JP2001234169A - Preparation process of flame retardance-imparting composite composition, flame retardance-imparting composite composition, flame-retardant polymer composite material and molded product of flame- retardant polymer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively obtain an ecological flame retardance-imparting composite composition which imparts a high flame retardance when added at a small amount and generates no harmful substance at production or combustion, to provide its preparation process, to obtain a flame-retardant polymer composite material with which the flame retardance- imparting composite composition is compounded and a molded product of the flame-retardant polymer material. SOLUTION: A sol composition wherein a compound containing a metal element and/or Si is dispersed and/or dissolved in a solvent is mixed with carrier material particles, and the mixed sol composition is dried to yield a gel composition to obtain the flame retardance- imparting composite composition wherein the gel composition is compounded with the carrier material particles. A flame retardance-imparting composite particle 10 contains a silicon component and/or a metal component and oxygen and has a structure wherein a gel composition 2 which becomes a glass or a ceramic when heated to generate a glassy ceramic is compounded with carrier material particles 1. This flame retardance-imparting composite composition is compounded (added) with a polymer material through either blending or coating to yield the flame-retardant polymer composite material and the molded product of the flame- retardant polymer material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant composite composition for imparting flame retardancy to a material composed of a resin or the like, a method for producing the same, and a flame-retardant composite composition. The present invention relates to a flame-retardant polymer composite material obtained by compounding a polymer material and a flame-retardant polymer material molded article obtained by molding the flame-retardant polymer composite material into a predetermined shape.

[0002]

2. Description of the Related Art Resin materials are used in a wide range of fields due to their excellent chemical and physical properties and excellent moldability and workability. The major drawback of resin materials is that they burn easily,
Its use is restricted, and flame retardancy of resin materials is desired.

[0003] Halogen-based flame retardants are mainly used as flame retardants for making resin materials flame-retardant. However, they are not preferable in terms of environmental protection due to the problem of dioxins and furans generated from halogen-based flame retardants. The development and commercialization of fuel agents are desired. Non-halogen phosphorus-based flame retardants are not preferred because phosphine, which is a hydride of phosphorus, is generated.

[0004] In addition, there are inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. Aluminum hydroxide has low harmfulness, low smoke emission, good electric insulation, and low cost, so that among the flame retardants, There is a lot of demand. However, there are problems such as a decrease in mechanical properties and water resistance, an increase in viscosity of the compound for compounding a large amount (150 parts or more), and an increase in 400.
There is a low flame-retardant effect at a high temperature of not less than ° C., or a resin having a high molding temperature tends to be dehydrated and foamed.

Magnesium hydroxide has the same flame-retardant effect as aluminum hydroxide, and does not have dewatering and foaming at the processing temperature of resin, which is a disadvantage of aluminum hydroxide. However, they have disadvantages such as reaction with carbon dioxide in the air to produce magnesium carbonate and whitening, and cost is higher than aluminum hydroxide. In addition, since these inorganic flame retardants alone have a small flame retardant effect, it is necessary to use them together with other flame retardants. In addition, a low-melting glass is used as a glass-based flame retardant. However, the manufacturing process is complicated, a large amount is required to be added to the resin, the manufacturing cost is high, and there is a problem in water resistance.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems, and can provide high flame retardancy with a low addition amount, and does not generate harmful substances during production or combustion. Ecologically providing a flame-retardant composite composition and a method for producing the same, and providing a flame-retardant polymer composite material and a flame-retardant polymer material molded article obtained by compounding the flame-retardant composite composition at low cost What you want to do.

[0007]

Means for Solving the Problems and Actions / Effects In order to solve the above problems, a method for producing a flame-retardant composite composition according to the present invention comprises a compound of a metal element and / or Si (for example, an inorganic compound). A) dissolving and / or dissolving a sol-like composition in a solvent, and contacting the sol-like composition with a carrier material; and drying the sol-like composition, wherein the gel is formed by drying the sol-like composition. A composite composition for imparting flame retardancy is obtained by compounding a liquid composition with the support material. The sol composition may be generated from a solution (for example, an alkoxide solution) in which a metal element and / or a compound of Si is dispersed and / or dissolved in a solvent.

As described above, a composite composition for imparting flame retardancy can be obtained by a so-called sol-gel method in which the sol composition is dried and the gel composition is composited with the carrier material. The sol-gel method as described above is simple and does not require special equipment, so that the production cost can be significantly reduced and no harmful substances are generated during the production as in the past. . The composite composition for imparting flame retardancy obtained by such a production method has a structure in which a gel-like metal element and / or a compound of Si are compounded on a supporting material. When this is mixed (added) with a material such as a resin or the like by coating or the like, for example, when high heat is applied to the material to be provided with flame retardancy, the high heat causes the material to be used for imparting flame retardancy. The compound in the composite composition is vitrified or ceramicized, and the vitrified or ceramicized compound serves as a protective film, which makes it possible to impart high flame retardancy to the material to be imparted with flame retardancy. .
Further, a material obtained by compounding such a composite material for imparting flame retardancy does not generate a harmful gas as in the past when a high heat is applied, and thus becomes an ecological flame retardant material. Note that in the above manufacturing method, the step of bringing the sol-like composition into contact with the support material may employ a method of dipping the support material in the sol-form composition, a method of spraying the sol-form composition on the support material, or the like. Can be.

The above-mentioned carrier material is used as carrier material particles, and the gel composition is compounded on the entire surface or a part of the surface thereof to obtain flame-retardant composite particles as the flame-retardant composite compound. Can be. In this case, according to the sol-gel method, it is possible to obtain composite particles for imparting flame retardancy in which the gel composition containing the compound is uniformly dispersed and composited with the carrier material particles. In the case of a composite particle for imparting flame retardancy, the surface of which is covered with a coating of the gel composition, the coating of the gel composition is, for example, 0.01
It becomes thin and uniform at about 1.0 μm. When such composite particles for imparting flame retardancy are composited (added) to a material to be imparted with flame retardancy, the gel-like composition is coated uniformly and in a thin film on the support material particles. The effect of imparting flame retardancy is large, and the amount of the composite particles for imparting flame retardancy is sufficient, for example, by adding a small amount of 5 to 150 parts by weight, preferably about 20 to 100 parts by weight, based on the material to be imparted with flame retardancy. It is possible to impart properties. In this case, since a small amount is added, there is little change in the physical properties of the material to which the flame retardancy is to be added, such as a resin to be added, and it is also possible to improve the moldability and greatly reduce the cost.

[0010] The production method using the sol-gel method specifically includes a mixing step of forming a mixture of carrier material particles and a sol-like composition, and a drying step of evaporating the solvent from the mixture to form a dry composition. And may include:
This is, for example, to put a sol-like composition in a predetermined container, immerse the carrier material particles into a mixture to form a mixture, and then evaporate the solvent from the mixture, and remove the solvent without draining the mixture. This is a very simple method because it can be evaporated and dried. The dry composition is preferably pulverized or crushed and used as composite particles for imparting flame retardancy. In this case, the composite particles for imparting flame retardancy are finely pulverized by pulverization or pulverization. The composite particles for imparting flame retardancy can be easily and uniformly dispersed and composited with the material to be imparted with flame retardancy. The drying step can be performed by heating drying or vacuum drying, or a combination thereof.

