CN106867366B - Highly effective flame-retardant epoxy coating - Google Patents
Highly effective flame-retardant epoxy coating Download PDFInfo
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- CN106867366B CN106867366B CN201710066384.0A CN201710066384A CN106867366B CN 106867366 B CN106867366 B CN 106867366B CN 201710066384 A CN201710066384 A CN 201710066384A CN 106867366 B CN106867366 B CN 106867366B
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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
- C09D163/04—Epoxynovolacs
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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
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses be related to epoxy coating technical field, more particularly to a kind of highly effective flame-retardant epoxy coating, it is made of the raw material of following weight fraction ratio: 30~40 parts of epoxy resin, 20~30 parts of polyurethane modified epoxy resin, 10~15 parts of curing agent, 5~10 parts of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, 15~20 parts of filler, balance of solvent.The formula of highly effective flame-retardant epoxy coating provided by the invention is reasonable, the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing is added in coating system, one side fire retardant has stronger surface migration, a kind of high flame retardant film can be formed in substrate surface, on the other hand, when flame retardant agent content reaches 5-10%, solidfied material can achieve UL94, V-0 grades, good flame retardation effect, conducive to being widely popularized.
Description
Technical field
The present invention relates to epoxy coating technical fields, and in particular to a kind of highly effective flame-retardant epoxy coating.
Background technique
Wiring board is the substrate for carrying electronic component, it is bound fraction indirect material on the basis of direct material, is led to
Cross what the tool of production completed the process.Wherein, direct material, which refers to, is directly used on product in production or directly connects with product
The main material of touching；Indirect material refers in production indirectly using the secondary material on product or with product mediate contact.
In wiring board production there are three types of most important direct materials, i.e. substrate, prepreg and copper foil.Substrate (core/laminte) is
It is suppressed by prepreg and copper foil.Prepreg is then to combine different strengthening material and filler system by resin, glass cloth
It makes.
On requiring fire-retardant electronic equipment, it is also necessary to which fire-retardant circuit board, these circuit boards are all to be coated with flame-retarded resin
Laminate.Epoxide resin material is because having many special energy outstanding, such as preferable thermal stability, insulating properties, adhesion, anti-corruption
Corrosion and good mechanical property are widely used in the fields such as electronics, electric appliance, and then become currently the most important ones electron chemistry
Material it.However, its oxygen index (OI) is not high, and only 20% or so, belong to flammability substance, its flame retardant property need to usually be changed
Good raising.Common flame resistant method first is that introducing the halogens such as chlorine, the bromine with fire retarding effect in the epoxy to mention
The flame retardant property of high epoxy resin solidfied material.In recent years, people have carried out big in terms of the anti-flammability for improving epoxide resin material
Amount and in-depth study.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviation DOPO contain P-H key in structure, to alkene
Hydrocarbon, epoxide and the great activity of carbonyls can react and generate many derivatives.DOPO and its derivative are due to molecule
Contain cyclohexyl biphenyl, phenanthrene ring, O=P-O key in structure, so there is stronger flame retardant property than common organophosphorus ester.By
Saito reported its synthetic route in 1972 for the first time.DOPO and its derivative can be used as response type and additive flame retardant, close
At fire retardant Halogen, smokeless, nontoxic, do not migrate, flame retardant property is lasting.While improving the flame retardant property of material, not shadow
Ring the mechanical performances such as the mechanical strength of material.It can be used for the multiple materials such as polyamide, linear polyester, polyurethane, epoxy resin
Flame retardant treatment, foreign countries are widely used in the fire-retardant of materials such as pressurized layer, circuit board in plastics for electronics, brass.
Although having good flame retardant property that can bring one to the performance of material itself with the increase of additional amount
A little detrimental effects.
