WO2004083295A1 - 反応性難燃剤及びそれを用いた難燃性樹脂加工品 - Google Patents
反応性難燃剤及びそれを用いた難燃性樹脂加工品 Download PDFInfo
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- WO2004083295A1 WO2004083295A1 PCT/JP2004/003163 JP2004003163W WO2004083295A1 WO 2004083295 A1 WO2004083295 A1 WO 2004083295A1 JP 2004003163 W JP2004003163 W JP 2004003163W WO 2004083295 A1 WO2004083295 A1 WO 2004083295A1
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- retardant
- flame retardant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Definitions
- the present invention relates to, for example, a flame retardant used for a resin molded product and the like, and a flame-retardant resin processed product using the same, and more particularly, to a halogen-free non-halogen flame retardant.
- Thermoplastic resins such as polyester and polyamide, and thermosetting resins such as epoxy have excellent moldability, mechanical strength, and electrical properties as general-purpose resins and engineering plastics. It is widely used, for example.
- Products such as resin molded products are required to be flame-retardant from the viewpoint of safety for the purpose of preventing fires due to high temperatures.
- standards such as UL 94 have been established as flame-retardant grades. Has been.
- halogen-based flame retardant In general, it is known that the addition of a halogen substance is effective in making such a resin material flame-retardant, and is used by adding it to a resin.
- the mechanism of the halogen-based flame retardant is that the halogenated radicals are mainly generated by thermal decomposition, and the halogenated radicals capture the organic radicals as the combustion source, thereby stopping the chain reaction of combustion. It is said to exhibit flammability.
- non-halogen flame retardants inorganic flame retardants such as metal hydrate and red phosphorus, and organic phosphorus flame retardants such as phosphate esters have been studied.
- metal hydrate the effect of imparting flame retardancy is not so high, so it is necessary to incorporate a large amount into the resin. Therefore, the moldability of the resin deteriorates, and the mechanical strength of the obtained molded product tends to decrease. Is limited.
- Red phosphorus has a high flame-retardant effect, but impairs electrical properties due to poor dispersion, generates dangerous gases, reduces formability, and easily causes bleeding.
- phosphate esters, ammonium polyphosphate, phosphazene, etc. are being studied as organophosphorus flame retardants.
- the phosphazene compound is known as one of the non-halogen flame retardants containing nitrogen and phosphorus.For example, Japanese Patent Application Laid-Open No.
- a metal hydroxide compound, and a silicate By compounding cyclic or chain-like phosphazenes, a metal hydroxide compound, and a silicate, it is possible to improve the flame retardancy of the resin composition and suppress the deterioration of the inherent properties of the resin with a small amount of addition. It has been disclosed.
- Japanese Patent Application Laid-Open No. 5-294980 discloses that a cured polymer having a high hardness and having no crack at the time of curing and after formation of a coating film comprises a specific curable group.
- the use of curable phosphazene compounds is disclosed.
- the phosphazene compound used in JP-A-2002-53865 has a reactive group for reacting with a resin component in the molecule.
- the flame retardant component easily migrates in the resin, volatilizes during molding and contaminates the mold, and the flame retardant bleeds out on the surface of the resin.
- Japanese Patent Application Laid-Open No. 5-294980 discloses a curable cyclic phosphazene compound, but the phosphazene compound itself is a cured product or a copolymerizable monomer. It crosslinks and cures with the body and is not used as an additive flame retardant that can be added to general-purpose resins.
- an object of the present invention is to provide a non-octogen reactive flame retardant which is excellent in flame retardancy and heat resistance even when added in a small amount to a resin, can prevent pre-adhesion and the like, and is difficult to use.
- An object of the present invention is to provide a flammable resin processed product. Disclosure of the invention
- the reactive flame retardant of the present invention is a reactive flame retardant having reactivity with a resin, and imparting flame retardancy by binding to the resin by the reaction.
- Y represents an alkylene group having 1 to 6 carbon atoms
- X represents hydrogen or a methyl group
- ⁇ 1 to! ⁇ 6 are the same or different. It may be.
- X represents hydrogen or a methyl group
- R 7 to R 14 are the same or different. It may be.
- the reactive flame retardant of the present invention since a cyclic phosphazene compound having at least one terminal unsaturated bond in one molecule is used, the terminal unsaturated bond is bonded to the resin by heat or radiation. To react. As a result, the flame retardant component is stably present in the resin, so that bleed out of the flame retardant can be prevented, and flame retardancy can be imparted for a long time even with a small amount of addition.
- the ring is stable in terms of energy, improving the thermal decomposition temperature, preventing kneading to resin, vaporization of the flame retardant during molding, and decomposition of the flame retardant due to heat and shear during molding. Moldability is improved.
- the flame-retardant resin processed product of the present invention comprises, after solidifying a resin composition containing the above-described reactive flame retardant and a resin, heating and irradiating the resin with the resin and the reactive flame retardant.
- the terminal unsaturated bond of the organic phosphorus compound is reacted with the resin by heating or irradiation with radiation, so that the flame retardant component is stably present in the resin. .