The drying step can be carried out, for example, while applying vibration and / or stirring to the aggregate of the carrier material particles while bringing the sol composition into contact therewith. In this case, the drying efficiency is improved by the vibration and / or stirring of the aggregate, and the drying time can be shortened. on the other hand,
It is also possible to mix a striking medium having a larger diameter with the carrier material particles and apply vibration and / or agitation to the aggregate of the carrier material particles and the striking medium, in which case the drying time is further reduced. It is possible to

Next, the sol composition is preferably produced by hydrolyzing a metal element and / or an alkoxide of Si. The sol composition produced by hydrolyzing such an alkoxide includes a metal element and / or S
The oxide of i is contained, and the organic matter derived from the alkoxide remains. This oxide is vitrified or ceramicized by high heat as described above to impart high flame retardancy to the material to be imparted with flame retardancy, and the remaining organic matter is, for example, a case where a resin is used as the material to be imparted with flame retardancy. The composite composition for imparting flame retardancy to the material to be provided with flame retardancy is improved in compatibility (affinity) when the composite composition for providing flame retardancy is combined with the material to be provided with flame retardancy. Can be uniformly dispersed, and also the moldability and the like of the material to be imparted with flame retardancy can be improved.

An alcohol can be used as a solvent for preparing the sol composition. Since alcohol has a relatively low boiling point, it has an advantage that the drying step can be performed in a short time. As such an alcohol, for example, methanol, ethanol, propanol, butanol and the like can be used. Other solvents include ketone solvents such as acetone and acetylacetone, aromatic hydrocarbon solvents such as toluene and xylene, cyclic hydrocarbon solvents such as cyclohexane, other chain hydrocarbon solvents, and mixed solvents thereof. (A mixed solvent with an alcohol is also possible). For example, a ketone-based solvent can disperse or dissolve alkoxide in a stabilized state, and the drying step can be performed in a short time because of its relatively low boiling point. Further, since the hydrocarbon-based solvent has a low water content, the alkoxide can be dispersed or dissolved in a stabilized state, and a gel composition film having a uniform film thickness can be formed.

The amount of the solvent for preparing the sol composition is 25 to 98% by weight, and the amount of the alkoxide is 0.1%.
It is preferable to set it to about 5 to 40% by weight. When the compounding amount of the solvent is less than 25% by weight, the alkoxide may be difficult to be uniformly dispersed and / or dissolved, and as a result, the sol composition may be difficult to be composited with the support material. When used, the composition of the gel composition may be non-uniform. If the amount of the solvent exceeds 98% by weight, the drying step for evaporating the solvent may take a long time, and the cost is increased due to wasteful consumption of the solvent. On the other hand, when the compounding amount of the alkoxide is less than 0.5% by weight, the flame retardant effect due to the vitrification or ceramicization of the metal and / or Si of the alkoxide may be reduced, and the flame retardancy due to the organic component of the alkoxide may be caused. The adaptability to the material to be applied may also be reduced. On the other hand, if the amount of the alkoxide exceeds 40% by weight, the dispersibility and / or solubility of the alkoxide in the solvent may be reduced, and the sol-like composition may be difficult to be uniformly composited with the supporting material.

[0015] The alkoxide may be Si and / or Ti
Is an essential component. When Si and / or Ti is used as a component of the alkoxide, oxides such as SiO ₂ and TiO ₂ which are generated by hydrolysis are easily vitrified or ceramicized by high heat, and therefore have a particularly high flame-retardant effect. Becomes In addition, since these alkoxides containing Si and / or Ti are hard to gel, a sol composition in a stable state can be obtained. Above all, Si is most excellent as an alkoxide component in consideration of the stability of the generated oxide, the stability of the sol composition, and the like. As the alkoxide using Si, for example, tetraethoxysilane (Si (OC ₂ H ₅ ))
₄ ) can be used. As the alkoxide using Ti, for example, titanium isopropoxide (Ti (iso
—OC ₃ H ₇ ) ₄ ) can be used. The components other than the above include, for example, Cu, Al, Zn, N
A material containing one or more of i and Zr, or a material containing another transition element may be employed. In this case, for example, aluminum isopropoxide (Al (OC ₃ H ₇ ) ₃ ) Etc. can be used.
The constituent components of the alkoxide can be changed according to the purpose, and in this case, the properties of the formed gel composition film are different from each other.

On the other hand, the sol composition contains an inorganic acid or
Metal salts of organic acids can be included. In this case, gold
The cationic metal elements of the genus salts are Cu, Al, Zn, Ni,
Contains one or more of Fe, Ti and Zr
It is also good, and especially as the inorganic acid of the anionic component,
Acids obtained by dissolving an acidic gas in water (hereinafter referred to as acidic gas
Inorganic acid). In addition,
Other transition sources other than the above as cation metal elements
It is also possible to use hydrogen, and the above acidic gas is dissolved in water.
A gas that shows acidity when heated. Acid gas base
Examples of inorganic acids include nitric acid, nitrous acid, sulfuric acid, and sulfurous acid.
One or more of acid and carbonic acid can be used
You. When such a metal salt is contained in the sol composition,
Material to which flame retardancy is to be added to which a composite composition for imparting flame retardancy is added
When high heat is applied to the material, the acidic gas-based inorganic
Gases derived from acids, for example, N as N-containing gas₂gas
And NO₂Gas, NO gas, SO as S-containing gas₂Moth
CO as a C-containing gas ₂Gas and the like
Has further improved the flame-retardant effect on the flame-retardant material
You. As a specific example of the metal salt, copper nitrate (Cu
(NO₃)₂・ 3H₂O), zinc nitrate (Zn (NO₃)
₂・ 6H₂O) and the like. Also,
In addition to the inorganic acids, for example, oxalic acid, vinegar as an organic acid
It is also possible to use an acid or the like.

The amount of the metal salt in the sol composition is 9
The content is preferably 5% by weight or less. When the amount of the metal salt exceeds 95% by weight, the effect of imparting flame retardancy by vitrification or ceramicization of metal and / or Si of the alkoxide, which is a main factor of the effect of imparting flame retardancy, may be reduced. In the sol composition, when the weight ratio of the alkoxide is WA and the weight ratio of the metal salt is WB, WA /
It is preferable that WB is set in the range of 0.01 to 30. If WA / WB is less than 0.01, the effect of imparting flame retardancy by vitrification or ceramicization derived from the alkoxide component may not be sufficiently obtained. In some cases, the effect of imparting flame retardancy by the gas generated from the composition may not be sufficiently obtained, and as a result, the effect of imparting flame retardancy of the composite composition for imparting flame retardancy may decrease.

The above sol composition contains 25 to 98% by weight of an alcohol as a solvent, 0.5 to 40% by weight of a silicon alkoxide as an alkoxide, and 5 to 95% by weight of a metal nitrate as a metal salt. And 0.1 to 20% by weight of water are preferably used. When the sol composition is formed in such a blending amount, the gel composition can be uniformly compounded to the carrier material by the sol-gel method, and a uniform coating is formed particularly on the carrier material particles. It becomes possible. As a result, the effect of imparting flame retardancy derived from the alkoxide and metal salt described above can be more effectively exerted.