Summary of the invention
In view of the above deficiencies, the object of the present invention is to provide a kind of formulas rationally, the highly effective flame-retardant ring of good flame resistance
Oxygen cold coating.The surface migration sex flame retardant of Nitrogen-and Phosphorus-containing is added in coating system, one side fire retardant has stronger
Surface migration can form a kind of high flame retardant film in substrate surface, on the other hand, when flame retardant agent content reaches 5~10%,
Solidfied material can achieve UL94, and V-0 grades.
To achieve the above object, the technical solution provided by the present invention is:
It is made of the raw material of following weight fraction ratio:
As an improvement of the present invention, the epoxy resin is bisphenol A epoxide resin, o-cresol formaldehyde epoxy resin or phenol
Formaldehyde epoxy resin.
As an improvement of the present invention, the polyurethane modified epoxy resin is SL3403.
As an improvement of the present invention, the curing agent is hexamethylenetetramine and bismaleimide.
As an improvement of the present invention, the surface migration sex flame retardant structural formula of the Nitrogen-and Phosphorus-containing are as follows:
The wherein preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, includes the following steps:
(1) bis- (3- aminophenyl) hexafluoropropane of 2,2- and pentafluorobenzaldehyde are heated in a solvent, after reaction, is obtained
Reaction system containing intermediate product I；
(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction,
Washing, drying, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.
Its reaction process are as follows:
Specifically, bis- (3- aminophenyl) hexafluoropropane of 2,2- and the molar ratio of pentafluorobenzaldehyde are in the step (1)
1:2.The reaction time is 8~10h in the step (1).Heating temperature is 62~68 DEG C in the step (1), preferably, heating
Temperature is preferably 65 DEG C.Solvent is ethyl alcohol, DMF or DMSO in the step (1).The additional amount of solvent is in the step (1)
6~12 times of bis- (3- aminophenyl) hexafluoropropane of 2,2- and pentafluorobenzaldehyde quality sum.
Specifically, the molar ratio of the DOPO in the step (2) and the pentafluorobenzaldehyde in step (1) is 1:1.The step
Suddenly the reaction temperature in (2) is 62~68 DEG C, preferably, heating temperature is preferably 65 DEG C.Reaction time in the step (2)
For 4~6h.
As an improvement of the present invention, the filler is calcium carbonate or silica.
As an improvement of the present invention, the solvent is dimethylbenzene or ethyl acetate.
The invention has the benefit that the formula of highly effective flame-retardant epoxy coating provided by the invention is reasonable, introduce
The surface migration sex flame retardant of Nitrogen-and Phosphorus-containing can make fire retardant have certain surface migration in solidfied material, make to solidify
The content of fire retardant gradually increases from inside to outside in object, makes solidfied material surface highest containing flame retardant amount, keeps its additive amount low, fire-retardant
Excellent effect；And fluorine element is introduced on fire retardant, but free radical cannot be effectively captured since C-F key is too strong, make
Fire retardant has excellent thermal stability；With the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases；Work as fire retardant
When content reaches 5~10% (phosphorus content 0.25wt%-0.5wt%), solidfied material can achieve UL-94, and V-0 grades, fire-retardant effect
Fruit is good.
Below with reference to embodiment, the present invention is further described.
Detailed description of the invention
Fig. 1 is nuclear magnetic spectrogram of the invention.
Specific embodiment
Embodiment 1, a kind of highly effective flame-retardant epoxy coating provided in the present embodiment, by following weight fraction ratio
Raw material composition: 30 parts of o-cresol formaldehyde epoxy resin, 30 parts of polyurethane modified epoxy resin (SL3403), hexamethylenetetramine 10
Part, 10 parts of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, 15 parts of calcium carbonate, 5 parts of dimethylbenzene.
