WO2001009251A1

WO2001009251A1 - Flame-retardant polymer composite material, composition for producing, formed article of flame-retardant polymer composite material, masterbatch for producing formed article of flame-retardant polymer composite material and method for producing flame-retardant polymer composite material

Info

Publication number: WO2001009251A1
Application number: PCT/JP2000/005191
Authority: WO
Inventors: Tatsuaki Oda; Makio Nomura; Toshikuni Ito
Original assignee: Ishizuka Garasu Kabushiki Kaisha
Priority date: 1999-08-03
Filing date: 2000-08-03
Publication date: 2001-02-08
Also published as: JP2001131431A; AU6471000A

Abstract

A flame-retardant polymer composite material characterized in that the composite material comprises a substrate (50) comprising a polymer material such as a resin and, dispersed therein or attached to the surface thereof by coating or the like, composite particles (10) for imparting flame retardancy which forms, upon heating, a glass-like ceramic containing oxides of silicon and/or a metal as main components; a composition for producing the flame-retardant polymer composite material; and a formed product of the flame-retardant polymer composite material. When the flame-retarded material is heated to a high temperature, compounds in composite particles (10) for imparting flame retardancy form, due to heat, a protective film hindering the material from burning, and as a result, the flame-retarded material can acquire, at a low cost, a high flame retardancy, for example, a flame retardancy satisfying the level of V-0 to V-2 according to UL94 flammability test. The formation of a protective film also allows the provision of satisfactory flame retardancy to the flame-retarded material by incorporation of a small amount of the compounds in the composite particles.

Description

Description Flame retardant polymer composite material, composition for producing flame retardant polymer composite material, flame retardant polymer composite material molded article, master batch for producing flame retardant polymer composite material molded article, and flame retardant Method for manufacturing polymer composites

The present invention relates to a flame-retardant polymer composite material, a composition for producing a flame-retardant polymer composite material, a flame-retardant polymer composite material molded article, a master batch for producing a flame-retardant polymer composite material molded article, and And a method for producing a flame-retardant polymer composite material. Background art

Resin materials (polymer materials) are used in a wide range of fields due to their excellent chemical and physical properties and excellent moldability and additivity, and demand is growing. However, the major drawback of most resin materials is that they are flammable, so their use is restricted, and flame retardancy of resin materials is desired.

Halogen-based flame retardants are the mainstream flame retardants used to make resin materials flame-retardant, but they are not environmentally friendly due to dioxins and furans generated from halogen-based flame retardants. The development and commercialization of this is desired. Non-halogen phosphorus-based flame retardants are not preferred because phosphine, which is a hydride of phosphorus, is generated.

In addition, there are inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.Aluminum hydroxide has low toxicity, low smoke emission, good electrical insulation, and low cost. There are many. However, there are problems with mechanical properties, reduced water resistance, increased viscosity of the compound for compounding a large amount (150 parts or more), and low flame retardancy at high temperatures of 400 ° C or more. Dehydration during processing of resin with high processing temperature It is easy to foam.

Magnesium hydroxide has the same flame-retardant effect as aluminum hydroxide, and there is no dehydration and foaming at the processing temperature of resin, which is a drawback of aluminum hydroxide.However, it is weak against acids and under high humidity conditions. It reacts with carbon dioxide in the air to produce magnesium carbonate and whitens, and has the disadvantages of higher cost than aluminum hydroxide. Since these inorganic flame retardants alone have a small flame-retardant effect, it is necessary to use them together with other flame retardants.

The present invention solves the above-mentioned conventional problems, and provides a flame-retardant polymer composite material which is inexpensive and exhibits high flame retardancy, a composition for producing a flame-retardant polymer composite material for producing the same, A molded article composed of the flame-retardant polymer composite material, a master batch for producing a flame-retardant polymer composite material molded article, and a method for producing a flame-retardant polymer composite material are provided. Yes <Disclosure of the Invention

In order to solve the above-mentioned problems, a first configuration of the flame-retardant polymer composite material of the present invention is mainly composed of a compound containing a silicon component and Z or a metal component and oxygen, and is heated by heating to silicon and / or The present invention is characterized in that the particles for imparting flame retardancy to produce glassy ceramics mainly composed of metal oxides are dispersed in a matrix made of a polymer material (hereinafter also referred to as a polymer matrix).

Further, the second configuration of the flame-retardant polymer composite material of the present invention is mainly composed of a compound containing a silicon component and / or a metal component and oxygen, and mainly composed of silicon and a metal oxide by heating. The present invention is characterized in that the particles for imparting flame retardancy to produce glassy ceramics are fixed on the surface of a substrate made of a polymer material. This configuration can be combined with the first configuration described above.

According to the above configuration, the particles for imparting flame retardancy, which produce vitreous ceramics mainly composed of silicon and / or metal oxides by heating, are formed on a substrate made of a polymer material such as resin. In other words, by dispersing in and / or coating on the surface of the material to be imparted with flame retardancy, for example, when high heat (for example, 500 ° C or more) is applied to the material to be imparted with flame retardancy, However, due to the high heat, the compound of the particles for imparting flame retardancy forms a protective film that inhibits combustion. As a result, the material to which the flame retardancy is to be imparted has high flame retardancy, for example, UL94 flammability test (In this specification, the one based on the 5th edition: October 26, 1996, was adopted. It is possible to provide flame-retardant performance that satisfies the range of V-0 to V-2. 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 flame retardancy is to be added is small, and as a result, the compounding amount of the flame retardant including the above particles is reduced. The conventional flame retardant can be used for the strength and durability of the final material, as well as its moldability and fluidity (for example, in the case of a material that can be injection molded, its flowability in the mold). An effect that can be improved as compared with the case where it is provided, that is, an effect of suppressing a decrease in strength, durability, moldability, fluidity, and the like can also be achieved.

The silicon component and / or the metal component contained in the compound constituting the particles for imparting flame retardancy as described above is liable to produce glassy ceramics in combination with the oxidation and the like caused by heating. Since vitreous ceramics mainly composed of Z or metal oxides have high heat resistance, they become an extremely strong protective film when high heat is applied, and provide even higher flame retardancy for the material to which flame retardancy is to be imparted. Property can be imparted. The vitreous ceramic as described above may exist as a part of the compound from the beginning, or may be converted to a vitreous ceramic when a part or all of the compound is heated. Good. As the metal component, for example, one or more of Ti, Cu, Al, Zn, Ni, and Zr, or other transition metal elements can be used. In the flame-retardant polymer composite material of the present invention, when tested in the UL 94 flammability test, the silicon-converted weight content WSi of the silicon component in the combustion residue was the same as the metal component. It is preferable that the total WSi + WM with the acid content in terms of acid content of WM be 0.5 to 60% by weight. When WSi + WM exceeds 0.5% by weight, the composite material Mechanical properties such as strength (eg, tensile strength) and elongation tend to be impaired, and if WSi + WM is less than 60% by weight, contribution to the effect of improving flame retardancy may be insufficient. Incidentally, the silicon component is converted into S I_〇 _2. When a metal component is contained, each metal component is converted to an oxide having a composition corresponding to the valence of the contained metal ion (which can be specified by X-ray photoelectron spectroscopy). For example, if Z n ^{2 +} is detected, the corresponding oxide is Z n O, and if Cu + is detected, the corresponding oxide is Cu ₂₀ .

The particles for imparting flame retardancy may be configured so as to contain no halogen component such as chlorine or fluorine, except for particles that are inevitably mixed in the form of, for example, impurity components. This makes it possible to realize ecological flame-retardant materials because no harmful gas is generated as in the past when high heat is applied.

