the pH of the reaction system to 6 or less, preferably about pH 3 to 4. On the other hand, when a dispersion stabilizer that dissolves in an aqueous dispersion medium in an acidic environment, such as magnesium hydroxide or calcium phosphate, is used, the polymerization is performed in an alkaline environment.

  Moreover, as a polymerization initiator used by suspension polymerization, what is generally used in this technical field can be adopted, but an oil-soluble polymerization initiator that is soluble in a polymerizable monomer is preferable. Examples of such polymerization initiators include dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and azo compounds.

  More specific examples of the polymerization initiator include dialkyl peroxides such as methyl ethyl peroxide, di-t-butyl peroxide, dicumyl peroxide; isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide. Diacyl peroxide such as oxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxy Neodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, (α, α -Bis-neodecanoyl peroxy) diisopropylbenzene, etc. Peroxyester, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl-oxydicarbonate, di-isopropylperoxydicarbonate, di (2-ethylethylperoxy) dicarbonate, di -Peroxydicarbonates such as methoxybutylperoxydicarbonate and di (3-methyl-3-methoxybutylperoxy) dicarbonate; 2,2'-azobisisobutyronitrile, 2,2'-azobis (4 -Methoxy) -2,4-dimethylvaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as 1,1′-azobis (1-cyclohexanecarbonitrile), and the like. it can.

  These polymerization initiators are usually contained in the polymerizable monomer mixture. However, when it is necessary to suppress early polymerization, a part or all of the polymerization initiator is included during or after the granulation step. It may be added to an aqueous dispersion medium and transferred into droplets of a polymerizable monomer mixture. The addition amount of the polymerization initiator is desirably 0.0001 to 3% by mass with respect to the mass of the aqueous dispersion medium. When the addition amount of the polymerization initiator is less than 0.0001% by mass, the polymerization rate decreases and the polymerization time becomes longer, so that the productivity may decrease. When it exceeds 3% by mass, per unit time This is because the polymerization exotherm becomes large and the polymerization is difficult to control.

  Further, in the aqueous dispersion medium, a polymerization aid may be present together with the polymerization initiator described above. Examples of the polymerization aid include alkali metal nitrites, stannous chloride, stannic chloride, ascorbic acids, boric acid and the like. When suspension polymerization is performed in the presence of these compounds, aggregation of polymer particles is suppressed during the polymerization, so that the polymer does not adhere to the polymerization can wall, and the heat generated by the polymerization is efficiently removed. However, a thermally foamable microsphere can be produced stably.

In the case of using an alkali metal nitrite as a polymerization aid, sodium nitrite and potassium nitrite are preferred from the viewpoint of availability and price. Examples of ascorbic acids include alcorbic acid, metal salts of ascorbic acid, and esters of ascorbic acid. Among these, water-soluble ones are preferably used. Among water-soluble ascorbic acids, L-ascorbic acid (vitamin C), sodium ascorbate, and potassium ascorbate are particularly preferable from the viewpoints of availability, price, and effects. The water-soluble alcorbic acid refers to those having a solubility in water at 23 ° C. of 1 g / 100 cm ³ or more.

  The polymerization assistant composed of these compounds is usually added in a proportion of 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer. In addition, when the addition amount of the polymerization aid is 0.001 part by mass, the aggregation of the polymer particles may not be sufficiently suppressed. When the addition amount exceeds 10 parts by mass, the effect of suppressing the polymerization becomes too large. As a result, the foaming performance may be reduced.

  In addition, the order of adding the above-described components to the aqueous dispersion medium is arbitrary, but usually an aqueous dispersion is added to deionized water by adding a dispersion stabilizer and, if necessary, a stabilizing aid or a polymerization aid. Adjust the media. Further, the foaming agent 3, the polymerizable monomer such as the nitrile monomer and the monomer having a carboxyl group, and the vinyl monomer and the crosslinkable monomer which are added as necessary are separately provided. May be added to the aqueous dispersion medium and integrated in the aqueous dispersion medium to form a polymerizable monomer mixture (oil-based mixture). Add to.