Wherein, the surface migration sex flame retardant structural formula of Nitrogen-and Phosphorus-containing are as follows:
Wherein, the synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) 145g by the pentafluorobenzaldehyde of bis- (3- aminophenyl) hexafluoropropane of the 2,2- of 11.1g and 13.1g at 65 DEG C
8h is heated in ethyl alcohol, after reaction, obtains the reaction system containing intermediate product I；
(2) DOPO of 14.4g is added in the reaction system containing intermediate product I that step (1) obtains in 65 DEG C of items
4h is heated under part, and after reaction, washing, drying obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 83.4%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-N characteristic peak 1288cm-1, P-O-C characteristic peak 1032cm-1,
P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1212cm-1。
Nuclear magnetic spectrogram as shown in Figure 1, nuclear-magnetism test result is as follows:
1H-NMR (400MHz, DMSO-d6) δ 7.50 (k, 2H), 7.30-7.31 (j, 6H), 7.20 (i, 2H), 7.05 (g,
2H), 6.91 (f, 4H), 6.88 (e, 2H), 6.79 (d, 2H), 6.35 (c, 4H), 4.00 (b, 2H), 3.90 (a, 2H).
Embodiment 2-6 is substantially the same manner as Example 1, the difference is that table 1；Comparative example 1-3 and the basic phase of embodiment 3
Together, the difference is that table 1:
Table 1.
Application Example:
A kind of highly effective flame-retardant epoxy coating paint film property of embodiment 1-4 and comparative example 1-3 is tested such as 2 institute of table
Show:
Table 2.
UL94 is carried out to a kind of highly effective flame-retardant epoxy coating paint film of embodiment 1-4 and comparative example 1-3 vertically to fire
Test is burnt, as a result shown in table 3:
Table 3.
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention cannot enumerate out whole embodiment party
Formula, all technical solutions using one of above-described embodiment, or the equivalent variations done according to above-described embodiment are protected in the present invention
It protects in range.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.Such as the present invention
Described in above-described embodiment, using other coating obtained from same or similar method and component in the scope of the present invention
It is interior.
Claims (6)
1. a kind of highly effective flame-retardant epoxy coating, which is characterized in that it is made of the raw material of following weight fraction ratio:
The surface migration sex flame retardant structural formula of the Nitrogen-and Phosphorus-containing are as follows:
2. highly effective flame-retardant epoxy coating according to claim 1, it is characterised in that: the epoxy resin is bis-phenol
A epoxy resin or novolac epoxy resin.
3. highly effective flame-retardant epoxy coating according to claim 1, it is characterised in that: the polyurethane modified epoxy
Resin is SL3403.
4. highly effective flame-retardant epoxy coating according to claim 1, it is characterised in that: the curing agent is six first
Urotropine and bismaleimide.
5. highly effective flame-retardant epoxy coating according to claim 1, it is characterised in that: the filler be calcium carbonate or
Silica.
6. highly effective flame-retardant epoxy coating according to claim 1, it is characterised in that: the solvent be dimethylbenzene or
Person's ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710066384.0A CN106867366B (en) | 2017-02-07 | 2017-02-07 | Highly effective flame-retardant epoxy coating |
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|---|---|---|---|
| CN201710066384.0A CN106867366B (en) | 2017-02-07 | 2017-02-07 | Highly effective flame-retardant epoxy coating |
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| CN106867366A CN106867366A (en) | 2017-06-20 |
| CN106867366B true CN106867366B (en) | 2019-08-13 |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897702B2 (en) * | 2008-11-24 | 2011-03-01 | Chung-Shan Institute Of Science And Technology, Armaments Bureau, Ministry Of National Defense | Epoxy resin, curing agent and 9,10-Dihydro-9-oxa-10-phosphaphenanthrene derivative |
| CN101705744B (en) * | 2009-11-02 | 2011-02-09 | 嘉兴学院 | Epoxy terrace material and preparation method thereof |
| CN101891896B (en) * | 2010-07-07 | 2012-08-22 | 安徽建筑工业学院 | Expansible fire retardant containing fluorine-phosphorus-nitrogen oligomer and preparation method thereof |
| CN103387589B (en) * | 2013-07-31 | 2015-10-21 | 中国科学技术大学 | Phosphorous acid esters halogen-free flame retardants of a kind of phosphorus-nitrogen containing silane A, Nitrogen-and Phosphorus-containing silicon and preparation method thereof |
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