CN103421289A - Fireproof composite material - Google Patents
Fireproof composite material Download PDFInfo
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- CN103421289A CN103421289A CN2012101611624A CN201210161162A CN103421289A CN 103421289 A CN103421289 A CN 103421289A CN 2012101611624 A CN2012101611624 A CN 2012101611624A CN 201210161162 A CN201210161162 A CN 201210161162A CN 103421289 A CN103421289 A CN 103421289A
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Abstract
The invention provides a fireproof composite material. The fireproof composite material comprises polycarbonate, silicon-based flame retardants, polytetrafluoroethylene and inorganic filling materials. The inorganic filling materials are talcum or mica. The component ratios are, by weight, 100 parts of polycarbonate, 2-3 parts of siloxane compounds, 3-5 parts of inorganic filling materials and 0.4-0.6 part of polytetrafluoroethylene. The fireproof composite material with a thickness of 1.0 cm or 1.2 cm can retain V0 fireproofing grade under UL 94vertical flame tests. The fireproof composite material still can retain V0 fireproofing grade at the request of light weight. The employed silicon-based flame retardants can enhance the impact strength of the fireproof composite material.
Description
Technical field
The invention belongs to the composition of macromolecular compound, more particularly, relevant for the composition of polycarbonate or the made Flameproof composite material of composition of polycarbonate derivative.
Background technology
General thermoplastic material (for example: polycarbonate) have greatly good physical strength, can be applicable to many industries, for example: building decoration, vehicle is in-built and the shell of electronic package or electrical appliance, and increasing product requirement will have flame retardancy, just can meet relevant rules and regulations to pass through authentication.
Although the application of different industries has the demand of different fire-protection ratings, but the design of more and more commodity is more also more compact at present, and finished product thickness is thinner, maintaining good fire performance more is not easy, but, under light-weighted requirement, at present the fire-protection rating of plastic material required but day by day to promote.
In the prior art at present, for example the U.S. announces patent specification US6001921, US6117542, US6184312, US6284824, US6326425, US6451906, US6509421, US7462662, and U.S. publication specification sheets US20010018487, US20010044484, disclosed Flameproof composite material in the documents such as US20060252890, it is (for example bromine salt Bromide) that general Flameproof composite material is used halogen (halogen) mostly, phosphorus system (Phosphor), U.S. anti-ware (Melamin) or aluminium hydroxide (Aluminum Trihydrate, ATH) etc. composition is as fire retardant.
And the halogen system and the phosphorus that wherein add bromide are the fire-retardant material of fire retardant, in making processes because can't meet the regulation of TCO ' 99 authentication, not only not environmental protection, and to use phosphorus be that the fire-retardant material of fire retardant easily makes the heat-drawn wire of fire-retardant material reduce, and cause mold fouling.And use the fire-retardant material of the compositions such as U.S. anti-ware or aluminium hydroxide as fire retardant, and it is higher that its product of making has processing temperature, but impact strength is not good etc., problem exists.
Summary of the invention
For solving the above problems, the invention provides a kind of Flameproof composite material, comprise polycarbonate, silica-based fire retardant, inorganic filling material and tetrafluoroethylene.Wherein, polycarbonate composition ratio is that 100 weight parts, silica-based fire retardant composition ratio are that 2～3 weight parts, inorganic filling material composition ratio are that 3～5 weight parts and tetrafluoroethylene composition ratio are 0.4～0.6 weight part.Inorganic filling material is talcum or mica.By this, Flameproof composite material provided by the present invention conforms with the V0 fire-protection rating after UL 94 testing vertical flammabilities.
Therefore, main purpose of the present invention is to provide a kind of Flameproof composite material, has UL 94V0 fire-protection rating, and, owing to using silica-based fire retardant, strengthens by this protecting against shock intensity of Flameproof composite material.
Another purpose of the present invention is to provide a kind of Flameproof composite material, its composition is with silica-based fire retardant, and as inorganic filling material, and drip a vertical agent with tetrafluoroethylene as anti-with talcum or mica, under light-weighted requirement, aforementioned component still can maintain UL 94V0 fire-protection rating.
In addition, the present invention also provides another kind of Flameproof composite material, the tetrafluoroethylene that the polycarbonate that to comprise the composition ratio be 100 weight parts, the silica-based fire retardant that the composition ratio is 2～3 weight parts, inorganic filling material that the composition ratio is 3～5 weight parts and composition ratio are 0.4～0.6 weight part.Inorganic filling material is talcum or mica.By this, when the thickness of Flameproof composite material is 1.0 centimetres, after UL 94 testing vertical flammabilities, conform with the V0 grade.And, when the thickness of Flameproof composite material is 1.2 centimetres, after UL 94 testing vertical flammabilities, conform with the V0 grade.