  The polymerization initiator can be used by adding to the polymerizable monomer in advance, but when it is necessary to avoid premature polymerization, for example, a polymerizable monomer mixture is added to the aqueous dispersion medium, While stirring, a polymerization initiator may be added and integrated in an aqueous dispersion medium. Alternatively, the polymerizable monomer mixture and the aqueous dispersion medium may be mixed in a separate container and stirred and mixed with a stirrer or disperser having high shearing force, and then charged into the polymerization can.

  After the suspension polymerization process is completed, the reaction mixture containing the produced microsphere 1 is treated by a method such as filtration, centrifugation, or sedimentation to separate the microsphere 1 from the reaction mixture. And the separated microsphere 1 is collect | recovered in the state of a wet cake, after wash | cleaning and filtering. Moreover, the surface of the recovered microsphere 1 can be coated with various materials as necessary.

Next, the expansion characteristic of the thermally expandable microsphere 1 of this embodiment will be described. FIG. 2 is a graph showing the expansion behavior of the thermally expandable microsphere 1 with the temperature on the horizontal axis and the expansion ratio on the vertical axis. As shown in FIG. 2, when the microsphere 1 is heated, the foaming agent 3 is vaporized to increase the internal pressure, the shell 2 is softened, and volume expansion starts. When the heating temperature exceeds the foaming start temperature (T _Start ), the volume of the microsphere 1 continues to increase until a predetermined expansion ratio is reached.

Further, when the microsphere 1 is cooled in this expanded state, the shell 2 is solidified and its shape is maintained. On the other hand, if the temperature exceeds the temperature at which the expansion ratio becomes maximum, that is, the maximum expansion temperature (T _max ), and the heating is continued, the foaming agent 3 leaks from the shell 2 and the internal pressure decreases, so that the microsphere 1 contracts. To do.

In the macrosphere 1 of the present embodiment, since the light paraffinic hydrocarbon having a 50% distillation temperature of 180 ° C. or higher is used as the foaming agent 3, the maximum foaming temperature (T _max ) and foam are higher than those of the conventional products. The starting temperature (T _start ) is high. Specifically, the maximum foaming temperature (T _max ) is 290 ° C. or higher, and the foaming start temperature (T _start ) is higher than 230 ° C. This makes it possible to apply to synthetic resins having a high processing temperature, particularly engineering plastics.

In addition, since light paraffinic hydrocarbons, particularly light isoparaffinic hydrocarbons, are bulky and difficult to leak from the shell 2 after expansion, the microsphere 1 of the present embodiment is at a higher temperature than conventional products. The degree of shrinkage when held is small and it is difficult to sag. Specifically, the ratio (d ₁ / d ₂ ) between the displacement d ₁ when held at 270 ° C. for 20 minutes and the displacement d ₂ at the maximum foaming temperature (T _max ) is 0.3 or more. can do. As a result, when the microsphere 1 is molded by injection molding or the like, it maintains an expanded state even when held for a relatively long time at a high temperature such as in a cylinder or a mold. Can do.

The foaming start temperature (T _start ) in the microsphere 1 of the present embodiment can be arbitrarily set by changing the softening temperature of the shell 2. The softening temperature of the shell 2 can be adjusted by changing the blending ratio of each monomer constituting the polymer. For example, in the case of “a copolymer in which a polymethacrylimide structure is formed by heating”, the softening temperature increases as the ratio of the nitrile group to the carboxyl group approaches equimolar, and the foaming start temperature (T _start ) increases. To rise.

In the case of the “acrylonitrile polymer”, when the ratio of the nitrile monomer is increased, the softening temperature is increased and the foaming start temperature (T _start ) is increased. In order to increase the foaming start temperature (T _start ), it is particularly effective to increase the ratio of methacrylonitrile among nitrile monomers. In addition, what is necessary is just to reduce the ratio of a nitrile type monomer, when lowering foaming start temperature ( _Tstart ).

