WO2006043460A1 - 難燃剤組成物 - Google Patents
難燃剤組成物 Download PDFInfo
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- WO2006043460A1 WO2006043460A1 PCT/JP2005/018838 JP2005018838W WO2006043460A1 WO 2006043460 A1 WO2006043460 A1 WO 2006043460A1 JP 2005018838 W JP2005018838 W JP 2005018838W WO 2006043460 A1 WO2006043460 A1 WO 2006043460A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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 a flame retardant composition. More specifically, the present invention relates to a flame retardant composition that is excellent in processability and excellent in flame retardancy, moisture absorption resistance, heat resistance, and extrusion workability when blended with rosin or the like.
- the action mechanism of the flame retardant is that the polyphosphoric acid phase generated on the surface of the resin during combustion and the carbonized layer resulting from the dehydration of the resin form a film, blocking the heat and oxygen supply to the resin during combustion. It is said that there is. It is particularly effective for a resin that easily forms a carbonized film, that is, is easily dehydrated. Conversely, when using a phosphorous and phosphorus compound to treat flame retardants that are difficult to form a carbonized film by dehydration, it is necessary to rely mainly on a polyphosphate phase film, so the amount must be increased. Goodbye
- Patent Document 3 proposes a method of using a crosslinked phosphazene compound and a polyphenylene ether resin as a flame retardant for a polyalkylene arylate resin. This imparts good flame retardancy to polyalkylene arylate-based resins, but is not fully satisfactory in processability, heat resistance, mechanical properties, dielectric properties, and appearance of molded products. It was.
- Patent Document 4 A technique using phenolic resin having a weight average molecular weight of 500,000 or more has been disclosed.
- Patent Document 4 A technique using phenolic resin having a weight average molecular weight of 500,000 or more has been disclosed.
- use of such a high molecular weight phenolic resin is not preferred because the processing fluidity is remarkably inferior and the effect of imparting flame retardancy is remarkably inferior when added to the resin.
- Patent Document 6 discloses a technique of using a phenolic resin and a phenol phosphazene in combination as a flame retardant technique for a polyalkylene terephthalate resin.
- phenolic resin has flame resistance, heat resistance and impact resistance.
- the flame retardant composition found by the present inventors such as a specific phenolic resin and a phosphorus compound, is not only flame retardant, but also has heat resistance, mechanical properties.
- the effect of maintaining or improving various physical properties such as characteristics, workability, and low smoke emission cannot be found. Such an excellent effect has been achieved for the first time by the present invention as described later.
- Patent Document 1 Japanese Patent Publication No. 3-73590
- Patent Document 2 JP-A-8-225714
- Patent Document 3 International Publication Number WO03Z002666 Pamphlet
- Patent Document 4 Japanese Patent Laid-Open No. 2000-273132
- Patent Document 5 Japanese Patent Laid-Open No. 2001-164256
- Patent Document 6 International Publication Number WO01Z048086 Pamphlet
- the present invention is a flame retardant composition that does not contain chlorine or bromine compounds and is excellent in flame retardancy, moisture absorption resistance, heat resistance, dielectric properties, low smoke generation, and extrusion workability when added to rosin. It is to provide.
- the present inventors have used a flame retardant composition comprising (A) a specific phenolic resin and (B) a specific phosphorus compound. Therefore, when added to a resin, it promotes the formation of a carbonized film on the surface of the resin, and can impart stable flame retardancy even to a resin that is difficult to form a film.
- the present inventors have found that a flame-retardant resin composition having heat resistance, hydrolysis resistance, thermal stability, impact resistance, mechanical properties, good extrusion workability, and molded product appearance can be obtained, and the present invention has been achieved.
- the flame retardant composition according to any one of 1 or 2 above, wherein the content of the trinuclear component is 7% or less,
- the flame retardant composition according to any one of 1 to 3 above, wherein the content of the dinuclear component is 10% or less,
- the component (B) contains at least a phosphazene compound as described above.
- the component (B) is a phosphazene compound, and the cyclic trimer and Z or cyclic tetramer content is 80% by weight or more.
- a resin composition comprising (C) a resin and the flame retardant composition according to any one of 1 to 13 above,
- Component (C) is a poly (phenylene ether) resin, a polystyrene resin, a polyalkylene arylate resin, a polyamide resin, a polycarbonate resin, a polypropylene olefin resin, polypropylene, polyethylene, ABS 16.
- a resin composition excellent in extrusion workability, mold release property, thermal stability, impact resistance, mechanical properties and the like can be obtained.
- (A) a specific phenolic resin and (B) a specific phosphorus compound are essential components.
- the growth of the carbonized layer can be promoted during high-temperature heating, and excellent flame retardancy, mechanical properties, and molded product appearance can be obtained with a small amount of addition.
- the synergistic effect provides the resin composition with excellent flame retardancy, heat resistance, mechanical properties, and good molded product appearance.
- a phenolic resin satisfying the above conditions that is, a retention time in GPC measured with a column temperature of 35 ° C and a flow rate of lmLZmin using tetrahydrofuran as a solvent 6.1 to 9 7-minute area fraction (a) and retention time 9.7-7:
- L 1 Area fraction (a) of 74% or more when the total area integration rate (b) of 9 minutes is 100% 98 % Or less, preferably 74% or more and 95% or less, more preferably 74% or more and 92% or less, and particularly preferably 74% or more and 90% or less, phenolic resin has excellent flame resistance and heat resistance. , Mechanical properties, workability, appearance of molded products, but especially synergistic high effect in flame retardancy.
- the GPC measurement method for phenol-based rosin was carried out using Waters Alliance (Nihon Waters Co., Ltd.) with tetrahydrofuran solvent at a column temperature of 35 ° C and a flow rate of lmLZmin. ) Waters Styragel HR1, HR3, HR4 manufactured by the company are connected in series and measured with a UV (Waters2487; wavelength 254 nm) and Z or RI (Waters 2414) detector. Retention times 6. The method of calculating the area fraction for each of 1 to 9.7 minutes and 9.7 to 11.9 minutes is calculated as follows.