In the production method of the present invention, for example, a step of preparing a first solution by dispersing and / or dissolving the metal salt in an alcohol, and dispersing and / or dissolving an alkoxide in the first solution to form a second solution. The method may include a step of forming a solution and a step of adding water to the second solution to form a sol composition. As described above, the metal salt and the alkoxide are sequentially dispersed and / or dissolved in the alcohol, and the subsequent steps of adding water to the second solution are performed in a stepwise manner, thereby efficiently producing the sol composition. Becomes possible. In addition, for example, it is also possible to disperse and / or dissolve the alkoxide in a solvent such as an alcohol, and to add a solvent such as a metal salt and an alcohol to the alkoxide. The order of the above steps can be arbitrarily changed.

Next, the sol composition is dried at 40 to 25.
It is good to carry out in the range of 0 ° C. If the temperature is lower than 40 ° C., it may take a long time to dry the sol composition,
When the temperature exceeds 250 ° C., the sol composition may be decomposed. When drying under reduced pressure, it is necessary to adjust the temperature and pressure so that the sol composition stably remains (adheres) to the support material.

Next, in the case where a mixture is prepared by immersing the carrier material particles in the sol composition and the mixture is dried without draining, for example, the amount of carrier per liter of the sol composition The mixing amount of the material particles is 1 g
It is good to be about 20 kg. When the amount is less than 1 g, the production efficiency of the composite composition for imparting flame retardancy decreases, and
If the amount exceeds g, the composite amount of the sol composition per unit support material particle is reduced, and the effect of imparting flame retardancy may be reduced. The mixing amount is preferably 1 kg.
It is good to make it about 10 kg. Further, for example, the total content of the alkoxide and the metal salt in the sol composition is Ws
(Unit: g), the specific surface area of the support material particles is Sg (unit: m ² / g), and the mixing amount of the support material particles in the sol composition is Wg (unit: g). (Sg × Wg)
Is preferably adjusted so as to be 0.002 to 2.0 g / m ² .

As the support material particles, for example, flame-retardant material particles can be used. In this case, in addition to the effect of imparting flame retardancy based on the alkoxide and the metal salt described above, the flame retardant effect of the flame retardant material particles as a support material is also added. The addition of flame retardancy to the material is more effective. As such flame-retardant material particles, inorganic material-based particles or metal material-based particles can be used. For example, hydrated metal compounds that are ecological non-halogen flame retardant materials, muscovite, phlogopite,
Mica such as biotite, sericite, minerals such as kaolin, talc, zeolite, borax, diaspore, gypsum, metal oxides such as magnesium oxide, aluminum oxide, silicon dioxide, metal compounds such as calcium carbonate, red phosphorus Inorganic flame-retardant material particles typified by phosphorus-based compounds such as ammonium polyphosphate, nitrogen-based compounds, and the like, and phosphorus-based, silicone-based, nitrogen-based organic flame-retardant material particles, and even metal powder particles are used. be able to. In addition, the additive property to the resin, the flame retardant effect,
In terms of cost and the like, it is most preferable to use inorganic flame-retardant material particles.

The flame-retardant material particles have, for example, an average particle size of 0.1.
It is preferable to use one having a thickness of from 0.5 to 100 μm. When the average particle size is less than the above lower limit, the production may be difficult, and when the composite (addition) is made to the material to be provided with flame retardancy, uneven distribution may occur, and the composite (addition) may not be uniform. Therefore, the effect of imparting flame retardancy may be reduced, or the performance of the material to be imparted with flame retardancy may be reduced particularly in the uneven distribution region. In addition, when the value exceeds the upper limit, the distribution of the composite (added) particles may be non-uniform, and the properties of the material to be imparted with flame retardancy, for example, properties such as fluidity may be reduced,
The material to be imparted with flame retardancy may cause poor appearance. The average particle size can be measured by using, for example, a laser diffraction particle size analyzer. In this case, the measurement by the laser diffraction type particle sizer does not cause a large difference between the diffraction behavior of the incident laser light by the aggregated particles and the diffraction behavior by the isolated primary particles. It cannot be distinguished from the particle size of the existing particles or the particle size of the aggregated secondary particles. Therefore, the average particle diameter measured by this method is a value reflecting the average particle diameter of the secondary particles that includes isolated primary particles that do not cause aggregation in a broad sense.

The use of particles containing at least one of aluminum hydroxide and magnesium hydroxide as the inorganic material-based particles further enhances the effect of imparting flame retardancy. When these hydroxides are used, for example, if the alkoxide is composed of Si and the metal salt is composed of Zn and / or Ni, the effect of imparting flame retardancy is further enhanced. .

On the other hand, polymer material particles can be used as the support material particles. As the polymer material particles, for example, those made of a thermoplastic polymer material, those made of a thermosetting polymer material, or a mixed material thereof can be used. In this case, when a resin is used as the material to be imparted with flame retardancy, the composite material (particles) for imparting flame retardancy is difficult because the polymer material as the carrier material has good affinity (affinity) with the resin. The material is uniformly dispersed in the material to be imparted with flame retardancy, so that the material to be imparted with flame retardancy can be effectively imparted with flame retardancy. When polymer particles are used, for example, if the alkoxide is made of Si and the metal salt is made of Cu and / or Fe, the effect of imparting flame retardancy is further enhanced. The polymer material particles have, for example, an average particle size of 0.1 to 10
In this case, the average particle size of the composite particles for imparting flame retardancy is about 0.1 to 10 mm.

As the polymer material particles, for example,
General-purpose resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), modified polyphenylene ether (PPE), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate ( PET), engineering plastics such as polyamide (PA) and PC / ABS alloy, PC /
Powder particles such as polymer alloys such as PBT alloy, PC / PET alloy, PC / elastomer, PA / PP and PA / elastomer can be used.

The composite particles for imparting flame retardancy as the composite composition for imparting flame retardancy are dispersed in a substrate made of the above-mentioned polymer material as a material to be imparted with flame retardancy or fixed on the surface of the substrate. Or you can. Thus, the flame-retardant polymer composite material obtained by compounding the flame-retardant composite particles exhibits high flame retardancy due to the flame-retardant effect given by the above-mentioned alkoxide, metal salt, flame-retardant material particles and the like. .

In addition, when the polymer substrate made of the above-mentioned polymer material is melted by raising the temperature together with the above-mentioned flame-retardancy-imparting composite composition (particles), a flow suppressing adjuvant which suppresses the flow and dripping of the polymer substrate is used. It can also be incorporated into a molecular substrate.
In this case, the melt flow of the polymer substrate is suppressed by the flow suppression auxiliary agent, and so-called drip prevention during combustion can be improved. Examples of the flow control adjuvant include boric acid-based inorganic compounds such as boric anhydride and zinc borate, and red phosphorus (for example, Novaled (trade name) manufactured by Suzuhiro Chemical Co., Ltd .; Hishigard (trade name) manufactured by Nippon Chemical Industry Co., Ltd.) ), Etc.), or carbon (eg, Tosoh: GREP-EG)
(Trade name), made by UCAR Carbon: GRAF Guard (trade name)
Inorganic materials such as expandable carbon represented by, for example, or silicone, or the like can be used.