It is also effective to change the type of light paraffinic hydrocarbon used as the foaming agent 3 to adjust the foaming start temperature (T _start ). By using a light paraffinic hydrocarbon having a higher boiling point, a thermally expandable microsphere having a high foaming start temperature (T _start ) can be obtained.

On the other hand, in the conventional heat-expandable Lee cross fair, when slightly heated at a temperature lower than the foaming start temperature (T _start), but the foaming start temperature (T _start) was observed a phenomenon that decreases, nitrile group and a carboxyl And forming a shell 2 with a copolymer or acrylonitrile polymer in which at least a part of these functional groups are cyclized by heating or the like to form a polymethacrylimide structure. A decrease in temperature (T _start ) can also be prevented.

Thus, in the thermally expansible microsphere 1 of this embodiment, since the light paraffin hydrocarbon whose 50% distillation temperature is 180 degreeC or more is used as the foaming agent 3, it is the largest foaming compared with a conventional product. it is possible to increase the temperature _{(T max)} and foamed start temperature _{(T start),} it is possible to reduce the shrinkage ratio when held at elevated temperatures. Thereby, also in the use processed at high temperature, generation | occurrence | production of an early foaming and a sag can be suppressed effectively. As a result, it can be applied to a synthetic resin that is molded at a high temperature such as an engineering plastic.

  In addition, the thermal expansion microsphere 1 of this embodiment can be used as a foaming agent, or can be mixed with a polymer material to form a composition. Further, it can be melt-kneaded with a thermoplastic resin in an unfoamed state and pelletized, and further blended with a polymer material, paint, ink, etc., and heated and foamed to contain an article (for example, foamed). (Molded article, foamed coating film, foamed ink).

  Next, the additive which concerns on the 2nd Embodiment of this invention is demonstrated. The additive of the present embodiment contains the above-described thermally expandable microspheres of the first embodiment, and includes a polymer material such as a synthetic resin (thermoplastic resin, thermosetting resin) and rubber, a paint, Used for ink, wallpaper, textile materials and various materials. For example, by adding the additive of the present embodiment to these materials, it is possible to achieve weight reduction and porosity, and to impart various functionalities such as slip properties, heat insulation properties, cushion properties, and sound insulation properties. . Furthermore, by using the expansibility of thermally expansible microspheres, it can also be used as paint fillers for automobiles, foaming agents for wallpaper and foamed ink (relief patterns such as T-shirts), and anti-shrinking agents. Can be used.

  Examples of the polymer material in which the additive of the present embodiment is blended include polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyphenylene sulfide (PPS), ABS (acrylic / butadiene / styrene) resin, styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene block copolymer (SIS), hydrogenated SIS, natural rubber, various synthetic rubbers , And thermoplastic polyurethane, but are not limited thereto.

  Moreover, the thermally expandable microsphere contained in the additive of the present embodiment may be in a state expanded by heating or an unexpanded state. Furthermore, in addition to the above-described thermally expandable microspheres, for example, a chemical foaming agent, a glass balloon, or the like can be blended with the additive of the present embodiment.

  Since the additive of the present embodiment contains thermally expandable microspheres with excellent heat resistance, it is also suitable for application fields that require processing steps such as kneading, calendering, extrusion, and injection molding. It can be used, and can also be applied to applications for molding at high temperatures. In addition, since the additive of the present embodiment has a high expansion ratio of the thermally expandable microsphere and a small amount of sag, the amount of the additive can be reduced and the processing window can be widened.

  Next, the molded object which concerns on the 3rd Embodiment of this invention is demonstrated. The molded body of this embodiment is composed of at least the above-described thermally expandable microsphere of the first embodiment and various polymer materials and / or fiber materials. Polymer materials used in the resin molded body of the present embodiment include, for example, PE, PP, PS, PA, PET, PBT, PPS, ABS resin, SBS, SIS, hydrogenated SIS, natural rubber, various synthetic rubbers, and heat. Examples include, but are not limited to, plastic polyurethane.