Therefore, main purpose of the present invention is to provide a kind of Flameproof composite material, has UL 94V0 grade, and, owing to using silica-based fire retardant, strengthens by this protecting against shock intensity of Flameproof composite material.
Another purpose of the present invention is to provide a kind of Flameproof composite material, its composition is to use silica-based fire retardant, and as inorganic filling material, and drip a vertical agent with tetrafluoroethylene as anti-with talcum or mica, under the requirement increased at thickness, aforementioned component still can maintain UL 94V0 fire-protection rating.
Embodiment
Owing to the invention discloses a kind of Flameproof composite material, the relevant processing procedure of the principles of chemistry wherein utilized and organic and inorganic materials, be that those of ordinary skills can understand, therefore, with explanation hereinafter, no longer do complete description.
The present invention's the first preferred embodiment is to provide a kind of Flameproof composite material, comprises polycarbonate (thermoplastic resin), silicone compounds (fire retardant), talcum or mica (inorganic filling material) and tetrafluoroethylene (an anti-vertical agent).Wherein, polycarbonate composition ratio is that the composition ratio that 100 weight parts, silicone compounds composition ratio are 2～3 weight parts, talcum or mica is that 1～5 weight part and tetrafluoroethylene composition ratio are 0.4 weight part.
General Flameproof composite material all judges its grade through UL 94 testing vertical flammabilities, testing standard is after vertical combustion the longest self-extinguishing time, total combustion time, the igniting property of cotton is divided into to V0, V1, V2 Three Estate after could dripping and drip, wherein, the V0 grade is best fire-retardant material, V1 takes second place, and V2 takes second place again.And the Flameproof composite material of this better first embodiment conforms with the V0 grade after UL 94 testing vertical flammabilities.
The present invention also provides the second preferred embodiment, is also Flameproof composite material, wherein each composition of material form with and the preferred range that forms of each composition and the first preferred embodiment described in roughly the same.When the thickness of test piece of the Flameproof composite material provided when the second preferred embodiment is 1.0mm, conform with UL 94V0 grade after testing vertical flammability.
Following experimental example below further is provided, uses the feature of explanation Flameproof composite material provided by the present invention.
Experimental example:
A. materials and methods:
I. the preparation of composite fire-proof material:
Polycarbonate (Polycarbonate) 100 weight parts that are 10 and 62 by melting index (Melting Index) (melting index is the numerical value that plastic material adds the mobility in man-hour), silicone compounds (Siloxane compound) 2～3 weight parts, talcum (Talc) 3～5 weight parts, tetrafluoroethylene (Polytetrafluoroethylene) 0.4 weight part and antioxidant (Antioxidant) 0.1 weight part, make the composite fire-proof material, with the experimental group as UL 94 testing vertical flammabilities.Further add the titanium dioxide (TiO of 15 weight parts in the sample of numbering 3
2).And number 1,2 sample and adopt polycarbonate 40 weight parts that polycarbonate 60 weight parts that melting index is 10 and melting index are 62, and number 3 sample, adopt polycarbonate 50 weight parts that polycarbonate 50 weight parts that melting index is 10 and melting index are 62.The material of each sample of experimental group forms as shown in Table 1:
In addition, by the tetrafluoroethylene of the silicone compounds of the polycarbonate of 100 weight parts, 3 weight parts, 0.4 weight part and the antioxidant of 0.1 weight part, the composite fire-proof material (numbering 4 samples) that to make thickness be 1.5 centimetres, as the first control group of UL 94 testing vertical flammabilities.And the first control group adopts polycarbonate 50 weight parts that polycarbonate 50 weight parts that melting index is 10 and melting index are 62, add up to the polycarbonate of 100 weight parts.
By the talcum of the perfluoro butyl potassium sulfonate of the polycarbonate of 100 weight parts, 0.01 weight part (Potassium perfluorobutane sulfonate), 1 weight part, the tetrafluoroethylene of 0.4 weight part and the antioxidant of 0.1 weight part, make composite fire-proof material (numbering 5 samples), with the second control group as UL 94 testing vertical flammabilities.The second control group with the perfluoro butyl potassium sulfonate as fire retardant.And the polycarbonate of the second control group is to adopt polycarbonate 40 weight parts that polycarbonate 60 weight parts that melting index is 10 and melting index are 62, adds up to the polycarbonate of 100 weight parts.
