CN1074016C - Flame-retarded thermosetting resin composition - Google Patents
Flame-retarded thermosetting resin composition Download PDFInfo
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- CN1074016C CN1074016C CN96104532A CN96104532A CN1074016C CN 1074016 C CN1074016 C CN 1074016C CN 96104532 A CN96104532 A CN 96104532A CN 96104532 A CN96104532 A CN 96104532A CN 1074016 C CN1074016 C CN 1074016C
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/82—Phosphorus-containing stabilizers
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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Abstract
A flame-retarded thermosetting resin composition comprising (a) a thermosetting resin and (b) an aromatic phosphate represented by the formula (I), wherein R1 and R2 are, the same or different, a lower alkyl group, R3 is a hydrogen atom or a lower alkyl group, R4 is a C6-20 aromatic hydrocarbon residue and n is an integer 2 or 3. The composition, compared with resin compositions containing conventional flame retardants, has excellent punchability at low temperatures, resistance to bleeding of the flame retardant from a laminated sheet, and particularly shows significant improvement in the tracking resistance heat resistance and insulation properties.
Description
The present invention relates to flame-retarded thermosetting resin composition.This flame-retarded thermosetting resin composition contains aromatic phosphate acid ester.
The thermosetting resin of urethane and resol class is widely used as electrical element, electronic component, vehicle component etc., and reason is that they can obtain with quite low cost, and has remarkable characteristic (as good mouldability).Yet these resins are combustible, and in case catch fire and just be tending towards causing uncontrollable burning, and are fire-retardant for it, industrially do a lot of work.In some field of using resin, just require fire-retardant legally at present.
For making thermosetting resin fire-retardant, when preparing the goods that make by resin, add fire retardant.The example of fire retardant is mineral compound, organic compound, Organohalogen compounds and Halogen Organophosphorous compounds.
Organohalogen compounds and Halogen Organophosphorous compounds have excellent flame, but along with thermolysis produces hydrogen halide.
Not halogen-containing fire retardant comprises mineral compound and Organophosphorous compounds.
Magnesium hydroxide and aluminium hydroxide class mineral compound only have less flame retardant effect, therefore must use in a large number, can damage the proper property (as workability and mechanical property) of resin like this.
Triphenylphosphate (TPP), Tritolyl Phosphate (TCP) and di(2-ethylhexyl)phosphate phenyltolyl base ester (CDP) organophosphorus thing have goodish flame retardant effect and generally use.Yet,, use this organophosphorus thing can reduce the thermotolerance and the mechanical property of resin because they are volatile.Openly flat 1 (1989)-242633 peace 2 (1990)-67310 of Japanese unexamined patent publication No. has disclosed the resol that contains aromatic phosphate acid ester.They have excellent punching at low temperatures.But find goods electricity prepared therefrom and bad mechanical property.
Thermosetting resin is widely used as the insulating substrate of circuit with the laminated sheet form, so need have good insulation performance performance and thermotolerance especially.For example, when laminated sheet is prepared by resol, 15 to 40 seconds thermotolerance and 1 * 10 when it is presented at welding
10To 1 * 10
13Insulativity.Yet, be during when adding auxiliary substance for the performance of improving resin such as flame retardant resistance, can improve set performance really, but (for example) reduces the salient features of resin because the volatilization of the auxiliary substance that adds through regular meeting simultaneously.
In view of such circumstances, need low volatility and do not weaken the thermosetting resin fire retardant of resin proper property.
Therefore, the object of the present invention is to provide a kind of flame-retarded thermosetting resin composition that contains low volatility and do not weaken the fire retardant of resin inherent nature, so that eliminate the above-mentioned shortcoming of prior art.
Particularly, the invention provides a kind of flame-retarded thermosetting resin composition that contains aromatic phosphate acid ester, this phosphoric acid ester has the excellent fire retardant effect, and its volatility is low thereby can not reduce the heat-drawn wire of resin or not weaken the resistance or the mechanical property of resin.