The content ratio of the composite composition (particles) for imparting flame retardancy in the polymer substrate is preferably 5 to 150 parts by weight based on 100 parts by weight of the polymer substrate. Content ratio is 5
If the amount is less than 10 parts by weight, the effect of imparting flame retardancy may be reduced.If the amount is more than 150 parts by weight, the amount becomes unnecessary for the purpose of imparting flame retardancy, resulting in high cost. In some cases, problems such as a significant change in properties may occur. The content ratio is preferably 20
It is preferable that the amount be 100 parts by weight. However, when the above-mentioned flow-suppressing aid is used, the composite composition (particles) for imparting flame retardancy is used.
Is desirably, for example, about 1 to 150 parts by weight. In addition, when the content ratio of the composite composition (particles) for imparting flame retardancy in the polymer substrate is represented by a volume fraction, it is 0.1%.
The content is preferably set to 5 to 75% by volume.

On the other hand, when the composite particles for imparting flame retardancy are compounded in a polymer matrix, the average particle size is 0.05 to 500.
It is good to be μm. When the average particle size is less than 0.05 μm, problems such as troublesome work may be caused when the particles are combined, and when the average particle size is more than 500 μm, the particles cannot be uniformly dispersed or fixed to the polymer substrate. Problem may occur. The average particle size of the composite particles for imparting flame retardancy is desirably 0.1 to 300 μm.

The above-mentioned flame-retardant polymer composite material has excellent moldability, and the flame-retardant polymer composite material molded article formed into a predetermined shape can be applied to various uses. For example, in automotive parts, interior parts such as instrument panels,
For exterior parts such as bumpers, plastic parts for engines, etc., and for home use, frame members (exterior members for electronic devices) of home appliances such as TVs, videos, personal computers, audio players, microwave ovens, etc. It can also be applied to members for use. Also, fiber curtains,
It is also applicable to rubber-like members (earthquake-resistant materials), sheet-like members, paints, and the like. The method for molding these resins is not particularly limited, and any molding method such as press molding, blow molding, extrusion molding, and injection molding can be used.

As the above-mentioned flame-retardant polymer composite material molded product, for example, a product formed as a final molded product without assuming remolding accompanied by softening of the polymer substrate. It may be used as a temporary formed body for reshaping into a secondary shape of the final stage. In this case, a masterbatch for re-molding the temporary molded body into a granular molded article in which the composite particles for imparting flame retardancy are dispersed in a polymer matrix, and reforming into a secondary shape having a larger volume than each granular molded article. It is also possible to use as. The master batch is
A polymer substrate is used to produce a secondary molded product with a smaller content of flame-retardant composite particles than the polymer itself by re-molding with a diluted polymer material composed of the same or different polymer material. can do. It is also possible to form the composite particles for molding by compounding the gel composition with a carrier material (core material) of a polymer material, and to perform the above molding while softening the core material of the composite particles. is there. In this case, the core portion of the composite particles forms a matrix after molding, and the coated compound portion has a tissue form dispersed in the matrix.

[0033]

Embodiments of the present invention will be described below with reference to the embodiments shown in the drawings. FIG. 1 is a schematic view conceptually showing one example of the composite particles for imparting flame retardancy produced by the production method of the present invention. The composite particles 10 for imparting flame retardancy contain a silicon component and / or a metal component and oxygen, and are, for example, a gel-like composition (also referred to as a glass precursor composition) which is vitrified or ceramicized by heating to produce a vitreous ceramic. 2) is composited with the carrier material particles 1 and can be manufactured by the sol-gel method described above. In addition, although the particle 10 is schematically drawn in a spherical shape, the shape changes variously depending on the manufacturing method, and the particle 10 is not always necessarily spherical. The form of the composite of the glass precursor composition 2 and the support material particles 1 is, for example, as shown in FIG. 1A, the glass precursor composition 2 uniformly covers the surface of the support material particles 1 over substantially the entire surface. The coated state is most desirable in terms of exhibiting the flame retardant effect. However, as long as a good flame-retardant effect can be maintained, FIG.
As shown in (b), the glass precursor composition 2 may be partially adhered to the surface of the support material particles 1 and a part of the surface may be uncoated and exposed. In addition, if a lump in which the composite particles 10 for imparting flame retardancy are dispersed in a compound bulk is pulverized or crushed, for example, the composite particles for imparting amorphous shape having a configuration as shown in FIG. It can be 10. In any case, the composite particles 10 as described above are composited (dispersed in a substrate and / or fixed on the surface) with a substrate made of a material to be imparted with flame retardancy, for example, made of a polymer material, etc. It is possible to impart flame retardancy to the material to be imparted with the property. In addition, as shown in FIG. 2, it is also possible to mix and use another flame retardant particle 11 with the composite particle 10 for imparting flame retardancy.

In FIG. 1A, the thickness of the glass precursor composition 2 coated or adhered to the carrier material particles 1 is, for example, about 0.01 to 1.0 μm. When the composite particles 10 for imparting flame retardancy are composited (added) to the material to be imparted with flame retardancy, the glass precursor composition 2 is coated or adhered to the support material particles 1 in a uniform and thin film form. Therefore, the effect of imparting flame retardancy is great, and the amount of the composite particles 10 for imparting flame retardancy is, for example, about 5 to 150 parts by weight, preferably about 20 to 100 parts by weight based on the material to be imparted with flame retardancy. Sufficient flame retardancy can be imparted by adding a small amount. In this case, since the addition is in a small amount, the change in the physical properties of the material to which the flame retardancy is to be imparted, such as a resin, is small, and the cost can be significantly reduced.

On the other hand, as shown in FIG. 2, it is also possible to mix the conventional flame-retardant material particles 11 with the flame-retardant composite particles 10 and to compound (add) them to the material to be provided with flame retardancy. It is possible. In this case, the composite particles 1 for imparting flame retardancy
In addition to the flame-retarding effect of 0, the flame-retarding effect of the flame-retardant material particles 11 is also synergistically added, so that the flame-retardant material to be imparted has high flame retardancy.

It is presumed that the glass precursor composition 2 has, for example, the structure schematically shown in FIG. 10 (the molecular formula is schematically shown in FIG.
It does not mean that the specific structure represented by the molecular formula is limited). In the glass precursor composition 2 that is compounded inside or on the surface of the material 50 to be imparted with flame retardancy,
Silicon and / or metal (these are indicated by M in the figure) are in the state of oxide or alkoxide 52 (for example, SiO ₂ , ZrO
₂ , Si (OCnHm) l (n ≧ 1, m ≧ 1, l ≧ 1)
And the like, or a structure in which the carbon component 51 is contained in a state of, for example, CnHm (n ≧ 1, m ≧ 1).

As shown in FIG. 3A, the composite particles 10 for imparting flame retardancy as described above may be used alone or, if necessary, with a different flame retardant from the composite particles for imparting flame retardancy. Along with a flame retardant aid, a filler, a coloring agent such as a pigment or a dye, a dispersing agent, etc., it is blended and kneaded in a polymer material 41 (a thermoplastic resin is used in this embodiment) to be a substrate. Thus, the compound 531 is obtained. The compound 531 can be used as the masterbatch particles 32 by forming the compound 531 into a granular form such as a pellet. Masterbatch particles 3
2 is, for example, 0.1 to 1 in terms of a sphere-converted diameter.
It has a size of about 0 mm (for example, about 1 to 4 mm). The shape of the master batch particles 32 is not particularly limited. For example, as shown in FIG. 3 (b), a softened compound is extruded into a strand and cut into a predetermined length to obtain a columnar shape. Particles in (eg, columnar) form can be obtained. Note that FIG.
(C) and (d) show another example of the shape of the masterbatch particles 32, the former being spherical (for example, it can be manufactured by molding) and the latter being flake-like (for example, sheet-like material). Can be produced by crushing and sizing))
It is not limited to this.