Next, the above compounds can be formed as containing a carbon component. As a result, the compatibility (affinity) when the particles for imparting flame retardancy are combined with the material for imparting flame retardancy is improved, and the particles for imparting flame retardancy are made uniform with respect to the material for imparting flame retardancy. In addition to being able to be dispersed, it is also possible to improve, for example, the moldability when molding the material to be imparted with flame retardancy.

Next, the 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 flame-retardant material, a combustion-inhibiting gas is generated, and the combustion-inhibiting gas further enhances the flame-retardant effect on the flame-retardant material. This improvement in flame retardancy is presumed to be due to the relative decrease in oxygen for combustion by the combustion inhibiting gas in the vicinity of the material to which flame retardancy is to be imparted.

Specifically, as the combustion inhibiting gas, a gas containing one or more of nitrogen, sulfur and carbon can be generated. In this case, C 0 ₂ gas or the like occurs, for example nitrogen-containing N ₂ gas and N 0 ₂ gas was used as gas, NO gas, S 0 ₂ gas as the sulfur-containing gas, as the carbon-containing gas, they are flame retardant Further enhance the flame retardant effect on the material to which the property is to be imparted. On the other hand, the average particle diameter of the particles for imparting flame retardancy is preferably 0.05 to 500 / zm. If the average particle size is less than 0.05 / im, it may be difficult to manufacture the particles for imparting flame retardancy, and uneven distribution may occur when compounded (added) to the material to be imparted with flame retardancy. Since the composite (addition) may not be uniform, the effect of imparting flame retardancy may decrease, or the performance of the material to which flame retardancy is imparted may decrease, particularly in the uneven distribution region. If it exceeds 500 / im, the distribution of the compounded (added) particles may be non-uniform, and the properties of the material to which flame retardancy is to be imparted, such as the flowability of a resin, may be reduced. In some cases, the material to which the flame retardant is to be imparted has poor appearance. The average particle size can be measured by using, for example, a laser diffraction type particle size analyzer. In this case, since the diffraction behavior of the incident laser light by the aggregated particles and the diffraction behavior by the isolated primary particles do not greatly differ in the measurement by the laser diffraction type particle sizer, the measured particle size is It cannot be distinguished from each other whether the particle size exists as a single particle or the particle size of the aggregated secondary particles. Therefore, the average particle size measured by this method is a value reflecting the average particle size of the secondary particles, which broadly includes isolated primary particles that do not cause aggregation. The average particle size of the particles for imparting flame retardancy is desirably 0.1 to 300 μπι.

The polymer material forming the substrate is, for example, a general-purpose resin such as polyethylene (ΡΡ), polypropylene (ΡΡ), polystyrene (PS), acrylonitrile 'butadiene' styrene (ABS), acrylic resin, and modified polyphenylene. Engineering plastics such as polyester (ΡΡΕ), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polyamide (PA), and PCZAB Salloy, PCZPBT alloy, PCZPET alloy, PC / elastomer 1.Polymer alloys such as PAZPP, PA elastomer, etc., and heat of isoprene-based, nitrile-based, epoxy-based rubber, epoxy resin, unsaturated polyester resin, phenol resin, melamine resin, etc. Use of curable resin Yes, but not limited to these.

In the polymer composite material of the present invention, inorganic or organic flame retardant particles or flame retardant auxiliary particles together with the flame retardant imparting particles comprising the above compound (when these are collectively referred to, the flame retardant material (Also referred to as particles). In addition to the effect of imparting the flame retardancy of the particles for imparting flame retardancy, the effect of imparting the flame retardancy of the flame retardant material particles is also synergistically added, so that a higher flame retardant effect can be achieved. Examples of the flame-retardant material particles include ecological non-halogen flame-retardant hydrated metal compounds, mica such as muscovite, phlogopite, biotite, sericite, kaolin, talc, zeolite, borax, and diaspore. , Gypsum and other minerals, metal oxides such as magnesium oxide, aluminum oxide and silicon dioxide, metal compounds such as calcium carbonate, phosphorus-based compounds such as red phosphorus and ammonium polyphosphate, and inorganics typified by nitrogen-based compounds Flame-retardant material particles (inorganic material particles), phosphorus-based, silicone-based, nitrogen-based organic flame-retardant material particles, and metal powder particles (metal material-based particles) can be used. It is preferable to use, for example, such flame-retardant material particles having an average particle size of 0.05 to 10 O jum. If the average particle size is less than the above lower limit, the production may be difficult, and if the composite (addition) is made to a polymer substrate, uneven distribution may occur, and the composite (addition) may not be uniform. The effect of imparting flammability may be reduced, or the performance of the polymer substrate may be reduced particularly in the unevenly distributed region. If the upper limit is exceeded, the distribution of the compounded (added) particles may become non-uniform, and the properties of the polymer substrate, for example, properties such as fluidity may be reduced, or the resulting flame-retardant polymer may be obtained. The appearance of the composite material may be poor. In particular, when the inorganic material-based particles are mainly composed of at least one of aluminum hydroxide and magnesium hydroxide, the effect of imparting flame retardancy to the substrate is further enhanced. The average particle size can be measured using, for example, a laser diffraction type particle size measuring device. When metal particles (for example, a metal mainly composed of Al, Ni, and Mg) are used, the composite material of the present invention is used for, for example, a housing of an electronic device, in addition to improving the effect of imparting flame retardancy. If you do, harmful electricity An electromagnetic shielding effect of shielding leakage of magnetic waves can also be achieved.

Next, by molding the flame-retardant polymer composite material of the present invention into a predetermined shape, a flame-retardant polymer composite material molded article suitable for various uses can be obtained. The molding method is not particularly limited, and any molding method such as press molding, blow molding, extrusion molding, injection molding or calendaring can be used. It is also possible to form the composite particles for molding by coating the above compound on a core material of a polymer material, and to perform the above molding while softening the core material of the composite particles. In this case, the core portion of the composite particles forms a matrix after molding, and the coated compound portion is dispersed in the matrix to form the structure of the flame-retardant polymer composite material of the present invention. It will be.

The above-mentioned flame-retardant polymer composite material molded article can be constituted as a final molded article (final molded product corresponds to this), for example, without assuming remolding accompanied by softening of the polymer matrix. The applicable object is any molded product that requires flame retardancy and is not particularly limited, but examples are as follows.

· Automotive parts: Interior parts such as instrument panels, exterior parts such as bumpers, plastic parts in engines, etc.

'—Generally weak electrical appliances: Housing and other parts for home appliances such as TVs, videos, personal computers, audio players, microwave ovens, etc.

• Architectural components (interior components, exterior components)

· Textile products (clothing, rugs, curtains, etc.)

• Rubber or elastomer material: flooring, sealing material, seismic material, etc. (The polymer material used as the substrate must be rubber or elastomer)

• Sheet materials, paints, etc.

— On the other hand, the molded article can be a temporary molded article for softening the polymer matrix and re-forming it into the desired secondary shape. By using such a temporary molding, the final molding The production efficiency of body products can be greatly increased. For example, when the material of the polymer substrate used lacks fluidity, local irregularities in material flow can be achieved by using a preform having an intermediate shape that individually corresponds to the final secondary shape as a temporary molded body. And products with few defects can be manufactured efficiently.