For the problems referred to above, the inventor furthers investigate, and obtains following discovery:
Except the excellent fire retardant effect, the aromatic phosphate acid ester by (I) expression adds fashionable as fire retardant, present remarkable improvement for the thermotolerance, resistance and the mechanical property that keep thermosetting resin.
The improvement of above-mentioned performance is considered to because due to the steric hindrance of aromatic phosphate acid ester.Promptly the aromatic phosphate acid ester of logical formula I has substituting group especially in the 2-and the 6-position of phenyl ring.Think that also steric hindrance is improved long-time interior hydrolytic resistance.
Therefore, the invention provides and contain (a) thermosetting resin and (b) flame-retarded thermosetting resin composition of the aromatic phosphate acid ester represented of logical formula I:
R wherein
1And R
2Be identical or different low alkyl group, R
3Be hydrogen atom or low alkyl group, R
4Be C
6-20Aromatic hydrocarbon residue, n are integer 2 or 3.
For flame-retarded thermosetting resin composition of the present invention, thermosetting resin (a) is mixed with aromatic phosphate acid ester (b).
The example of thermosetting resin of the present invention (a) comprises acrylic resin, urethane resin, resol, Resins, epoxy, melmac, urea resin, unsaturated polyester resin and diallyl phthalate resin.Above-mentioned resin can use by its two or more mixture.
Aromatic phosphate acid ester as component (b) is represented by logical formula I.
In logical formula I by R
1, R
2And R
3The low alkyl group of expression comprises C
1-4The straight or branched alkyl is as methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl groups.By R
4The C of expression
6-20The example of aromatic hydrocarbon residue comprises that arbitrariness ground is by C
1-4The phenyl or naphthyl group that alkyl (for example methyl or ethyl group) replaces is specifically as phenyl, tolyl, xylyl, base, cumenyl, naphthyl, first naphthyl, diformazan how base and ethylnaphthalene base group.
The preferred example of the aromatic phosphate acid ester of logical formula I comprises tricresyl phosphate (2, the 6-xylyl) ester, tricresyl phosphate (2,4, the 6-trimethylphenyl) ester, phosphoric acid two (2, the 6-xylyl) phenylester, two (mesityl) phenylesters of phosphoric acid, phosphoric acid two (2, the 6-xylyl) tolyl ester, phosphoric acid two (2,4, the 6-trimethylphenyl) the tolyl ester, two (2, the 6-xylyl) the xylyl esters of phosphoric acid, phosphoric acid two (2,4, the 6-trimethylphenyl) xylyl ester, two (2, the 6-xylyl) naphthyl esters of phosphoric acid and phosphoric acid two (2,4, the 6-trimethylphenyl) naphthyl ester, tricresyl phosphate (2, the 6-xylyl) ester wherein, tricresyl phosphate (2,4, the 6-trimethylphenyl) two (2, the 6-xylyl) the tolyl esters of ester and phosphoric acid are preferred.
Aromatic phosphate acid ester as component (b) can be by known method production itself.For example, it can be by the reaction of aromatic monohydroxy compound and phosphoryl chloride, or by aromatic monohydroxy compound and phosphorus trichloride reaction, follows the product that oxidation obtains and produces.
In this production method, the compound of being represented by n=1 in the logical formula I (for example di(2-ethylhexyl)phosphate phenyl (2, the 6-xylyl) ester) can be used as the by product generation.This by product when its amount little when being not enough to obviously influence the character of resin combination, needn't separate, the aromatic phosphate acid ester of producing directly can be used as component (b).When containing, aromatic phosphate acid ester has an appointment 10% or during more this by product, it has disadvantageous effect to the hydrolytic resistance and the thermotolerance of resin combination.
Aromatic phosphate acid ester (b) is crystalline solid or liquid, and crystalline solid and liquid aromatic phosphoric acid ester all can be used in the composition of the present invention.In addition, itself be that the component (b) of suitable flame retardant has been kept the heat-drawn wire and the performance of component (a) substantially.
If need, resin combination of the present invention can contain various additives such as other fire retardant, filler, lubricant and tinting material.
In addition, the fire retardant as component (b) can use with thermoplastic resin and thermosetting resin (a).