- the area enclosed between the baseline of the GPC chart and the GPC curve of 6.1 to 9.7 minutes and the straight line drawn perpendicular to the retention time of 9.7 minutes is (a ').
- the GPC curve from 9.7 to 11.9 minutes and the straight line drawn at the retention time 11.9 minutes is (b '), () and (
- the value of (a ') with respect to the sum of b') is the percentage of area (a), and the value of 0) with respect to the sum of () and (b ') is the percentage of area (b).
- a calibration curve was created using standard polystyrene, and the molecular weight calculated for the retention time of 9.7 minutes based on the calibration curve was approximately 870.
- the method for measuring the trinuclear content is a trinuclear peak with a peak top in the vicinity of a retention time of 10.0 to: LO. 1 minute in the GPC measurement under the above conditions.
- the next retention time is 9.8.
- the point where the absorption between the peak with the peak top near 8 minutes is the lowest (bottom 1), the force is also a straight line, and the peak top is around 10.4 minutes.
- Examples of the phenolic resin used in the present invention include any type of phenolic resin having a conventionally known structure, such as novolac type phenolic resin, resol type phenolic resin, phenol.
- examples thereof include aralkyl-based resins and polyvinylphenol-based resins, which may be modified with a cache, oil, rubber or the like.
- novolac type phenolic resin can be particularly preferably used.
- the method for producing the novolac type phenolic resin suitably used in the present invention is not particularly limited as long as it satisfies the scope of the invention of the present application, but in general, phenols and aldehydes are used. Can be obtained by addition and condensation without an acid catalyst or without an acid catalyst.
- resol type phenolic resin can be obtained by adding and condensing phenols and aldehydes with a basic catalyst.
- Phenols preferably used include those having 0 to 12 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, bisphenolanol A, bisphenolanol F, butynolephenol, pentylphenol, alkylphenol, resorcin and the like. Examples include phenols substituted with an alkyl group.
- aldehydes examples include formaldehyde, acetoaldehyde, propyl aldehyde, and benzenes having a formyl group.
- the acid catalyst that can also be used in the condensation reaction of phenols and aldehydes is not particularly defined, but for example, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, toluenesulfonic acid and the like are preferable. Can be used.
- the weight average molecular weight in terms of polystyrene of the phenolic resin used in the present invention is from 2,000 to 80,000 in consideration of the balance between flame retardancy imparting effect, mechanical properties, workability, and workability. Suitable for strength! Better, more preferred ⁇ or 2,000-50,000, more preferred ⁇ Is between 3,000 and 50,000, especially preferred ⁇ is between 3,000 and 30,000.
- the phenolic resin used in the present invention preferably has a low binuclear content in view of processing fluidity, mechanical properties, low smoke generation, and the like.
- the binuclear content measured according to the GPC measurement method for free monomers and dinuclears shown in the Examples of the present application is preferably 10% by area or less of the total phenolic resin.
- phenol resin having a free monomer content of 5% or less, preferably 3% or less is suitably used.
- the total of free monomers, dinuclear bodies, and trinuclear bodies is 17.5% or less, more preferably Is preferably 10.7% or less, more preferably 16.5% or less.
- the method for producing such a phenolic resin is not specified at all, but examples thereof include methods described in JP-A-2004-323822 and JP-A-11-246643.
- non-condensed phosphate esters As used in the present invention, conventionally known phosphorous compounds can be suitably used except for non-condensed phosphate esters.
- Non-condensed phosphate esters such as triphenyl phosphate and tricresyl phosphate are not preferred because they are inferior in workability and workability when used in combination with (A) specific phenolic resin.
- phosphazene compounds that can be suitably used in the present invention
- conventionally known compounds can be widely used.
- the structure of the phosphazene compound preferably used in the present invention is described in, for example, James E. Mark, Harry R. Allcock, Robert West, Inorganic Polymers Pretice-Hall International, Inc., 1992, p61-pl40.
- n in the formula is an integer of 3 to 25
- m is an integer of 3 to 10,000
- the substituent X is an alkyl group having a carbon number of Sl to 6 and an aryl group of 6 to L1:
- Rl, R2, R3, R4 and R5 are selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a phenyl group, and a hetero element-containing group. Represents at least one substituent group
- a naphthyloxy group or a substituent represented by an alkoxy group having 1 to 6 carbon atoms or an alkoxy-substituted alkoxy group, and at least one of the substituents is hydrogen. It may be replaced.
- These compounds may be used alone or as a mixture of two or more.
- One of the factors determining flame retardancy is the concentration of phosphorus atoms contained in the molecule.
- a chain phosphazene having a chain structure has a substituent at the molecular end, and therefore has a lower phosphorus content than a cyclic phosphazene compound.
- the cyclic phosphazene compound has higher flame retardancy than the chain phosphazene compound. From the above, in the present invention, those containing 95% by weight or more of a cyclic phosphazene compound for which use of a phosphazene compound having a cyclic structure is preferred are preferable.
- Substituent X in the phosphazene compound is not particularly limited. Examples thereof include methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, s butyl group, tert butyl group, n-amyl group, isoamyl group.
- Alkyl groups such as alkyl group, fullerene group, 2-methylfuran group, 3-methylphenyl group, 4-methylphenol group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenol -Aryl groups, 2,4 dimethylphenol groups, 3,4 dimethylphenol groups, 4-tertiarybutylphenol groups, 2-methyl-4-tertiarybutylphenyl groups, etc., methoxy groups , Ethoxy group, n-propyloxy group, isopropyloxy group, n butyloxy group, tert butyloxy group, s butyloxy group, n-amyloxy group, isoamyloxy group, tert amyloxy group, n xyloxy group, etc.
