WO2001009235A1

WO2001009235A1 - Flame-retardant polymer composite material, composition for producing flame-retardant polymer composite material, formed article of flame-retardant polymer composite material and masterbatch for producing formed article of flame-retardant polymer composite material

Info

Publication number: WO2001009235A1
Application number: PCT/JP2000/005190
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: JP2001131292A; AU6470900A

Abstract

A flame-retardant polymer composite material characterized in that the composite material comprises a substrate comprising a polymer material such as a resin (i.e., a material to be flame-retarded) and, dispersed therein or attached to the surface thereof by coating or the like, composite particles (10) for imparting flame retardancy having a structure wherein a carrier particle (1) is combined with a layer (2) of compounds containing a silicon component and/or a metal component and oxygen; a composition for producing the flame-retardant polymer composite material; and a formed product of the flame-retardant polymer composite material. The flame-retardant polymer composite material can impart high flame retardancy to a material to be flame-retarded at a low cost, since, when the flame-retarded material is heated to a high temperature, the layer (2) forms a protective film hindering the material from burning, and the formation of a protective film allows the provision of satisfactory flame retardancy to the flame-retarded material by incorporation of a small amount of the compounds of the layer (2), which results in reducing the amount of a retardant including the above composite particles.

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

TECHNICAL FIELD The present invention relates to a flame-retardant polymer composite material, a composition for producing a flame-retardant polymer composite material, and a flame-retardant polymer

Sekida, masterbatch for the production of fire-retardant polymer composite material and flame-retardant polymer composite material

I do.

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 calorie properties, and demand is growing. However, a major drawback is that most resin materials 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. Ecological flame retardants are not favorable for environmental protection 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, the problems are mechanical properties, low water resistance, large amount (more than 150 parts), increased viscosity of the compound for compounding, and low flame retardancy at high temperatures of 400 ° C or higher. In addition, dehydration and foaming are likely to occur during processing of a resin having a high processing temperature. Magnesium hydroxide has the same flame-retardant effect as aluminum hydroxide, and dehydration and foaming at the processing temperature of the resin, which is a drawback of aluminum hydroxide, is weak to acids and humid. Under the conditions, there are drawbacks such as reaction with carbon dioxide in the air to form magnesium carbonate and whitening, and the cost is higher 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. In addition, although low melting point glass is used as a glass-based flame retardant, the manufacturing process is complicated and requires a large amount of addition to the resin, resulting in high manufacturing cost and water resistance.

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, An object of the present invention is to provide a molded article composed of the flame-retardant polymer composite material and a master batch for producing the flame-retardant polymer composite material molded article. Disclosure of the invention

In order to solve the above-described problems, a first configuration of the flame-retardant polymer composite material of the present invention is as follows: a carrier material particle comprising one or more of a polymer material, an inorganic material, and a metal material; The composite particles for imparting flame retardancy having a structure in which a compound layer containing a metal component and / or a metal component and oxygen are compounded in a polymer substrate (hereinafter also referred to as a polymer substrate). It is characterized by being dispersed.

Further, the second configuration of the flame-retardant polymer composite material of the present invention is such that a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material includes a silicon component and a Z or metal component. Characterized in that the flame-retardant composite particles having a structure in which a compound layer containing oxygen and oxygen are compounded 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 carrier material particles contain a silicon component and Z or a metal component and oxygen. The composite particles for imparting flame retardancy having a structure in which the compound layer is compounded are dispersed in a substrate made of a high molecular material such as a resin (that is, the material to which flame retardancy is to be imparted) and the surface is coated by coating or coating. For example, when high heat (for example, 500 ° C. or more) is applied to the material to which the flame retardancy is to be applied, the compound layer of the composite particles for imparting flame retardancy is protected by the high heat. By forming a film, it becomes possible to impart high flame retardancy to the material to be imparted with flame retardancy. In addition, due to the effect of forming the protective film, it is possible to provide sufficient flame retardancy even if the amount of the flame retardant material is small, and as a result, the flame retardant including the composite particles is mixed. The amount can be reduced. As a result, the strength and durability of the material finally obtained, as well as the moldability and fluidity (for example, in the case of injection-moldable materials, the flowability in the mold), etc., can be reduced by using conventional flame retardants. An effect that can be improved as compared with the case where it is used, that is, an effect of suppressing a decrease in strength, durability, moldability, fluidity, and the like can be achieved.

Further, a third configuration of the flame-retardant polymer composite material of the present invention is that a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material is heated to form a silicon and / or metal material by heating. Composite particles for imparting flame retardancy, which have a structure in which a compound layer that forms a vitreous ceramic mainly composed of oxides, are dispersed in a matrix made of a polymer material (hereinafter also referred to as a polymer matrix). And UL-94 flammability test (in this specification, the fifth edition: adopted on October 26, 1996, October 26), V-0 to V-2 The flame retardant performance that satisfies the range is provided.

Further, a fourth configuration of the flame-retardant polymer composite material of the present invention is such that a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material is added to silicon or metal by heating. The composite particles for imparting flame retardancy, which have a structure in which a compound layer that forms a vitreous ceramic mainly composed of an oxide of iron, is fixed on the surface of a substrate made of a polymer material and has a UL 94 flammability When tested in the test, it is characterized by imparting flame retardancy that satisfies the range of V-0 to V-2. According to the above configuration, the flame-retardant composite particles having a structure in which the carrier material particles are compounded with a compound layer that generates a vitreous ceramic mainly composed of oxides of silicon and Z or a metal by heating, By dispersing in a substrate made of a polymer material such as (eg, a material to be provided with flame retardancy) and fixing to the surface by Z or coating, for example, the material to be provided with flame retardancy has a high heat (eg, 500 ° C). When the above is applied, the high heat forms a glassy ceramic protective film in which the compound layer of the composite particles for imparting flame retardancy inhibits combustion. This makes it possible to achieve high flame retardancy for the material to which flame retardancy is to be imparted, specifically, the flame retardancy that satisfies the range of V_0 to V-2 when tested in the UL94 flammability test. Can be provided. Further, due to the effect of forming the protective film, it is possible to impart sufficient flame retardancy even if the compounding amount to the flame retardancy imparting material is small, and as a result, the flame retardant including the composite particles can be provided. The above-mentioned flame retardancy can be achieved even if the blending amount is relatively small. As a result, the strength and durability of the final material, as well as moldability and fluidity (for example, in the case of a material that can be injection-molded, the flow in the mold) are determined using conventional flame retardants. It is also possible to achieve 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. Preferably, the flame retardant performance satisfies V-0.

On the other hand, the fifth configuration of the flame-retardant polymer composite material according to the present invention is such that a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material includes a silicon component and / or a metal component. When flame-retardant composite particles having a structure in which a compound layer containing oxygen and oxygen are compounded are dispersed in a matrix composed of a polymer material and tested in a UL 94 flammability test The flame retardant performance that satisfies the range of V-0 to V-2 is provided.

Further, a sixth configuration of the flame-retardant polymer composite material of the present invention is such that a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material includes a silicon component and a Z or metal component. Flame-retardant composite particles having a structure in which a compound layer containing oxygen and oxygen is compounded The element was fixed on the surface of a substrate made of a polymer material, and when tested in the UL 94 flammability test, it provided flame retardancy that satisfies the range of V-0 to V_2. Features.