On the other hand, the temporary molded body is a granular molded article in which the particles for imparting flame retardancy are dispersed in a polymer matrix, and is used as a master bar for reshaping into a secondary shape having a larger volume than each granular molded article. It can be made as a stick. Specifically, the master-batch (hereinafter, also simply referred to as a master batch) for manufacturing a molded body of a flame-retardant polymer composite material mainly includes a compound containing a silicon component and / or a metal component and oxygen, Particles for imparting flame retardancy, which produce glassy ceramics mainly composed of silicon and Z or metal oxides by heating, are composed as granular molded products dispersed in a matrix made of a polymer material, and each granular molded It is characterized by being used for reshaping into a secondary shape that has a larger volume than an object. Such a masterbatch can be used as a molding base having high fluidity in various molding machines such as an injection molding machine, and greatly contributes to simplification of a molding process and higher efficiency. In this case, the masterbatch is remolded together with a dilute polymer material consisting of a polymer material of the same or different nature as the polymer substrate, so that the secondary batch has a smaller content of particles for imparting flame retardancy than itself. Can be used to make body. In this way, the content of the particles for imparting flame retardancy in the final secondary molded body can be freely and easily adjusted by changing the mixing ratio of the master batch to the diluted high molecular weight material. It becomes possible to do. In addition, during the production of the masterbatch, the polymer matrix and the particles for imparting flame retardancy are kneaded, and during molding, the masterbatch is mixed with the diluted high-molecular material so that the polymer matrix is difficult to mix into the polymer substrate. Dispersion of the particles for imparting flammability is achieved in two stages, so to say, the dispersion state of the particles in the finally obtained secondary molded article can be made more uniform.

Specifically, the flame-retardant polymer composite material of the present invention is produced by the following production method. Can be manufactured. In the production method, a sol composition in which a metal element and a compound of Z or si (for example, an inorganic compound) are dispersed and Z or dissolved in a solvent is dried to form a gel composition, and the gel composition is formed. The composition is dispersed in a matrix composed of a polymer material to obtain a flame-retardant polymer composite material.

Thus, the particles for imparting flame retardancy can be easily produced by the so-called sol-gel method, in which the sol composition is dried to obtain gel composition particles. The sol-gel method as described above is simple and does not require special equipment, so it is possible to significantly reduce the production cost and generate harmful substances as in the past. no _t flame retardant particles obtained by such a production method is configured by a compound of gel-like metal element and Z or S i. If this is mixed (coated) with a material such as a resin by adding or coating the flame-retardant material, for example, when a high heat is applied to the material to which the flame-retardant material is applied, the high heat makes the flame-retardant. The above compound in the particles for imparting property becomes glass or ceramic, and the compound obtained by vitrification or ceramic becomes a protective film, thereby imparting high flame retardancy to the material to be imparted with flame retardancy. It becomes possible, and a material obtained by compounding such particles for imparting flame retardancy does not generate a harmful gas as in the prior art when a high heat is applied, so that it becomes an ecological flame retardant material.

In addition, as a method of dispersing the gel composition in a matrix composed of a polymer material, for example, the above gel composition is pulverized into gel composition particles to form the gel composition particles. After mixing and dispersing in a softened thermoplastic resin or uncured thermosetting resin, the resin is cured to disperse the gel-like composition particles in a matrix composed of thermoplastic resin or thermosetting resin. Can be blended. By such a method, the sol composition can be easily and uniformly dispersed and mixed in the substrate. The sol composition may be spray-dried to form gel-like yarn particles. The above-mentioned composite particles for molding can be produced by coating the surface of a core material of a polymer material with a sol composition. The average particle size of the gel composition particles is preferably adjusted to 0.5 to 500 μπι. Gel composition particles having a particle size of less than 0.5 / m are difficult to produce, and when blended in a substrate, uneven distribution may occur and dispersion may not be uniform, resulting in gel composition particles. In some cases, the effect of imparting flame retardancy to the polymer substrate is reduced, and the performance of the manufactured flame retardant polymer composite material is reduced particularly in the unevenly distributed region. If it exceeds 500 m, the dispersion distribution of the gel-like composition becomes non-uniform, and the flame retardancy of the flame-retardant polymer composite material may decrease, and the fluidity of the flame-retardant polymer composite material And the like, and the flame-retardant polymer composite material may cause poor appearance.

The mixing ratio of the gel composition to the above-mentioned substrate is preferably from 0.0 :! to 100 parts by weight per 100 parts by weight of the substrate. In the present invention, high flame retardancy can be imparted to the polymer substrate even when the amount of the gel composition having the effect of imparting flame retardancy is as small as described above. . If the mixing ratio is less than 0.1 part by weight, the effect of imparting flame retardancy by the gel-like composition particles may be reduced. If it exceeds 100 parts by weight, the flame-retardant polymer composite material may be used. In some cases, problems such as drastically changing the properties such as fluidity and physical properties of the material may occur.

On the other hand, the sol composition can be produced by hydrolyzing a metal element and / or an alkoxide of Si. The sol-like composition produced by hydrolyzing such an alkoxide contains a metal element and / or an oxide of Si, and an organic substance (carbon component) derived from the alkoxide remains. Therefore, the gel composition obtained by drying the sol composition also contains oxides and organic substances. As described above, this oxide is vitrified or ceramicized by high heat and has high flame retardancy to the polymer substrate. Can be granted. In addition, the residual organic matter improves the affinity (affinity) when, for example, dispersing the gel composition (particles) in a polymer substrate, and makes the gel composition (particles) uniform with the polymer substrate. In addition to being able to disperse, the moldability of the flame-retardant polymer composite material can be improved. Alcohol can be used as a solvent for preparing the sol composition. Since alcohol has a relatively low boiling point, it has the advantage that the drying process 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 acetyl acetone, aromatic hydrocarbon solvents such as toluene and xylene, cyclic hydrocarbon solvents such as cyclohexane, other chain hydrocarbon solvents, and These mixed solvents (a mixed solvent with alcohol is also possible) can be used. 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 solvent has a low water content, the alkoxide can be dispersed or dissolved in a stabilized state.

In addition, the compounding quantity of the solvent for making a sol-like composition is 25-98 weight. / ₀ , the amount of the alkoxide is preferably about 0.5 to 40% by weight. If the amount of the solvent is less than 25% by weight, the alkoxide may be difficult to uniformly disperse and / or dissolve, so that the hydrolysis reaction of the alkoxide may be difficult to occur, and the gel composition may be unsatisfactory. May be stable. If the amount of the solvent exceeds 98% by weight, the drying step for evaporating the solvent may take a long time. On the other hand, when the compounding amount of the alkoxide is less than 0.5% by weight, the effect of imparting flame retardancy due to vitrification or ceramicization of the metal element and / or Si of the alkoxide may be reduced, and the alkoxide organic compound may not be used. The compatibility of the components with the polymer substrate may also be reduced. If the amount of the alkoxide exceeds 40% by weight, the dispersibility and solubility of the alkoxide in the solvent may decrease, and the gel composition may become unstable.

The alkoxide preferably contains Si and no or Ti as essential components. With S i and Z or T i as a component of alkoxide, oxide hydrolyzed by such for example S i 0 ₂ and T i 0 ₂ produced was easily vitrified or ceramic by high fever Therefore, the effect of imparting flame retardancy is particularly high. Further, since alkoxides containing si and Z or τ i are hard to gel, it is possible to obtain a sol composition in a stable state. Above all, s 〖is most excellent as an alkoxide component in consideration of the stability of the generated oxide, the stability of the sol-like composition, and the like. As an alkoxide using Si, for example, tetraethoxysilane (S i (OC ₂ H ₅ ) J) or the like can be used. As an alkoxide using Ti, for example, titanium isopropoxide (T i ( iso-OC ₃ H ₇ ) ₄ ) etc. In addition, other components include, for example, one or more of Cu, Al, Zn, Ni and Zr Or an element containing another transition element, for example, aluminum isopropoxide (A 1 (OC ₃ H ₇ ) ₃ ), etc. can be used. The constituents can be changed according to the purpose, and in this case, the properties of the gel composition compound formed are different from each other.