  Further, the thermally expandable microsphere contained in the molded body of the present embodiment may be in a state expanded by heating, an unfoamed state, or a contracted state.

Since the molded body of the present embodiment contains thermally expandable microspheres with excellent heat resistance, it has been difficult to reduce the weight of the molded body using an engineering plastic such as polyamide and impart designability. Can be realized.

  Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, first, thermally expandable microspheres of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared by the following method.

Example 1
(I) Preparation of aqueous dispersion medium 20% by weight colloidal silica (solvent: water) 40 g, 50% by weight diethanolamine-adipic acid condensation product (acid value: 78 mgKOH / g, solvent: water) 1.6 g, sodium nitrite 0 .12 g, 177 g of sodium chloride, and 565 g of water were mixed, and hydrochloric acid was added to adjust the pH to 3.2 to obtain an aqueous dispersion medium.

(Ii) Preparation of polymerizable mixture: 140 g of methacrylonitrile and 60 g of methacrylic acid as polymerization monomers, 40 g of light isoparaffinic hydrocarbon as a foaming agent, and 2 g of 2,2′-azobisisobutyronitrile as a polymerization initiator. Mixing to prepare a polymerizable mixture. At that time, a mixture of 36 g of IP solvent 2835 (50% distillation temperature: 316 ° C.) manufactured by Idemitsu Petrochemical Co., Ltd. and 4 g of isooctane (boiling point: 99 ° C.) was used as the light isoparaffinic hydrocarbon. The molar ratio of methacrylonitrile and methacrylic acid was approximately 2: 0.7. In the present embodiment, isooctane is mixed with the IP solvent in order to improve the initial foamability by adding a low boiling point component. Moreover, since isooctane was contained in the IP solvent, the 50% distillation temperature thereof was not greatly lowered, and the 50% distillation temperature of these mixtures was 313 ° C.

(Iii) Suspension polymerization The aqueous dispersion medium prepared by the above-described method and the polymerizable mixture were stirred and mixed with a homogenizer to form fine droplets of the polymerizable monomer mixture in the aqueous dispersion medium. Then, an aqueous dispersion medium containing minute droplets of this polymerizable mixture is charged into a polymerization can equipped with a stirrer (volume: 1.5 liter), and the entire polymerization can is heated at 60 ° C. for 15 hours using a hot water bath. Then, the polymerization reaction was further advanced by heating at 70 ° C. for 9 hours. Thereafter, the slurry containing the produced microspheres was filtered and washed with water, and then dried to obtain the thermally expandable microspheres of Example 1.

(Example 2)
While using 80 g of methacrylonitrile and 60 g of methacrylic acid as a polymerization monomer, 20 g of IP Solvent 2835 manufactured by Idemitsu Petrochemical Co., Ltd. alone is used as a foaming agent (light isoparaffinic hydrocarbon). The thermally expandable microsphere of Example 2 was produced by the same method and conditions as in Example 1.

(Example 3)
While 120 g of methacrylonitrile and 80 g of methacrylic acid are used as polymerization monomers, IP solvent 2835: 36 g and isododecane (boiling point: 178 ° C.): 4 g made by Idemitsu Petrochemical Co., Ltd. as a blowing agent (light isoparaffinic hydrocarbon) A thermally expandable microsphere of Example 3 was prepared in the same manner and under the same conditions as in Example 1 except that 40 g of the mixture was used. In this example, isododecane is mixed in the IP solvent for the same reason as in Example 1 described above. Also, isododecane did not significantly reduce the 50% distillation temperature of the IP solvent, and the blowing agent (mixture) used in Example 3 had a 50% distillation temperature of 313 ° C.

Example 4
Example 4 was the same as Example 1 except that 40 g of a mixture of IP solvent 2835: 30 g and isooctane: 10 g manufactured by Idemitsu Petrochemical Co., Ltd. was used as the blowing agent (light isoparaffinic hydrocarbon). Thermally expandable microspheres were prepared. The 50% distillation temperature of the foaming agent (mixture) used in Example 4 was 302 ° C.