In the flame-retardant polymer composite material of the present invention, when tested in a UL 94 flammability test, the metal content is equivalent to the oxide-equivalent weight content WSi of the silicon component in the combustion residue. It is preferable that the total WSi + WM of the component and the oxide equivalent weight content WM be 0.5 to 60% by weight. 60 weight of WSi + WM. /. If WSi + WM is less than 0.5% by weight, the effect of improving the flame-retardant performance is insufficient if the mechanical properties such as the strength (eg, tensile strength) and elongation of the composite material exceed 0.5% by weight. May be. Incidentally, silicofluoride-containing component is converted into sio _2. When a metal component is contained, each metal component is converted into 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 Z n ² + the corresponding oxide when it is detected is Z n O, corresponding oxides if C u + is detected is C u ₂ 〇.

Hereinafter, requirements that can be added in common to the first to sixth configurations will be described.

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

The above-mentioned compound layer can generate a vitreous ceramic mainly composed of silicon and a metal oxide by heating. The silicon component and / or metal component contained in the above-mentioned compound layer is liable to produce vitreous ceramics in combination with oxidation by heating, etc., and mainly contains the silicon and Z or metal oxides produced. Since glassy ceramics have high heat resistance, they become an extremely strong protective film when high heat is applied, making it possible to impart even higher flame retardancy to the material to which flame retardancy is to be applied. . It should be noted that such a vitreous ceramic forms a part of the compound layer from the beginning. It may be present as such, or it may be in the form of being converted into a glassy ceramic when a part or all of the compound layer is heated. As the metal component, for example, one or more of Ti, Cu, Al, Zn, Ni and Zr, or other transition metal elements can be employed.

Next, the compound layer can be formed as containing a carbon component. Improves the familiarity (affinity) when the composite particles for imparting flame retardancy are combined with the material to which flame retardancy is to be applied, and makes the composite particles for imparting flame retardancy uniform with the material to which flame retardancy is to be imparted. 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 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

: A combustion-inhibiting gas is generated, and the combustion-inhibiting gas is difficult for the material to be provided with flame retardancy; The flame retardancy improvement is oxygen for combustion by the combustion inhibiting gas, the _c specific suspected to be due to relative decrease in the vicinity of the flame retardancy-imparting material of interest, as a combustion inhibition gas Can be produced containing one or more of nitrogen, sulfur and carbon. In this case, for example, nitrogen-containing N ₂ gas and N 0 ₂ gas was used as gas, NO gas, S_〇 ₂ gas as a sulfur-containing gas, is C 0 ₂ gas or the like as a carbon-containing gas occurs, they 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 size of the composite particles for imparting flame retardancy is preferably 0.05 to 500 μπι. If the average particle size is less than 0.05 μπι, the production of the composite particles for imparting flame retardancy may become difficult, and uneven distribution may occur when the composite particles are added (added) to the material to be imparted with flame retardancy. In some cases, the composite (addition) cannot be made uniform, so that 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 0 m, the distribution of composite (added) particles becomes uneven In addition, the properties of the material to which flame retardancy is to be imparted, such as the properties of a resin, such as fluidity, may be reduced, or the material to be imparted with flame retardancy may have poor appearance. The average particle size can be measured using, for example, a laser diffraction particle size analyzer. In this case, in the measurement using a laser single-diffraction particle sizer, there is no significant difference between the diffraction behavior of the incident laser light due to the aggregated particles and the diffraction behavior due to the isolated primary particles. It cannot be distinguished from each other whether the particle size exists as a simple substance or whether it is the particle size of 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.

Next, the above-mentioned carrier material particles can be made into flame-retardant material particles. In this case, in addition to the effect of imparting flame retardancy by heating the above-mentioned compound to produce, for example, a vitreous ceramic, the flame retardant effect of the flame retardant material particles as the support material particles is added. The effect of imparting flame retardancy to the material to which the particles are imparted flame retardancy is further improved. Examples of such flame-retardant material particles include ecological non-halogen flame retardant materials, hydrated metal compounds, mica such as muscovite, phlogopite, biotite, sericite, kaolin, talc, zeolite, Minerals such as 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; and nitrogen compounds Use inorganic flame-retardant material particles (inorganic material-based particles) represented by compounds, etc., phosphorus-based, silicone-based, and nitrogen-based organic flame-retardant material particles, as well as metal powder particles (metal-based particles). be able to. It is most preferable to use inorganic flame-retardant material particles from the viewpoint of the additive properties to the resin, the flame-retardant effect, the cost, and the like. 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 is further enhanced. When these hydroxides are used, for example, the above-mentioned alkoxide is composed of Si, and the above-mentioned metal salt is composed of Zn and / or Ni. If so, the effect of imparting flame retardancy is further enhanced.

The flame-retardant material particles preferably have, for example, an average particle diameter of 0.05 to 100 μπι. If the average particle size is less than the above lower limit, the production may be difficult, and when the compound is added (combined) to the material to which flame retardancy is to be imparted, uneven distribution may occur, and the compound (addition) may not be uniform. Therefore, 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 the value exceeds the upper limit, 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, for example, properties such as fluidity may be reduced or flame retardancy may be imparted. The target material may cause poor appearance. When such inorganic material-based and metal or metal-based flame-retardant material particles are used as carrier material particles, the average particle diameter of the flame-retardant composite particles of the present invention is 0.05 to 0.5 as described above. It is about 500 m. The average particle size can be measured by a laser diffraction type particle size measuring device. On the other hand, polymer material particles can be used as the support material particles. As the polymer material particles, for example, those made of a thermoplastic polymer material, those made of a thermosetting polymer material, or a mixed material thereof can be used. In this case, when a resin is used as the material to be imparted with flame retardancy, the polymer material as a carrier material has good affinity (affinity) with the resin, and thus the composite particles for imparting flame retardancy are subjected to the object to be imparted with flame retardancy. It becomes evenly dispersed in the material, and it becomes possible to effectively impart the flame retardancy to the material to which the flame retardancy is to be imparted. When polymer particles are used, for example, if the alkoxide is composed of Si and the metal salt is composed of Cu and / or Fe, the effect of imparting flame retardancy is further enhanced. be able to. As the polymer material particles, for example, those having an average particle size of about 0.1 to 10 mm can be used. In this case, the average particle diameter of the composite particles for imparting flame retardancy is also about 0.1 to 10 mm. It will be.

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

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 force rendering can be used.

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.