- the resin is cross-linked to a three-dimensional network structure by bonding the Nada fuel with the resin, the resulting resin processed product has chemical stability, heat resistance, mechanical properties, electrical properties, dimensional stability, and flame retardancy. It is possible to obtain a resin molded product excellent in all properties and moldability, and particularly to improve heat resistance and mechanical strength. Further, thin-wall molding can be performed.
- the resin composition contains two or more types of the reactive flame retardants, and at least one type is the polyfunctional reactive flame retardant.
- the reaction rate required for crosslinking can be controlled by the combined use of flame retardants having different reactivities, so that it is possible to prevent the resin from shrinking due to rapid progress of the crosslinking reaction.
- a polyfunctional flame retardant forms a uniform three-dimensional network structure of the above-mentioned cyclic phosphazene compound (which improves heat resistance and flame retardancy and obtains more stable resin properties).
- the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant has at least one unsaturated group at a terminal. It is preferably a cyclic nitrogen-containing compound.
- a cyclic nitrogen-containing compound having at least one unsaturated group at a terminal can be cross-linked into a three-dimensional network structure by bonding the flame retardant and the resin.
- the combined use of the flame retardant reduces the overall cost of the flame retardant, and the chemical stability, heat resistance, and mechanical properties of the resulting resin product It is possible to obtain a resin molded product having excellent properties, electrical properties, dimensional stability, flame retardancy, and moldability. Further, since it contains nitrogen, the compatibility with the resin is further improved especially when a polyamide resin is used as the resin.
- the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant is an addition-type flame retardant having no reactivity.
- a flame retardant such as phosphate ester, melamine, metal hydroxide, silicon, etc.
- the reactive flame retardant alone due to a synergistic effect
- the flame retardancy can be further improved as compared with the case (1), and the cost of the flame retardant can be reduced.
- the resin composition further contains a cross-linking agent having no flame retardancy but having reactivity with the resin, and the cross-linking agent has a main skeleton. Is preferably a polyfunctional monomer or oligomer having an unsaturated group at the terminal of the compound.
- the resin can be cross-linked into a three-dimensional network structure by bonding the cross-linking agent and the resin, so that the obtained resin processed product has chemical stability, heat resistance, mechanical properties, electrical properties, dimensional stability, A resin molded product with excellent flame retardancy and excellent moldability can be obtained.
- the inorganic filler contains 1 to 35% by mass of the inorganic filler with respect to the whole of the flame-retardant resin processed product.
- the inorganic filler contains a layered clay formed by laminating a silicate layer, and the layered clay is contained in an amount of 1 to 10% by mass based on the entire flame-retardant resin processed product.
- the layered clay formed by laminating silicate layers is contained as an inorganic filler, the layered clay is dispersed in the resin on the order of nanometers to form a hybrid structure with the resin. This improves the heat resistance, mechanical strength, and the like of the obtained flame-retardant resin processed product.
- the mechanical strength of the resin processed product such as tension, compression, bending, impact, and the like is improved by the inclusion of the reinforcing fiber.
- the resin and the reactive flame retardant are obtained by reacting by irradiation with an electron beam or ⁇ -ray at a dose of 10 kGy or more.
- the resin can be cross-linked by radiation, so that a resin processed product can be manufactured with high productivity.
- the dose By setting the dose within the above range, it is possible to prevent uneven formation of the three-dimensional network structure due to insufficient dose and bleed-out due to residual unreacted crosslinking agent.
- the irradiation dose is set to 10 to 45 kGy, deformation and shrinkage due to internal distortion of the resin processed product due to oxidative decomposition products caused by excessive dose can be prevented.
- the resin and the reactive flame retardant are obtained by reacting at a temperature 5 ° C. or more higher than the temperature at which the resin composition is molded.
- a radiation irradiating device or the like is not required, and it can be suitably used particularly in a resin composition containing a thermosetting resin.
- the processed flame-retardant resin product is preferably one selected from a molded product, a coating film, and a sealant.
- the flame-retardant resin processed product of the present invention has excellent flame retardancy as described above and can prevent bleed-out, so it can be used not only as a normal resin molded product but also as a coating agent or the like. It is also suitably used as a sealant for semiconductors and liquid crystal materials.
- the flame-retardant resin processed product is used as an electric component or an electronic component. Since the flame-retardant resin product of the present invention has excellent heat resistance, mechanical properties, electrical properties, dimensional stability, flame retardancy, and moldability as described above, the above-mentioned physical properties are particularly strict. It is particularly suitably used as required electrical and electronic components.
- the reactive flame retardant of the present invention is a reactive flame retardant having reactivity with a resin, and imparting flame retardancy by binding to the resin by the reaction, and has the following general formula (I) or Is characterized by containing a cyclic phosphazene compound represented by (II). (I)
- Y—CX CH 2 , a group selected from a phenyl group, a hydroxyphenyl group, a diphenyl group, a benzyl group, a para-naphthyl group, and a 3-naphthyl group.
- Y represents an alkylene group having 1 to 6 carbon atoms, and X represents hydrogen or a methyl group.
