JP2001131552A - Composite particle for imparting flame retardance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively provide an ecological composite particle for imparting flame retardance, capable of imparting a high flame retardance at a small amount added thereto, and hardly causing a harmful material at the time of production and combustion. SOLUTION: This composite particle 10 for imparting flame retardance has a structure obtained by covering a carrier material particle (a flame retardant particle) 1 with a compound layer 2 comprising a silicon component and/or a metal component, and oxygen. The compound layer 2 is the one capable of forming a glassy ceramic by being heated. The high flame retardance can be imparted to a material targeted for imparting the flame retardance by compounding (adding) the composite particle 10 for imparting the flame retardance, e.g. the one comprising a high-molecular material with the material targeted for imparting the flame retardance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to flame-retardant composite particles capable of imparting high flame retardancy to a material composed of a resin or the like.

[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 small amount of addition, and at the same time produces no harmful substances during production or combustion. It is an object to provide inexpensive composite particles for imparting flame retardancy.

[0007]

Means for Solving the Problems and Actions / Effects In order to solve the above problems, the composite particles for imparting flame retardancy of the present invention are:
Carrier material particles made of a flame-retardant material that is used to impart flame retardancy to the object by dispersing or fixing on the surface of the object to which flame retardancy is to be imparted (material to which flame retardancy is to be imparted) It has a structure in which a compound layer containing a silicon component and / or a metal component and oxygen is compounded on the surface.

The flame-retardant composite particles having a structure in which a compound layer containing a silicon component and / or a metal component and oxygen is compounded on the surface of such a carrier material particle made of a flame-retardant material are made of resin or the like. It can be mixed (added) to the material to be imparted with flame retardancy by mixing or coating. In this case, for example, high heat (for example, 50
(0 ° C. or higher), the compound layer of the composite particles for imparting flame retardancy forms a protective film that inhibits combustion due to the high heat, and provides high flame retardancy to the material to be imparted with flame retardancy. Can be granted. In addition, due to the effect of forming the protective film, it is possible to impart sufficient flame retardancy even if the compounding amount to the material to which the flame retardancy is to be imparted is small. As a result, the compounding amount of the flame retardant including the composite particles is reduced. it can. As a result, the strength and durability of the finally obtained material, as well as the moldability and fluidity (for example, in the case of a material that can be injection molded,
(Flowability in a mold) can be improved compared to the case of using a conventional flame retardant, that is, strength, durability, moldability,
The effect of suppressing a decrease in fluidity or the like can also be achieved. In addition,
The composite particles for imparting flame retardancy can impart flame retardancy by being dispersed in the material to be imparted with flame retardancy or by being fixed on the surface of the material to be imparted with flame retardancy.

On the other hand, in the above configuration, since the carrier material particles are composed of flame-retardant material particles, in addition to the effect of imparting flame retardancy by the formation of the protective film described above, in addition to the effect of the flame-retardant material particles as carrier material particles, Since the flame-retardant effect is added, the effect of the flame-retardant composite particles for imparting flame retardancy to the material to be imparted with flame retardancy is further improved.

The above-mentioned compound layer and carrier material particles may be constituted so as to contain no halogen component such as chlorine or fluorine, except for those which are inevitably mixed in the form of, for example, impurity components. Thereby, since no harmful gas is generated during the application of high heat as in the related art, ecologically complex particles for imparting flame retardancy can be realized.

[0011] The compound layer may be formed by heating to produce a vitreous ceramic mainly composed of silicon and / or metal oxide. The silicon component and / or metal component contained in the above-mentioned compound layer is liable to produce vitreous ceramics in combination with oxidation or the like by heating, and mainly contains the generated silicon and / or metal oxide. Since the vitreous ceramic has high heat resistance, it becomes an extremely strong protective film when high heat is applied, and it is possible to impart higher flame retardancy to the material to which flame retardancy is to be imparted. In addition, the vitreous ceramic as described above is
It may be present as a part of the compound layer from the beginning, or may be in a form in which a part or all of the compound layer is converted to a vitreous ceramic when heated. Also,
As the metal component, for example, Ti, Cu, Al, Zn, N
One or more of i and Zr or other transition metal elements can be employed.

[0012] The compound layer may contain a carbon component. When a carbon component is contained, for example, when a resin is used as the material to be imparted with flame retardancy, the compatibility (affinity) when the composite particles for imparting flame retardancy are combined with the material to be flame retarded is improved. In addition to being able to uniformly disperse the composite particles for imparting flame retardancy to the material to be imparted with flame retardancy, it is also possible to improve, for example, moldability when molding the material to be imparted with flame retardancy. It is.