'' General electric appliances: Housings 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-molding into a desired secondary shape. By using such a temporary molding, the final molding The production efficiency of body products can be greatly increased. For example, if the material of the polymer matrix used lacks fluidity, a preform having an intermediate shape individually corresponding to the final secondary shape can be used as a temporary molded body to reduce local material flow. Variations can be suppressed 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 composite particles for imparting flame retardancy are dispersed in a polymer matrix, and is used as a master for remolding into a secondary shape having a larger volume than each granular molded article. It can be a batch. Specifically, a masterbatch (hereinafter, also simply referred to as a masterbatch) for producing a molded article of a flame-retardant polymer composite material is a carrier material composed of one or more of a polymer material, an inorganic material, and a metal material. The composite particles for flame-retardant imparting having a structure in which a compound layer containing a silicon component and a metal component or a metal component and oxygen are composited with the particles are configured as a granular molded product in which the composite particles are dispersed in a polymer matrix, It is characterized by being used for reshaping into a secondary shape having a larger volume than individual granular molded products. Such a masterbatch can be used as a molding base having high fluidity in various molding machines such as an injection molding machine, and thus greatly contributes to simplification of the 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 a different nature as the polymer substrate, so that the secondary batch has a smaller content of flame-retardant composite particles than itself. In this way, the content of the composite particles for imparting flame retardancy in the final secondary molded product can be used. The mixing ratio of the masterbatch to the diluted polymer material can be used. By changing, it is possible to adjust freely and easily. In addition, during the production of the masterbatch, the polymer matrix and the composite particles for imparting flame retardancy are kneaded, and at the time of molding, the masterbatch is mixed with the diluted polymer material, so that the polymer matrix is mixed into the polymer matrix. By dispersing the composite particles for imparting flame retardancy in two stages, the dispersion state of the composite particles in the finally obtained secondary molded body can be made more uniform.

The composite particles for imparting flame retardancy used in the flame-retardant polymer composite material of the present invention include: Specifically, those obtained by the following production method can be used. In the production method, a step of contacting a sol-like composition generated from the force of a solution (for example, an alkoxide solution) obtained by dispersing and / or dissolving a metal element and / or a compound of Si in a solvent with a supporting material; A step of drying the sol composition, wherein the gel composition produced by drying the sol composition is combined with the carrier material to obtain a flame-retardant composite composition. To

As described above, a composite composition for imparting flame retardancy can be obtained by a so-called sol-gel method in which the sol composition is dried to composite the gel composition with the support material. The sol-gel method as described above is simple and does not require any special equipment, so that the production cost can be significantly reduced and no harmful substances are generated during the production. The composite composition for imparting flame retardancy obtained by such a production method has a configuration in which a gel-like metal element and a compound of phosphorus or Si (for example, an inorganic compound) are composited on a support material. If this is mixed or coated (added) to the material to be imparted with flame retardancy such as resin, for example, if the material to be imparted with flame retardancy is given high heat, then the flame is imparted by the high heat. The above compound in the composite composition for glass is not vitrified or ceramicized, and the vitrified or ceramicized compound serves as a protective film to impart high flame retardancy to the material to be provided with flame retardancy. Becomes possible. In addition, a material obtained by compounding such a composite material for imparting flame retardancy does not generate a harmful gas as in the past when a high heat is applied, so that it is an ecological flame retardant material. In the above manufacturing method, the step of bringing the sol-like composition into contact with the supporting material employs a method of immersing the supporting material in the sol-like composition, a method of spraying the sol-like composition onto the supporting material, or the like. Can be

The above-mentioned carrier material is used as carrier material particles, and the gel composition is compounded on the entire surface or a part of the surface thereof to obtain flame-retardant composite particles as the flame-retardant composite compound. In this case, according to the sol-gel method, the compound It is possible to obtain composite particles for imparting flame retardancy, in which the gel composition containing is uniformly dispersed and compounded. For example, coated flame retardancy in which the surface of the carrier material particles is covered with a film of the gel composition In the case of providing composite particles for application, the coating of the gel composition is thin and uniform, for example, about 0.01 to 1.0 μm. When such composite particles for imparting flame retardancy are combined (added) to a material to which flame retardancy is to be imparted, the gel-like composition is coated uniformly and in a thin film on the carrier material particles. The effect of imparting flame retardancy is great, and the amount of the composite particles for imparting flame retardancy is, for example, about 5 to 150 parts by weight, preferably about 20 to 100 parts by weight, based on the material to be imparted with flame retardancy. Sufficient flame retardancy can be imparted by adding a small amount of. In this case, since a small amount is added, there is little change in the physical properties of the material to which flame retardancy is to be added, such as a resin to be added, and the cost can be significantly reduced.

The production method using the sol-gel method specifically includes a mixing step of forming a mixture of the carrier material particles and the sol composition, and a drying step of evaporating the solvent from the mixture to form a dry composition. Can be included. This involves, for example, placing a sol-like composition in a predetermined container, immersing the carrier material particles in the sol-like composition to form a mixture, and evaporating the solvent from the mixture, and removing the solvent without draining the mixture. This is a very simple method because it can be evaporated and dried. The dried composition is preferably pulverized or crushed and used as composite particles for imparting flame retardancy. In this case, the composite particles for imparting flame retardancy are finely pulverized by pulverization or pulverization, so that they can be easily handled when mixed with the material to be imparted with flame retardancy or combined (added) by coating or the like. The composite particles for imparting flammability can be easily and uniformly dispersed and compounded with the material to be imparted with flame retardancy. The drying step can be performed by heating drying or vacuum drying, or a combination thereof.

The drying step can be performed, for example, while applying vibration and / or stirring to the aggregate of the support material particles and bringing the sol-like composition into contact therewith. In this case, drying efficiency can be improved by vibration and / or stirring of the aggregate, and drying time can be shortened. It becomes possible. On the other hand, a striking medium having a larger diameter can be mixed with the supporting material particles, and vibration, Z or agitation can be applied to the aggregate of the supporting material particles and the striking medium. The time can be further reduced.

Next, the sol-like composition is preferably produced by hydrolyzing a metal element and an alkoxide of silicon or si. The sol-like composition produced by hydrolyzing such an alkoxide contains a metal element and / or an oxide of Si, and further contains an organic substance derived from an alkoxide (the above-mentioned carbon component in the compound layer is not included in the composition). ) Will remain. As described above, this oxide is vitrified or turned into ceramics by high heat to impart high flame retardancy to the material to which flame retardancy is to be imparted, and the remaining organic matter is, for example, a case where a resin is used as the material to be imparted with flame retardancy. In addition, by improving the compatibility (affinity) when the composite composition for imparting flame retardancy is combined with the material to which flame retardancy is to be added, the composite composition for imparting flame retardancy to the material to be imparted with flame retardancy is improved. In addition to being able to uniformly disperse the material, it is also possible to improve the moldability of the material to which flame retardancy is to be imparted. 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-based solvent has a low water content, the alkoxide can be dispersed or dissolved in a stabilized state, and a gel-like composition film having a uniform film thickness can be formed. In addition, the compounding amount of the solvent for making the sol composition was 25 to 98% by weight, It is preferred that the compounding amount of the metal be 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, and as a result, the sol-like composition may not be easily compounded with the support material. When a gel is used, the composition of the gel composition may not be uniform. Further, the amount of the solvent exceeds 9 8 wt%, may take a long time enough to dry E evaporation of the solvent, also the cost high to consume useless solvent _c Meanwhile, the alkoxide If the compounding amount is less than 0.5% by weight, the flame retardant effect due to the vitrification or ceramicization of the metal and / or Si of the alkoxide may be reduced. May also be reduced. The alkoxide content was 40% by weight. If it exceeds / ₀ , the dispersibility and Z or solubility of the alkoxide in the solvent may decrease, and the sol-like composition may be difficult to be uniformly composited with the carrier material.