On the other hand, a metal salt of an inorganic acid or an organic acid can be added to the sol composition. In this case, the cationic metal element of the metal salt preferably contains one or more of Cu, Al, Zn, Ni, Fe, Ti, and Zr. In particular, as the inorganic acid, an acid obtained by dissolving an acidic gas in water (hereinafter referred to as an acidic gas-based inorganic acid) is preferably used. Note that other transition elements other than those described above can be used as the cation metal element. The above-mentioned acidic gas refers to a gas that shows acidity when dissolved in water. As the acidic gas-based inorganic acid, for example, one or more of nitric acid, nitrous acid, sulfuric acid, sulfurous acid, and carbonic acid can be used. When such a metal salt is contained in the sol-like composition, when high heat is applied to the flame-retardant material to which the flame-retardant particles are added, the metal salt is derived from the acidic gas-based inorganic acid. gas, for example, N ₂ gas or N0 ₂ gas and NO gas as the N-containing gas, S_〇 ₂ gas as a S-containing gas, the combustion inhibition gases such C_〇 ₂ gas as C-containing gas generated that , That These further improve the flame-retardant effect on the material to be provided with flame-retardancy. As specific examples of the metal salt is copper nitrate _{(C u (N 0 3)} 2 - 3 H 2 0), zinc nitrate _{_{(Z n (N0 3) 2}} · 6 Η 2 0) to illustrate the like Can be. In addition to the above-mentioned inorganic acids, for example, oxalic acid, acetic acid and the like can be used as organic acids.

The content of the metal salt in the sol composition is preferably 95% by weight or less. If the content of the metal salt exceeds 95% by weight, the effect of imparting flame retardancy due to vitrification or ceramicization of the metal element of alkoxide and Ζ or Si, which is the main factor of the effect of imparting flame retardancy, is reduced There is. In the sol-like composition, when the weight ratio of the alkoxide is WA and the weight ratio of the metal salt is WB, WA / WB may be set in the range of 0.01 to 30. preferable. When WAZWB is less than 0.01, the effect of imparting flame retardancy due to vitrification or ceramicization derived from the alkoxide component may not be sufficiently obtained, and when WAZWB exceeds 30, it is derived from metal salts. In some cases, the effect of imparting flame retardancy due to the generated gas may not be sufficiently obtained, and as a result, the effect of imparting flame retardancy to the substrate may be reduced.

The sol-like 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. It is preferable to use a mixture of 0.1% by weight and 0.1 to 20% by weight of water. When the sol composition is formed in such an amount, the hydrolysis reaction of the sol composition proceeds efficiently, and the gel composition produced by the sol-gel method can be stabilized. . As a result, the effect of imparting flame retardancy to the polymer substrate derived from the alkoxides and metal salts described above can be more effectively exerted. In the above production method, for example, a step of dispersing and / or dissolving the metal salt in alcohol to form a first solution, and a step of dispersing and / or dissolving 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. Thus, metal salt for alcohol, By sequentially dispersing and dissolving or dissolving the alkoxide and then adding water to the second solution in a stepwise manner, it is possible to efficiently produce the sol composition. In addition, for example, it is also possible to disperse and disperse Z or dissolve the alkoxide in a solvent such as alcohol, and to add a solvent such as a metal salt or alcohol to the alkoxide. The order of the above steps can be arbitrarily changed. Next, the sol composition is preferably dried at a temperature in the range of 40 to 250 ° C. If the temperature is lower than 40 ° C, it may take a long time to dry the sol composition.If the temperature exceeds 250 ° C, the metal element of the alkoxide and the silicon or Si do not vitrify. It may become ceramic. When performing drying under reduced pressure, it is necessary to adjust the temperature and the pressure so that the gel composition is generated in a stable state.

In addition, when the polymer substrate made of the polymer material is melted by increasing the temperature together with the flame-retardant-imparting particles, a flow-suppressing aid that suppresses the flow and dripping of the polymer substrate may be added to the polymer substrate. it can. 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 suppression adjuvant include boric acid-based inorganic compounds such as boric anhydride and zinc borate, and red phosphorus (for example, Suzuhiro Chemical: Novaled (trade name); ) Etc. or inorganic materials such as carbon (for example, expandable carbon represented by GREP-EG (trade name) manufactured by Tosoh, GRAF Guard (trade name) manufactured by UCAR Carbon), etc. System or silicone or the like can be used.

In the flame-retardant polymer composite material of the present invention, the content ratio of the particles for imparting flame retardancy in the polymer substrate is 0.1 to 100 parts by weight with respect to 100 parts by weight of the polymer substrate. It is better to If the content is less than 0.1 part by weight, the effect of imparting flame retardancy may be reduced.If the content is more than 100 parts by weight, the properties of the polymer substrate may be greatly changed. May occur. The content ratio is preferably 1 to 50 parts by weight. JP 51 1

15 Brief description of the drawings

FIG. 1 is a schematic view showing a form in which particles for imparting flame retardancy are dispersed in a polymer material matrix.

FIG. 2 is a schematic diagram showing an example in which another flame-retardant material particle is blended and used with particles for imparting flame retardancy.

FIG. 3 is a schematic diagram showing an example of a method for producing a masterbatch made of the flame-retardant polymer composite material of the present invention, together with various forms of master-batch particles.

FIG. 4 is a schematic cross-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.

Figure 6 is an explanatory diagram showing some usage patterns of the master batch.

FIG. 7 is an explanatory diagram illustrating a method for obtaining a flame-retardant polymer composite material of the present invention using a two-component mixed resin, and some application forms thereof.

FIG. 8 is a process explanatory view showing some examples of a method of fixing particles for imparting flame retardancy to the surface of a polymer material substrate.

FIG. 9 is a schematic diagram inferring the molecular level structure of a compound. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to examples shown in the drawings.

FIG. 1 is a view conceptually showing one embodiment of the flame-retardant polymer composite material of the present invention. This material has a structure in which particles 10 for imparting flame retardancy are dispersed in a polymer material substrate 50. The particles 10 for imparting flame retardancy contain a silicon component and a metal component or a metal component and oxygen, and are composed of, for example, a compound that generates a vitreous ceramic by heating. Specifically, the particles are produced by the sol-gel method described above. can do. Although the particle 10 is schematically drawn in a spherical shape, the shape varies in various ways depending on the manufacturing method, and the particle 10 is not always necessarily spherical. The amount of the flame retardancy-imparting particles 10 with respect to the polymer material substrate 50 is, for example, 0.1 to 100 parts by weight based on the former as 100 parts by weight, and is preferably as small as about 1 to 50 parts by weight. Sufficient flame retardancy can be imparted by addition. Since it is added in a small amount, there is little change in the physical properties of the material to which flame retardancy is to be imparted, such as a resin, and the cost can be significantly reduced. As shown in FIG. 2, the flame-retardant particles 10 can be added to the flame-retardant material (polymer substrate) 50 together with the conventional flame-retardant material particles 11. Noh. In this case, in addition to the effect of imparting the flame retardancy of the particles 10 for imparting flame retardancy, the effect of imparting the flame retardancy of the flame retardant material particles 11 is also synergistically added. Will be shown.

It is presumed that the compound constituting the particles for imparting flame retardancy has, for example, a structure schematically shown in FIG. 9 (the molecular formula is schematically shown in FIG. 9). Does not mean that it has a limited specific structure shown by.). In the compound 2 compounded inside or on the surface of the flame retardant material 50, silicon and Z or a metal (these are indicated by M in the figure) contain oxides or alkoxides 52 (for example, Si). 0 ₂ , Zr 0 ₂ , S i (OC n Hm) 1 (n 1, m ≥ 1, 1 ≥ 1), etc.) or in a single state, and the carbon component 51 is, for example, C n Hm ( The structure contained in the state of n≥l, m≥1) can be estimated.