[0013] Next, the composite particles for imparting flame retardancy can decompose and generate a combustion inhibiting gas by heating. In this case, when high heat is applied to the material to be imparted with flame retardancy, a combustion inhibiting gas is generated, and the combustion inhibiting gas further improves the flame retardant effect on the material to be imparted with flame retardancy. It is presumed that this improvement in flame retardancy is due to the fact that oxygen for combustion is relatively reduced by the combustion inhibiting gas in the vicinity of the material to which flame retardancy is imparted.

Specifically, the combustion inhibiting gas may be one which contains one or more of nitrogen, sulfur and carbon. In this case, for example, N ₂ gas, NO ₂ gas, and NO gas are generated as the nitrogen-containing gas, SO ₂ gas is generated as the sulfur-containing gas, CO ₂ gas is generated as the carbon-containing gas. To further improve the effect of imparting flame retardancy to steel.

On the other hand, the average particle size of the composite particles for imparting flame retardancy is preferably 0.05 to 500 μm. When the average particle size is less than 0.05 μm, it may be difficult to produce the composite particles for imparting flame retardancy, and when composite (added) to the material to be imparted with flame retardancy, uneven distribution occurs and the composite ( ) May not be uniform, and the effect of imparting flame retardancy may decrease, or the performance of the material to be imparted with flame retardancy may decrease, particularly in the uneven distribution region. Also, 500 μm
If the ratio exceeds 1, the distribution of composite (added) particles may become non-uniform, and the properties of the material to be imparted with flame retardancy, for example, if it is a resin, the properties such as fluidity may be reduced or flame retardancy may be imparted. The target material 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.

Examples of the flame-retardant material particles as the support material particles include hydrated metal compounds which are ecological non-halogen flame-retardant materials, mica such as muscovite, phlogopite, biotite and sericite, and kaolin. Minerals such as talc, zeolite, borax, diaspore, and gypsum; metal oxides such as magnesium oxide, aluminum oxide and silicon dioxide; metal compounds such as calcium carbonate; phosphorus compounds such as red phosphorus and ammonium polyphosphate; nitrogen Inorganic flame-retardant material particles (inorganic material-based particles) typified by organic compounds, phosphorus-based, silicone-based, nitrogen-based organic-based flame-retardant material particles, and metal powder particles (metal-based particles) Can be used. In addition,
It is most preferable to use inorganic flame-retardant material particles from the viewpoint of the addition to the resin, the flame-retardant effect, the cost and the like. In particular,
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.

The flame-retardant material particles have, for example, an average particle size of 0.1.
Those having a thickness of from 0.5 to 100 μm can be used. 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. If the upper limit is exceeded, 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 or the flame retardancy may not be imparted. The target material may cause poor appearance. The average particle size can be measured using, for example, a laser diffraction type particle size measuring device.

On the other hand, polymer material particles can be used together with the flame-retardant material particles as carrier 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 polymer material as the support material particles improves the affinity (affinity) with the resin, and the composite particles for imparting flame retardancy provide the flame retardancy. The material is uniformly dispersed in the target material, and the flame retardancy can be effectively imparted to the material to which the flame retardancy is to be imparted.

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 /
Fine powder particles such as polymer alloys such as PBT alloy, PC / PET alloy, PC / elastomer, PA / PP and PA / elastomer can be used.

As a method for producing the composite particles for imparting flame retardancy as described above, a so-called sol-gel method can be used. Hereinafter, the sol-gel method will be described in detail.

In the sol-gel method, for example, a sol-like composition generated from a solution (for example, an alkoxide solution) in which a metal element and / or an inorganic compound of Si is dispersed and / or dissolved in a solvent is made of a flame-retardant material. The method includes at least a step of bringing the sol-form composition into contact with the support material particles and a step of drying the sol-form composition. The purpose is to obtain composite particles for imparting properties. Such a sol-gel method 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. . In the above manufacturing method, the step of bringing the sol composition into contact with the carrier material particles includes a method of dipping the carrier material particles in the sol composition, a method of spraying the sol composition on the carrier material particles, and the like. Can be adopted.