By the polycarbonate of 100 weight parts, silicone compounds 2 weight parts, talcum 1 weight part, tetrafluoroethylene 0.4 weight part and antioxidant 0.1 weight part, make composite fire-proof material (numbering 6 samples), with the 3rd control group as UL 94 testing vertical flammabilities.And the polycarbonate of the 3rd control group is to adopt polycarbonate 40 weight parts that polycarbonate 60 weight parts that melting index is 10 and melting index are 62, adds up to the polycarbonate of 100 weight parts.In aforementioned each control group, each sample material forms as shown in Table 2:
*: the first control group;
*: the second control group;
$: the 3rd control group
Comply with the aforementioned composite fire-proof material that proportion of composing makes of respectively organizing, it is cut into to the thick composite fire-proof material test piece that is respectively 120 centimetres, 13 centimetres, 1.0 centimetres or 1.2 centimetres or 1.5 centimetres (120mm x 13mm x 1.0mm or1.2mmor1.5mm) of length and width, carries out in the following manner UL 94 testing vertical flammabilities and the test of otch impact strength.
II.UL 94 testing vertical flammabilities:
Prepare five of the composite fire-proof material test pieces that composition forms and length and width thickness is all identical, according to UL 94 testing vertical flammability standards, carry out combustion testing.At first, each composite fire-proof material test piece is folded on sample rack, test piece below 300 centimeters are placed surgery and are used cotton.The Bunsen burner of lighting is placed in to test piece to be measured below, lights a fire for the first time, continue to remove after 10 seconds, after measuring flame and removing to test piece to be measured from putting out required time, record is the first self-extinguishing time.Remove after 10 seconds the Bunsen burner dislocation test piece to be measured once again below of will light, carry out refire time, after continuing to remove and measure once again flame after 10 seconds and removing to test piece to be measured from putting out required time, record is the second self-extinguishing time.And if, test piece burning vertical according to whether dripping in the longest self-extinguishing time of each test piece, total combustion time, test piece burning whether prolong burn have that dripping hangs down and whether ignite between cotton and test piece main combustion period to fixture test piece burning in smog whether hide results such as putting out Bunsen burner, judge that each sample is whether by UL 94 testing vertical flammabilities, with and fire-protection rating.Refer to the first combustion time that five test pieces of single sample record after combustion testing and the summation of the second combustion time total combustion time.Each grade (V0, V1, V2) pass through standard as shown in Table 3.
In addition, the longest self-extinguishing time shown in table three, could drip vertical, the standard of cotton of could igniting of drip hanging down, each sample needs five test pieces all to meet ranking norm just to pass through at last.And, in fire-protection rating V0, V1, V2, five test pieces all can not be prolonged the phenomenon of burning to fixture.
III. otch impact strength test (Notched Izod testing):
The fire-retardant material that differing materials in above-mentioned experimental group or control group is formed, the ASTM D256 test method of announcing according to American Society for testing and materials (American Society for Testing and Materials), the thick test piece that is of a size of 2.5x 0.5x 0.125 inch of the preparation wide x of growth x, carry out the impact strength test, and note down the total energy (kg-cm/cm) born when test piece is ruptured.
B
. the fire-protection rating test result:
I. the experimental group Flameproof composite material meets V0 through the best fire-protection rating of UL 94 combustion tests:
According to Flameproof composite material provided by the present invention (experimental group), after UL 94 testing vertical flammabilities, measured fire-protection rating is V0.The sampling test result of each numbering is as shown in following table four:
*: T
1, T
2Mean respectively each test piece self-extinguishing time and self-extinguishing time for the second time for the first time
By upper table, learnt, the sample thickness of experimental group numbering 1 is 1.2 centimetres, and the longest self-extinguishing time is less than 10 seconds, and the longest self-extinguishing time comes across the self-extinguishing time for the second time of test piece 5, is 7.1 seconds.Be 31.9 seconds total combustion time, is shorter than 50 seconds.The combustion position of sample all occurs to drip to hang down, and does not also prolong and burns to fixture, and between main combustion period, middle smog does not hide and puts out Bunsen burner.Therefore its fire-protection rating is judged to be V0.
The sample thickness of experimental group numbering 2 is 1.0 centimetres, and the longest self-extinguishing time is less than 10 seconds, and the longest self-extinguishing time comes across the self-extinguishing time for the second time of test piece 3, is 6.3 seconds.Be 18.3 seconds total combustion time, is shorter than 50 seconds.The combustion position of sample all occurs to drip to hang down, and does not also prolong and burns to fixture, and between main combustion period, middle smog does not hide and puts out Bunsen burner.Therefore its fire-protection rating is judged to be V0.