- Alkoxy-substituted alkoxy groups such as xy group, methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, phenoxy group, 2 methylphenoxy group, 3 methylphenoxy group, 4-methylphenoxy 2,6 dimethylphenoxy group, 2,5 dimethylphenoxy group, 2,4 dimethylphenoxy group, 3,5 dimethylphenoxy group, 3,4 dimethylphenoxy group, 2, 3, 4 Trimethylphenoxy group, 2, 3, 5 Trimethylphenoxy group, 2, 3, 6 Trimethylphenoxy group, 2, 4, 6 Trimethylenophenoxy group, 2, 4, 5 Trimethinolephenoxy group 3, 4, 5 Trimethylphenoxy group, 2 Ethylphenoxy group, 3 Ethylphenoxy group, 4 Ethylphenoxy group, 2, 6 Jetylphenoxy group, 2, 5 Jetylph Noxyl group, 2,4 Diethylphenoxy group, 3,5-Detylphenoxy group
- the group containing a hetero element is a group containing B, N, 0, Si, P, and S atoms.
- groups containing an amino group, amide group, aldehyde group, glycidyl group, carboxyl group, hydroxyl group, mercapto group, silyl group and the like can be mentioned.
- these compounds are crosslinked by a technique disclosed in International Publication No. WO00Z09518 by a crosslinking group selected from the group consisting of a phenylene group, a biphenylene group, and a group (4) shown below. It ’s okay.
- X represents C (CH 2) —, —SO—, —S, or —O, and y represents 0 or 1).
- the phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount.
- phosphazene compounds may be used alone or as a mixture of two or more.
- the phosphazene compound is a mixture having a structure different from that of a cyclic trimer or cyclic tetramer or a chain phosphazene.
- the workability when added to cocoa tends to be more favorable as the cyclic trimer and tetramer content is higher.
- a phosphazene compound containing 80% by weight or more of cyclic trimer and Z or tetramer compound, more preferably 85% by weight or more of trimer and Z or tetramer compound, A phosphazene compound containing 93% by weight or more is preferable.
- the trimer when used in combination with the specific phenolic resin according to the present application, is 70% by weight or more, more preferably the trimer is 76% by weight or more, and further preferably the trimer is 80% by weight or more.
- a phosphazene compound containing 85% by weight or more of a trimer is used, a particularly excellent flame retardancy imparting effect can be obtained, and an excellent mechanical property improving effect can be obtained.
- the phosphazene compound can take various forms such as a liquid-liquid state, a wax-like state, and a solid-like state depending on the type and structure of the substituent, and does not impair the effects of the present invention. Any shape can be used. If the solid state, the bulk density of 0. 45 g ZCM 3 or more and preferably 0. 45gZcm 3 or more and 0. 75gZcm 3 below
- the alkali metal components such as sodium and potassium contained in the phosphazene compound are each 200 ppm or less, more preferably 50 ppm or less, and more preferably, the total alkali metal component is 50 ppm or less. It is.
- the content of the phosphazene compound in which at least one of the substituents X in the general formula (1) is a hydroxyl group, that is, the phosphazene compound containing a P—OH bond is less than 1% by weight. It is desirable that the chlorine content is lOOOppm or less, preferably 500ppm or less, more preferably 300ppm or less.
- the phosphazene compound in which at least one of the substituents X is a hydroxyl group may have an oxo structure represented by the general formula (5).
- Such an oxo compound is also preferably less than 1% by weight, like the hydroxyl group-containing phosphazene compound.
- n is an integer of 3 or more, and X in the formula may be the same or different, and represents an aryloxy group and Z or an alkoxy group
- Ql, Q2, Q3, Q4, Q9, Q10, Ql l, Q12 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Q5, Q6, Q7, Q8, Q13 independently Represents a hydrogen atom or a methinore group ml, m2, m3, m4, m7, m8, m9, mlOi, independently represents an integer of 3 from 0 force
- m5 and m6 independently represent an integer of 0 to 2
- Mi l independently represents an integer from 0 to 4 o
- the phosphinic acid salt that can be used in the present invention is at least one selected from phosphinic acid salts represented by the following general formula (8) and Z or (9) and Z or their polymer strength.
- [0042] [Chemical 9] (9) (Where Ql, Q2, Q3 and Q4 represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group and an aryloxy group, and Q5 represents a carbon atom.
- An anoleylene having a number of 1 to 18, an arylenoreoxylene, an arylene, an anolequinolearylene, a diary one-lens force represents at least one group selected, wherein n and m are each an integer of 1 to 3, X is 1 or 2.
- M represents at least one group selected from metal atoms, amides, ammonium groups and melamine derivatives from the fourth period of the periodic table.
- phosphines that can be used in the present invention
- conventionally known phosphines can be suitably used.
- triarylphosphine, trialkylphosphine, triaryloxyphosphine, trialkoxyphosphine and the like can be mentioned. More specifically, among them, triarylphosphines represented by the following general formula (10) are preferably used.
- Tl, ⁇ 2, ⁇ 3, ⁇ 4 independently represent a hydrogen atom or an alkyl or aryl group having 1 to 12 carbon atoms
- ⁇ 5 represents a hydrogen atom or a methyl group.
- Ml, m2, m3, m4 Independently represents an integer from 0 to 5
- m5 independently represents an integer from 0 to 4.
- n in the formula represents an integer from 0 to 3.
- a naphthyl group is also suitable as an aryl group.
- all three aryl groups on the phosphorus atom may be the same group or different groups.
- the amount of water contained in the phosphorus compound (B) preferably used in the present invention is a dielectric property. In consideration of hydrolysis resistance, etc., it is preferably 100 ppm or less, preferably 800 ppm or less, more preferably 650 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less.
- the acid value measured based on JIS K6751 is 1.0 or less, preferably 0.5 or less, more Preferably it is 0.3 or less, particularly preferably 0.1 or less.
- the component (B) preferably used in the present invention has a solubility in water (sample is mixed with distilled water at a concentration of 0.1 lgZmL) from the viewpoint of hydrolysis resistance and moisture absorption resistance. 1OOOppm or less, preferably 500 ppm or less, more preferably lOOppm or less, still more preferably 50 ppm, particularly preferably 25 ppm or less. !
- the specific phosphorus compound of the present invention is an inert gas produced by TGA in consideration of flame retardancy when used in combination with component (A), low smoke generation during combustion, low volatility, etc.
- the difference between the temperature at 50% weight reduction and the temperature at 5% weight reduction is 20-150 ° C, preferably What is 20-120 degreeC is preferable.