Further, 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 a solvent from the mixture to form a dry composition. And a step. This is, for example, put the sol composition in a predetermined container,
After the support material particles are immersed in the mixture to form a mixture, the solvent is evaporated from the mixture. This is a very simple method because the solvent can be evaporated and dried without draining the mixture. . The drying step can be performed by heating drying or vacuum drying, or a combination thereof. Furthermore, the vibration and / or stirring may be applied to the aggregate of the support material particles while the sol-like composition is being brought 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 supporting material particles and to apply vibration and / or agitation to the aggregate of the supporting material particles and the striking medium. In this case, the drying time is reduced. It is possible to further shorten it.

Next, the sol composition is preferably prepared by hydrolyzing a metal element and / or an alkoxide of Si. The sol composition (gel composition) produced by hydrolyzing such an alkoxide contains metal and / or Si in the form of an oxide or the like, and the carbon component derived from the alkoxide remains. Becomes
As described above, the metal and / or Si generates vitreous ceramics due to high heat and imparts high flame retardancy to the material to which the flame retardancy is to be imparted. When used, the compatibility (affinity) when the composite particles for imparting flame retardancy are combined with the material to be imparted with flame retardancy is improved.

Alcohol can be used as the 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, it is possible to disperse or dissolve the alkoxide in a stabilized state, and to form a gel-like composition (compound layer) film having a uniform film thickness. it can.

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 can be 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 not be easily combined with the carrier material particles,
For example, the composition of the gel composition (compound layer) 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 by vitreous ceramics derived from the metal and / or Si of the alkoxide may be reduced, and the flame retardancy is imparted by the carbon component of the alkoxide. The adaptability to the target material 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 is reduced, and the sol-like composition may be difficult to be uniformly composited with the carrier material particles. .

The above alkoxide is composed of Si and / or Ti
Is an essential component. When Si and / or Ti is used as a component of an alkoxide, oxides such as SiO ₂ and TiO ₂ which are generated by hydrolysis are easily vitrified or turned into ceramics by high heat, and therefore have a particularly high effect of imparting flame retardancy. 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. Examples of the alkoxide using Si include, for example, tetraethoxysilane (Si (OC
₂ H ₅ ) ₄ ) can be used. As the alkoxide using Ti, for example, titanium isopropoxide (T
_{i (iso-OC 3 H 7} ) 4) or the like can be used.
Further, as other components, for example, Cu, Al,
A material containing one or more of Zn, Ni 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 (compound layer) coating are different from each other.

On the other hand, the sol-like 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,
Flame retardant material to which the composite particles for flame retardancy are added
When high heat is applied to the
Incoming gas (combustion inhibiting gas), for example, N-containing gas
N₂Gas or NO₂Gas, NO gas, and S-containing gas
SO₂Gas, CO as C-containing gas₂Gas etc.
And they further enhance the flame retardant effect on the
To improve. In addition, as a specific example of the above metal salt,
Copper oxide (Cu (NO₃) ₂・ 3H₂O), zinc nitrate (Zn
(NO₃)₂・ 6H₂O) and the like.
Further, in addition to the above inorganic acids, for example, organic acids may be used.
It is also possible to use oxalic acid, acetic 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. If the amount of the metal salt exceeds 95% by weight, the effect of imparting flame retardancy by vitreous ceramics derived from the metal and / or Si of the alkoxide, which is the 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. When WA / WB is less than 0.01, the effect of imparting flame retardancy by vitreous ceramics derived from the alkoxide component may not be sufficiently obtained.
If A / WB is more than 30, the effect of imparting flame retardancy by the generated gas derived from the metal salt may not be sufficiently obtained, and as a result, the effect of imparting flame retardancy of the composite particles for imparting flame retardancy decreases. May be.

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 (compound layer) is formed on the carrier material particles by the sol-gel method.
Can be made uniform. 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 above production method, for example, a step of preparing a first solution by dispersing and / or dissolving the metal salt in alcohol, and dispersing and / or dissolving an alkoxide in the first solution to form a second solution. And a step of adding water to the second solution to form a sol-like 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 water or alcohol, and to add a metal salt and a solvent such as alcohol or water to the alkoxide. If so, 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, when 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. If the amount is less than 1 g, the production efficiency of the composite particles for imparting flame retardancy is reduced, and 20 kg
When the ratio exceeds the above, the composite amount of the sol composition per unit support material particle may decrease, and the effect of imparting flame retardancy may decrease. The mixing amount is preferably 1 kg to
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 .