The sample thickness of experimental group numbering 3 is 1.5 centimetres, and the longest self-extinguishing time is less than 10 seconds, and the longest self-extinguishing time comes across the self-extinguishing time for the second time of test piece 1, is 6.1 seconds.Be 23.1 seconds total combustion time, is shorter than 50 seconds.The combustion position of sample all occurs to drip to hang down, and does not also prolong and burns to fixture, and between main combustion period, middle smog does not hide and puts out Bunsen burner.Therefore its fire-protection rating is judged to be V0.
Therefore, according to the above results, the composite fire-proof sample that the thickness that experimental group of the present invention provides is 1.0 centimetres, 1.2 centimetres, see through the weight part of adjustment silicone compounds (fire retardant) and the weight part of talcum (inorganic silicate stratified material).Again through UL 94 combustion tests, confirm that the sample of numbering 1,2 all can meet the V0 fire-protection rating after adjusting.
In addition, the composite fire-proof sample that the thickness that experimental group of the present invention provides is 1.5 centimetres, see through the weight part of adjustment silicone compounds (fire retardant) and the weight part of talcum (inorganic silicate stratified material), and further add titanium dioxide.Again through UL 94 combustion tests, confirm that the sample of numbering 3 meets the V0 fire-protection rating after adjusting.
II. do not add inorganic filling material, can affect fire-protection rating:
The sample of the first control group numbering 4, find through UL 94 testing vertical flammabilities, and its fire-protection rating is in the situation that thickness is 1.5 centimetres is V2.Test-results is as shown in following table five:
*: T
1, T
2Mean respectively each test piece self-extinguishing time and self-extinguishing time for the second time for the first time
By upper table, learnt, the sample thickness of the first control group numbering 4 is 1.5 centimetres.The longest self-extinguishing time was lower than 10 seconds, and total combustion time was lower than 50 seconds.Wherein, test piece 2,3,4, in the combustion position of the first self-extinguishing time, occurs to drip to hang down, and does not also prolong and burns to fixture, and between main combustion period, middle smog does not hide and puts out Bunsen burner.Test piece 1,5, in the first self-extinguishing time and test piece 1,2,3,4,5 in the combustion position of the second self-extinguishing time, all occurs to drip to hang down and the cotton of igniting.Therefore its fire-protection rating is judged to be V2.
According to the above results, the sample of the first control group numbering 4 does not adopt inorganic filling material, even when the thickness of sample is 1.5 centimetres, only reaches the V2 fire-protection rating yet.
III. adopt the perfluoro butyl potassium sulfonate as fire retardant, its fire-protection rating is the V1 fire-protection rating:
The sample of the second control group numbering 5, find through UL 94 testing vertical flammabilities, and its fire-protection rating is in the situation that thickness is 1.2 centimetres is V1.Test-results is as shown in following table six:
*: T
1, T
2Mean respectively each test piece self-extinguishing time and self-extinguishing time for the second time for the first time
By upper table, learnt, the sample of the second control group numbering 5 is when thickness is 1.2 centimetres, and the longest self-extinguishing time surpasses 10 seconds, is shorter than 30 seconds, and the self-extinguishing time for the second time that the longest self-extinguishing time comes across test piece 3 is 19 seconds.Total combustion time was over 50 seconds.Do not occur during burning to drip and hang down and prolong the situation of burning to fixture, therefore fire-protection rating meets the standard of V1.
According to the above results, the sample of the second control group numbering 5 adopts the perfluoro butyl potassium sulfonate as fire retardant, although the second control group adopts talcum as inorganic filling material with experimental group, also only reaches the V1 fire-protection rating.
IV. adopt the perfluoro butyl potassium sulfonate as fire retardant, its fire-protection rating is the V1 fire-protection rating:
The sample of the 3rd control group numbering 6, find through UL 94 testing vertical flammabilities, and its fire-protection rating is in the situation that thickness is 1.2 centimetres is V1.Test-results is as shown in following table seven:
*: T
1, T
2Mean respectively each test piece self-extinguishing time and self-extinguishing time for the second time for the first time
By upper table, learnt, the sample thickness of the 3rd control group numbering 6 is 1.2 centimetres, and the longest self-extinguishing time surpasses 10 seconds, is shorter than 30 seconds, and the self-extinguishing time for the second time that the longest self-extinguishing time comes across test piece 3 is 22.1 seconds.Be 70.2 seconds total combustion time, is shorter than 250 seconds.The combustion position of sample all occurs to drip to hang down, and does not also prolong and burns to fixture, and between main combustion period, middle smog does not hide and puts out Bunsen burner.Therefore its fire-protection rating is judged to be V1.。
According to the above results, the sample of the 3rd control group numbering 6 adopts talcum as inorganic filling material, and the 3rd control group, in the situation that the ratio of talcum reduces, only reaches the V1 fire-protection rating.