- ⁇ 1 to! ⁇ 6 may be the same or different.
- Y—CX represents a group selected from CH 2 , a phenyl group, a hydroxyphenyl group, a diphenyl group, a benzyl group, a naphthyl group and a / 3-naphthyl group.
- Y represents an alkylene group having 1 to 6 carbon atoms, and X represents hydrogen or a methyl group.
- R 7 to R 14 may be the same or different.
- the cyclic phosphazene compound of the present invention is a cyclic trimer or tetramer of the phosphazene compound and has at least one terminal unsaturated bond.
- the above compounds have an increased molecular weight by introducing an aromatic ring such as a phenyl group, a hydroxyphenyl group, a diphenyl group, a benzyl group, an ⁇ -naphthyl group, or a) -naphthyl group into a side chain, Since the thermal decomposition temperature is improved by stabilizing the energy, Kneading and vaporization of the flame retardant during molding and decomposition of the flame retardant due to heat and shear during molding can be prevented, and moldability is improved.
- an aromatic ring such as a phenyl group, a hydroxyphenyl group, a diphenyl group, a benzyl group, an ⁇ -naphthyl group, or a) -naphthyl group into a side chain
- so-called shine effect is obtained, in which soot is generated and deposited during decomposition of the resin to improve flame retardancy.
- cyclic phosphazene compound of the above structural formula (I) include compounds represented by the following structural formulas (1-1) to (1-13).
- the above cyclic phosphazene compound is a phosphonitrile chloride cyclic trimer or tetramer
- Ri ⁇ Rl 4 can it to synthesize the phosphate ester reaction by reaction with an alcohol having.
- the above compound (1-1) is obtained by dissolving phenol in pyridine, stirring and mixing under a nitrogen stream, and dropwise adding a pyridine solution of hexachlorophosphazene (chlorophosphazene cyclic trimer) to reflux. Thereafter, it can be obtained by dropwise addition of aryl alcohol, refluxing, removing excess alcohol and solvent and drying.
- Examples of such a combination include a combination of a monofunctional type such as the above compound (1-4) and a trifunctional type such as the compound (1-1), and a compound (1-10) And a bifunctional type such as compound (II-12).
- a polyfunctional reactive flame retardant it is preferable to contain at least a polyfunctional reactive flame retardant.
- a uniform three-dimensional network structure is formed by the cyclic phosphazene compound.
- a flame-retardant resin processed product using the reactive flame retardant will be described. .
- the flame-retardant resin processed product of the present invention is obtained by solidifying a resin composition containing a resin and the cyclic phosphazene compound represented by the general formula (I) or (II), and then heating or irradiating the resin composition with radiation. It is obtained by reacting the resin with the reactive flame retardant, and contains the reactive flame retardant in an amount of 1 to 20% by mass based on the whole resin composition.
- the resin used in the present invention any of a thermoplastic resin and a thermosetting resin can be used and is not particularly limited.
- thermoplastic resin examples include polyamide resins, polybutyrene terephthalate resins, polyester resins such as polyethylene terephthalate, polyacrylic resins, polyimide resins, polycarbonate resins, polyurethane resins, and polystyrene acrylonitrile-styrene.
- Polystyrene resins such as copolymers, acrylonitrile-butadiene-styrene copolymers, polyacetylene resins, polyolefin resins, polyphenylene oxide resins, polyphenylene sulfide resins, polybutadiene resins, etc.
- thermosetting resin examples include an epoxy resin, a urethane resin, an unsaturated polyester resin, a phenol resin, a urea resin, a melamine resin, an alkyd resin, and a gay resin.
- an epoxy resin, a phenol resin, an unsaturated polyester resin, and a urea resin from the viewpoint of mechanical properties and heat resistance.
- the content of the reactive flame retardant is preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, based on the entire resin composition.
- the content of the reactive flame retardant is less than 1% by mass, the crosslinking by the reaction is insufficient, and the mechanical, thermal, and electrical properties of the obtained resin processed product are not favorable. %, The reactive flame retardant becomes excessive, unreacted monomers and decomposed gas of the reactive flame retardant are generated, and the oligomerized product bleeds out, and the mechanical properties of the resin processed product are deteriorated. It is not preferable because it decreases.
- cyclic phosphazene compounds represented by the above general formula (I) or ( ⁇ ) in the present invention, two or more compounds having different reactivities, that is, different numbers of the above functional groups in one molecule It is preferable to use two or more compounds in combination. Thereby, the reaction rate required for crosslinking can be controlled, so that the resin composition can be prevented from shrinking due to rapid progress of the crosslinking reaction.
- a uniform three-dimensional network structure is formed by the organic phosphorus compound.
- an addition-type flame retardant having no reactivity other than the reactive flame retardant may be further contained.
- a flame retardant a non-halogen flame retardant is preferable, and a metal hydrate represented by aluminum hydroxide / magnesium hydroxide and the like, and triphenyl phosphate, tricresyl phosphate and the like can be used.