[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 embodiment of the composite particles for imparting flame retardancy of the present invention. The composite particles 10 for imparting flame retardancy include a silicon component and / or
Alternatively, a compound layer 2 containing a metal component and oxygen and generating a glassy ceramic by heating, for example, has a configuration in which the compound layer 2 is composited with the carrier material particles 1 made of flame-retardant material particles, and is manufactured by the sol-gel method described above. Can be. 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 compounding of the compound layer 2 and the support material particles 1 is as follows.
For example, as shown in FIG. 1A, a state in which the compound layer 2 covers the surface of the carrier material particles 1 substantially uniformly over the entire surface is most desirable in terms of exhibiting the flame retardant effect. However, as long as a good flame-retardant effect can be maintained, as shown in FIG. 1B, the compound layer 2 partially adheres to the surface of the support material particles 1 and a part of the surface is uncoated. It may be in the form of being 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 FIG. 1A, the thickness of the compound layer 2 coated or adhered to the carrier material particles 1 is, for example, 0.0
It is about 1 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 compound layer 2 is coated or adhered to the support material particles 1 in a uniform and thin film form. The effect of imparting flame retardancy is great, and the amount of the composite particles 10 for imparting flame retardancy is
For example, 5 to 150 parts by weight based on the material to be provided with flame retardancy,
Preferably, a small amount of about 20 to 100 parts by weight can provide sufficient flame retardancy. 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.

The compound layer 2 is schematically shown, for example, in FIG.
It is presumed that it has such a structure.
And the molecular formula is schematically shown, and the molecular formula is
It also means that it has a specific structure shown
Not). Inside or surface of the material 50 to be provided with flame retardancy
Silicon and / or metal in the compound layer 2
(These are indicated by M in the figure) are oxides or alkoxides 5
2 (for example, SiO 2 ₂, ZrO₂, Si (OCnH
m) l (n ≧ 1, m ≧ 1, l ≧ 1 etc.), or a single unit
And the carbon component 51 is, for example, CnHm (n
≧ 1, m ≧ 1)
You.

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 (compound layer) 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 the gel composition (compound layer) 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, Ni, O, N and C.

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 the gel composition (compound layer) 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 the gel composition (compound layer) 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 the gel composition (compound layer) 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 the tensile test by the tensile test, the tensile strength was 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 the gel composition (compound layer) 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).

The electron micrographs before and after coating the gel composition (compound layer) with respect to the composite particles for imparting flame retardancy obtained by coating the carrier material particles in the present example by the sol-gel method are shown in FIG. Shown in FIG.
(A) is a carrier material particle before coating, and FIG.
Indicates carrier material particles (composite particles for imparting flame retardancy) after coating, and it can be seen that the carrier material particles are uniformly coated with the sol composition (compound layer).

[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 Support material particle (flame retardant material particle) 2 Gel composition (compound layer) 10 Composite particle for imparting flame retardancy 11 Flame retardant material particle 50 Material to be imparted with flame retardancy

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hisakuni Ito 11-15 Takatsuji-cho, Showa-ku, Nagoya-shi, Aichi F-term inside Ishizuka Glass Co., Ltd. 4H028 AA05 AA10 AA12 AA42 AB04 BA04 BA06 4J002 AA001 BB03W BB12W BC03W BN15W CD00W CF06W CF07W CG00W CG00X CH07W CK02W CL00W CL00X CP03W DA056 DE076 DE146 DE236 DG056 DH056 DJ016 DJ036 DJ046 DJ056 DK006 DL006 EC076 FA086 FB076 FD136

Claims (8)

[Claims] 1. A method for imparting flame retardancy to an object by dispersing or fixing it on the surface of the object to which flame retardancy is imparted, wherein the surface of the carrier material particles made of a flame retardant material is used. Composite particles for imparting flame retardancy, having a structure in which a compound layer containing a silicon component and / or a metal component and oxygen is compounded. 2. The composite particles for imparting flame retardancy according to claim 1, wherein the compound layer is converted into a vitreous ceramic by heating. 3. The composite particle for imparting flame retardancy according to claim 1, wherein the compound layer contains a carbon component. 4. The composite particles for imparting flame retardancy according to claim 1, wherein the combustion-inhibiting gas is decomposed and generated by heating. 5. The flame-retardant composite particles according to claim 4, wherein the combustion-inhibiting gas contains one or more of nitrogen, sulfur and carbon. 6. The flame-retardant composite particles according to claim 1, having an average particle size of 0.05 to 500 μm. 7. The composite particles for imparting flame retardancy according to claim 1, wherein the support material particles are inorganic material-based particles or metal material-based particles. 8. The flame-retardant composite particles according to claim 7, wherein the inorganic material-based particles are mainly composed of at least one of aluminum hydroxide and magnesium hydroxide.