Hereinafter, a method of manufacturing a molded article (secondary molded article) using the above-mentioned master batch will be described with reference to an example in which injection molding as shown in FIG. 4 is employed. The injection molding apparatus 501 includes a molding section 502 and an injection apparatus 503 such as a screw-type injection apparatus for supplying a molten resin to the molding section 502. The molding unit 502 includes a mold 505, a mechanical drive mechanism such as a cam or a crank mechanism, and a drive mechanism 506 including a fluid pressure mechanism such as a hydraulic cylinder for clamping and opening the mold 505. An injection nozzle 503b of an injection device 503 is connected to a runner 521 that supplies and supplies a molten resin to a mold 505 via a sprue 503a.

In the injection device 503, a supply screw 509 driven by a hydraulic motor 513 via a shaft 512 is accommodated in a heating cylinder 507 heated by a heat source such as a band heater 508. And a hopper 510 for supplying the pressure. The master batch P is supplied from the hopper 510 by rotating the screw 509, and the polymer material substrate is melted by heating in the heating cylinder 507 to become a molten compound, which is stored in the storage section 507a. afterwards,
When the screw 509 is advanced by a predetermined distance by the hydraulic cylinder 511, a predetermined amount of the molten compound is injected from the nozzle 503 b into the mold 505 through the runner 521.

As shown in FIG. 5, the molten compound C injected into the cavity 505a of the mold 505 is formed by solidification of the polymer material substrate to form the high-composite composite particles for imparting flame retardancy of the present invention. By forming a molecular composite material and opening the mold, a secondary molded body 36 as a polymer composite material molded body corresponding to the cavity shape is obtained.

As shown in FIG. 6A, a molded article may be obtained by using the master batch particles 32 alone, but as shown in FIG. By mixing an appropriate amount of diluted polymer material particles 40 made of the same or different polymer material with the polymer substrate, the content of the composite particles is smaller than the content in the masterbatch particles 32 of the secondary molded body. Can also be manufactured. In this case, the content of the composite particles in the secondary molded body is determined by the content of the composite particles in the masterbatch particles 32 and the diluted polymer material particles 40 with respect to the masterbatch particles 32.
Is determined by the mixing ratio.

The content of the composite particles in the masterbatch particles for dilution is, for example, 20% by weight.
Although it is as high as about 67% by weight, it is desirable to add a dispersant in order to uniformly disperse the composite particles in the substrate at such a high content. As the dispersant, for example, metal soap can be suitably used. The metal soap is
For example, when the organic acid component is naphthenic acid (naphthate), lauric acid (laurate), stearic acid (stearate), oleic acid (oleate), 2-ethylhexanoic acid (octate), linseed oil or soybean oil fatty acid (linoleate) ), Tall oil (tolate), rosin and the like (resinate). In addition, the following types of metals can be exemplified. Naphthenate (Al, Ca, Co, Cu, Fe, P
b, Mn, Zn, etc.) Resinates (Al, Ca, Co, Cu, Fe, P
b, Mn, Zn, etc.) Linoleate (Co, Fe, Pb, Mn, etc.) Stearate (Ca, Zn, etc.) Octate (Ca, Co, Fe, Pb, Mn, Zn)
Etc.)-Torrate type (Ca, Co, Fe, Pb, Mn, Zn)
Etc.) Of these, Cu stearate and Zn stearate
Can be cited as a specific example of a metal soap that is particularly excellent in the dispersing effect. If the amount of the metal soap in the composite material is too large, there is a problem in the material strength and homogeneity. If the amount is too small, the dispersing effect becomes insufficient. 01 to 3% by weight
(For example, 0.3% by weight).

A main agent containing an uncured resin component such as an epoxy resin, urethane resin (including urethane rubber) or silicone resin, and a curing agent containing a curing agent for curing the uncured resin component 2 consisting of
It is also possible to configure a liquid mixture type casting resin material, adhesive or paint as a flame retardant polymer composite material in which the composite particles for imparting flame retardancy of the present invention are composited. In particular,
For this purpose, it is composed of a main agent containing an uncured resin component and a curing agent for curing the uncured resin component, and the composite particles for imparting flame retardancy are blended in at least one of the main agent and the curing agent. By mixing the main agent and the curing agent, it is possible to obtain a flame-retardant polymer composite material in which composite particles for imparting flame retardancy are dispersed in a thermosetting resin as a substrate. A composition for producing a conductive polymer composite material can be used.

FIG. 7 shows a specific example of the case of an epoxy resin. That is, the main agent 550
For example, in a bisphenol-based uncured epoxy resin component, flame-retardant composite particles and, if necessary, a flame retardant or a flame-retardant auxiliary, a filler, a pigment different from the flame-retardant composite particles And a coloring agent such as a dye or a dye, or a dispersant, and the viscosity is adjusted by an appropriate solvent. on the other hand,
The curing agent 551 is obtained by dissolving or dispersing a curing component such as an amine, an isocyanate, and an acid anhydride in a solvent. Immediately before use, both agents 550 and 551 are mixed at a predetermined ratio as shown in FIG.
The treatment according to the purpose is performed within the pot life time of 2. That is, when the mixed composition 552 is used as a casting resin material, it is cast into a mold 553 and cured as shown in FIG. A material compact is obtained. In the case where the mixed composition 552 is used as a paint, as shown in (c), this is applied to the coating surface of the work 554 and cured.
A flame-retardant polymer composite coating 555 is obtained. Further, when the mixed composition 552 is used as an adhesive, as shown in (d), the mixed composition 552 is applied to and bonded to the bonding surfaces of the bonded objects 556a and 556b. An adhesion structure in which 556a and 556b are adhered is obtained.

Next, the composite particles for imparting flame retardancy can be fixed on the surface of the polymer substrate. FIG. 8 shows some examples. FIG. 8A shows a polymer substrate 50.
An example is shown in which the composite particles 10 for imparting flame retardancy are fixed in an adhesive form via an adhesive resin layer 560 formed on the surface of the composite resin.
The composite particles 10 for imparting flame retardancy may be further dispersed in the polymer substrate 50 (the same applies to the following). Further, as shown in FIG. 8B, the surface side of the fixed particles 10 may be further covered with an overcoat 561 made of resin or the like.

In FIG. 8C, for example, the flame-retardant composite particles 10 are applied to the inner surface of a cavity of a molding die 505, and then the cavity is filled with a molten resin 570 and solidified to form a coating. This is an example in which the obtained particles 10 are integrated with the surface of the substrate 50 forming the molded body 536. FIG. 8D shows that the surface of the composite particle 10 is fixed to the fixing resin layer 5.
This is an example in which the composite particles 10 are fixed in advance by being covered with 62 and adhered to the surface of the substrate 50 while softening the fixing resin layer 562 by heating and thereafter curing the resin.
In this case, if the substrate 50 is preheated at a temperature at which unnecessary deformation does not occur, the fixing resin layer 562 can be easily softened and adhered. FIG. 8E shows the composite particles 1
By projecting 0 on the surface of the substrate 50 or by press-fitting,
In this method, the composite particles 10 are embedded in the surface layer of the substrate 50. In this case, embedding can be performed easily if at least the surface layer of the substrate 50 is softened by heating or the like.