The blending ratio of component can suitably be determined according to used resin kind and required flame retardant resistance in flame-retarded thermosetting resin composition of the present invention.Generally with 0.1 to 100 weight part, the component of preferred 5 to 50 weight parts (b) is used with the component (a) of 100 weight parts.
Resin combination of the present invention is pressed the currently known methods preparation, promptly by with aromatic phosphate acid ester (b) blending and with warming mill or single screw extrusion machine heating it being mixed thermosetting resin (a) with blending machine, makes fire-retardant thing then.
Resin combination of the present invention also useable solvents is made lacquer, and can be applied to or immerse in the base material, makes it have flame retardant resistance.The example of this kind solvent is toluene, ethanol, methyl ethyl ketone, acetone, dimethyl formamide and vinylbenzene.The example of base material is paper, woven fiber glass, glass non-woven and synthetic cloth.Can and be pressed into laminated sheet with the double-deck or multi-layer fire-retarded base material heating of individual layer.
Aromatic phosphate acid ester as component of the present invention (b) is a low volatility, it can not reduce the heat-drawn wire of flame-retarded thermosetting resin composition, and it shows for the resistance that keeps resin and mechanical property improves greatly and have an excellent flame retardant effect that conventional organophosphorous fire retardant can not provide.
The present invention will further be described with reference to the following example; Yet these embodiment are used to illustrate of the present invention but not limitation of the scope of the invention.In these embodiments, except as otherwise noted, umber/umber is meant weight part/weight part.
Synthetic embodiment 1
(366g, 3.0ml add as catalyzer with Aluminum chloride anhydrous (6.1g) and have in the four neck flasks of agitator, dropping funnel, thermometer and the condenser that links to each other with water scrubber, and heating mixes with 2.When the reaction soln temperature rose to 100 ℃, (153g 1.0mol), sent into the spirit of salt gas that generates in the water scrubber simultaneously to add phosphoryl chloride in about 2 hours.After adding phosphoryl chloride, temperature of reaction was risen to 230 ℃ gradually in four hours, then under same temperature with reaction mixture slaking 2 hours, being decompressed under 300 torrs slaking 8 hours, finish reaction thus again.With reaction mixture with acid and use hot wash.Produce the aromatic phosphate acid ester precipitation then.With settled crystal filtering separation, with methanol wash and drying under reduced pressure.Obtain 308g (yield 75%) tricresyl phosphate (2, the 6-xylyl) ester white crystalline powder,, be found to be 99.8% or higher with gas Chromatographic Determination crystalline purity.Fusing point is 137 to 138 ℃.Be referred to as compound 1.
Synthetic embodiment 2
Described in synthetic embodiment 1, carry out same reaction, but with 2,4, (409g 3.0mol) replaces 2 (3.0mol) to 6-front three phenol.Make 353g (yield 78%) tricresyl phosphate (mesityl) ester.Crystal purity with gas Chromatographic Determination is 99.8% or higher.Fusing point is 108 to 109 ℃.Be referred to as compound 2.
Synthetic embodiment 3
Adding has in the four neck flasks of agitator, dropping funnel, thermometer and the condenser that links to each other with water scrubber as catalyzer with Magnesium Chloride Anhydrous (1.5g) with 2 (244g, 2.0mol), and heating mixes.When the temperature of reaction soln rose to 120 ℃, (153g 1.0mol), sent into the hydrogen chloride gas that generates in the water scrubber simultaneously to add phosphoryl chloride in about 2 hours.
After adding phosphoryl chloride, in two hours, temperature of reaction is risen to 180 ℃ gradually, finish reaction thus.
After the cooling, with reaction mixture and p-Cresol (108g, 1.0mol) and Magnesium Chloride Anhydrous mixes and heating.Reaction mixture temperature was risen to 180 ℃ gradually with dehydrochlorination in 2 hours.Then with reaction mixture slaking 2 hours under same temperature, and, finish reaction thus being decompressed under 200 torrs further slaking 2 hours.Also use this reaction mixture of hot wash with acid at last.Through distillation, make 376g (yield 95%), phosphoric acid two (2, the 6-xylyl) right-tolyl ester white solid.Through gas Chromatographic Determination solid purity is 98.5% or higher.Fusing point is 70 to 71 ℃.Below be referred to as compound 3.