C. impact strength test result:
According to Flameproof composite material provided by the present invention (experimental group numbering the 1,3 and second control group numbering 5), after the impact strength test, the sampling test result of measured each numbering is as shown in following table eight:
By upper table, learnt, the sample (adopting silica-based fire retardant) of experimental group numbering 1 and 3, both impact strengths are respectively 64.3 and 43.65; The impact strength of the second control group numbering 5 (adopting the perfluoro butyl potassium sulfonate as fire retardant) sample is 10.3.From experimental result, learn, the impact strength of experimental group numbering 1 and 3 all is better than the impact strength of the second control group numbering 5.
That is, by the sample comparative result of numbering 1,3,5, Flameproof composite material provided by the present invention, owing to adopting silica-based fire retardant, therefore, compared to the fire-retardant material that adopts the sulfonate fire retardant, have higher impact strength.
The foregoing is only preferred embodiment of the present invention, not in order to limit the right of applying for a patent of the present invention; Simultaneously above description, should understand and implement for those of ordinary skills, so other does not break away from the equivalence completed under disclosed spirit and change or modification, all should be included in claims.
Claims (4)
1. a Flameproof composite material comprises:
One polycarbonate, its composition ratio is 100 weight parts;
One silica-based fire retardant, comprise a silicone compounds, and its composition ratio is 2～3 weight parts;
One inorganic filling material, its composition ratio is 3～5 weight parts, this inorganic filling material is selected from the group consisted of talcum and mica; And
One tetrafluoroethylene, its composition ratio is 0.4～0.6 weight part.
2. Flameproof composite material according to claim 1 conforms with UL 94V0 grade after a testing vertical flammability.
3. a Flameproof composite material comprises:
One polycarbonate, its composition ratio is 100 weight parts;
One silica-based fire retardant, include a silicone compounds, and its composition ratio is 2～3 weight parts;
One inorganic filling material, its composition ratio is 3～5 weight parts, this inorganic filling material is selected from the group consisted of talcum and mica; And
One tetrafluoroethylene, its composition ratio is 0.4～0.6 weight part, by this, when the thickness of test piece of this Flameproof composite material is 1.0mm, conforms with UL 94V0 grade after a testing vertical flammability.
4. a Flameproof composite material comprises:
One polycarbonate, its composition ratio is 100 weight parts;
One silica-based fire retardant, include a silicone compounds, and its composition ratio is 2～3 weight parts;
One inorganic filling material, its composition ratio is 3～5 weight parts, this inorganic filling material is selected from the group consisted of talcum and mica; And
One tetrafluoroethylene, its composition ratio is 0.4～0.6 weight part, by this, when the thickness of test piece of this Flameproof composite material is 1.2mm, conforms with UL 94V0 grade after this testing vertical flammability.
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| CN2012101611624A CN103421289A (en) | 2012-05-22 | 2012-05-22 | Fireproof composite material |
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| CN2012101611624A CN103421289A (en) | 2012-05-22 | 2012-05-22 | Fireproof composite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094904A (en) * | 2006-10-10 | 2008-04-24 | Teijin Chem Ltd | Method for producing flame-retardant resin composition |
| JP2009249550A (en) * | 2008-04-09 | 2009-10-29 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded product |
| JP2010138412A (en) * | 2010-03-15 | 2010-06-24 | Mitsubishi Engineering Plastics Corp | Flame-retardant polycarbonate resin composition and light ray reflector |
| US20110052895A1 (en) * | 2009-08-25 | 2011-03-03 | Sabic Innovative Plastics, Ip B.V. | Flame retardant thermoplastic polycarbonate compositions and films made therefrom |
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2012
- 2012-05-22 CN CN2012101611624A patent/CN103421289A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094904A (en) * | 2006-10-10 | 2008-04-24 | Teijin Chem Ltd | Method for producing flame-retardant resin composition |
| JP2009249550A (en) * | 2008-04-09 | 2009-10-29 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded product |
| US20110052895A1 (en) * | 2009-08-25 | 2011-03-03 | Sabic Innovative Plastics, Ip B.V. | Flame retardant thermoplastic polycarbonate compositions and films made therefrom |
| JP2010138412A (en) * | 2010-03-15 | 2010-06-24 | Mitsubishi Engineering Plastics Corp | Flame-retardant polycarbonate resin composition and light ray reflector |
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Application publication date: 20131204 |