[0047]

EXAMPLES (Example 1) As a metal salt, 21.93 g of zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ .6H ₂ O) was placed in 20 ml of ethanol and dissolved. 6.92 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution.
Then, 4.18 g of pure water was added dropwise, and the solution was stirred to prepare a sol composition. 75 g of aluminum hydroxide having an average particle size of 55 μm was added as the support material particles to the sol composition and mixed with stirring. Then, 12
The mixture was placed in a dryer at 0 ° C., and the solvent was evaporated to form a coating film of the gel composition (glass precursor composition) on the surface of the aluminum hydroxide. In order to estimate the components of the coating film, when the gel composition obtained by drying only the sol composition was analyzed, it was found to be a compound containing each element of Si, Zn, O, N and C. I understood.

The aluminum hydroxide coated by the above sol-gel method is mixed with a powder or pellet of polypropylene (J708 made by Grand Polymer).
Part), and thereafter, it was placed in an injection molding machine and injection molded at 180 ° C. into a sample shape for a flame retardancy test. The shape of the sample for the flame retardancy test has a length of 12 based on the UL94 flammability test.
The thickness was 5 mm, the width was 13 mm, and the thickness was 1.6 mm.

Using the prepared sample for flame retardancy test in the UL94 flammability test, the sample passed the V-0 standard of the test.

Example 2 As a metal salt, nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) 23.36 g was put in ethanol 20 ml and dissolved. _5. Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) is added to the solution.
92 g was added, and then 4.18 g of pure water was added dropwise, and the solution was stirred to produce a sol composition. 75 g of aluminum hydroxide as in Example 1 was put into this sol composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide. In order to estimate the components of the coating film, the gel composition obtained by drying only the sol composition was analyzed. I understood.

The aluminum hydroxide coated by the sol-gel method was mixed with 250 g of the same polypropylene powder or pellets as in Example 1 (100 parts of polypropylene and 30 parts of aluminum hydroxide), and then placed in an injection molding machine. Injection molding was performed at 180 ° C. in a sample shape for a flame retardancy test. The sample shape for the flame retardancy test was the same as in Example 1. As a result of a UL94 flammability test using the prepared sample for flame retardancy test, the sample passed the V-2 standard of the test.

Further, a combustion test by the oxygen index method (JIS)
K7201), length 120mm, width 6.5m
A sample having a thickness of 3 mm and a thickness of 3 mm was prepared and tested in the same combustion test. As a result, an oxygen index value of 32% was obtained.

Example 3 Ethanol blended amount was 80 ml
A sol composition was prepared with the same formulation as in Example 1 except that In this sol-like composition, the average particle size is 0.85 μm.
m of magnesium hydroxide was added and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of magnesium hydroxide. The aluminum hydroxide coated by the above sol-gel method and 250 g of the same polypropylene powder or pellets as in Example 1 were mixed (100 parts of polypropylene and 50 parts of magnesium hydroxide), and then placed in an injection molding machine. Into a sample for flame retardancy testing. The sample shape for the flame retardancy test was the same as in Example 1. As a result of a UL94 flammability test using the prepared sample for flame retardancy test, the sample passed the V-2 standard of the test.

Example 4 A sol composition was prepared with the same composition as in Example 1 above. Example 1 in this sol composition
20 g of the same aluminum hydroxide and 10 g of the same magnesium hydroxide as in Example 3 were added and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surfaces of aluminum hydroxide and magnesium hydroxide.

In the same manner as in Example 1, a flame-retardant test sample having the same shape was prepared and tested in a UL94 flammability test. As a result, the test passed the V-2 standard. When the oxygen index of this sample was measured in the same manner as in Example 2, an oxygen index value of 31% was obtained.

(Comparative Example 1) As in Example 1, 75 g of aluminum hydroxide and 100 g of polypropylene were mixed.
Thereafter, the mixture was placed in an injection molding machine and injection molded at 180 ° C. into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test is the same as in Example 1. Using this sample for flame retardancy test, it was tested by UL94 flammability test.
The sample ignited immediately after the start of the test. When the oxygen index of this sample was measured in the same manner as in Example 2, an oxygen index value of 20% was obtained.

Comparative Example 2 The same 150 g of magnesium hydroxide and 100 g of polypropylene as in Example 3 were mixed, then placed in an injection molding machine, and injection molded at 180 ° C. into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test is the same as in Example 1. Using this sample for flame retardancy test, a UL94 flammability test was conducted, and as a result, the test passed the V-0 standard.

Table 1 summarizes the results of Examples 1 to 4 and Comparative Examples 1 and 2.

[0059]

[Table 1]

From these results, it was found that the sample of the comparative example not coated by the sol-gel method had no flame-retardant effect at a small amount of about 75 parts with respect to 100 parts of polypropylene, and was added to a large amount (for example, 150 parts). You need to do it. On the other hand, as shown in the examples, it can be seen that the sample obtained by coating the carrier material particles by the sol-gel method has an effect of imparting flame retardancy even in a small amount (for example, 30 to 75 parts).

Example 5 As a metal salt, 93.43 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) was placed in 80 ml of ethanol and dissolved. Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ )
7.74 g was added, followed by dropwise addition of 16.76 g of pure water, and the solution was stirred to produce a sol composition. 500 g of aluminum hydroxide having an average particle diameter of 55 μm was added as the support material particles to the sol composition and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide.

The aluminum hydroxide coated by the sol-gel method and a powder or pellet of polypropylene (made by Grand Polymer: J708) were mixed (100 parts of polypropylene and 50 parts of aluminum hydroxide were mixed).
Part) Then, the above-mentioned mixed pellets were prepared by an extrusion molding machine, and injection-molded into a sample shape for a flame retardancy test at 180 ° C. by an injection molding machine. Sample shape for flame retardancy test is 125m in length based on UL94 flammability test
m, width 13 mm, thickness 1.6 mm. Using this test sample, a UL94 flammability test was performed, and as a result, the test passed the V-2 standard.

A combustion test by the oxygen index method (JIS
K7201), for the above composition, a length of 120
mm, width 6.5mm, thickness 3mm sample,
As a result of the test in the combustion test, an oxygen index value of 33% was obtained.

Further, for the above composition, a No. 1 type test piece was prepared based on the tensile test method (JIS K7113) and tested in the same test. As a result, the tensile strength was 15.5 × 1.
0 to obtain a ⁶ [Pa].

Example 6 93.43 g of zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ .6H ₂ O) as a metal salt was placed in 80 ml of ethanol and dissolved. Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution at 27.7.
4 g was added, and then 16.76 g of pure water was added dropwise, and the solution was stirred to produce a sol composition. 500 g of aluminum hydroxide as in Example 5 was put into this sol composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide.

The aluminum hydroxide coated by the sol-gel method was mixed with the same polypropylene powder or pellets as in Example 5 (polypropylene 1).
(00 parts with respect to 50 parts of aluminum hydroxide), and then put into an injection molding machine and injection molded at 180 ° C. into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test was the same as in Example 5, and a UL94 flammability test was performed.
Further, a sample for measuring an oxygen index and a sample for measuring a tensile test similar to those in Example 5 were prepared, and a combustion test by an oxygen index method and a tensile strength test by a tensile test were also performed.