Synthetic embodiment 4
Carry out same reaction by synthetic embodiment 3 is described, but (122g 1.0mol) replaces cresylol (1.0mol) with xylenol.Make two (2, the 6-xylyl) the xylyl ester yellow liquids of 390g (yield 95%) phosphoric acid.Purity through gas Chromatographic Determination liquid is 98.0% or higher.Be referred to as compound 4.
Embodiment 1 to 4
The compound 1 to 4 that comes from synthetic embodiment 1 to 4 all depressed at the 2atm saturation steam when the 120 ℃/100%RH carried out Pressure Cooker Test 96 hours, measure its acid number and hydrolytic resistance then.
The result who obtains provides in table 1.
Table 1
| Embodiment | Comparing embodiment | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| Compound 1 | Compound 2 | Compound 3 | Compound 4 | Compound 5 (TPP) | Compound 6 (TCP) | Compound 7 (TXP) | |
| Initial acid value | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Acid number behind the Pressure Cooker Test | 5.30 | 6.50 | 16.1 | 7.80 | 180.2 | 125.0 | 69.6 |
Comparing embodiment 1 to 3
Replace compound among the synthetic embodiment 1 to 4 with following compounds 5 to 7, carry out same measurement by embodiment 1 is described:
Compound 5: triphenylphosphate (by Daihachi Chemical Industry Co., Ltd. (Japan) produces, trade(brand)name TPP)
Compound 6: Tritolyl Phosphate (by Daihachi Chemical Industry Co., Ltd. produces, trade(brand)name TCP)
Compound 7: trixylyl phosphate (by Daihachi Chemical Industry Co., Ltd. produces, trade(brand)name TXP)
The result provides in table 1.
Table 1 clearly illustrates that aromatic phosphate acid ester hydrolytic resistance of the present invention is better.
Embodiment 5 to 8
With component (b): the compound of one of 15 parts of above-mentioned synthetic compounds 1 to 4 adds component (a): in 100 parts the commercial phenolic resin coating (solid content is 60%) and mix, then it is immersed in velveteen scraps of paper and the dry resin impregnated sheet with resin content 45% that makes.9 synusia materials are stacked, and in the time of 150 ℃ at 90g/cm
2Suppress down and obtained the thick laminated sheet of 2mm in 50 minutes.Other synthetic compound is repeated said procedure, make 4 laminated sheets.
The laminated sheet that makes by following method test: by UL (Underwriters Lab-oratories)-94 standard test flame retardant resistances and be divided into 4 grade: V-0, V-1, V-2 and HB; Represent by the thermotolerance in JIS (Japanese Industrial Standards) C-6481 when welding test and with the time period (second) when expanding or peel off beginning under 260 ℃; At 18.6kg/cm
2Press ASTM (American Society for Testing Materials) standard D-617 test punching property down; Press ionogen dropping method test tracking index
Table 2
(tracking resistance)。
| Embodiment | Comparing embodiment | ||||||
| 5 | 6 | 7 | 8 | 4 | 5 | 6 | |
| (a) component phenolic resins (b) component compound 1 compound 2 compounds 3 compounds 4 compounds 5 compounds 6 compounds 7 | 100 15 - - - - - - | 100 - 15 - - - - - | 100 - - 15 - - - - | 100 - - - 15 - - - | 100 - - - - 15 - - | 100 - - - - - 15 - | 100 - - - - - - 15 |
| The flame retardant resistance insulativity, (Ω) tracking index, thermotolerance when (V) welding, (sec) punching property is anti-exudative * | V-0 10 12-10 13＞600 68 good zero | V-0 10 12-10 13＞600 73 good zero | V-0 10 12-10 13＞600 57 good zero | V-0 10 12-10 13＞600 62 good zero | V-1 10 9-10 10500 15 expansions * | V-1 10 9-10 10500 23 expansions * | V-0 10 9-10 10500 55 good * |
Gained is the result provide in table 2.