As shown in FIG. 3 (a), the particles 10 for imparting flame retardancy as described above may be used alone or, if necessary, in a flame retardant or a flame retardant different from the particles for imparting flame retardancy. It is blended and kneaded in a polymer material to be used as a substrate (a thermoplastic resin is used in this embodiment) along with a fuel aid, filler, coloring agent such as pigment and dye, dispersant, etc. Compound 5 3 1 The compound 5331 can be formed into master batch particles 32 by, for example, forming into a granular form such as a pellet. The master batch particles 32 have a size of, for example, about 0.1 to 10 mm (for example, about 1 to 4 mm) in terms of a sphere-converted diameter. The shape of the master batch particles 32 is particularly limited. However, as shown in FIG. 3 (b), for example, as shown in FIG. 3 (b), a softened compound is extruded into a strand and cut into a predetermined length to obtain columnar (eg, columnar) particles. . FIGS. 3 (c) and 3 (d) show another example of the shape of the masterbatch particles 32. The former is spherical (for example, it can be manufactured by molding) and the latter is flake. (For example, it can be produced by crushing and sizing a sheet-like material), but the present invention is not limited to this.

Hereinafter, a method of manufacturing a molded body (secondary molded body) using one master batch will be described with reference to FIG. The injection molding apparatus 501 includes a molding section 502, an injection apparatus 503 such as a screw-type injection apparatus for supplying a molten resin to the molding section 502, and the like. The molding section 502 is a mold 505, a mechanical drive mechanism such as a cam or a crank mechanism for clamping and opening the mold 505, and a fluid pressure mechanism such as an hydraulic cylinder. In addition to the drive mechanism 506 constituted, a runner 521 for supplying molten resin to the mold 505 is provided with an injection nozzle 503 of an injection device 503 via a sprue 503a. b is connected.

The injection device 503 includes a heating cylinder 507 0 heated by a heat source such as a band heater 508, and a supply screw 503 driven by a hydraulic motor 513 via a shaft 511. 9 is accommodated therein, and a hopper 510 for supplying a master batch P is provided therein. Master #batch P is supplied from the hopper 5110 by rotating the screw 509, and the polymer material substrate is melted by heating in the heating cylinder 507 to become a molten compound. It is stored in. Thereafter, when the screw 509 is advanced by a predetermined distance by the hydraulic cylinder 511, a predetermined amount of the molten compound is injected into the mold 505 from the nozzle 503b through the runner 521. . As shown in FIG. 5, the molten compound C injected into the cavity 505a of the mold 505 becomes the polymer composite material of the present invention by solidifying the polymer material substrate, and this is opened. By doing so, it is possible to obtain a polymer composite material Thus, a secondary molded body 36 is obtained.

As shown in FIG. 6 (a), the molded body may be obtained by using the master batch particles 32 alone, but as shown in FIG. 6 (b), the height of the master batch particles 32 may be reduced. By mixing an appropriate amount of diluted polymer material particles 40 composed of the same or different polymer material with the molecular substrate, the secondary molded body having a particle content smaller than the content in the master batch particles 32 Can also be manufactured. In this case, the content of the particles in the secondary compact is determined by the content of the particles in the master batch particles 32 and the mixing ratio of the diluted polymer material particles 40 to the master batch particles 32.

The master batch particles to be used in such a diluted state have a high particle content i, for example, 20 to 67% by weight, but the particles are contained in the substrate at such a high content. It is desirable to add a dispersing agent for uniform dispersion. As the dispersant, for example, metal soap can be suitably used. Metallic soap components include, for example, organic acid components such as naphthenic acid (naphthate), lauric acid (laurate), stearic acid (stearate), oleic acid (oleate), 2-ethylhexanic acid (octate), Flax oil or soybean oil fatty acid (linoleate), tall oil (tolate), rosin, etc. (resinate) can be exemplified. In addition, examples of the type of metal include the following.

'Naphthenates (A1, Ca, Co, Cu, Fe, Pb, Mn, Zn, etc.) • Resinates (A1, Ca, Co, Cu, Fe, Pb, Mn, Zn, etc.)

· Linoleate (Co, Fe, Pb, Mn, etc.)

• Stearate type (Ca, Zn, etc.)

• Octate (Ca, Co, Fe, Pb, Mn, Zn, etc.)

• Trate type ( _Ca , Co, Fe, Pb, Mn, Zn, etc.)

Among these, Ca stearate and Zn stearate can be mentioned as specific examples of metal segens that are particularly excellent in dispersing effect. It should be noted that in the composite material of metal Seggen If the amount is too large, problems may occur in the strength and homogeneity of the material. If the amount is too small, the dispersing effect becomes insufficient. For example, 0.01 to 3 wt. It is better to select within the range of / ₀ (for example, 0.3% by weight).

A main agent containing an uncured resin component such as epoxy resin, urethane resin (including urethane rubber) or silicone resin, and a curing agent containing a component for curing the uncured resin component. It is also possible to constitute a two-component mixed type cast resin material, adhesive or paint composed of the flame-retardant polymer composite material of the present invention. More specifically, for this purpose, a main agent containing an uncured resin component and a curing agent for curing the uncured resin component are used. A flame-retardant polymer composite obtained by mixing a base resin and a curing agent with a thermosetting resin as a substrate and dispersing particles for imparting flame retardancy thereto. A composition for producing a flame-retardant polymer composite material from which a material can be obtained can be used. <FIG. 7 illustrates a specific example using an epoxy resin as an example. That is, the main agent 550 is contained in, for example, a bisphenol-based uncured epoxy resin component, and contains a flame retardant or a flame retardant different from the flame retardant imparting particles, if necessary. It contains a combustion aid, a filler, a colorant such as a pigment 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-isocyanate and an acid anhydride in a solvent. Immediately before use, the two agents 550 and 551 are mixed at a predetermined ratio as shown in (a), and a treatment according to the purpose is performed within the pot life time of the mixed composition 552. In other words, when the mixed composition 552 is used as a resin material for casting, it is cast into a mold 553 and cured as shown in FIG. To obtain a molded article of a conductive polymer composite material. When the mixed composition 552 is used as a paint, as shown in (c), it is applied to the painted surface of the object 554 and cured to obtain a flame-retardant polymer composite material. Coating film 5 5 5 is obtained. Further, the mixed composition 552 is used as an adhesive. In this case, as shown in (d), this is applied to the bonding surfaces of the adherends 556a and 556b and bonded together, so that the adherends 556a and A bonded bonded structure is obtained.

Next, the particles for imparting flame retardancy can be fixed on the surface of the polymer substrate. Figure 8 shows some examples. FIG. 8A shows an example in which the flame-retardant particles 10 are fixed in an adhesive form via an adhesive resin layer 560 formed on the surface of the polymer substrate 50. The particles 10 for imparting flame retardancy may be further dispersed in the polymer substrate 50 (the same applies to the following). Also, as shown in FIG. 8 (b), the surface side of the fixed particles 10 may be further covered with an overcoat 561 made of resin or the like. The flame retardancy-imparting particles 10 are applied to the inner surface of the cavity of the mold 505, and then the cavity is filled with a molten resin 570 and solidified, so that the applied particles 10 are formed into a substrate 50 for forming a molded body 536. This is an example of integration on the surface. FIG. 8 (d) shows that the surface of the particles 10 is previously covered with the fixing resin layer 562, and the fixing resin layer 562 is softened by heating, adhered to the surface of the substrate 50 while being softened, and then the resin is cured. This is an example of fixing particles 10. 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. 8 (e) shows a method of embedding the particles 10 in the surface layer of the substrate 50 by projecting or pressing the particles 10 onto the surface of the substrate 50. In this case, embedding can be performed easily by softening at least the surface layer of the substrate 50 by heating or the like. Example

(Example 1)

Zinc nitrate hexahydrate _{_{(Zn (NO 3) 2 ·}} 6Η 2 0) 21. 93 g were placed in ethanol 100 m 1 as the metal salt was dissolved. Tetraethoxysilane (S i 6.92 g of (OC ₂ H ₅ ) ₄ ) was added, followed by dropwise addition of 4.18 g of pure water, and the solution was stirred to produce a sol composition. The sol composition is placed in a dryer at 150 ° C., and the solvent is volatilized to form a gel composition, which is pulverized to obtain fine powdery gel composition particles (to impart flame retardancy). Particles). When the gel composition was analyzed, it was found that the gel composition was a compound containing each element of Si, Zn, 0, N and C.