As a result of the test in the UL94 flammability test,
The test passed the V-2 standard. As a result of a combustion test by the oxygen index method, an oxygen index value of 29% was obtained. Further, as a result of a tensile test by a tensile test method, a tensile strength of 16.
1 × 10 ⁶ [Pa] was obtained.

Example 7 As a metal salt, 93.43 g of zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ .6H ₂ O) was placed in 400 ml of ethanol and dissolved. 27. Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution.
74 g was added, and then 16.76 g of pure water was added dropwise, and the solution was stirred to produce a sol composition. 500 g of aluminum hydroxide having an average particle size of 1 μm as support material particles was added to the sol composition and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide.

The aluminum hydroxide coated by the sol-gel method was mixed with the same polypropylene powder or pellets as in Example 5 (polypropylene 1).
(00 parts with respect to 50 parts of aluminum hydroxide), and then put into an injection molding machine and injection molded at 180 ° C. into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test was the same as in Example 5, and a UL94 flammability test was performed.
Further, a sample for measuring an oxygen index and a sample for measuring a tensile test similar to those in Example 5 were prepared, and a combustion test by an oxygen index method and a tensile strength test by a tensile test were also performed.

As a result of the test in the UL94 flammability test,
The test passed the V-2 standard. As a result of a combustion test by the oxygen index method, an oxygen index value of 32% was obtained. Further, as a result of a tensile test by a tensile test method, a tensile strength of 23.
1 × 10 ⁶ [Pa] was obtained.

(Comparative Example 3) Average particle size 1 similar to that of Example 7
μm aluminum hydroxide and polypropylene are mixed (100 parts by weight of polypropylene and 50 parts by weight of aluminum hydroxide), and then placed in an injection molding machine,
Was injection molded into a sample shape for flame retardancy test. The sample shape for the flame retardancy test is the same as in Example 5. As a result of performing a UL94 flammability test using this sample for a flame retardancy test, the sample was ignited immediately after the start of the test. Further, a sample for measuring an oxygen index similar to that of Example 5 was prepared, and a combustion test was performed by an oxygen index method.
An oxygen index value of 19.7% was obtained. Further, a tensile test measurement sample similar to that of Example 5 was prepared, and a tensile strength test was performed by a tensile test method. As a result, a tensile strength of 19.6 × 10
⁶ [Pa] was obtained.

Comparative Example 4 100 g of polypropylene was put into an injection molding machine and injection-molded at 180 ° C. into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test is the same as in Example 5. As a result of performing a UL94 flammability test using this sample for a flame retardancy test, the sample was ignited immediately after the start of the test. In addition, a sample for measuring an oxygen index similar to that of Example 5 was prepared, and a combustion test was performed by an oxygen index method, whereby an oxygen index value of 17.5% was obtained. Further, a tensile test measurement sample similar to that of Example 5 was prepared, and a tensile strength test was performed by a tensile test method. As a result, a tensile strength of 22.3 × 10 ⁶ [Pa] was obtained.

Table 2 summarizes the results of Examples 5 to 7 and Comparative Examples 3 and 4.

[0074]

[Table 2]

From these results, it can be seen that the polypropylene added with aluminum hydroxide coated by the sol-gel method has high flame retardancy. However, when aluminum hydroxide having a large average particle size is used, the resin properties (tensile strength) are reduced. Therefore, when aluminum hydroxide having a small average particle size is used,
It can be seen that it is possible to improve the flame retardancy while maintaining the resin properties (tensile strength).

Note that the composite particles for imparting flame retardancy obtained by coating the carrier material particles in the present example with the sol-gel method are photographed by an electron microscope before and after coating with the gel composition (glass precursor composition). Is shown in FIG. FIG. 9A shows the carrier material particles before coating.
FIG. 9 (b) shows the carrier material particles (composite particles for imparting flame retardancy) after coating, and shows that the carrier material particles are uniformly coated with the sol composition (glass precursor composition). I understand.

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating some forms of composite particles for imparting flame retardancy.

FIG. 2 is a schematic view showing an example in which another flame retardant particle is blended with a composite particle for imparting flame retardancy.

FIG. 3 is a schematic view showing an example of a method for producing a masterbatch comprising a flame-retardant polymer composite material obtained by combining the flame-retardant composite particles of the present invention, together with various forms of masterbatch particles.

FIG. 4 is a schematic sectional view showing an example of an injection molding machine.

FIG. 5 is a process explanatory view showing an example of manufacturing a molded body by injection molding.

FIG. 6 is an explanatory view showing some usage patterns of a master batch.

FIG. 7 shows a method for obtaining a flame-retardant polymer composite material in which the composite particles for imparting flame retardancy of the present invention are composited with a two-component mixed resin,
Explanatory drawing which illustrates some of the application forms.

FIG. 8 is a process explanatory view illustrating several methods for fixing the composite particles for imparting flame retardancy to the surface of a polymer material substrate.

FIG. 9 is an electron micrograph of the support material particles before coating, and the composite particles for imparting flame retardancy obtained by coating the support material particles.

FIG. 10 is a schematic diagram showing a molecular level structure of a compound layer inferred.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Carrier material particle 2 Gel composition (glass precursor composition) 10 Composite particle for imparting flame retardancy 11 Flame retardant material particle 50 Material to be imparted with flame retardancy

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/09 C08K 5/09 C08L 83/02 C08L 83/02 83/04 83/04 85/00 85 / 00101/00 101/00 C09K 21/14 C09K 21/14 (72) Inventor Toshikuni Ito 11-15 Takatsuji-cho, Showa-ku, Nagoya-shi, Aichi F-term inside Ishizuka Glass Co., Ltd. 4F070 AA13 AA15 AA18 AA34 AA40 AA47 AA50 AA52 AA54 AB08 AB11 AC16 AC19 AC20 AC42 AC84 AE07 DA33 DA41 DB04 DB08 DC02 DC05 FA05 FA10 FA11 FA17 4H028 AA05 AA08 AA12 AA42 AA49 AB02 AB04 BA06 4J002 BB03W BB12 WCP03W03W03W CP03W03 DA056 DA057 DE076 DE146 DE236 DE246 DF036 DG046 DH056 DH057 DJ016 DJ036 DJ056 DK007 EG046 FB096 FB166 FB266

Claims (41)