*Oily exudate detects by an unaided eye after keeping 48 hours under 120 ℃.
Comparing embodiment 4 to 6
Prepare laminated sheet by the same way as described in the embodiment 5, but compound 5 to 7 is replaced the compound of synthetic embodiment 1 to 4 as compound (b).Test the sheet material that makes by embodiment 5.
The result provides in table 2.
From table 2, clearly realize that flame-retarded thermosetting resin composition that the present invention contains aromatic phosphate acid ester not only punching when flame retardant resistance and low temperature but also anti-fire retardant is exudative from laminated sheet, the tracking index that especially brings because of good hydrolytic resistance and insulativity all are better than containing conventional flame retardants compositions of thermosetting resin.
Embodiment 9 to 12
With component (b): any adding component (a) of the compound 1 to 4 of 15 parts of synthetic embodiment 1 to 4: in 100 parts of commercial epoxy resin-based paints (its solid content is 50%) and mix, the same quadrat method of press then among the embodiment 5 prepares four laminated sheets.
By testing the laminated sheet that makes described in the embodiment 5.
The result provides in table 3.
Table 3
*Oily exudate detects by an unaided eye after keeping 48 hours under 120 ℃.
| Embodiment | Comparing embodiment | ||||||
| 9 | 10 | 11 | 12 | 7 | 8 | 9 | |
| (a) component epoxy resin dicyandiamide (b) component compound 1 compound 2 compounds 3 compounds 4 compounds 5 compounds 6 compounds 7 | 100 3 15 - - - - - - | 100 3 - 15 - - - - - | 100 3 - - 15 - - - - | 100 3 - - - 15 - - - | 100 3 - - - - 15 - - | 100 3 - - - - - 15 - | 100 3 - - - - - - 15 |
| The flame retardant resistance insulativity, (Ω) tracking index, thermotolerance when (V) welding, (sec) punching property is anti-exudative * | V-0 10 13-10 14＞600 110 good zero | V-0 10 13-10 14＞600 121 good zero | V-0 10 13-10 14＞600 87 good zero | V-0 10 13-10 14＞600 96 good zero | V-0 10 10-10 11500 35 expansions * | V-0 10 10-10 11500 47 expansions * | V-0 10 10-10 12500 63 good * |
Ratio embodiment 7 to 9
By preparing laminated sheet, but replace the compound 1 to 4 of synthetic embodiment 1 to 4 with compound 5 to 7 with mode identical described in the embodiment 5.
By testing the laminated sheet that makes described in the embodiment 5.
The result provides in table 3.
The not only punching during low temperature but also anti-fire retardant is exudative from laminated sheet, especially tracking index, thermotolerance and insulativity are all more excellent than the compositions of thermosetting resin reason that contains conventional flame retardants of the flame-retarded thermosetting resin composition that table 3 proof is of the present invention to contain aromatic phosphate acid ester.
Compare with the compositions of thermosetting resin that contains conventional flame retardants, the compositions of thermosetting resin that contains aromatic phosphate acid ester of the present invention shows that better low temperature punching property, better anti-fire retardant are exudative from laminated sheet, especially show remarkable improvement to tracking index, thermotolerance and insulativity.
Claims (9)
1. flame-retarded thermosetting resin composition, it comprises (a) thermosetting resin and the aromatic phosphate acid ester of (b) being represented by logical formula I:
R wherein
1And R
2Be identical or different C
1-C
4Alkyl, R
3Be hydrogen atom or C
1-C
4Alkyl, R
4Be C
6-20Aromatic hydrocarbon residue, n are integer 2 or 3.
2. according to the composition of claim 1, wherein the component (b) of 0.1 to 100 weight part is mixed with the component (a) of 100 weight parts.
3. according to the composition of claim 1, wherein the component (b) of 5 to 50 weight parts is mixed with the component (a) of 100 weight parts.
4. according to the composition of claim 1, the R of its formula of (I)
1And R
2Be identical C
1-C
4Alkyl.