The alkoxide preferably contains si and Z or τi as essential components. s i and

When Z or tau i used as a component of alkoxide, oxides such as, for example, S i 0 ₂ and T I_〇 ₂ generates are hydrolysis liable vitrified or ceramic by high fever, especially flame retardant effect Will be higher. Moreover, since the alkoxide containing Si and T or Ti is hard to gel, a sol composition in a stable state can be obtained. Above all, Si is most excellent as an alkoxide component in consideration of the stability of the generated oxide, the stability of the sol composition, and the like. As the alkoxide using Si, for example, tetraethoxysilane (S i (OC ₂ H ₅ ) ₄ ) can be used. As the alkoxide using Ti, for example, titanium isopropoxide (T i ( iso-OC ₃ H ₇ ) J, etc. In addition, components other than the above include, for example, those containing one or more of Cu, A, Zn, Ni, and Zr , Or those containing other transition elements can be employed. In this case, for example, aluminum isopropoxide (A 1 (OC ₃ H ₇ ) ₃ ) Can be The constituent components of the alkoxide can be changed according to the purpose. In this case, the properties of the formed gel composition film (compound layer) 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. Particularly, as the inorganic acid of the component, 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 composite material is added, the acidic gas-based inorganic acid is used. from the gas, for example, N ₂ gas and N 0 ₂ gas and NO gas as the N-containing gas, S 0 ₂ gas as S-containing gas, the combustion inhibition gases such C_〇 ₂ gas as C-containing gas generation However, they further improve the flame-retardant effect on the material to be provided with flame-retardant properties. As specific examples of the gold Shokushio is copper nitrate (C u (N_〇 ₃₎ _₂ · _{3 Η} ₂ 〇), zinc nitrate _{(Ζ η (Ν 0 3)} 2 - 6 Η 2 0) illustrate like can do. 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. The metal salt content is 95 weight. If it exceeds / ₀ , the effect of imparting flame retardancy due to vitrification or ceramicization of 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 or composition, WAZWB may be 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. preferable. If WAZWB is less than 0.01, alkoxide component In some cases, the effect of imparting flame retardancy due to vitrification or ceramic formation derived from water may not be sufficiently obtained.When WAZWB exceeds 30, the effect of imparting flame retardancy due to gas generated from metal salts may not be obtained. In some cases, the composition may not be sufficiently obtained, and as a result, the effect of imparting flame retardancy of the composite composition for imparting flame retardancy may decrease.

The 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 a sol composition is formed with each of the above amounts, the gel composition can be uniformly compounded with the carrier material by the above-mentioned sol-gel method, and a uniform coating can be formed particularly on the carrier material particles. It is possible to do. 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 dispersing and / or dissolving the metal salt in alcohol to form a first solution, and a step of dispersing and Z or dissolving the 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, whereby the sol composition can be efficiently produced. It 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 preferably dried at a temperature in the range of 40 to 250 ° C. When the temperature is lower than 40 ° C, it may take a long time to dry the sol composition, and when the temperature exceeds 250 ° C, the sol composition may be decomposed. When drying under reduced pressure, the temperature and the pressure should be adjusted so that the sol-like yarn stably remains (adheres) to the supporting material. Need to adjust.

Next, in the case where a mixture is formed by immersing the carrier material particles in the sol composition and the mixture is dried without draining, for example, the carrier material particles per liter of the sol composition The mixing amount is preferably about 1 _g to 20 kg. If the amount is less than 1 g, the production efficiency of the composite composition for imparting flame retardancy decreases, and if it exceeds 20 kg, the amount of the composite of the sol composition per unit support material particle decreases, and the flame retardancy increases. The effect of imparting properties may be reduced. The mixing amount is preferably about lkg to 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: g / m ² ), and the sol composition mixing amount Wg (unit: g) of the carrier material particles to.. when the Ws / in (S g X Wg) 0 0 0 2 to 2 mixture of 0 g Zm ² become as carrier material particles It is better to adjust.

The usable materials of the above-mentioned carrier material particles are exactly the same as those exemplified in the description of the configuration of the composite particles for imparting flame retardancy, and thus detailed description thereof will be omitted.

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

In addition, when the polymer substrate composed of the polymer material is melted by raising the temperature together with the flame-retardancy-imparting composite composition (particles), a flow-suppression auxiliary agent that suppresses the flow and dripping of the polymer substrate is contained in the polymer substrate. Can also be blended. In this case, the flow suppression auxiliary agent suppresses the melt flow of the polymer substrate, so that the 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, red phosphorus (for example, Suzuhiro Chemical: Nova Red (trade name), Nippon Chemical Industrial Co., Ltd.) : Phosphorous inorganic compounds such as Hishigard (trade name) or carbon (eg, expandable carbon represented by Tosoh: GREP-EG (trade name), UCAR Carbon: GRAF Guard (trade name)) Etc.), or inorganic materials, or silicone.

The content ratio of the composite particles for imparting flame retardancy in the polymer substrate is preferably 5 to 150 parts by weight based on 100 parts by weight of the polymer substrate. If the content ratio is less than 5 parts by weight, the effect of imparting flame retardancy may be reduced.If the content ratio exceeds 150 parts by weight, problems such as a significant change in the properties of the polymer substrate may occur. There are cases. The content ratio is preferably 20 to 100 parts by weight. However, in the case where the above-mentioned flow suppressing aid is used, the content ratio of the composite composition (particles) for imparting flame retardancy is desirably, for example, about 1 to 150 parts by weight. In addition, when the content ratio of the composite composition (particles) for imparting flame retardancy in the polymer substrate is represented by a volume fraction, it is preferable that the content be 0.5 to 75% by volume.

On the other hand, when the composite particles for imparting flame retardancy are compounded in a polymer matrix, the average particle size is preferably 0.05 to 500 m. If the average particle size is less than 0.05 μm, it may cause problems such as trouble in compounding the particles, and if the average particle size exceeds 500, the uniformity with the polymer substrate may occur. This may cause problems such as dispersal or inability to fix. The average particle size of the composite particles for imparting flame retardancy is desirably 0.1 to 300 μm. BRIEF DESCRIPTION OF THE FIGURES

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

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

FIG. 3 shows one example of a method for producing a masterbatch comprising the flame-retardant polymer composite material of the present invention. FIG. 3 is a schematic diagram showing examples 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.

Fig. 6 is an explanatory diagram showing some usage patterns of the master patch.

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 the composite particles for imparting flame retardancy to the surface of a polymer material substrate.

FIG. 9 is an observation diagram of the support material particles before coating and the composite particles for imparting flame retardancy obtained by coating the support material particles with an electron microscope.