(Comparative Example 1)
A thermally expandable microsphere of Comparative Example 1 was produced in the same manner and under the same conditions as in Example 1 except that 60 g of isododecane was used as the foaming agent.

(Comparative Example 2)
A thermally expandable microsphere of Comparative Example 2 was produced by the same method and conditions as in Example 2 described above, except that 60 g of isododecane was used as the foaming agent.

(Comparative Example 3)
A thermally expandable microsphere of Comparative Example 3 was produced in the same manner and under the same conditions as in Example 3 except that 30 g of isododecane was used as the foaming agent.

  The composition of the shell and the foaming agent in each microsphere of these examples and comparative examples is summarized in Table 1 below.

Next, for each of the microspheres of Examples and Comparative Examples prepared by the above-described method, the average particle diameter, the foaming start temperature ( _Tstart ), the maximum foaming temperature ( _Tmax ), and the degree of shrinkage when held at a high temperature are as follows. The foaming characteristics were measured and evaluated. The measurement method of each parameter is shown below.

A. Average Particle Size The average particle size of each macrosphere in the examples and comparative examples was measured using a particle size distribution analyzer SALD-3000J manufactured by Shimadzu Corporation.

B. Foam start temperature (T _start ) and maximum foam temperature (T _max )
The foaming start temperature (T _start ) and the maximum foaming temperature (T _max ) were measured by a thermomechanical analyzer (TMA) TMA-7 manufactured by PerkinElmer. Specifically, about 0.25 mg of each of the microspheres of Examples and Comparative Examples is placed in a container and heated under the conditions of a load of 0.01 N and a heating rate of 5 ° C./min. Measured. The temperature at which the height of the microspheres began to change in the container was defined as the foaming start temperature ( _Tstart ), and the temperature at which the height reached the maximum was defined as the maximum foaming temperature ( _Tmax ).

C. The degree of shrinkage when held at high temperature The measurement of the degree of shrinkage was similarly performed using TMA-7 model manufactured by PerkinElmer. Specifically, about 0.25 mg of each of the microspheres of Examples and Comparative Examples was put in a container, and the displacement d ₁ when held at 270 ° C. for 20 minutes was measured, and the maximum foaming temperature (T _max ) was measured. A ratio (d ₁ / d ₂ ) with the displacement amount d ₂ was determined.

  The above results are summarized in Table 2 below. FIG. 3 is a graph showing the foaming behavior of the microsphere of Example 1 with the temperature on the horizontal axis and the amount of displacement on the vertical axis. Further, FIG. 4 is a graph showing the change in the foaming state when the microsphere of Example 1 is held at 270 ° C. with the holding time on the horizontal axis and the amount of displacement on the vertical axis.

As shown in Table 2 and FIG. 3, the microsphere of Example 1 has a foaming start temperature (T _start ) of 280 ° C., a maximum foaming temperature (T _max ) of 321 ° C., and the difference thereof is 41 ° C. Excellent heat resistance than the product. Further, as shown in FIG. 4, when this microsphere was held at 270 ° C., foaming started in about 8 minutes, and the displacement d ₁ when held at that temperature for 20 minutes and the maximum foaming temperature. The ratio (d ₁ / d ₂ ) to the displacement d ₂ at 321 ° C. was 0.9. Thus, the microsphere of Example 1 had a small degree of shrinkage when held at a high temperature.

Similarly, the microspheres of Examples 2 to 4 also exhibited excellent heat resistance with a foam start temperature (T _start ) exceeding 230 ° C. and a maximum foaming temperature (T _max ) of 290 ° C. or higher. Furthermore, the ratio (d ₁ / d ₂ ) between the displacement d ₁ when held at 270 ° C. for 20 minutes and the displacement d ₂ at the maximum foaming temperature (T _max ) is 0.3 or more, The degree of shrinkage when held was also small.