- the temperature at a 50% weight reduction is 320 to 500 ° C. 350 ⁇ 460. C.
- the phosphorus compound suitably used in the present invention may take various forms such as liquid, waxy, solid, etc., although it varies depending on the type and structure of the substituents contained. Any shape may be used as long as the effect of the present invention is not impaired.
- condensed phosphate esters, phosphinates, and phosphazene compounds are preferable.
- a condensed phosphate ester synthesized using bisphenol A and phenol as raw materials a condensed phosphate ester obtained using bisphenol A or resorcin and 2,6-xylenol as raw materials, and a phosphazene compound are used.
- a cyclic phosphazene compound is particularly preferably used.
- the blending ratio of the flame retardant composition is not particularly specified as long as the effects of the present application are obtained.
- the blending ratio of the (A) component and the (B) component is 1 to 90 parts of the (A) component in 100 parts by weight of the total of the (A) component and the (B) component. Parts by weight, 99 to 10 parts by weight of component (B), preferably 3 to 80 parts by weight of component (A), 97 to 20 parts by weight of component (B), more preferably 10 to 10 parts of component (A) 80 parts by weight and 90-20 parts by weight of component (B) are preferred.
- the shape of the flame retardant composition in the present invention is not particularly defined as long as the effects of the present invention can be achieved.
- it is supplied in the form of powder, tablet, pellet, lump, wax, liquid, oil or the like.
- each component may be completely compatible or simply mixed. Also, a mixture of a compatible and a simple mixture may be used.
- the flame retardant composition of the present invention can be suitably used in a wide range, and the usage method and field of use are not particularly defined.
- suitable usage methods include flame retardants for resin, rubber, lubricants, lithium ion batteries, solar cells, fuel cells, non-flammable electrolytes, battery electrical equipment, release agents, release films, It is suitably used for roughened surface forming materials, water repellents and the like.
- the flame retardant composition of the present invention can be used in combination with a conventionally known rosin.
- a known thermoplastic or hardenable resin is preferably used as the resin used for use is not limited in any way.
- the thermoplastic resin polycarbonate-based resin, polyphenylene ether-based resin, polyphenylene sulfide-based resin, polypropylene-based resin, polyethylene-based resin, polystyrene-based resin.
- Polyolefin ether-based resins polystyrene-based resins, ABS-based resins, polycarbonate-based resins, polyamide-based resins, poly (alkylene acrylate) -based resins, polyphenylene ether and polystyrene alloys, Alloys of lenether and polyamide, alloys of polyphenylene ether and thermopick liquid crystal, and alloys of polyphenylene ether and polyphenylene sulfide are preferably used.
- Curing resins include unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, cyanate resins, xylene resins, triazine resins, urea resins, melamine resins, benzoguanamine resins. , Urethane resin, oxetane resin, ketone resin, alkyd resin, furan resin, styrylpyridine resin, silicon resin, and synthetic rubber. In particular, epoxy resin is preferably used.
- the resin used in the present invention may be used alone or in combination of two or more kinds.
- polyamide-based resin used in the present invention conventionally known polyamide resins are preferably used and are not particularly limited.
- Monomers for synthesizing these polyamide resins include, for example, hexamethylene diamine, pentamethylene diamine, 2-methylpentamethylene diamine, otatamethylene diamine, 2-methyl otatamethi.
- Dicarboxylic acids include adipic acid, otatamethylene dicarboxylic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 3, 3 Jetyl succinic acid, 2, 2 dimethyl daltaric acid, 2 methyl adipic acid, trimethyl adipic acid, 1, 3 cyclopentane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, 2, 6 naphthalenedicarboxylic acid 2, 7 naphthalene dicarboxylic acid, 1, 4 naphthalene dicarboxylic acid, 1, 4 phenylenediacetic acid, 1, 3 phenylenediacetic acid, diphenic acid, 4, 4, monobidicarboxylic acid, 4, 4 4
- polyamide-based resin obtained by combining these monomers is Polyamide 6, Polyamide 66, Polyamide 66Z6, Polyamide 46, Polyamide 610, Polyamide 612, Polyamide 11, Polyamide 12, Polyamide 61, Polyamide 6T, Polyamide 9 ⁇ , polyamide MXD 6, polyamide, 66/61, polyamide, 66 / 6 ⁇ , polyamide, 6 ⁇ / 6 ⁇ , polyamide, 66/61/6, polyamide, 66/61/11, positive amide, 66/61/12, positive amide 66/61/610, positive amide, 6 6/61/612, polyamide 10 ⁇ , polyamide 12T, and the like. These can be used alone or as a mixture of two or more.
- the polyamide-based resin polymerization reaction method of the present invention is not particularly limited as long as it is a general polyamide polymerization method.
- an equivalent salt of the amine and acid is made, or an equivalent equivalent is added separately to carry out the condensation polymerization reaction.
- a small amount of water, amino acid, mineral acid, etc. is added as a ring-opening catalyst and subjected to a condensation polymerization reaction.
- Melt polymerization in which a monomer or aqueous monomer solution is heated to carry out polymerization while removing water, is widely used industrially.
- the polymerization degree control agent amine oxalic acid is added.
- phosphoric acid, phosphorous acid, hypophosphorous acid, a salt or ester thereof can be added as a catalyst.
- the salt or ester include phosphoric acid, phosphorous acid or hypophosphorous acid and metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, connort, manganese, tin, tungsten, germanium, titanium, and antimony.
- Ammonium salt of phosphoric acid, phosphorous acid or hypophosphorous acid Ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, phosphoric acid, phosphorous acid or hypophosphorous acid
- Examples include kutadecyl ester, decyl ester, stearyl ester, and phenol ester.
- the aromatic ring component content in the main chain is 5 to 75% by weight.
- Polyamide-based rosin preferably 25 to 65% by weight, more preferably 31 to 55% by weight, is preferably used.
- the aromatic ring component content in the main chain is represented by the formula (1).