FIG. 10 is a schematic diagram inferring the molecular level structure of the compound layer. 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 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 a metal component and oxygen. For example, it has a configuration in which a compound layer 2 that produces a vitreous ceramic by heating is compounded with the carrier material particles 1 and can be manufactured by the sol-gel method described above. The shape of the composite of the compound layer 2 and the support material particles 1 is, for example, as shown in Fig. 1 (a). As shown in Fig. 5, it is most desirable that the state in which the compound layer 2 is uniformly coated on almost the entire surface of the carrier material particles 1 in terms of exhibiting the flame retardant effect. As shown in Fig. 1 (b), As described above, the compound layer 2 may be partially adhered to the surface of the carrier material particles 1 and a part of the surface may be uncovered and exposed. Replacement paper for imparting properties (Kaikai IJ26) If the aggregate in which the composite particles 10 for use are dispersed is crushed or crushed, the composite particles 10 for imparting indefinite flame retardancy having the structure as shown in FIG. 1 (c), for example, may be obtained. In any case, the composite particles 10 described above are complexed (dispersed in the substrate and fixed on the surface or fixed on the surface) made of, for example, a material to which flame retardancy is to be imparted, such as a polymer material. It becomes possible to impart flame retardancy to the material to which flammability is to be applied.

In FIG. 1A, the thickness of the compound layer 2 coated or adhered to the carrier material particles 1 is, for example, about 0.01 to 1.0. 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 uniformly or thinly coated or adhered to the carrier material particles 1. 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, preferably 20 to 100 parts by weight, based on the material to be imparted with flame retardancy. Sufficient flame retardancy can be imparted by the addition of a small amount of about parts by weight. In this case, since a small amount is added, 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. On the other hand, as shown in FIG. 2, it is also possible to mix the conventional flame-retardant material particles 11 together with the flame-retardant composite particles 10 and to combine (add) them to the flame-retardant material. Noh. In this case, in addition to the effect of imparting the flame retardancy of the composite particles 10 for imparting the flame retardancy, the effect of imparting the flame retardancy of the particle 11 of the flame retardant material is also synergistically added, so that the material to be imparted with the flame retardancy is high It will show flammability.

It is presumed that the compound layer 2 has, for example, a structure schematically shown in FIG. 10 (in this figure, the molecular formula is schematically shown, and a specific structure represented by the molecular formula is shown). Is not meant to have limited). In the compound layer 2 compounded inside or on the surface of the material 50 to be imparted with flame retardancy, silicon and / or metal (these are indicated by M in the figure) contain oxides or alkoxides 52 (for example, Si S). _{_{2, Z r 0 2, S}} i (OC n H m) 1 (n≥ 1, m≥ 1, 1≥ 1) , etc.), or is contained in a single state, further carbon component 5 1 is, for example C n Hm ( n≥l, m≥1) Structure can be estimated.

As shown in FIG. 3 (a), the composite particles 10 for imparting flame retardancy as described above may be used alone or, if necessary, in a different flame retardant or flame retardant from the composite particles for imparting flame retardancy. Along with auxiliaries, fillers, coloring agents such as pigments and dyes, dispersants, etc., polymer materials to be used as substrates (in this embodiment, a thermoplastic resin is used) 41 Compound 5 3 1 The compound 531 can be formed into masterbatch particles 32 by, for example, forming the compound into granules such as pellets. The masterbatch 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 masterbatch particles 32 is not particularly limited. For example, as shown in FIG. 3 (b), the softened compound is extruded into a strand and cut into a predetermined length. Columnar (for example, columnar) particles can be obtained. FIGS. 3 (c) and 3 (d) show another example of the shape of the master batch particles 32, the former being spherical (for example, it can be produced by molding), and the latter being flake-like. (For example, it can be manufactured by crushing a sheet-like material and sizing), but is not limited thereto.

Hereinafter, a method of manufacturing a molded article (secondary molded article) using the above-described 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, an ejection 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 includes a mold 505, a mechanical drive mechanism such as a cam or a crank mechanism, and a fluid pressure mechanism such as a hydraulic cylinder for clamping and opening the mold 505. In addition to the driving mechanism 506 that is driven, the runner 521 that supplies the molten resin to the mold 505 is connected to the injection nozzle 503 of the injection device 503 via the sprue 503 a. b is connected.

The injection device 503 includes a supply cylinder driven by a hydraulic motor 513 via a shaft 511 in a heating cylinder 507 heated by a heat source such as a cylinder heater 508. A hopper 510 that accommodates a screw 509 and supplies a master batch P thereto is provided. By rotating the screw 509, a master batch P is supplied from the hopper 510, and the polymer material substrate is melted by heating in the heating cylinder 507 to become a molten compound, and the pool 507a is formed. 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, a secondary molded body 36 as a polymer composite material molded body corresponding to the cavity shape is obtained.

As shown in FIG. 6 (a), the master-batch particles 32 may be used alone to obtain a compact, but as shown in FIG. 6 (b), the master-batch particles 32 may be obtained. By mixing an appropriate amount of diluted polymer material particles 40 composed of different polymer materials, the content of the composite particles can be made higher than the content in the masterbatch particles 32 It is also possible to produce a secondary compact having a small size. 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 master batch particles 32 and the mixing ratio of the diluted polymer material particles 40 to the master batch particles 32. _(Note that the master batch particles for use such dilution to the containing chromatic ratio of composite particles, for example, as high as 2 0-6 7 wt. / ₀ by weight, of such composite particles It is desirable to incorporate a dispersing agent in order to uniformly disperse in the substrate at a high content, for example, a metal soap can be suitably used as the dispersing agent. Ingredients: naphthenic acid (naphthate), lauric acid (laurate), stearic acid (stearate), oleic acid (oleate), 2-ethylhexanic acid (octate), linseed oil Rui soybean oil fatty acids (linoleate), bets -. Can be exemplified those composed of Le oil (Toreto), rosin (resinate) also. The following types of metals can be exemplified.

• Naphthenates (A1, Ca, Co, Cu, Fe, Pb, Mn, Zn, etc.) • Resinates (A1, Ca, Co, Cu, Fe, Pb, Mn, Z n, etc.) • Linoleate type (Co, Fe, Pb, Mn, etc.)

.Stearate (Ca, Zn, etc.)

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

. Torate system (Ca, Co, Fe, Pb, Mn, Zn, etc.)

Among these, Ca stearate and Zn stearate can be mentioned as specific examples of metal soaps that are particularly excellent in 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, and if the amount is too small, the dispersing effect becomes insufficient. It is better to select within the range of 01 to 3% by weight (for example, 0.3% by weight).

In addition, 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 curing agent for curing the uncured resin component are used. It is also possible to configure a two-component mixed type casting resin material, adhesive or paint as the flame-retardant polymer composite material of the present invention. Specifically, 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. A flame-retardant polymer composite material comprising a thermosetting resin as a substrate and composite particles for imparting flame retardancy dispersed therein by mixing the main agent and the curing agent. The composition for producing a flame-retardant polymer composite material prepared as described above can be used.

FIG. 7 illustrates a specific example using an epoxy resin as an example. That is, the main agent 550 is, for example, a bisphenol-based uncured epoxy resin component containing a flame retardant or a flame retardant different from the composite particles for imparting flame retardancy and, if necessary, the composite particles for imparting flame retardancy. Assistance It is a mixture of an agent, 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 amine diisocyanate and 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 (b) to obtain the desired shape. A flame-retardant polymer composite material molded article is obtained. When the mixed composition 552 is used as a paint, as shown in (c), this is applied to the painted surface of the workpiece 554 and cured to obtain a flame-retardant polymer composite material. Coating film 5 5 5 is obtained. Further, when the mixed composition 552 is used as an adhesive, as shown in (d), the mixed composition 552 is applied to the adhered surfaces of the adherends 5556a and 5556b, and then bonded. However, an adhesive structure in which the adherends 556-1a and 5556b are adhered by the flame-retardant adhesive layer 557-1 is obtained.