A mixture of 15.0 g of the above gel composition particles, 75 g of aluminum hydroxide having an average particle size of 55 m as flame-retardant material particles, and 100 g of powdery or pelletized polypropylene as a polymer material substrate. The mixture was put into an injection molding machine and injection molded at 180 ° C into a sample shape for a flame retardancy test. Flame retardant test sample shape, based on the UL 94 flammability test, the length 1 25 mm, width 1 3 mm, the flame retardance test _{sample c} prepared above was the thickness 1. 6 mm using, UL 94 flammability As a result of the test, it passed the V-0 standard of the test. Further, it was found that the formed glass ceramic you think that you containing S i 0 ₂ during combustion residue. In addition, it was confirmed that gas containing nitrogen or nitrogen oxides was generated during combustion.

(Example 2)

Zinc nitrate hexahydrate as the metal salt _{_{(Zn (NO 3) 2 ·}} 6Η 2 0) 8. The 77 g Etano - placed in Le 10 Om 1, were dissolved. 2.77 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, 1.7 g of pure water was added dropwise, and the solution was stirred to prepare a sol composition. The sol composition was placed in a dryer at 150 ° C., and the solvent was evaporated to form a gel composition, which was pulverized to produce fine powder gel composition particles.

6.0 g of the gel-like composition particles, 30 g of aluminum hydroxide as in Example 1 as flame-retardant material particles, and 100 g of powdery or pelletized polypropylene as a polymer material substrate were mixed. The mixture was put into an injection molding machine and injection-molded at 180 ° C into a sample shape for a flame-retardant test. Example 1 for sample shape for flame retardancy test And the same.

Using the sample for flame retardancy test prepared above, it was tested in the UL 94 flammability test. As a result, it passed the V-2 standard of the test.

(Example 3)

10.97 g of zinc nitrate hexahydrate (Ζη (Ν0 ₃ ) ₂ · 6Η ₂₀ ) as a metal salt was placed in ethanol 10 Om 1 and dissolved. 3.47 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the liquid, 2.lg of pure water was added dropwise, and the liquid was stirred to prepare a sol composition. This sol-like composition was placed in a dryer at 150 ° C., and the solvent was evaporated to form a gel-like composition, which was pulverized to produce fine powdery gel-like composition particles.

7.5 g of the gel composition particles, 20 g of the same aluminum hydroxide as in Example 1 as flame-retardant material particles, and 100 g of powdery or pelletized polypropylene as a polymer material substrate were mixed. The mixture was put into an injection molding machine and injection-molded at 180 ° C into a sample shape for a flame-retardant test. The sample shape for the flame retardancy test was the same as in Example 1.

(Example 4)

Nickel nitrate hexahydrate as the metal salt _{(N i (N0 3) 2} - 6H 2 0) 1 1. Put 68 g in ethanol 10 Om 1, were dissolved. 3.47 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, 2.lg of pure water was added dropwise, and the solution was stirred to prepare a sol composition. This sol-like composition was placed in a dryer at 150 ° C., and the solvent was evaporated to form a gel-like composition, which was pulverized to prepare fine powdery gel-like composition particles. When the gel composition was analyzed, it was found to be a compound containing each of the elements Si, Ni, 0, N and C. 7.7 g of the gel composition particles, 20 g of aluminum hydroxide as in Example 1 as the flame-retardant material particles, and 100 g of powdery or pelletized polypropylene as the polymer material substrate. After mixing, the mixture 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 was the same as in Example 1.

Using the sample for flame retardancy test prepared above, it was tested in the UL 94 flammability test. As a result, it passed the V-2 standard of the test. Further, it was found that the formed glass ceramic you think that you containing S i 0 ₂ during combustion residue. In addition, it was confirmed that gas containing nitrogen or nitrogen oxides was generated during combustion.

(Comparative Example 1)

75 g of aluminum hydroxide and 100 g of polypropylene as in Example 1 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. As a result of a UL 94 flammability test using this flame-retardant test sample, the sample ignited immediately after the start of the test.

(Comparative Example 2)

30 g of aluminum hydroxide and 100 g of polypropylene as in Example 1 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-retardant test is the same as in Example 1. As a result of a UL 94 flammability test using this sample for a flame retardancy test, the sample ignited immediately after the start of the test.

(Comparative Example 3)

20 g of aluminum hydroxide and 100 g of polypropylene as in Example 1 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. This flame retardant test As a result of the test using the test sample in the UL 94 flammability test, the sample ignited immediately after the start of the test.

Table 1 summarizes the results of Examples 1 to 4 and Comparative Examples 1 to 3. The amount of each component is shown in parts by weight based on 100 parts by weight of polypropylene (PP resin). For SiO ₂ (a hydrolyzate of tetraethoxysilane), zinc nitrate hexahydrate and Ni nitrate hexahydrate contained in the gel composition, they are combined in terms of oxide. Indicates the amount.

From these results, the comparative example in which the gel composition was not blended had almost no flame retardancy, whereas the gel composition was blended in polypropylene as shown in the examples. It was found that even a small amount of the flame-retardant polymer composite material (for example, about 5 to 15 parts by weight) has the effect of imparting flame retardancy.

(Example 5)

Zinc nitrate hexahydrate (Ζη (ΝΟ,) ₂ · 6Η ₂₀ ) 93.43 g as metal salt And dissolved in 8 ml of ethanol. The liquid tetraethoxysilane in _{_{(S i (OC 2 H 5}} ) 4) and 27. 74 g was added and then dropwise pure water 16. 76 g, to prepare a sol-like composition in Rukoto to stir the liquid . This sol-like composition was placed in a dryer at 150 ° C., and the solvent was evaporated to form a gel-like composition, which was pulverized to produce fine powdery gel-like composition particles.

A mixture of 6 g of the gel composition particles, 50 g of aluminum hydroxide having an average particle diameter of 1 m as flame-retardant material particles, and 100 g of powdery or pellet-like polypropylene as a polymer material substrate was mixed. The mixture was put into an injection molding machine and injection-molded at 180 to obtain a sample of a predetermined shape.

First, a sample with a length of 12 Omm, a width of 6.5 mm, and a thickness of 3 mm was prepared for the combustion test using the oxygen index method (JI SK7201). 31% was obtained. Furthermore, a No. 1 test piece was prepared based on the tensile test method (JI SK7113) and tested in the same test, and as a result, a tensile strength of 21.1 X 10 ⁶ [Pa] was obtained.

(Example 6)

Zinc nitrate hexahydrate (Zn (N_〇 _{_{_{3) 2 · 6Η 2 0)}}} 93. 43 g were placed in ethanol 80 m l as a metal salt were dissolved. The liquid tetraethoxysilane in _{_{(S i (OC 2 H 5}} ) 4) and 27. 74 g was added and then dropwise pure water 16. 76 g, to prepare a sol-like composition in Rukoto to stir the liquid . This sol-like composition was placed in a dryer at 150 ° C., and the solvent was evaporated to form a gel-like composition, which was pulverized to produce fine powdery gel-like composition particles.