- Examples thereof include condensed phosphoric acid esters such as (diphenyl) phosphate, ammonium polyphosphate, polyphosphoramide, red phosphorus, guanidine phosphate, and the like, derivatives of sialic acid or isocyanuric acid, melamine derivatives, and silicon-based flame retardants. These flame retardants may be used alone or in combination of two or more.
- the content of the flame retardant other than the reactive flame retardant is 1 to 2 with respect to the entire resin composition in order to prevent bleeding and deterioration of mechanical properties.
- the content is preferably 0% by mass, more preferably 3 to 15% by mass.
- a flame retardant having a reactivity other than the reactive flame retardant per 1 part by mass of the reactive flame retardant a cyclic nitrogen-containing compound having at least one unsaturated group at a terminal may be used. It is more preferable to contain the parts by mass.
- Examples of the above group having an unsaturated group at the terminal include diatalylate, dimethacrylate, diarylate, triacrylate, trimethacrylate, toriarylate, tetraacrylate, tetramethacrylate, and tetramethacrylate. Related, etc. However, from the viewpoint of reactivity, it is more preferable to use an acrylate such as diacrylate, triacrylate or tetraacrylate.
- examples of the cyclic nitrogen-containing compound include an isocyanuric ring and a cyanuric ring.
- cyclic nitrogen-containing compound having at least one unsaturated group at the terminal include the above-mentioned derivatives of sialic acid or i'socyanuric acid.
- sialic acid or i'socyanuric acid for example, isocyanuric acid E ⁇ modified diacrylic acid And EO-modified isocyanuric acid triacrylate, triisocyanuryl triacrylate and the like.
- a crosslinking agent which does not have flame retardancy but has reactivity with the resin may be further contained.
- a crosslinking agent a polyfunctional monomer or oligomer having an unsaturated group at the terminal of the main skeleton can be used.
- the cross-linking agent having no flame retardancy but having reactivity with the resin means one having cross-linking property (reactivity) but not having flame retardancy itself. Excludes reactive flame retardants that have both crosslinkability and flame retardance, such as the above-mentioned cyclic nitrogen-containing compounds having at least one unsaturated group at the terminal.
- Examples of such a crosslinking agent include difunctional to tetrafunctional compounds represented by the following general formulas (a) to (c).
- X is a main skeleton
- R 15 to R 18 are functional groups having an unsaturated group at the terminal
- (a) is a bifunctional compound
- (b) is a trifunctional compound
- (c) is a tetrafunctional compound.
- the main skeleton X is an aliphatic alkyl such as glycerin or a pen-erythol derivative, or a trimellit, pyromellit, tetrahydrofuran, or a trimethylenetrioxane.
- the structure include an aromatic ring and bisphenol.
- cross-linking agent examples include bifunctional monomers and oligomers such as bisphenol F-E ⁇ modified diacrylate, bisphenol A_E ⁇ modified diacrylate, tripropylene glycol diacrylate, and polypropylene glycol.
- diacrylates such as polyethylene acrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate morphostearate, and dimethacrylates and diarylates thereof.
- trifunctional monomers or oligomers examples include triacrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane P ⁇ modified triacrylate, and trimethylolpropane EO modified triacrylate. And their trimethacrylates and triarylates.
- tetrafunctional monomer or oligomer examples include ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and the like.
- the cross-linking agent mentioned above is used as the main skeleton X: trimellitic acid, pyromellitic acid tetrahydrofurantetracarboxylic acid, 1,3,5-trihydroxybenzene, glycerin, Penno Eristol, 2,4,6-tris (Chloromethyl)
- One selected from 1,3,5-trioxane and the like, is a functional group having an unsaturated group at a terminal, such as aryl bromide, aryl alcohol, arylamine, methallyl bromide, It is obtained by reacting one selected from methallyl alcohol methallylamine and the like.
- the crosslinking agent is preferably contained in an amount of 0.5 to 10 parts by mass based on 1 part by mass of the reactive flame retardant.
- the resin composition used in the present invention may contain an inorganic filler, a reinforcing fiber, various additives, and the like, in addition to the resin and the flame retardant.
- the mechanical strength of the resin processed product can be improved and the dimensional stability can be improved.
- it serves as a substrate on which the reactive flame retardant is adsorbed, and makes the dispersion of the reactive flame retardant uniform.
- the inorganic filler conventionally known ones can be used, and typical ones are metal powders such as copper, iron, nickel, zinc, tin, stainless steel, aluminum, gold, silver, humid silica, Aluminum silicate, calcium silicate, silicic acid, hydrous calcium silicate, hydrous aluminum silicate, glass beads, carbon black, quartz powder, mica, Examples include talc, myric, clay, tidan oxide, iron oxide, zinc oxide, calcium carbonate, magnesium carbonate, magnesium oxide, calcium oxide, magnesium sulfate, potassium titanate, and diatomaceous earth. These fillers may be used alone or in combination of two or more, or may be those treated with a known surface treatment agent.