5. according to the composition of claim 1, wherein aromatic phosphate acid ester is two (2, the 6-xylyl) the tolyl esters of tricresyl phosphate (2, the 6-xylyl) ester, tricresyl phosphate (mesityl) ester or phosphoric acid.
6. according to the composition of claim 1, wherein component (a) is selected from any in acrylic resin, urethane resin, resol, Resins, epoxy, melmac, urea resin, unsaturated polyester resin and the diallyl phthalate resin.
7. according to the composition of claim 1, wherein component (a) is a resol.
8. according to the composition of claim 1, wherein component (a) is a Resins, epoxy.
9. ignition resistant substrate that makes by coating or the dipping solution of claim 1 to 8 any composition in organic solvent.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP83925/1995 | 1995-04-10 | ||
| JP83925/95 | 1995-04-10 | ||
| JP8392595 | 1995-04-10 | ||
| JP8053025A JPH08337683A (en) | 1995-04-10 | 1996-03-11 | Flame-retardant thermosetting resin composition |
| JP53025/96 | 1996-03-11 | ||
| JP53025/1996 | 1996-03-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1138597A CN1138597A (en) | 1996-12-25 |
| CN1074016C true CN1074016C (en) | 2001-10-31 |
Family
ID=26393729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104532A Expired - Fee Related CN1074016C (en) | 1995-04-10 | 1996-04-09 | Flame-retarded thermosetting resin composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH08337683A (en) |
| KR (1) | KR100426301B1 (en) |
| CN (1) | CN1074016C (en) |
| MY (1) | MY134600A (en) |
| SG (1) | SG67926A1 (en) |
| TW (1) | TW426713B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005070990A1 (en) * | 2004-01-12 | 2005-08-04 | Taizhou Repow Chemical And Material Institute Co., Ltd | An epoxy resin curing agent containing elemental phosphorus and the method for preparing the same |
| US7087703B2 (en) * | 2004-07-26 | 2006-08-08 | Georgia-Pacific Resins, Inc. | Phenolic resin compositions containing etherified hardeners |
| ATE460459T1 (en) * | 2004-12-02 | 2010-03-15 | Chemtura Corp | SCORCH RESISTANT FLAME RETARDANT POLYURETHANE FOAM |
| TW200710208A (en) * | 2005-06-27 | 2007-03-16 | Nippon Kayaku Kk | Dispersions of phosphorous flame retarding agent for fibers, flame retarding modification method using the dispersions and flame retarding modified fibers by the method |
| JP6038639B2 (en) * | 2012-12-26 | 2016-12-07 | ダイセルポリマー株式会社 | Thermoplastic cellulose ester composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242633A (en) * | 1988-03-24 | 1989-09-27 | Hitachi Chem Co Ltd | Laminate |
| JPH0267310A (en) * | 1988-08-31 | 1990-03-07 | Shin Kobe Electric Mach Co Ltd | Non-flammable phenol resin composition and laminate |
-
1996
- 1996-03-11 JP JP8053025A patent/JPH08337683A/en active Pending
- 1996-04-03 SG SG1996007809A patent/SG67926A1/en unknown
- 1996-04-05 TW TW085103947A patent/TW426713B/en not_active IP Right Cessation
- 1996-04-05 MY MYPI96001302A patent/MY134600A/en unknown
- 1996-04-08 KR KR1019960010447A patent/KR100426301B1/en not_active IP Right Cessation
- 1996-04-09 CN CN96104532A patent/CN1074016C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242633A (en) * | 1988-03-24 | 1989-09-27 | Hitachi Chem Co Ltd | Laminate |
| JPH0267310A (en) * | 1988-08-31 | 1990-03-07 | Shin Kobe Electric Mach Co Ltd | Non-flammable phenol resin composition and laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| SG67926A1 (en) | 1999-10-19 |
| MY134600A (en) | 2007-12-31 |
| TW426713B (en) | 2001-03-21 |
| CN1138597A (en) | 1996-12-25 |
| KR960037765A (en) | 1996-11-19 |
| KR100426301B1 (en) | 2004-07-19 |
| JPH08337683A (en) | 1996-12-24 |
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