6 g of the gel composition particles, 50 g of an aluminum hydroxide having an average particle diameter of 55 tm as flame-retardant material particles, and 100 g of powdery or pelletized polypropylene as a polymer material substrate were mixed. The mixture was put into an injection molding machine and injection molded at 180 ° C. to obtain the same samples for oxygen index measurement and tensile test measurement as in Example 5. Using the sample prepared above, a combustion test was conducted by the oxygen index method. As a result, an oxygen index value of 29% was obtained. Further, as a result of a tensile test, a tensile strength of 16.5 × 10 ⁶ [Pa] was obtained.

(Comparative Example 4)

A mixture of 50 g of aluminum hydroxide having an average particle diameter of 1 μπι and 100 g of polypropylene as in Example 5 was then placed in an injection molding machine and injection molded at 180 ° C., and an oxygen index similar to that of Example 5 was obtained. Samples for measurement and tensile test measurement were obtained.

Using the sample prepared above, a combustion test was conducted by the oxygen index method. As a result, an oxygen index value of 19.7% was obtained. Furthermore, as a result of a tensile test, a tensile strength of 19.6 × 10 ⁶ [Pa] was obtained.

(Comparative Example 5)

100 g of polypropylene was put into an injection molding machine and injection-molded at 180 ° C. to obtain the same samples for oxygen index measurement and tensile test measurement as in Example 5.

As a result of a test using the sample prepared above in a combustion test by the oxygen index method, an oxygen index value of 17.5% was obtained. Further, as a result of a tensile test, a tensile strength of 22.3 × 10 ⁶ [Pa] was obtained.

Table 2 summarizes the results of Examples 5 and 6 and Comparative Examples 4 and 5 above. The amount of each component is shown in parts by weight based on 100 parts by weight of polypropylene (PP resin). Further, S i 0 ₂ (hydrolyzate of tetraethoxysilane) contained in the gel composition, and shows the amount in value of the terms of oxide for zinc nitrate hexahydrate. Table 2

From these results, it can be seen that the polypropylene added with the gel composition has a high oxygen index value, that is, a high flame retardancy. However, when aluminum hydroxide having a large average particle size (Example 6) is used, resin properties (tensile strength) are reduced, while aluminum hydroxide (Example 5) having a small average particle size is used. It can be seen that flame retardancy can be improved while maintaining resin properties (tensile strength) (Example 7).

Cupric nitrate trihydrate as a metal salt _{_{(Cu (N0 3) 2 '}} 3H 2 0) 9. llg was placed in ethanol 3 Om 1, were dissolved. 3,47 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 2.07 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . 100 g of a polypropylene resin powder having an average particle diameter of 650 μπι was added to the sol composition as carrier material particles, and mixed with stirring. After that, the mixture was placed in a dryer at 90 ° C to evaporate the solvent to form a coating film of a gel-like composition (compound layer) on the resin surface (hereinafter, coating using the sol-gel method was referred to as sol-gel coating). Coating). The components of the coating film are estimated. For this reason, when the gel composition obtained by drying only the sol composition was analyzed, it was found that it was a compound containing each element of Si, Cu, 0, N and C. When the particles coated with the coating film are burned, the weight ratio in the combustion residue is 1 part by weight of SiO ₂ and 100 parts by weight of the resin as carrier material particles in terms of oxide conversion. u O was 3 parts by weight.

The sol-gel coated powder was put into an injection molding machine and injection-molded at 200 ° C into a sample shape for a flame-retardant test. The sample shape for the flame retardancy test was 125 mm long, 13 mm wide and 1.6 mm thick based on the UL 94 flammability test. In this case, the support material particles (polypropylene) form a matrix after molding, and the coated compound portion is dispersed in the matrix and has the same structure as that of the flame-retardant polymer composite material described above. Form.

(Example 8)

Zinc nitrate hexahydrate _{_{(Zn (NO 3) 2 ·}} 6Η 2 0) 10. 97 g were placed in ethanol 3 Om l as a metal salt were dissolved. 3.47 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 2.07 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . 100 g of propylene resin powder as support material particles was put into the sol composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 90 ° C., and the solvent was evaporated to form a coating film of the gel composition (compound layer) on the resin surface. 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, 0, N and C. I understand. When the particles coated with the coating were burned, the weight ratio in the combustion residue was calculated as oxide ₂ l parts by weight and Zn 03 parts by weight with respect to 100 parts by weight of resin as carrier material particles in terms of oxide. Met. The sol-gel coated powder was injection-molded in the same manner as in Example 7 into a sample shape for a flame-retardant test. Also in this case, the carrier material particles (polypropylene) form a matrix after molding, and the coated compound portion is dispersed in the matrix, and has the same morphology as the flame-retardant polymer composite material described above. Become. Using the prepared sample for flame retardancy test, it was tested in UL 94 flammability test. As a result, it passed the V-2 standard of the test.

(Example 9)

Ferric nitrate nonahydrate as metal salt _{_{(F e (ΝΟ 3) 2}} · 9Η 2 0) 16. Put 87 g in E methanol 3 Om 1, were dissolved. 3.47 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 2.07 g of pure water was added dropwise, and the solution was stirred to produce a sol composition. 100 g of polypropylene resin powder as carrier material particles was put into this sol composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 90 ° C., and the solvent was evaporated to form a coating film of the gel composition (compound layer) on the resin surface. In order to estimate the components of the coating film, when the gel composition obtained by drying only the sol composition was analyzed, a compound containing each element of Si, Fe, 0, N and C was obtained. I understood that. When the particles coated with the coating were burned, the weight ratio in the combustion residue was calculated as oxide ₂ l parts by weight, 100 parts by weight of resin as carrier material particles, and Fe ₂ parts by weight. 〇3 parts by weight. The sol-gel coated powder was injection-molded in the same manner as in Example 7 into a sample shape for a flame-retardant test. Also in this case, the support material particles (polypropylene) force S form a matrix after molding, and the coated compound portion is dispersed in the matrix, and has the same morphology as the flame-retardant polymer composite material described above. Becomes Using the prepared sample for flame retardancy test in the UL 94 flammability test, it passed the V-2 standard of the test.

(Comparative Example 6) 36.6 g of zinc nitrate hexahydrate (Ζη (水和 0 ₃ ) ₂ · 6 _{2 2} 〇) as a metal salt was placed in 30 ml of ethanol, and the solution was stirred. 100 g of the same polypropylene resin powder as the support material particles as in Example 7 was added to this solution, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 85 ° C., and the solvent was evaporated to form deposits on the resin surface. The composition obtained by drying only the above solution was analyzed to estimate the components of the deposits, and it was found that the composition was a compound containing the Zn element. Further, when the particles formed with the above-mentioned attachment were burned, the weight ratio in the combustion residue was 10 parts by weight of Z ηθ based on 100 parts by weight of resin in terms of oxide.

The powder on which the deposits were formed was mixed with a polypropylene powder or pellet as a substrate similar to that in Example 7, and injection-molded into a sample shape for flame retardancy test in the same manner as in Example 7. . In addition, as a molded body, Zn05 parts by weight was used for 100 parts of the resin in terms of an acid substance. Using the prepared sample for flame retardancy test in a UL 94 flammability test, the sample was ignited immediately after the start of the test.

Table 3 summarizes the results of Examples 7 to 9 and Comparative Example 6.

Table 3

From these results, it can be seen that the sample of Comparative Example in which tetraethoxysilane (silicon component) is not blended has no effect of imparting flame retardancy to the base resin (material to which flame retardancy is imparted). I understand. On the other hand, as shown in the examples, the samples coated with the gel-like composition containing tetraethoxysilane (silicon component) (Examples 7 to 9) have high levels of flame retardancy even in a small amount. It turns out that there is an effect.