- metal powders such as copper, iron, nickel, zinc, tin, stainless steel, aluminum, gold, silver, humid silica, Aluminum silicate, calcium silicate, silicic acid, hydrous calcium silicate, hydrous aluminum silicate, glass beads, carbon black, quartz powder, mica, Examples include talc, myric, clay, tidan oxide,
- the content of the inorganic filler is preferably from 1 to 35% by mass, more preferably from 1 to 20% by mass, and preferably less than 1% by mass, based on the whole flame-retardant resin product.
- the mechanical strength of the flame-retardant resin processed product is insufficient, the dimensional stability is insufficient, and the adsorption of the reactive flame retardant is insufficient.
- it exceeds 35% by mass the flame-retardant resin processed product becomes brittle, which is not preferable.
- a layered clay comprising a stack of silicate layers is a clay having a structure in which a silicate layer having a thickness of about I nm and a side length of about 100 nm is stacked. is there. Therefore, this layered clay is dispersed in the resin on the order of nanometers to form a hybrid structure with the resin, thereby improving the heat resistance of the flame-retardant resin processed product obtained. .
- the average particle size of the layered clay is preferably 100 nm or less.
- the layered clay examples include montmorillonite, kaolinite, and my strength, but montmorillonite is preferred because of its excellent dispersibility.
- the layered clay may have been subjected to a surface treatment in order to improve the dispersibility in the resin.
- commercially available clays may be used, such as “Nanoma Ichi” (trade name, manufactured by Nissho Iwai Bentonite Co., Ltd.) and “Somasif” (trade name, manufactured by Corpo Chemical Company). Can be used.
- the content of layered clay is preferably 1 to 10% by mass based on the entire flame-retardant resin processed product.
- the layered clay may be used alone or in combination with another inorganic filler.
- the reinforcing fibers for example, in the case of a molded product, the mechanical strength is improved and the dimensional stability can be improved.
- the reinforcing fibers include glass fibers, carbon fibers, and metal fibers. It is preferable to use glass fibers from the viewpoints of strength and adhesion to a resin or an inorganic filler. These reinforcing fibers can be used alone or
- Two or more kinds may be used in combination, and a known surface treatment such as a silane coupling agent may be used. It may be treated with a physical agent. ⁇
- the glass fiber is surface-treated and further coated with a resin.
- a resin e.g., ethylene glycol dimethacrylate
- the adhesiveness with the thermoplastic polymer can be further improved.
- a known silane coupling agent can be used. Specifically, at least one alkoxy group selected from the group consisting of a methoxy group and an ethoxy group, an amino group, a bier group, Examples thereof include a silane coupling agent having at least one reactive functional group selected from the group consisting of an acrylic group, a methacryl group, an epoxy group, a mercapto group, a halogen atom, and an isocyanate group.
- the coating resin is not particularly limited, and examples thereof include a urethane resin and an epoxy resin.
- the compounding amount of the reinforcing fiber is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, based on the whole flame-retardant resin product. If the content is less than 5% by mass, the mechanical strength of the flame-retardant resin processed product is reduced, and the dimensional stability is insufficient, which is not preferable. If the content exceeds 40% by mass, the resin is processed. In addition, it is preferable to contain the above-mentioned inorganic filler and the reinforcing fiber, and to contain the inorganic filler and the reinforcing fiber in an amount of 65% by mass or less based on the whole flame-retardant resin product. More preferably, the content is 5% by mass or less.
- the resin composition used in the present invention includes, in a range that does not significantly impair the physical properties such as heat resistance, weather resistance, and impact resistance, which are the objects of the present invention, various commonly used components other than those described above, for example,
- Additives such as crystal nucleating agents, coloring agents, antioxidants, release agents, plasticizers, heat stabilizers, lubricants, and UV inhibitors can be added.
- an ultraviolet initiator or the like can be used.
- the colorant is not particularly limited, but is preferably one that does not fade by irradiation as described below.
- inorganic pigments such as red iron black, carbon black, graphite, and metal complexes such as phthalocyanine are preferably used.
- the flame-retardant resin processed product of the present invention is obtained by heating or To cause the resin and the reactive flame retardant to react with each other.
- thermoplastic resin in the case of a resin composition containing a thermoplastic resin, the thermoplastic resin and the reactive flame retardant are melt-kneaded and pelletized. It can be formed by conventionally known injection molding, extrusion molding, vacuum molding, inflation molding or the like. Melt kneading can be carried out using a conventional melt kneading machine such as a single-screw or twin-screw extruder, a Banbury mixer, a nipper, and a mixing port.
- a conventional melt kneading machine such as a single-screw or twin-screw extruder, a Banbury mixer, a nipper, and a mixing port.
- the kneading temperature can be appropriately selected depending on the type of the thermoplastic resin.
- the kneading temperature is preferably 240 to 280 ° C., and the molding conditions can also be set as appropriate. Not limited. At this stage, since the crosslinking has not progressed at all, the extra spool during molding can be recycled as a thermoplastic resin.
- thermosetting resin similarly to the above, after the thermosetting resin and the reactive flame retardant are melt-kneaded and pelletized, for example, conventionally known injection molding, compression molding, transfer It can be molded using molding or the like.