- Aromatic ring component content ( ⁇ ) (total atomic weight of carbon and hydrogen constituting the aromatic ring) Z (total atomic weight of repeating units of polyamide) X 100 (%) ⁇ ⁇ ⁇ ⁇ ⁇ Equation (1)
- Aromatic ring component content ( ⁇ ) ⁇ (MX a i X lOO (%) ⁇ ⁇ ⁇ ⁇ Equation (2)
- the polyamide resin used in the present invention preferably has a degree of polymerization within a specific range, that is, a relative viscosity.
- the preferred relative viscosity is 1.5% to 4.0, preferably 1.8 to 3.0 for semi-aromatic polyamide as measured at 98% sulfuric acid concentration 1% and temperature 25 ° C according to JIS K 6810. Range. It is preferable to have an appropriate relative viscosity from the viewpoint of material strength, fluidity, moldability and product appearance.
- the ends of the polyamide of the present invention may be sealed.
- Polyamide as end sealant Any monofunctional compound having reactivity with the terminal amino group or carboxyl group is not particularly limited. Monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters Monoalcohols can be used. Point powers such as reactivity and stability of the sealing end Monocarboxylic acids or monoamines are preferred. Ease of handling, points of toxicity, etc. Monocarboxylic acids are more preferable.
- the monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group.
- aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, proproic acid, pourlic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, bivalic acid, isobutyric acid; Alicyclic monocarboxylic acids such as hexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, naphthalenecarboxylic acid, j8-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenolacetic acid be able to.
- acetic acid propionic acid, butyric acid, valeric acid, caproic acid, strong prillic acid, lauric acid, tridecylic acid, myristic acid, nord, in terms of reactivity, stability of the sealing end, price, etc.
- Mytic acid, stearic acid and benzoic acid are preferred.
- the monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group.
- aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, jetylamine, dipropylamine, dibutylamine and the like; alicyclic monoamines such as cyclohexylamine, dicyclohexylamine and the like; Aromatic monoamines such as errin, toluidine, diphenylamine, naphthylamine and the like can be mentioned.
- polyalkylene arylate-based resin conventionally known ones are preferably used. Examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polypropylene. And n-naphthalate, polybutylene naphthalate, and poly 1,4-cyclohexanedimethylene terephthalate.
- the polyalkylene arylate-based resin used in the present application is a conventionally known method such as alkylene glycol and an aromatic dicarboxylic acid or an ester thereof (for example, terephthalic acid dimethyl terephthalate, as a copolymer component).
- alkylene glycol and an aromatic dicarboxylic acid or an ester thereof for example, terephthalic acid dimethyl terephthalate, as a copolymer component.
- polyalkylene arylate resins can be used alone or in combination of two or more.
- the polyphenylene ether resin preferably used in the present invention is preferably a homopolymer or a copolymer having a repeating unit represented by the general formula (11) and Z or (12). .
- Rl, R2, R3, R4, R5, R6 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen, provided that R5 and R6 are not hydrogen at the same time.
- Typical examples of homopolymers of poly (phenylene ether) resins include poly (2, 6 dimethyl — 1, 4 phenylene) ether, poly (2-methyl 6 ethyl 14 phenylene) ether, poly (2 , 6 Jetyl 1,4 Phenylene) Ether, Poly (2 Ethyl-6- n —Propinole 1,4 Phenylene) Etherenopoli (2, 6 Di n-Propinole 1,4 Phenylene) Ether, Poly ( 2-methyl-6-n-butyl-1,4 phenylene) ether, Examples include homopolymers such as poly (2-ethyl-6-isopropyl 1,4-phenylene) ether and poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether.
- poly (2,6 dimethyl-1,4-phenylene) ether is preferred, as described in JP-A-63-3301222 and the like, 2- (dialkylaminomethyl) 6-
- Polyphenylene ether containing a partial structure such as a methyl phenol ether unit or a 2- (N alkyl 1 N phenol aminomethyl) 6-methyl phenol ether unit is particularly preferred.
- the polyphenylene ether copolymer is a copolymer having a phenol ether structure as a main monomer unit.
- examples include copolymers of 2,6 dimethylphenol and 2,3,6 trimethylphenol, copolymers of 2,6 dimethylphenol and o-taresol, or 2,6 dimethylphenol and 2, 3,6 dimethylphenol.
- R7, R8, R9, R10 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen.
- X represents C (CH) 2 SO—, —S—, or —O
- Y is 0 or
- some or all of the polyphenylene ether resin is reactive with a reactive group such as a force carboxy group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydrous dicarboxyl group.
- a reactive group such as a force carboxy group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydrous dicarboxyl group.
- a modified polyphenylene ether resin introduced with a functional group by some method such as graft reaction or copolymerization can be used within the range not impairing the object of the present invention. These may be used alone or in combination of two or more.
- a modified polyphenylene ether resin in which a part or all of the polyphenylene ether resin is modified with an unsaturated carboxylic acid or a functional derivative thereof is disclosed in JP-A-2-276823 and JP-A-63. — It is described in 108059, JP 59-59724, etc.
- The is produced by melting and kneading an unsaturated carboxylic acid or a functional derivative thereof with a poly (phenylene ether) resin in the presence or absence of a radical initiator.
- it is produced by dissolving a polyphenylene ether, an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.
- Examples of the unsaturated carboxylic acid or functional derivative thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, endo-cis-bicyclo (2. 2. 1) — 5 Heptene 1, 2, 3 dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methatalic acid, etc., esters of these monocarboxylic acids, Examples include amides.
- a compound which is a sulphonic power rubonic acid but can itself be thermally decomposed at the reaction temperature at the time of producing a modified polyphenylene ether to become a functional derivative used in the present invention can be used.
- Specific examples include malic acid and citrate. These may be used alone or in combination of two or more.
- the molecular weight of the polyphenylene ether that can be used in the present invention is not limited as long as it does not impair the effects of the present invention. Specifically, those having a number average molecular weight of 500 to 30,000 can be suitably used. When it is necessary to obtain a composition particularly excellent in moldability, a polyphenylene ether having a number average molecular weight of 500 or more and 5000 or less, preferably 1200 or more and 4000 or less is preferably used. be able to. When it is necessary to obtain a composition with particularly excellent heat resistance, it is preferable to use a polyphenylene ether having a number average molecular weight exceeding 5000! /. Polyphenylene ether having an appropriate molecular weight may be used as appropriate in accordance with the characteristics particularly required when a resin composition is used.