Next, the composite particles for imparting flame retardancy can be fixed on the surface of the polymer substrate. Figure 8 shows some examples. FIG. 8 (a) shows an example 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 polymer substrate 50. The composite particles 10 for imparting flame retardancy may be further dispersed in the polymer substrate 50 (the same applies hereinafter). Further, as shown in FIG. 8 (b), the surface side of the fixed particles 10 may be further covered with an overcoat 561 made of a resin or the like.

In FIG. 8 (c), for example, the composite particles 10 for imparting flame retardancy are applied to the inner surface of the cavity of the molding die 505, and then the cavity 満た is filled with the molten resin 570 and solidified. Thus, this is an example in which the applied particles 10 are formed on the surface of the substrate 50 forming the molded body 536. FIG. 8 (d) shows that the surface of the composite particles 10 is covered in advance with a fixing resin layer 562, and is applied to the surface of the substrate 50 while heating to soften the fixing resin layer 562. This is an example in which the composite particles 10 are fixed by curing the resin after being attached. In this case, if the substrate 50 is preheated at a temperature that does not cause unnecessary deformation, the fixing resin layer 562 can be easily softened and adhered. FIG. 8 (e) shows a method of embedding the composite particles 10 in the surface layer of the substrate 50 by projecting or pressing the composite particles 10 onto the surface 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. Example

(Example 1)

As a metal salt, zinc nitrate hexahydrate (Ζ η (Ν0 ₃ ) ₂ · 6Η ₂₀ ) 2 1.93 g was put in 20 ml of ethanol and dissolved. 6.92 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 4.18 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . 75 g of aluminum hydroxide having an average particle diameter of 55 Aim was added to the sol composition as carrier material particles, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide. In order to estimate the components of the coating film, when the gel composition obtained by drying only the sol composition was analyzed, it became a compound containing each element of Si, Zn, 0, N and C. I knew it was there.

The aluminum hydroxide coated by the above sol-gel method is mixed with polypropylene (Grand Polymer: J708) powder or pellets (75 parts of aluminum hydroxide per 100 parts of polypropylene) and then put into an injection molding machine. Injection molding was performed at 180 ° C into a sample shape for flame retardancy test. The sample shape for the flame retardancy test was 125 mm in length, 13 mm in width, and 1.6 mm in thickness based on the UL 94 flammability test. 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-0 standard of the test.

(Example 2)

23.36 g of nickel nitrate hexahydrate (N i ({0 ₃ ) ₂ .6} ₂ 〇) as a metal salt was placed in ethanol 2 Om 1 and dissolved. 6.92 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 4.18 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . 75 g of aluminum hydroxide as in Example 1 was put into this sol composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide. In order to estimate the components of the coating film, when a gel composition obtained by drying only the sol composition was analyzed, a compound containing each element of Si, Ni, 0, N and C was obtained. I understood that.

The aluminum hydroxide coated by the sol-gel method and 250 g of the same polypropylene powder or pellet as in Example 1 were mixed (100 parts of polypropylene and 30 parts of aluminum hydroxide), and then placed in an injection molding machine. It was injection molded at 80 ° C into a sample shape for flame retardancy testing. The sample shape for the flame retardancy test was the same as in Example 1. Using the prepared sample for flame retardancy test, it was tested in the UL 94 flammability test, and it passed the V-2 standard of the test.

In addition, a sample with a length of 12 Omm, a width of 6.5 mm, and a thickness of 3 mm was prepared for a combustion test using the oxygen index method (JI SK 7201). A value of 32% was obtained.

(Example 3)

A sol-like composition was prepared with the same composition as in Example 1 except that the amount of ethanol was changed to 80 m 1. 50 g of magnesium hydroxide having an average particle size of 0.85 μm was added to the sol composition, and mixed with stirring. Then put in a dryer at 120 ° C, The mixture was volatilized to form a coating film of a gel composition (glass precursor composition) on the surface of the magnesium hydroxide. The aluminum hydroxide coated by the above sol-gel method was mixed with 250 g of the same polypropylene powder or pellet as in Example 1 (100 parts of polypropylene and 50 parts of magnesium hydroxide). It was placed in a molding machine and injection molded at 180 ° C into a sample shape for flame retardant testing. The sample shape for the flame retardancy test was the same as in Example 1. Using the prepared sample for flame retardancy test, it was tested in UL94 flammability test, and as a result, it passed the V-2 standard of the test.

(Example 4)

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

A flame-retardant test sample of the same shape was prepared in the same manner as in Example 1, 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)

A mixture of 75 g of aluminum hydroxide and 100 g of polypropylene as in Example 1 was then placed in 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 is the same as in Example 1. Using this flame-retardant test sample in a UL 94 flammability test, the sample ignited immediately after the test started. 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 flame retardant test sample in the UL 94 flammability test, it passed the V-0 standard of the test.

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

* PP… Polypropylene

Based on these results, the comparative sample without the sol-gel coating did not have the effect of imparting flame retardancy in a small amount of about 75 parts with respect to 100 parts of polypropylene, and was added in a large amount (for example, 150 parts). It turns out that it is necessary. On the other hand, as shown in the examples, it can be seen that even a small amount (for example, 30 to 75 parts) of the sample obtained by coating the carrier material particles by the sol-gel method has the effect of imparting flame retardancy.

(Example 5) Nickel nitrate hexahydrate _{_{(N i (N0 3) 2}} · 6Η 2 〇) 93. 43 g were placed in ethanol 8 Om 1 as a metal salt were dissolved. 27.74 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and 16.76 g of pure water was added dropwise. The solution was stirred to prepare a sol-like composition. . 500 g of aluminum hydroxide having an average particle size of 55 πι was added to the sol composition as support material particles and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the surface of the aluminum hydroxide.

The aluminum hydroxide coated by the above sol-gel method is mixed with a powder or pellet of polypropylene (made by Grand Polymer: J708) (100 parts of polypropylene and 50 parts of aluminum hydroxide). A mixed pellet was prepared and injection molded at 180 ° C into a sample shape for flame retardancy test using an injection molding machine. The sample shape for the flame-retardant test was 125 mm long, 13 mm wide and 1.6 mm thick based on the UL 94 flammability test. Using this test sample, it was tested in the UL 94 flammability test. As a result, the test passed the V-2 standard.

In addition, for the combustion test by the oxygen index method (JI SK 7201), a sample of the above composition with a length of 120 mm, a width of 6.5 mm and a thickness of 3 mm was prepared and tested in the same combustion test. As a result, an oxygen index value of 33% was obtained.

Further, the above composition, the tensile based on the test method (JI SK71 1 3) Create a No. 1 form specimen, a result of the test at the same test, tensile strength ^{1 5. 5 X 10 6 [P} a] a Obtained.