- the resin composition When a film is formed, the resin composition may be applied as it is, or may be appropriately diluted with a solvent or the like to obtain a coatable solution or suspension, and then dried and formed into a film by a conventionally known method. Is also good.
- a coating method such as one coating with a roller, spraying, dipping, spin coating or the like can be used, and the method is not particularly limited.
- the unsaturated bond at the terminal of the reactive flame retardant reacts with the resin and undergoes a crosslinking reaction by heating or irradiation with radiation, and is stably present in the resin.
- the reaction temperature is preferably at least 5 ° C higher than the resin molding temperature, and at least 10 ° C higher. Is more preferred.
- the radiation in the present invention means radiation in a broad sense, and specifically includes not only particle beams such as electron beams and ⁇ -rays but also electromagnetic waves such as X-rays and ultraviolet rays.
- irradiation with an electron beam or a beam is preferable.
- a known electron accelerator or the like can be used, and the acceleration energy is preferably 2.5 MeV or more.
- an irradiation device using a known cobalt 60 radiation source or the like can be used.
- Irradiation equipment using a known cobalt 60 radiation source or the like can be used for r-ray irradiation.
- r-rays are preferable because they have a higher transparency than electron beams, so that irradiation is uniform and preferable. However, since the irradiation intensity is high, dose control is necessary to prevent excessive irradiation.
- the irradiation dose of radiation is preferably 10 kGy or more, more preferably 10 to 45 kGy. Within this range, a crosslinked resin article having excellent physical properties can be obtained. If the irradiation dose is less than 10 kGy, the formation of a three-dimensional network structure due to cross-linking becomes nonuniform, and an unreacted cross-linking agent may bleed out. On the other hand, if it exceeds 45 kGy, internal distortion of the resin-processed product due to the oxidative decomposition product remains, which is not preferable because deformation or shrinkage occurs.
- the flame-retardant resin processed product of the present invention obtained as described above has, as a molded product, excellent mechanical properties, electrical properties, dimensional stability, and moldability in addition to heat resistance and flame retardancy. Therefore, electrical or electronic parts that require high heat resistance and flame retardancy, as well as automobile parts and optical parts, such as members for supporting contacts such as electromagnetic switches and switches, and prints Substrate such as a substrate. It can be suitably used as a package for an integrated circuit, a housing for electric components, and the like.
- Class 1 includes diodes, transistors, semiconductor devices such as integrated circuits, and the like.
- an interior component such as a cooling fan, a bumper, a brake cover, and a panel, a sliding component, a sensor, and an automobile component such as a motor.
- the electronic components and electric elements such as semiconductor chips and ceramic capacitors are encapsulated by sealing the resin composition and curing the resin, and further performing the reaction by heating or irradiation as described above. It can be used as a flame retardant sealant.
- sealing method sealing by injection molding, potting, transfer molding, injection molding, compression molding or the like is possible.
- electronic parts and electric parts to be sealed are particularly limited although not included, examples include a liquid crystal, an integrated circuit, a transistor, a thyristor, a diode, and a capacitor.
- a non-halogen-based reactive flame retardant and a flame retardant using the same which are excellent in flame retardancy even when added to a resin in a small amount and can prevent bleed-out and the like.
- a resin processed product can be provided. Therefore, this flame-retardant resin processed product can be suitably used for resin molded products such as electric parts and electronic parts, sealing agents for semiconductors and the like, coating films, and the like.
- the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.
- the structure of the compound was determined by TOF-Mass (time-of-flight mass spectrometry) spectrum and elemental analysis.
- a compound of the following structural formula (1-6) was obtained as a pale yellow solid in the same manner as in Synthesis Example 1 except that 5.1-06 g (0.30 mol) of 4, -hydroxybiphenyl was used instead of phenol. Got.
- Elemental analysis values of this compound are calculated from the structural formula (I-13a) or the structural formula (I-13b). (C: 60.82, H: 4.80, N: 6.26, P: 13.82). From the T ⁇ F—Mass spectrum, the calculated molecular weight of the structural formula (I-13a) or the structural formula (I-13b) can be calculated as follows:
- the elemental analysis value (C: 60.08, H: 4.77, N: 7.12, P: 15.80) of this compound is-.
- thermoplastic resin 68Z6 nylon (Ube Industries: 2 1 2 3B) as thermoplastic resin 68 parts by mass, glass fiber with a fiber length of approximately 3 mm surface-treated with a silane coupling agent as a reinforcing fiber (Asahi Fiberglass: 03. JAFT2Ak25) 2 5 parts by weight, 1 part by weight of car pump rack as a coloring agent, compound of Synthesis Example 5 as a flame retardant (Structural formula (II-2) above).
- the mixture was kneaded with a screw extruder (manufactured by Nippon Steel Corporation) at 250 ° to obtain resin pellets, and dried at 105 ° (:, 4 hours).
- the above pellets were molded using an injection molding machine (manufactured by FUNUC: Q! 50C) under the conditions of a resin temperature of 270 ° C and a mold temperature of 80 ° C.