In this specification, the term “main component” or “mainly” is used to mean a component having the highest weight content unless otherwise specified.

Claims

The scope of the claims

1. The flame-retardant-imparting particles which are mainly composed of a compound containing a silicon component and a metal component or a metal component and oxygen, and which produce a glassy ceramic mainly composed of oxides of silicon and / or metal by heating are made of a polymer. A flame-retardant polymer composite material which is dispersed in a substrate made of a material and / or is fixed on a surface of a polymer material.

2. The flame-retardant polymer composite material according to claim 1, having a flame-retardant property satisfying a range of V-0 to V-2 when tested in a UL 94 flammability test.

3. The flame-retardant polymer composite material according to claim 1, wherein the compound contains a carbon component.

4. The flame-retardant polymer composite material according to any one of claims 1 to 3, which decomposes and generates a combustion-inhibiting gas by heating.

5. The flame-retardant polymer composite material according to claim 4, wherein a substance containing one or more of nitrogen, sulfur and carbon is generated as the combustion inhibiting gas.

6. The flame-retardant polymer composite material according to any one of claims 1 to 5, wherein the average particle diameter of the particles for imparting flame retardancy is 0.05 to 500 µm.

7. The method according to any one of claims 1 to 6, wherein inorganic or organic flame retardant particles or flame retardant auxiliary particles are dispersed and compounded together with the flame retardant-imparting particles comprising the compound. Flame retardant polymer composite material.

8. A main agent containing an uncured thermosetting resin, which is used for producing the flame-retardant polymer composite material according to any one of claims 1 to 7, and curing the main agent. The flame-retardant-imparting particles are compounded with at least one of the main agent and the curing agent, and the thermosetting resin is mixed by mixing the main agent and the curing agent. A composition for producing a flame-retardant polymer composite material, characterized in that a flame-retardant polymer composite material in which the flame-retardant particles are dispersed as a substrate is obtained.

9. A molded article of a flame-retardant polymer composite material, which is formed by molding the flame-retardant polymer composite material according to any one of claims 1 to 7 into a predetermined shape.

10. The flame-retardant polymer composite material molded article according to claim 9, wherein the molded article is configured as a final molded article without assuming remolding accompanied by softening of the polymer substrate.

10. The flame-retardant polymer composite material molded article according to claim 9, wherein the molded article is used as a temporary molded article for softening the polymer substrate to re-mold it into an intended secondary shape.

12. The flame-retardant-imparting particles mainly composed of a compound containing a silicon component and Z or a metal component and oxygen, and producing a glassy ceramic mainly composed of silicon, Z or a metal oxide by heating, have a high particle size. Flame-retardant polymer composed as a granular molded product dispersed in a substrate made of a molecular material and used for reshaping into a secondary shape having a larger volume than individual granular molded products Master batch for manufacturing composite material moldings.

13. A sol-like composition in which a metal element and / or a compound of Si is dispersed and dissolved or dissolved in a solvent is dried to form a gel-like composition, and the gel-like composition is a substrate made of a polymer material. A method for producing a flame-retardant polymer composite material, which comprises dispersing the compound in a flame-retardant polymer composite material.

14. The above-mentioned gel composition is pulverized, and the pulverized gel composition particles are mixed and dispersed in a softened thermoplastic resin or an uncured thermosetting resin, and then the resin is cured. The flame-retardant polymer composite according to claim 13, wherein a flame-retardant polymer composite material in which gel-like composition particles are dispersed in a substrate made of the thermoplastic resin or the thermosetting resin is obtained. Material manufacturing method.

15. The sol composition is spray-dried to form gel composition particles, mixed and dispersed in a softened thermoplastic resin or an uncured thermosetting resin, and then the resin is cured. The flame-retardant polymer composite material according to claim 13, wherein a flame-retardant polymer composite material in which gel composition particles are dispersed in a substrate made of the thermoplastic resin or the thermosetting resin is obtained. Manufacturing method.

16. The flame-retardant polymer composite material according to claim 14, wherein the average particle size of the gel composition particles is adjusted to 0.5 to 500 μm. Production method.

17. The mixing ratio of the gel composition to the substrate, wherein the gel composition is 0.1 to 100 parts by weight relative to 100 parts by weight of the substrate. 13. The method for producing a flame-retardant polymer composite material according to any one of items 3 to 16.

18. The flame-retardant composition according to any one of claims 13 to 17, wherein the sol composition is produced by hydrolyzing a metal element and / or an alkoxide of Si. A method for producing a molecular composite material.

19. The method for producing a flame-retardant polymer composite material according to any one of claims 13 to 18, wherein the solvent for producing the sol composition is an alcohol.

20. The compound according to claim 18, 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. Item 19. The method for producing a flame-retardant polymer composite material according to Item 19.

21. The method for producing a flame-retardant polymer composite material according to any one of claims 18 to 20, wherein the alkoxide has Si and no or Ti as an essential component. Law.

22. The method for producing a flame-retardant polymer composite material according to any one of claims 13 to 21, wherein a metal salt of an inorganic acid or an organic acid is blended with the sol composition. .

23. The cation metal element of the metal salt, wherein the cation metal element contains one or more of Cu, A and Zn, Ni, Fe, Ti and Zr. For producing flame-retardant polymer composite materials.

24. The method according to claim 22, wherein the inorganic acid is an acid obtained by dissolving an acidic gas in water (hereinafter referred to as an acidic gas-based inorganic acid). Flame retardant A method for producing polymer composite materials.

25. The acidic gas-based inorganic acid is one of nitric acid, nitrous acid, sulfuric acid, sulfurous acid, and carbonic acid. 25. The method for producing a flame-retardant polymer composite material according to claim 24, which is a kind or two or more kinds.

26. The flame-retardant polymer according to any one of claims 22 to 25, wherein the amount of the metal salt in the sol composition is 95% by weight or less. Manufacturing method of composite material.

27. In the sol composition, WAZWB is set in the range of 0.01 to 30 when the weight ratio of the alkoxide is WA and the weight ratio of the metal salt is WB. Item 30. The method for producing a flame-retardant polymer composite material according to any one of Items 22 to 26.

28. The sol-like composition contains 25 to 98% by weight of an alcohol as the solvent, 0.5 to 40% by weight of a silicon alkoxide as the alkoxide, and metal nitrate as the metal salt. 28. The flame-retardant polymer composite according to claim 26, wherein a mixture of 5 to 95% by weight of a salt and 0.1 to 20% by weight of water is used. The method of manufacturing the material.

29. The production of the flame-retardant polymer composite material according to any one of claims 13 to 28, wherein the sol-like composition is dried in a range of 40 to 250. Method.

30. The flame-retardant material according to any one of claims 13 to 29, wherein, in the matrix, a flame-retardant material particle different from the material is dispersed together with the gel composition.方法 Manufacturing method of molecular composite material.

31. The method for producing a flame-retardant polymer composite material according to claim 30, wherein said flame-retardant material particles are composed of inorganic material particles or metal material particles.

32. The method for producing a flame-retardant polymer composite material according to claim 21, wherein the inorganic material-based particles are mainly composed of at least one of aluminum hydroxide and magnesium hydroxide. .

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 gel-like composition, is added to the substrate. 3. The method for producing a flame-retardant polymer composite material according to any one of Items 13 to 32.

34. The flow control adjuvant is a boric acid-based inorganic compound such as boric anhydride or zinc borate, a phosphorus-based inorganic compound such as red phosphorus or an inorganic material-based material such as carbon, or a phosphorus-based material such as ammonium polyphosphate. The method for producing a flame-retardant polymer composite material according to claim 33, wherein a system-based organic compound or silicone is used.