- the polycarbonate resin that can be suitably used in the present invention is preferably a polymer having a repeating unit represented by the following general formula (14).
- Rl l, R12, R13, R14, R15, R16 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, and the hydrogen atom on the substituent is substituted with a fluorine atom. May be
- the polycarbonate resin that can be suitably used in the present invention may have a branched structure.
- Polyorganosiloxane-modified polycarbonate-based resins modified with organosiloxane can also be used suitably (for example, the resins described in JP-A-6-100684, JP-A-10-182832, etc.). etc). These may be used alone or in combination of two or more.
- the terminal group of the polycarbonate resin is not particularly defined as long as the effects of the present invention can be obtained.
- Illustrative examples include an alkyl group, an alkyl carbonate group, an aryl group, an aryl carbonate group, and the like, and one or more groups can be bonded as a terminal group.
- the molecular weight of the polycarbonate resin that can be suitably used in the present invention depends on the effect of the present invention. There is no limitation as long as the results are not impaired. Specifically, a polystyrene-equivalent number average molecular weight force s of 1000 to 100,000, preferably 2000 to 70000, more preferably 5000 to 25000 can be suitably used. Polycarbonate resin may be used having an appropriate molecular weight as appropriate in accordance with characteristics particularly required when a resin composition is used.
- a method for producing a polycarbonate resin that can be suitably used in the present invention a conventionally known method can be widely used, and is not limited at all.
- those produced by a phosgene method, a transesterification method, or the like can be suitably used.
- thermopick liquid crystal that can be suitably used in the present invention
- any conventionally known liquid crystal can be used as long as it exhibits the effects of the present invention, and is not particularly limited.
- P-hydroxybenzoic acid and ethylene terephthalate are the main structural units of thermo-mouth-pick liquid crystal polyester
- p-hydroxybenzoic acid and 2-hydroxy 6-naphthoic acid are the main structural units
- P-hydroxy-benzoic liquid-crystal polyester P-hydroxybenzoic acid
- P-hydroxybenzoic acid Examples include, but are not particularly limited to, thermopick liquid crystal polyesters having perfuming acid, 4,4′-hydroxybiphenyl, and terephthalic acid as the main structural unit.
- thermopick liquid crystal suitably used in the present invention may contain other aromatic dicarboxylic acids, aromatic diols, aromatics in a small amount range that does not impair the features and effects of the present invention as necessary. Hydroxycarboxylic acid force
- the structural unit to be generated can be introduced.
- the temperature at which the liquid crystal state of the thermopick pick liquid crystal of the present invention starts to show (hereinafter referred to as the liquid crystal start temperature) is preferably 150 to 350 ° C, more preferably 180 to 320 ° C. By setting the liquid crystal start temperature within this range, the obtained resin composition has a good balance of color tone, heat resistance, and molding force.
- the apparent melt viscosity (liquid crystal onset temperature + 30 ° C and shear rate of 100 Zsec) of the thermopick liquid crystal suitably used in the present invention is not particularly limited as long as the effect of the present invention is obtained.
- the melt viscosity is preferably 10 to 3, OOOPa's, more preferably 10 to 2,000 Pa-s, particularly preferably 10 to: L, OOOPa's. . (Mixing ratio)
- the blending ratio of the flame retardant composition according to the present invention and rosin is not particularly limited as long as it is a ratio capable of obtaining the effects of the present invention.
- a flame retardant composition having component (A) and component (B) it is preferable to add 0.1 to 200 parts by weight of a flame retardant composition having component (A) and component (B) to 100 parts by weight of the resin component (C). More preferably, the component (b) is 1 to 150 parts by weight, more preferably 5 to 120 parts by weight, with respect to 100 parts by weight of the component (C).
- the flame retardant composition and the flame retardant resin composition according to the present invention for the purpose of enhancing the flame retardancy imparting effect of the flame retardant composition comprising the specific phenol resin and (B) phosphorus compound according to the present application. Further, a nitrogen-containing compound may be added.
- tertiary amines such as triarylamine, dialkylarylamine, alkyldiarylamine, quaternary ammonium salts, melamine, melam, melem, melon, methylenedimelamine, Ethylenedimmelamine, decamethylenedimmelamine, 1,3-cyclohexyldimmelamine, 4,4'-diethylenedimelamine, diethylenetrimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methyldaanamine, acetate guanamine, melamine fat, etc.
- a triazine compound is preferably used. Furthermore, when heat stability, volatility resistance, etc.
- melamine condensate such as melam, melem, melon, or a reaction product of the triazine compound and cyanuric acid, particularly a reaction product of melamine and cyanuric acid.
- a certain melamine cyanurate is preferably used.
- the hydroxyl group and Z or amino group of the reaction product of the triazine compound and cyanuric acid may be partially or entirely substituted with other substituents.
- the method for producing a melamine condensate such as melem, melam, melon and the like suitably used in the present invention is not particularly limited.
- melamine or a melamine salt can be obtained by self-condensation by heating to about 280 to 320 ° C. in an inert gas atmosphere or under vacuum, without a catalyst or under an organic acid catalyst. it can.
- the melamine cyanurate preferably used in the present invention is an equimolar amount of melamine and cyanuric acid. It is a reactant. For example, it can be obtained as a white solid by stirring and mixing a melamine aqueous solution and a cyanuric acid aqueous solution at a temperature of about 90 to 100 ° C., and precipitating and filtering the product obtained by the reaction. It is preferable to pulverize and use in the form of fine powder.
- the above nitrogen-containing compounds may be used singly or as a mixture of two or more. These compounds do not necessarily have to be completely pure, and some unreacted substances may remain.
- the addition amount of the nitrogen-based compound is not specified as long as the effect of the present invention can be exerted, but is preferably 1 to 200 with respect to 100 parts by weight of the total of the components (A) and (B). Part by weight, more preferably 5 to 150 parts by weight, still more preferably 10 to 120 parts by weight.