- thermoplastic resin As a thermoplastic resin, 66 nylon (made by Ube Industries, Ltd .: 200 B) 61.4 mass parts, glass fiber with a fiber length of about 3 mm surface-treated with a silane coupling agent as a reinforcing fiber (Asahi Fiberglass) Company: 03.
- JAFT2Ak 25 25 parts by mass, 5 parts by mass of talc of about 2 t diameter as an inorganic filler, 1.5 parts by mass of iron black as a coloring agent, and trifunctional as a flame retardant Compound of 1 (the above structural formula (I-11)) 5 parts by mass, monofunctional compound of Synthesis Example 4 (mixture of the above structural formulas (I-11a) and (I-11b)) 2 parts by weight, an antioxidant (Ciba-Geigy I. Co., Ltd .: Irganox 101.10) 0.1 part by weight is compounded and kneaded at 270 ° C with a side flow type twin screw extruder (Nippon Steel Corporation). Thus, resin pellets were obtained and dried at 105 ° C. for 4 hours.
- Non-anti A resin-processed product of Example 3 was obtained under the same conditions as in Example 2 except that 4 parts by mass of an organic phosphorus-based flame retardant (manufactured by Sanko Chemical Co., Ltd .: EP0CLEAN) was used.
- Polyethylene terephthalate resin as thermoplastic resin (Toray Industries, Inc .: Trecon 1401 X06) 61.1 parts by mass, flame retardant compound of Synthesis Example 2 (Structural formula (I-16) above) 6 Using a part by mass, kneading at a kneading temperature of 245 ° C to obtain a resin compound pellet, drying at 130 ° C for 3 hours, and changing the cylinder temperature during molding to 250 ° C A molded product was molded under the same conditions as in Example 2.
- the molded article was irradiated with an electron beam having an irradiation dose of 25 kGy at an acceleration voltage of 4.8 MeV using an accelerator manufactured by Sumitomo Heavy Industries, Ltd. to obtain a resin processed article of Example 4.
- a molded article was molded under the same conditions as in Example 1 except that 2 parts by mass of a thermal catalyst (NOFMER BC, manufactured by NOF Corporation) was added to the system of Example 1.
- NOFMER BC a thermal catalyst
- Example 2 Molded under the same conditions as in Example 2 except that 7 parts by mass of an ultraviolet initiator (2: 1 mixture of Irganox 651 and Irganox 369 manufactured by Ciba Geigy) were added to the system of Example 2. The product was molded.
- an ultraviolet initiator 2: 1 mixture of Irganox 651 and Irganox 369 manufactured by Ciba Geigy
- the molded product was irradiated with an ultra-high pressure mercury lamp at a wavelength of 365 nm at an illuminance of 15 OmW / cm 2 for 2 minutes to obtain a resin processed product of Example 7.
- Thermosetting epoxy mold resin manufactured by Nagase Chemical Co., Ltd., main agent XNR4012: 100, curing agent XNH4012: 50, curing accelerator FD400: 1)
- main agent XNR4012 100
- curing agent XNH4012 50
- curing accelerator FD400 1
- 47 parts by mass of silica is dispersed in 48 parts by mass
- Epoxy resin for semiconductor encapsulation (Shin-Etsu Chemical Co., Ltd .: Semicoat 1 15) After adding 4 parts by mass of the compound of the above structural formula (1-7) as a flame retardant to 96 parts by mass to obtain a molded product The mixture was reacted at 150 ° C. for 4 hours to obtain a processed resin product (sealing agent) of Example 9.
- Example 10
- Resin processed products of Comparative Examples 1 to 10 were obtained in the same manner as in Examples 1 to 10, except that the reactive flame retardant used in the present invention was not used in Examples 1 to 10.
- Example 3 is the same as Example 3 except that only 15 parts by mass of a non-reactive organic phosphorus-based flame retardant (manufactured by Sanko Chemical Co., Ltd .: EP0CLEAN) was added as a flame retardant in place of the reactive flame retardant. Under the same conditions as in Example 3, a resin processed product of Comparative Example 11 was obtained.
- a non-reactive organic phosphorus-based flame retardant manufactured by Sanko Chemical Co., Ltd .: EP0CLEAN
- test pieces (length 5 inches, width 1Z2 inches, thickness 3.2 mm) in accordance with UL-94, which is a flame retardancy test ), And prepare a glow-wire test piece (60 mm square, 1.6 mm thick) compliant with the IEC 60695-2 method (GWF I), UL 94 test, glow-wire test (IEC compliant), A heat resistance test was performed. In addition, 300 x 3 hours A pre-out test was performed.
- test specimens (5 inches long and 1/2 inch wide) conforming to UL-94 were prepared. An evaluation was performed. Table 1 summarizes the results.
- the test specimen was mounted vertically, and the burning time after flame contact for 10 seconds with a Bunsen burner was recorded.
- the second indirect flame for 10 seconds after the fire extinguishing and the burning time after the flame contact was recorded again.