(Example 6)

93.43 g of zinc nitrate hexahydrate (Ζ η (Ν0 ₃ ) ₂ · 6Η ₂ 〇) as a metal salt was put in 8 Oml of ethanol and dissolved. 27.74 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 16.76 g of pure water was added dropwise, and the solution was stirred. Thus, a sol composition was prepared. 500 g of aluminum hydroxide as in Example 5 was put into this sol-like composition, and mixed with stirring. Thereafter, the mixture was placed in a dryer at 120 ° C., and the solvent was evaporated to form a coating film of a gel composition (glass precursor composition) on the aluminum hydroxide surface.

The aluminum hydroxide coated by the above sol-gel method was mixed with the same polypropylene powder or pellet as in Example 5 (100 parts of polypropylene and 50 parts of aluminum hydroxide), and then placed in an injection molding machine. Injection molded into sample shape for flame retardancy test in C. The sample shape for the flame retardancy test was the same as in Example 5, and a UL 94 flammability test was performed. Further, a sample for measuring an oxygen index and a sample for measuring a tensile test were prepared in the same manner as in Example 5, 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 testing in the UL 94 flammability test, it passed the V-2 standard of the test. As a result of a combustion test using the oxygen index method, an oxygen index value of 29% was obtained. Further, as a result of a tensile test by a tensile test method, a tensile strength of 16.1 × 10 ⁶ [Pa] was obtained.

(Example 7)

Zinc nitrate hexahydrate (Z n (N_〇 _{_{_{3) 2 · 6Η 2 0)}}} 93. 43 g were placed in ethanol 40 Om 1 as a metal salt were dissolved. Tetraethoxysilane (S i

27.74 g of (OC ₂ H ₅ ) ₄ ) 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 size of 1 μιη was added to the sol composition as support material particles 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 aluminum hydroxide surface.

The aluminum hydroxide coated by the sol-gel method was mixed with the same polypropylene powder or pellet as in Example 5 (100 parts of polypropylene and 50 parts of aluminum hydroxide), and then placed in an injection molding machine at 180 ° C. Flame retardant at It was injection molded into a sample shape for the test. The sample shape for the flame retardancy test was the same as in Example 5, and a UL 94 flammability test was performed. Further, a sample for measuring an oxygen index and a sample for measuring a tensile test were prepared in the same manner as in Example 5, 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 testing in the UL 94 flammability test, it passed the V-2 standard of the test. As a result of a combustion test using 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)

As in Example 7, aluminum hydroxide having an average particle size of 1 zm and polypropylene were mixed (50 parts by weight of aluminum hydroxide with respect to 100 parts by weight of polypropylene), and then placed in an injection molding machine. The sample shape for the flame retardancy test, which was injection-molded in C into the sample shape for the flame retardancy test, is the same as that of Example 5. Using this flame retardant test sample, the sample was ignited immediately after the start of the test as a result of a UL 94 flammability 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. As a result, an oxygen index value of 19.7% was obtained. Furthermore, to create a similar tensile test measurement sample as in Example 5, where the tensile strength test by a tensile testing method was one row, to obtain a tensile strength ^{1 9. 6 X 1 0 6 [} P a].

(Comparative Example 4)

100 g of polypropylene was placed in an injection molding machine and injection molded at 180 ° C into a sample shape for flame retardancy test. The sample shape for the flame retardancy test is the same as in Example 5. The sample was ignited immediately after the start of the test as a result of a UL 94 flammability test using this flame retardant test sample. Further, a sample for oxygen index measurement similar to that of Example 5 was prepared, and a combustion test was performed by the oxygen index method. As a result, an oxygen index value of 17.5% was obtained. Further, a sample for tensile test measurement 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. _C Table 2 summarizes the results of Example 5-7, and Comparative Example 3, 4 in Table 2

* PP: polypropylene 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, the resin properties (tensile strength) are reduced. It can be seen that it is possible to improve the flame retardancy while maintaining.

(Example 8)

Cupric nitrate trihydrate as a metal salt _{_{(Cu (Ν0 3) 2 ·}} 3Η 2 0) 18. Put 22 g in E methanol 3 Om 1, were dissolved. Tetraethoxysilane (S i

6.94 g of (OC ₂ H ₅ ) ₄ ) was added, followed by dropwise addition of 4.14 g of pure water, and the solution was stirred to produce a sol composition. 100 g of polypropylene resin powder having an average particle diameter of 650 Atm was added as carrier material particles to 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-like composition (adhesive compound layer) on the resin surface. In order to estimate the components of the coating film, when a gel composition obtained by drying only the sol composition was analyzed, a compound containing each element of Si, Cu, 0, N, and C was obtained. I understood that. When particles coated with a coating film (combustible particles for imparting flame retardancy) are burned, the weight ratio in the combustion residue is 100 parts by weight of resin as carrier material particles in terms of oxides, i O ₂ 2 parts by weight, was Cu06 parts.

The powder coated with the sol-gel method (composite particles for imparting flame retardancy) is mixed with a powder or pellet of polypropylene (made by Grand Polymer: J708) as a substrate. The composite particles for application (100 parts) were then placed in an injection molding machine and injection molded at 200 ° C into a sample shape for a flame retardancy test. The sample shape for the flame retardancy test was 125 mm in length, 13 mm in width and 1.6 mm in thickness based on the UL 94 flammability test. As the moldings, to tree fat 100 parts in terms of oxide, S I_〇 ₂ l parts by weight and Cu_rei_3 parts.

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 9)

As a metal salt, 21.94 g of zinc nitrate hexahydrate (Ζ η (Ν0 ₃ ) ₂ · 6Η ₂ 〇) was placed in 30 ml of ethanol and dissolved. 6.94 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added to the solution, and then 4.14 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . 100 g of the same polypropylene resin powder as the carrier material particles as in Example 8 was put into this sol-like 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, Si, Zn, It turned out to be a compound containing each element of 0, N and C. When particles coated with a coating film (composite particles for imparting flame retardancy) are burned, the weight ratio in the combustion residue is 100 parts by weight of resin as carrier material particles in terms of oxides. i 0 ₂ 2 parts by weight, was Z n06 parts.

The powder coated with the sol-gel method (composite particles for imparting flame retardancy) was mixed with a polypropylene powder or pellet as a substrate similar to that in Example 8, and the flame retardancy was determined in the same manner as in Example 8. It was injection molded into a test sample shape. As the moldings, per 100 parts of resin in terms of oxide, S I_〇 ₂ l parts by weight and Z n03 parts. Using the prepared flame-retardant test sample in the UL 94 flammability test, it passed the V-2 standard of the test.

(Example 10)

33.74 g of ferric nitrate nonahydrate (F e ({0 ₃ ) ₂ · 9 ₂ }) as a metal salt was placed in ethanol 3 Om 1 and dissolved. 6.94 g of tetraethoxysilane (Si (〇C ₂ H ₅ ) ₄ ) was added to the solution, and then 4.14 g of pure water was added dropwise, and the solution was stirred to prepare a sol-like composition. . Into this sol-like composition, 100 g of polypropylene resin powder as the same support material particles as in Example 8 were added 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 became a compound containing each element of Si, Fe, 0, N and C. I knew it was there. When particles coated with a coating film (composite particles for imparting flame retardancy) are burned, the weight ratio in the combustion residue is 100 parts by weight of resin as carrier material particles in terms of oxides. I_〇 ₂ 2 parts by weight, was F E_rei_6 parts.