On the other hand, in the microsphere of Comparative Example 2 using isododecane as the foaming agent, the maximum foaming temperature (T _max ) was as low as 268 ° C. In addition, the microspheres of Comparative Examples 1 and 3 in which the maximum foaming temperature (T _max ) exceeds 290 ° C. are also obtained by the displacement d ₁ when held at 270 ° C. for 20 minutes and the maximum foaming temperature (T _max ). The ratio (d ₁ / d ₂ ) to the displacement amount d ₂ was less than 0.3, and the degree of shrinkage when held at high temperature was large.

  From the above results, according to the present invention, it is possible to obtain a thermally expandable microsphere that is particularly excellent in heat resistance, has a small degree of shrinkage when held at high temperature, and can suppress early foaming even in applications that are processed at high temperature. It was confirmed.

  The thermally foamable microspheres according to the present invention can be used as additives for paints such as automobiles, wallpapering and foaming ink foaming agents, shrinkage prevention agents, etc. by utilizing the expansibility thereof, Due to its volume increase properties, it can be used as an additive for the purpose of imparting various functions such as weight reduction and porosity of polymer materials such as synthetic resins (thermoplastic resins and thermosetting resins) and rubber, paints and various materials. . In addition, it can be suitably used in the paint, wallpaper, and ink fields that require surface properties and smoothness, and because it has excellent processability, it requires processing steps such as kneading, calendering, extrusion, and injection molding. It can be used for application fields.

1 Microsphere 2 Shell 3 Foaming agent

Claims (12)

A microsphere having a structure in which a volatile foaming agent is included in an outer shell made of a polymer,
The blowing agent, 50% distillation temperature is light iso paraffinic hydrocarbons above 180 ° C., the foaming start temperature _{(T start)} is highly heat-expandable microspheres than 230 ° C.. Maximum expansion temperature (T _max) is heat-expandable microspheres according to claim 1, this and the feature is 290 ° C. or higher. The ratio (d ₁ / d ₂ ) between the displacement d ₁ when held at 270 ° C. for 20 minutes and the displacement d ₂ at the maximum foaming temperature (T _max ) is 0.3 or more, The thermally expandable microsphere according to claim 1 or 2 . The light iso paraffinic hydrocarbons claims, characterized in that the number of carbon atoms of two or more hydrocarbons hydrocarbons and carbon atoms is selected from the group consisting of hydrocarbons 15 to 30 6 to 13 The thermally expandable microsphere according to any one of 1 to 3 . The polymer constituting the outer shell is a copolymer having an nitrile group and a carboxyl group, and at least a part of which forms a polymethacrylimide structure by heating, or an acrylonitrile-based polymer. The thermally expandable microsphere according to any one of claims 1 to 4 . The thermally expandable microsphere according to claim 5 , wherein the polymer constituting the outer shell is a copolymer of methacrylonitrile and methacrylic acid. In an aqueous dispersion medium containing a dispersion stabilizer, in the presence of 50% distillation temperature is from light iso paraffinic hydrocarbons over 180 ° C. blowing agent, by suspension polymerization of a polymerizable monomer, heavy A method for producing a thermally expandable microsphere in which the foaming agent is enclosed in an outer shell made of coalescence to obtain a thermally expandable microsphere having a foaming start temperature (T _start ) higher than 230 ° C. The light iso paraffinic hydrocarbons claims, characterized in that the number of carbon atoms of two or more hydrocarbons hydrocarbons and carbon atoms is selected from the group consisting of hydrocarbons 15 to 30 6 to 13 8. A method for producing a thermally expandable microsphere according to 7 . The thermal expansion property according to claim 7 or 8 , wherein a nitrile monomer or a mixture of a nitrile monomer and a monomer having a carboxyl group is used as the polymerizable monomer. Microsphere manufacturing method. The method for producing a thermally expandable microsphere according to claim 9 , wherein acrylonitrile or methacrylonitrile is used as the nitrile monomer, and methacrylic acid is used as the monomer having a carboxyl group. . An additive comprising the thermally expandable microsphere according to any one of claims 1 to 6 . A molded body comprising the thermally expandable microsphere according to any one of claims 1 to 6 .

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