- the total burning time, the glowing time (glowing) time after the second fire extinguishing, and the drops that ignite the cotton was determined by the presence or absence of.
- the solder heat resistance test showed the dimensional deformation rate after immersion in 350 solder bath for 10 seconds.
- Comparative Example 110 which does not contain a flame retardant, the flame retardancy was insufficient, ⁇ , and all failed in the glow wire test. Furthermore, the dimensional deformation rate after the soldering heat test was 30% or more. It turns out that it is inferior to Example.
- Comparative Example 11 in which a non-reactive organophosphorus flame retardant was used as the flame retardant, the flame retardancy was insufficient at V-2, and the bleed-out of the flame retardant after 3 hours at 30 OX. Admitted. Industrial applicability
- the present invention is suitable for non-halogen flame retardants and flame-retardant resin processed products that do not contain octogen, such as resin molded products such as electric parts and electronic parts, sealants for semiconductors and the like, and coating films.
- octogen such as resin molded products such as electric parts and electronic parts, sealants for semiconductors and the like, and coating films.
Description
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006137843A (ja) * | 2004-11-12 | 2006-06-01 | Fuji Electric Holdings Co Ltd | 難燃性樹脂加工品の製造方法 |
JP2008088217A (ja) * | 2006-09-29 | 2008-04-17 | Fushimi Pharm Co Ltd | 反応性基含有環状ホスファゼン化合物からなる難燃剤およびその製造方法 |
CN103451912A (zh) * | 2013-09-03 | 2013-12-18 | 际华三五零九纺织有限公司 | 利用电子束辐照对织物的耐久阻燃后整理方法 |
JP2014058691A (ja) * | 2013-12-27 | 2014-04-03 | Fushimi Pharm Co Ltd | 難燃性樹脂組成物 |
WO2015019945A1 (ja) * | 2013-08-05 | 2015-02-12 | 株式会社カネカ | ホスファゼン含有ゴムグラフト共重合体及びその熱可塑性樹脂組成物 |
CN110615928A (zh) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | 改性煤矸石粉填充聚烯烃阻燃复合材料及制备工艺 |
KR102451262B1 (ko) * | 2021-03-25 | 2022-10-06 | 금오공과대학교 산학협력단 | 복합경화형 방염가공조성물, 이를 이용한 직물방염가공방법 및 이를 이용한 방염가공직물 |
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JPH04134090A (ja) * | 1990-09-21 | 1992-05-07 | Nippon Soda Co Ltd | ホスファゼン誘導体及びその重合体 |
JPH08302124A (ja) * | 1995-05-15 | 1996-11-19 | Denki Kagaku Kogyo Kk | 難燃性樹脂組成物 |
JP2001335703A (ja) * | 2000-03-21 | 2001-12-04 | Otsuka Chem Co Ltd | 難燃剤、及び難燃性樹脂組成物、及び成形物、及び電子部品 |
JP2002146147A (ja) * | 2000-11-07 | 2002-05-22 | Techno Polymer Co Ltd | 難燃性熱可塑性樹脂組成物 |
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- 2004-03-11 JP JP2005503658A patent/JP4331722B2/ja not_active Expired - Fee Related
- 2004-03-11 WO PCT/JP2004/003163 patent/WO2004083295A1/ja active Application Filing
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JPH04134090A (ja) * | 1990-09-21 | 1992-05-07 | Nippon Soda Co Ltd | ホスファゼン誘導体及びその重合体 |
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JP2001335703A (ja) * | 2000-03-21 | 2001-12-04 | Otsuka Chem Co Ltd | 難燃剤、及び難燃性樹脂組成物、及び成形物、及び電子部品 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006137843A (ja) * | 2004-11-12 | 2006-06-01 | Fuji Electric Holdings Co Ltd | 難燃性樹脂加工品の製造方法 |
JP2008088217A (ja) * | 2006-09-29 | 2008-04-17 | Fushimi Pharm Co Ltd | 反応性基含有環状ホスファゼン化合物からなる難燃剤およびその製造方法 |
WO2015019945A1 (ja) * | 2013-08-05 | 2015-02-12 | 株式会社カネカ | ホスファゼン含有ゴムグラフト共重合体及びその熱可塑性樹脂組成物 |
CN103451912A (zh) * | 2013-09-03 | 2013-12-18 | 际华三五零九纺织有限公司 | 利用电子束辐照对织物的耐久阻燃后整理方法 |
JP2014058691A (ja) * | 2013-12-27 | 2014-04-03 | Fushimi Pharm Co Ltd | 難燃性樹脂組成物 |
CN110615928A (zh) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | 改性煤矸石粉填充聚烯烃阻燃复合材料及制备工艺 |
CN110615928B (zh) * | 2019-09-30 | 2022-03-08 | 北京工业大学 | 改性煤矸石粉填充聚烯烃阻燃复合材料及制备工艺 |
KR102451262B1 (ko) * | 2021-03-25 | 2022-10-06 | 금오공과대학교 산학협력단 | 복합경화형 방염가공조성물, 이를 이용한 직물방염가공방법 및 이를 이용한 방염가공직물 |
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