- conventionally known non-halogen and non-antimony flame retardants and flame retardant aids may be used in combination as long as the effects of the present invention can be achieved.
- it can.
- a silicon-containing compound such as resin and an inorganic silicon compound such as silica, kaolin clay, talc and wollastonite.
- a conventionally well-known filler can be mix
- fibrous reinforcing agents such as aluminum, magnesium borate, kenaf fibers, carbon fibers, silica fibers, alumina fibers, and quartz fibers, and non-fibrous reinforcing agents. These may be used alone or in combination of two or more. In addition, these may be coated with an organic material, an inorganic material, or the like.
- the strength of the incombustible layer (or carbonized layer) generated during combustion can be further improved.
- the non-combustible layer (or carbonized layer) once generated during combustion is less likely to break, and can exhibit a stable heat insulation capability, resulting in a greater flame retardant effect. Further, high rigidity can be imparted to the material.
- the blending amount of the filler is not particularly specified as long as the effect of the present application can be exhibited.
- 1 to 200 parts by weight preferably 3 to 150 parts by weight, more preferably 5 parts by weight of the filler with respect to 100 parts by weight of the total components other than the filler.
- To 120 parts by weight particularly preferably 10 to: L00 parts by weight.
- the flame retardant composition of the present invention and the flame retardant resin composition containing the flame retardant composition are used, other characteristics such as rigidity and dimensional stability are imparted, so the effects of the present invention are impaired.
- Other additives such as plasticizers, antioxidants, and stabilizers such as UV absorbers and light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity imparting agents, stress relaxation agents, Release agents, crystallization accelerators, hydrolysis inhibitors, lubricants, impact imparting agents, slidability improvers, compatibilizers, nucleating agents, reinforcing agents, reinforcing agents, flow modifiers, dyes, sensitizers, Coloring pigments, rubber polymers, conductive polymers and the like can be added in advance.
- the method for blending the flame retardant composition and the thermoplastic resin in the present invention is not particularly defined as long as the effect of the present invention can be achieved.
- it can be kneaded and produced by using a kneader such as an extruder, a heating roll, a kneader, or a vannolly mixer.
- a kneader such as an extruder, a heating roll, a kneader, or a vannolly mixer.
- melt kneading with an extruder is preferable in terms of productivity.
- the melt kneading temperature is in the range of 140 to 360 ° C, preferably in the range of 180 to 320 ° C, as a guide according to the preferred processing temperature of the base resin.
- the molded product of the composition of the present invention can be molded by a known method such as injection molding, sheet molding, blow molding, instruction blow molding, inflation molding, extrusion molding, foam molding, film molding, and the like. Secondary processing molding methods such as pressure forming and vacuum forming can be used.
- Secondary processing molding methods such as pressure forming and vacuum forming can be used.
- the components for producing the resin composition are mixed without a solvent or with a solvent that can be uniformly mixed as required, A method may be used in which the solvent is removed to obtain a resin mixture, which is cast into a mold and cured, cooled, and then taken out of the mold. It can also be cast into a mold and cured by hot pressing.
- the solvent for dissolving each component is not particularly limited as long as various materials can be uniformly mixed and the effect of the present invention is not impaired by use.
- Examples include toluene, xylene, acetone, methyl ethyl ketone, jetyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, methyl cellosolve, methanol, ethanol, n-propanol, iso-propanol, n-butano monoole, n- Examples thereof include pentanomonole, n-hexanol, cyclohexanol, n-hexane, n-pentane and the like.
- a kneader such as a heating roll, an ada, a Banbury mixer, and an extruder
- cooling and pulverization are performed, and further molding is performed by transfer molding, injection molding, compression molding, and the like.
- the method can also be mentioned as an example.
- the curing method varies depending on the curing agent used, but is not particularly limited. Examples include thermal curing, photocuring, UV curing, curing by pressure, curing by moisture, and the like, but are not specified as long as the curing method can achieve the effects of the present invention.
- the order of mixing the components is not particularly limited as long as the effect of the present invention can be achieved.
- a method for producing a rosin composition a method can be preferably used according to the suitability of each greaves.
- the flame retardant resin composition using the flame retardant composition of the present invention is composed of electrical electronic parts such as coil bobbins, flyback transformers, connectors, polarizing yokes, printed wiring boards, printed boards, sealants, electrical Insulating materials, electrical coatings, laminates, high-speed computing varnishes, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials, etc. for electrical and electronic materials, paints, adhesives, coating materials, tableware, buttons , Textiles, paper treatment agent, decorative board, UV curable ink
- Sealants synthetic leather, heat insulating cushioning materials, waterproofing coatings, anticorrosion linings, saddle type noinders, lacquers, paints, ink modifiers, oil-repellent modifiers, aircraft interior materials, matrix for composite materials, household products , OA equipment, AV equipment, battery electrical equipment, lighting equipment, automobile parts It is optimally used for applications, housing applications, ETC, ITC, mobile phones, etc.
- the method for measuring GPC of phenolic resin is Waters Alliance (manufactured by Nippon Waters Co., Ltd.), tetrahydrofuran solvent, column temperature of 35 ° C, flow rate of lmLZmin, and column manufactured by Nippon Waters Co., Ltd. Waters Styragel HR1, HR3, HR4 are connected in series and measured with a UV (Waters2487; wavelength 254 nm) and Z or RI (Waters 2414) detector. Retention times 6. The method of calculating the area fraction for each of 1 to 9.7 minutes and 9.7 to 11.9 minutes is calculated as follows.
- the area enclosed between the baseline of the GPC chart and the GPC curve of 6.1 to 9.7 minutes and the straight line drawn perpendicular to the retention time of 9.7 minutes is (a ').
- the GPC curve from 9.7 to 11.9 minutes and the straight line drawn at the retention time 11.9 minutes is (b '), () and (
- the value of (a ') with respect to the sum of b') is the percentage of area (a), and the value of 0) with respect to the sum of () and (b ') is the percentage of area (b).
- a calibration curve was created using standard polystyrene, and the molecular weight calculated for the retention time of 9.7 minutes based on the calibration curve was approximately 870.
- the method for measuring the trinuclear content is based on the GPC measurement under the above conditions.