[Claims] 1. A method comprising the steps of: contacting a sol composition in which a compound of a metal element and / or Si is dispersed and / or dissolved in a solvent with a carrier material; and drying the sol composition. Producing a composite composition for imparting flame retardancy by compounding a gel composition produced by drying the sol composition with the support material to obtain a composite composition for imparting flame retardancy. . 2. The flame-retardant composite particles obtained by compounding the gel composition on the entire surface or a part of the surface of the support material particles made of the support material are used as the flame-retardant composite particles. The method for producing a composite composition for imparting flame retardancy according to claim 1 to be obtained. 3. The composite particles for imparting flame retardancy, wherein the surface of the carrier material particles made of the carrier material are covered with a film of the gel composition as the composite particles for imparting flame retardancy. A method for producing a composite composition for imparting flame retardancy. 4. A mixing step of forming a mixture of the carrier material particles and the sol composition, and a drying step of evaporating the solvent from the mixture to form a dry composition.
Or the manufacturing method of the composite composition for imparting flame retardancy described in 3. 5. The flame-retardant composite according to claim 4, wherein the mixture is formed by immersing the carrier material particles in the sol composition, and then the mixture is dried without draining the mixture. A method for producing the composition. 6. The method for producing a flame-retardant composite composition according to claim 4, wherein the flame-retardant composite composition is obtained by crushing or crushing the dry composition. 7. A vibration and / or
The composite composition for imparting flame retardancy according to any one of claims 2 to 6, wherein the composite particles for imparting flame retardancy are obtained by drying while contacting the sol composition with the composition while stirring. Manufacturing method. 8. A striking medium having a larger diameter than the supporting material particles is mixed with the carrier material particles, and vibration and / or stirring is applied to an aggregate of the carrier material particles and the striking media.
A method for producing the composite composition for imparting flame retardancy according to the above. 9. The method for producing a flame-retardant composite composition according to claim 1, wherein the sol composition is produced by hydrolyzing a metal element and / or an alkoxide of Si. Method. 10. The method for producing a flame-retardant composite composition according to claim 1, wherein the solvent for producing the sol composition is an alcohol. 11. The method according to claim 9, wherein the amount of the solvent for preparing the sol composition is 25 to 98% by weight, and the amount of the alkoxide is 0.5 to 40% by weight. A method for producing a composite composition for imparting flammability. 12. The method for producing a flame-retardant composite composition according to claim 9, wherein the alkoxide contains Si and / or Ti as an essential component. 13. The method for producing a flame-retardant composite composition according to claim 1, wherein a metal salt of an inorganic acid or an organic acid is added to the sol composition. 14. The cation metal element of the metal salt is C
14. The method for producing a flame-retardant composite composition according to claim 13, comprising one or more of u, Al, Zn, Ni, Fe, Ti and Zr. 15. The composite composition for imparting flame retardancy according to claim 13, wherein an acid obtained by dissolving an acidic gas in water (hereinafter referred to as an acidic gas-based inorganic acid) is used as the inorganic acid. Method of manufacturing a product. 16. The acidic gas-based inorganic acid includes nitric acid,
The method for producing a flame-retardant composite composition according to claim 15, which is one or more of nitrous acid, sulfuric acid, sulfurous acid, and carbonic acid. 17. The composition according to claim 13, wherein the amount of the metal salt in the sol composition is 95% by weight or less.
7. The method for producing the composite composition for imparting flame retardancy according to any one of 6. 18. In the sol composition, when the weight ratio of the alkoxide is WA and the weight ratio of the metal salt is WB, WA / WB is set in the range of 0.01 to 30. A method for producing the composite composition for imparting flame retardancy according to any one of claims 13 to 17. 19. The sol-like composition contains 25 to 98% by weight of an alcohol as the solvent and 0.5 to 40% by weight of a silicon alkoxide as the alkoxide.
And 5 to 95% by weight of the metal nitrate as the metal salt
19. The method for producing a flame-retardant composite composition according to claim 17, wherein a mixture of water and 0.1 to 20% by weight of water is used. 20. Drying of the sol composition by 40 to 25.
The method for producing a flame-retardant composite composition according to any one of claims 1 to 19, which is performed at a temperature of 0 ° C. 21. The total content of the alkoxide and the metal salt in the sol composition is Ws (unit: g), the specific surface area of the carrier material particles is Sg (unit: m ² / g), The mixing amount of the support material particles in the powdery composition is Wg
When (unit: g), Ws / (Sg × Wg) is equal to 0.
The method for producing a flame-retardant composite composition according to claim 13, wherein the composition is adjusted to 002 to 2.0 g / m ² . 22. The method for producing a flame-retardant composite composition according to claim 2, wherein flame-retardant material particles are used as the support material particles. 23. The method according to claim 22, wherein the flame-retardant material particles have an average particle diameter of 0.05 to 100 μm. 24. The flame-retardant material particles are made of inorganic material-based particles or metal material-based particles.
24. The method for producing the flame-retardant composite composition according to 2 or 23. 25. The method for producing a composite composition for imparting flame retardancy according to claim 24, wherein the inorganic material-based particles mainly include at least one of aluminum hydroxide and magnesium hydroxide. 26. The method for producing a composite composition for imparting flame retardancy according to claim 2, wherein polymer particles are used as the support material particles. 27. The method for producing a flame-retardant composite composition according to claim 26, wherein the polymer material particles are made of a thermoplastic polymer material. 28. The method for producing a composite composition for imparting flame retardancy according to claim 26, wherein the polymer material particles are made of a thermosetting polymer material. 29. A flame-retardant composite composition produced by the method according to claim 1. Description: 30. The composite composition for imparting flame retardancy produced by the method according to any one of claims 1 to 28, which is composited with a substrate made of a polymer material (hereinafter, also referred to as a polymer substrate). And a flame-retardant polymer composite material. 31. The flame-retardant polymer composite material according to claim 30, wherein the flame-retardant composite particles are dispersed in the polymer matrix as the flame-retardant composite composition. 32. The flame-retardant polymer composite material according to claim 30, wherein the flame-retardant composite particles are fixed on the surface of the polymer substrate as the flame-retardant composite composition. 33. A flow-suppressing adjuvant, which suppresses the flow and dripping of the polymer substrate when the polymer substrate is melted by raising the temperature, together with the composite composition for imparting flame retardancy, is blended in the polymer substrate. The flame-retardant polymer composite material according to any one of claims 30 to 32. 34. The flow control adjuvant, comprising: boric anhydride;
34. The method according to claim 33, wherein a boric acid-based inorganic compound such as zinc borate, a phosphorus-based inorganic compound such as red phosphorus or an inorganic material such as carbon, a phosphorus-based organic compound such as ammonium polyphosphate, or silicone is used. Flame retardant polymer composite material. 35. The method according to claim 30, wherein the content ratio of the composite material for imparting flame retardancy in the polymer substrate is 5 to 150 parts by weight based on 100 parts by weight of the polymer substrate. The flame-retardant polymer composite material according to the above. 36. The flame-retardant composite composition is composited with the flame-retardant polymer composite material in a particle form, and the composite particle for flame-retardant composite has an average particle diameter of 0.05. ~ 50
The flame-retardant polymer composite material according to any one of claims 31 to 35, which has a thickness of 0 µm. 37. A flame-retardant polymer composite material formed by molding the flame-retardant polymer composite material according to claim 30 into a predetermined shape. 38. The molded article as a final molded article which does not assume remolding accompanied by softening of the polymer substrate.
The molded article of the flame-retardant polymer composite material according to the above. 39. The flame-retardant polymer composite material molded article according to claim 37, wherein the molded article is used as a temporary molded article for softening the polymer matrix to re-mold it into a desired secondary shape. 40. The temporary molded body is a granular molded product in which the composite particles for imparting flame retardancy are dispersed in a polymer matrix, and is reshaped into a secondary shape having a larger volume than each granular molded product. 40. The flame-retardant polymer composite material according to claim 39, which is used as a master batch. 41. The masterbatch is remolded together with a diluted polymer material composed of a polymer material of the same or different nature as the polymer substrate, whereby the content of the composite particles for imparting flame retardancy is higher than that of the master batch itself. The flame-retardant polymer composite material molded article according to claim 40, which is used for producing a secondary molded article having a small particle size.