The powder coated with the sol-gel method (composite particles for imparting flame retardancy) was mixed with a polypropylene powder or pellet as the same substrate as in Example 8, and In the same manner as in Example 8, injection molding was performed into a sample shape for a flame retardancy test. As the moldings, per 100 parts of resin in terms of oxide, S I_〇 ₂ l parts by weight, F E_rei_3 parts. 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 5)

36.6 g of zinc nitrate hexahydrate (Ζ η (Ν0 ₃ ) ₂ · 6Η ₂ 〇) as a metal salt was placed in ethanol ₃ Om1, and the solution was stirred. To this solution, 100 g of polypropylene resin powder as the same carrier material particles as in Example 8 was added and mixed with stirring. After that, it was placed in a dryer at 90 ° C to evaporate the solvent to form deposits on the resin surface.In order to estimate the components of the deposits, the composition obtained by drying only the above solution was analyzed. As a result, it was found that the compound contained a Zn element. When the particles formed with the above-mentioned attachment were burned, the weight ratio in the combustion residue was 100 parts by weight of the resin and 10 parts by weight of Zηθ in terms of oxide.

The powder on which the deposits were formed was mixed with a polypropylene powder or a pellet as a substrate as in Example 8, and injection-molded into a sample shape for a flame retardancy test in the same manner as in Example 8. In addition, as a molded body, Zn05 parts by weight was calculated based on 100 parts of resin in terms of oxide. Using the prepared sample for flame retardancy test in the UL 94 flammability test, the sample ignited immediately after the start of the test.

Table 3 summarizes the results of Examples 8 to 10 and Comparative Example 5 described above.

Table 3

From these results, it is understood 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). On the other hand, as shown in the examples, the samples (Examples 8 to 10) coated with the gel composition in which tetraethoxysilane (silicon component) was blended exhibited high flame retardancy even in a small amount. It can be seen that there is a property imparting effect.

FIG. 9 shows an observation diagram of the support material particles in this example when observed before and after coating the gel composition with an electron microscope. Fig. 9 (a) shows the carrier particles before coating, and Fig. 9 (b) shows the carrier particles (composite particles for imparting flame retardancy) after coating. You can see that it is coated.

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

Corrected form (Rule 91)

Claims

The scope of the claims

1. Flame retardant having a structure in which a compound layer containing a silicon component and a metal component and oxygen and a compound layer containing oxygen are combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material. A flame-retardant polymer composite material, characterized in that composite particles for imparting property are dispersed in a substrate made of a polymer material (hereinafter also referred to as a polymer substrate).

2. Flame retardant with a structure in which a compound layer containing a silicon component and / or a metal component and oxygen is combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material. A flame-retardant polymer composite material, characterized in that the composite particles for imparting property are fixed on the surface of a substrate made of a polymer material.

3. The flame-retardant high molecular weight composite material according to claim 1, wherein the compound layer generates a vitreous ceramic mainly composed of silicon, Z or a metal oxide by heating.

4. The flame-retardant polymer composite material according to any one of claims 1 to 3, wherein the compound layer contains a carbon component.

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

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

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

8. The flame-retardant polymer composite material according to any one of claims 1 to 7, wherein the carrier material particles are flame-retardant material particles.

9. The flame-retardant polymer composite material according to claim 8, wherein the flame-retardant material particles are inorganic material-based particles or metal material-based particles.

10. The flame-retardant polymer composite material according to claim 9, wherein the inorganic material-based particles are mainly composed of at least one of aluminum hydroxide and magnesium hydroxide.

11. The flame-retardant polymer composite material according to any one of claims 1 to 10, wherein the carrier material particles are polymer material particles.

12. The flame-retardant polymer composite material according to claim 11, wherein the polymer material particles are made of a thermoplastic polymer material.

13. The flame-retardant polymer composite material according to claim 11, wherein the polymer material particles are made of a thermosetting polymer material.

14. 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 13, and curing the main agent. The composite particles for imparting flame retardancy are blended with at least one of the main agent and the curing agent, and the thermosetting is performed 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 is obtained by dispersing the flame-retardant composite particles in a resin as a substrate.

15. A flame-retardant polymer composite material formed by molding the flame-retardant polymer composite material according to any one of claims 1 to 13 into a predetermined shape.

16. The flame-retardant polymer composite material molded article according to claim 15, wherein the molded article is configured as a final molded article without assuming remolding accompanied by softening of the polymer substrate.

17. The flame-retardant polymer composite material molded article according to claim 15, wherein the molded article is used as a temporary molded article for softening the polymer matrix to re-mold it into an intended secondary shape. .

18. Composite particles of carrier material composed of one or more of polymer materials, inorganic materials, and metal materials, which form glassy ceramics mainly composed of silicon, oxides, or metal oxides when heated Composite particles with flame retardant properties When dispersed in a substrate composed of a mixture (hereinafter also referred to as a polymer substrate) and tested in the UL 94 flammability test, it has provided flame-retardant performance that satisfies the range of V-0 to V-2 A flame-retardant polymer composite material, characterized in that:

19. Combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material, a compound layer that generates a glassy ceramic mainly composed of silicon, silicon, or a metal oxide when heated. When the composite particles for imparting flame retardancy having a structured structure are fixed on the surface of a substrate made of a polymer material (hereinafter also referred to as a polymer substrate) and tested in a UL 94 flammability test A flame-retardant polymer composite material characterized by having a flame-retardant property satisfying the range of V-0 to V-2.

20. A structure in which a compound layer containing a silicon component and / or a metal component and oxygen is combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material. When the composite particles for imparting flame retardancy are dispersed in a matrix made of a polymer material (hereinafter, also referred to as a polymer matrix) and tested in a UL 94 flammability test, V-0 to V- 2. A flame-retardant polymer composite material characterized by imparting flame-retardant performance satisfying the range of 2.

21. A structure in which a compound layer containing a silicon component and / or a metal component and oxygen is combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material. When the composite particles for imparting flame retardancy are fixed to the surface of a substrate made of a polymer material (hereinafter also referred to as a polymer substrate) and tested in a UL 94 flammability test, V — 0 to V — A flame-retardant polymer composite material with flame retardancy that satisfies the range of 2.

22. A structure in which a compound layer containing a silicon component and / or a metal component and oxygen is combined with a carrier material particle composed of one or more of a polymer material, an inorganic material, and a metal material. The composite particles for imparting flame retardancy are composed as a granular molded product dispersed in a polymer matrix, and are used to re-mold a secondary shape that has a larger volume than individual granular molded products A masterbatch for producing a flame-retardant polymer composite material molded body, characterized in that:

23. Compounding a compound layer that generates glassy ceramics mainly composed of silicon and / or metal oxides by heating onto particles of one or more of polymeric materials, inorganic materials, and metallic materials The composite particles for imparting flame retardancy with a distorted structure are composed as a granular molded product dispersed in a polymer matrix, and are used to re-mold into a secondary shape having a larger volume than individual granular molded products A masterbatch for producing a flame-retardant polymer composite material molded body.