- the peak with a peak top in the vicinity of 10.0 to 10.1 min is defined as the trinuclear peak, and the adjacent retention time. 9.
- the point at which the absorption between the peak with the peak top near 8 minutes is the lowest (bottom 1), the force is also a straight line, and the peak between the peaks with the peak top near 10.4 minutes
- the point that shows the lowest absorption (bottom 2) force The area (S1) surrounded by the straight line, base line, and GPC curve that descends vertically is the retention time of 6.1 to 11.9 minutes. Divide by the area surrounded by the line (total area S 2) and multiply by 100.
- the peak area fraction (%) of the nuclei is used to obtain the trinuclear content.
- the peak having a peak top in the vicinity of 10.4 to 10.7 minutes is a dinuclear body, and 11.1 to: L 1.
- the peak having a peak top in the vicinity of 3 minutes is a free monomer. calculate.
- the area fraction obtained here was used as the content of each component.
- test piece having a thickness of about 6.4 mm was used and measured under a load of 18.6 kg.
- test piece Based on ASTM-D-790, measurement was performed using a test piece having a thickness of about 6.4 mm.
- a 2 mm molded piece was prepared.
- the colored piece was colored X, the relatively colored one was marked ⁇ , and the one with little coloring was marked ⁇ .
- the evaluation was made visually by setting X to indicate that sink marks were found in the molded product and ⁇ if not.
- the length is about 128mm X width about 12.8mm X thickness
- a molded specimen of about 1.6 mm was molded, and the mold surface condition after 20 shots was visually observed.
- Phenolic novolak resin PR— 50731 (manufactured by Sumitomo Bakelite Co., Ltd.), (a) 78.0%, (b) 22.0%, Mwl0366, free monomer: 1.9%, Dinuclear: 8.1%, Trinuclear: 6.0%
- Phenolic novolak resin Tamanoru 759 (Arakawa Chemical Co., Ltd.), (a) 63 5%, (b) 36.5%, Mw2205, free monomer: 0%, dinuclear: 14.1%, trinuclear: 10.0%
- TPP Triphenyl phosphate
- Condensed phosphate ester PX 200 (produced by Daihachi Chemical Industry Co., Ltd.) synthesized from resorcin and 2,6-xylenol
- Caliber 301—10 manufactured by Sumitomo Dow.
- ABS Acrylonitrile, butadiene, styrene resin (ABS) M8801 (UMG Co., Ltd.)
- Polyamide MXD6 resin (Reny 6002: manufactured by Mitsubishi Gas Chemical Company, Inc.)
- (A) a specific phenolic resin and (B) a flame retardant composition having a specific phosphorus compound strength, particularly when added to a resin, have flame retardancy, heat resistance, Excellent extrudability, releasability, thermal stability, mechanical properties, workability, etc., flame retardant for resin, rubber, lubricant, lithium ion battery, solar cell, fuel cell, nonflammable electrolyte, battery electrical equipment
- flame retardant for resin, rubber, lubricant, lithium ion battery, solar cell, fuel cell, nonflammable electrolyte, battery electrical equipment For example, it is preferably used for an agent, a release agent, a release film, a roughened surface forming material, a water repellent and the like.
- the flame retardant resin composition using the flame retardant composition of the present invention includes electrical and electronic equipment parts such as coil bobbins, flyback transformers, connectors, polarizing yokes, printed wiring boards, printed boards, sealants. , Electrical insulation materials, electrical coatings, laminates, varnishes for high-speed computing, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials, etc. for electrical and electronic materials, paints, adhesives, coating materials, food Container, button, fiber 'paper treatment agent, decorative board, UV curable ink, sealant, synthetic leather, thermal insulation material, waterproof coating material, anticorrosion lining, vertical binder, lacquer, paint, ink modifier , Oil-modified material, aircraft interior agent, matrix for composite materials, household goods,
- electrical and electronic equipment parts such as coil bobbins, flyback transformers, connectors, polarizing yokes, printed wiring boards, printed boards, sealants.
- FIG. 1 is a GPC spectrum diagram of phenol resin (A-1).
- FIG. 2 is a GPC spectrum diagram of phenol resin (A-2).
- FIG. 3 is a GPC spectrum diagram of phenol resin (A-4).
- FIG. 4 is a GPC spectrum diagram of phenol resin (A-5).
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CN112745675B (zh) * | 2020-12-29 | 2022-10-04 | 金发科技股份有限公司 | 一种无卤阻燃聚酰胺复合材料及其制备方法与应用 |
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JP2010509419A (ja) * | 2006-11-10 | 2010-03-25 | ロディア オペレーションズ | 難燃性ポリアミド組成物 |
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JP2015030751A (ja) * | 2013-07-31 | 2015-02-16 | 三菱樹脂株式会社 | ポリアミド系樹脂組成物、及びそれを成形してなるフィルム、射出成形体 |
JP2016003262A (ja) * | 2014-06-16 | 2016-01-12 | 帝人デュポンフィルム株式会社 | ポリエステル樹脂組成物 |
CN108368349A (zh) * | 2015-11-30 | 2018-08-03 | 纳美仕有限公司 | 热固性树脂组合物、热固性树脂膜、印刷电路板及半导体装置 |
WO2017094489A1 (ja) * | 2015-11-30 | 2017-06-08 | ナミックス株式会社 | 熱硬化性樹脂組成物、熱硬化性樹脂フィルム、プリント配線板、および半導体装置 |
WO2020196217A1 (ja) * | 2019-03-25 | 2020-10-01 | 大日本印刷株式会社 | 化粧シート及び化粧板 |
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JPWO2020196218A1 (ja) * | 2019-03-25 | 2020-10-01 | ||
JP7537423B2 (ja) | 2019-03-25 | 2024-08-21 | 大日本印刷株式会社 | 化粧シート及び化粧板 |
JP7537424B2 (ja) | 2019-03-25 | 2024-08-21 | 大日本印刷株式会社 | 化粧シート及び化粧板 |
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JPWO2006043460A1 (ja) | 2008-05-22 |
US20080051495A1 (en) | 2008-02-28 |
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