CN102786858B - Flame resistance epoxy resin powder paint - Google Patents
Flame resistance epoxy resin powder paint Download PDFInfo
- Publication number
- CN102786858B CN102786858B CN201210154946.4A CN201210154946A CN102786858B CN 102786858 B CN102786858 B CN 102786858B CN 201210154946 A CN201210154946 A CN 201210154946A CN 102786858 B CN102786858 B CN 102786858B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin powder
- powder coating
- flame resistance
- powder paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of even if also having excellent anti-flammability without using halogenated flame retardant and improve the epoxy resin powder coating of mechanical strength.A kind of Flame resistance epoxy resin powder paint, it is that thermal coefficient of expansion more than the epoxy resin powder coating containing epoxy resin, curing agent, packing material, laser colour former and phosphate flame retardant, the glass transition temperature of above-mentioned epoxy resin powder coating is 10 × 10‑5/ DEG C below.
Description
Technical field
The present invention relates to epoxy resin powder coating.
Background technology
In the past since, for insulating package electric component, the purpose of electronic unit and use epoxy resin powder coating.For
Ensure the security of electric component, electronic unit to fire, also require that such epoxy resin powder coating in insulating package
There is the anti-flammability of height in film.Therefore the various compounds for assigning anti-flammability are coordinated in the composition of powder coating.
As the method for assigning anti-flammability, for example, proposing and implementing following various methods:Reduce flammable resin into
Point, largely coordinate non-flame properties inorganic filling material, it is particularly a large amount of to coordinate containing the crystallization water and discharge the crystallization water in burning
And the method that the inorganic filling materials such as aluminium hydroxide as flame retardant effect or magnesium hydroxide are presented;By epoxy resin flammability
Low organic siliconresin or the resin modified method containing cyanurate ring etc.;What is be most widely implemented is to coordinate various halogen system resistances
Fire the method for agent(Such as patent document 1).
Patent document 1:Japanese Unexamined Patent Publication 6-57101 publications
The content of the invention
The present invention be in view of said circumstances and complete there is provided it is a kind of even if without using halogenated flame retardant also have it is excellent
Anti-flammability and the epoxy resin powder coating for improving mechanical strength.
The present inventor etc. has found that the mechanical strength of epoxy resin powder coating depends on epoxy resin powder coating
Glass transition temperature(Tg)Thermal coefficient of expansion above, so as to complete the present invention.
In order to solve the above problems, a kind of Flame resistance epoxy resin powder paint is provided according to the present invention, is containing epoxy
Resin, curing agent, packing material, the epoxy resin powder coating of laser colour former and phosphate flame retardant,
More than the Tg of above-mentioned epoxy resin powder coating thermal coefficient of expansion is 10 × 10-5/ DEG C below.
In an embodiment of the invention, relative to the quality of above-mentioned epoxy resin powder coating, above-mentioned packing material
For more than 50 mass %.
In an embodiment of the invention, above-mentioned laser colour former contains copper compound or zirconium compounds.
In an embodiment of the invention, above-mentioned packing material is fused silica.
In an embodiment of the invention, above-mentioned curing agent contains acid anhydrides.
In an embodiment of the invention, the modulus of elasticity in static bending of above-mentioned epoxy resin powder coating for 1.0 ×
104More than MPa.
In an embodiment of the invention, the glass transition temperature of above-mentioned epoxy resin powder coating is less than 100 DEG C.
In an embodiment of the invention, above-mentioned epoxy resin powder coating is used for electric component, the bag of electronic unit
Fill film.
Also there is excellent anti-flammability even if without using halogenated flame retardant and improve machinery there is provided a kind of according to the present invention
The epoxy resin powder coating of intensity.
Embodiment
The Flame resistance epoxy resin powder paint to the present invention is illustrated below.In addition, "~" is being not particularly illustrated
In the case of represent with up to following.
The Flame resistance epoxy resin powder paint of the present invention contains epoxy resin, curing agent, packing material, laser colour former
And phosphate flame retardant, and more than Tg thermal coefficient of expansion is 10 × 10-5/ DEG C below.Herein, above-mentioned Tg represents to press
According to JIS C 2161 determine, utilize thermo-mechanical analysis(TMA)The glass transition temperature of method.
As long as the epoxy resin used in the present invention has at least one epoxy radicals and is non-halogenated epoxy in the molecule
Resin and applied to general epoxy resin powder coating be at room temperature solid-state epoxy resin, then can use.As
Such epoxy resin, for example, can enumerate bisphenol A-type, bisphenol-f type, bisphenol S type, phenol novolak type, cresol novolak
Type, biphenyl type, naphthalene type, aromatic series amine type etc., but it is not limited to these.It should illustrate, these can be used alone, can also group
Close multiple use.
The curing agent used in the present invention, can be by various curing agent according to the purpose of application epoxy resin powder coating
It is a variety of alone or in combination to use.For example, can enumerate the aromatic amines such as diaminodiphenyl-methane or anline resin, aliphatic amine and
Condensation product, dicyandiamide and its derivative of aliphatic dicarboxylic acid, various imidazoles or imidazolinium compounds, adipic acid, decanedioic acid, benzene
The poly- dicarboxylic acids such as dioctyl phthalate, maleic acid, trimellitic acid, benzophenone dicarboxylic acids, benzophenone tetrabasic carboxylic acid, Pyromellitic Acid or its
Acid anhydrides, two hydrazides such as adipic acid, phthalic acid, the phenolic aldehyde as phenol, cresols, xylenol, bisphenol-A etc. and the condensation product of aldehyde is clear
Paint class, carboxylic acid amide, methylolated melamine class, block type isocyanide urea esters etc..Wherein, the powder coating obtained from raising
The angle of curing characteristics set out, the curing agent of preferred anhydrides system.
Can be according to the species adjustment curing agent and the ratio of epoxy resin of the epoxy resin and curing agent used.It is preferred that one
As used relative to epoxy resin, curing agent in the scope of 0.6~1.2 equivalent.If above range, then it can obtain good
Curing characteristics.It should illustrate, for these curing agent, tertiary amines, imidazoles, organophosphor chemical combination can also be used as needed
The curing accelerators such as thing, wherein, in order to further improve anti-flammability, preferably use organic phosphorus compound.
Relative to the gross mass of epoxy resin powder coating, the total amount of epoxy resin and curing agent is preferably 10~80 matter
Measure %, more preferably 25~60 mass %.Become good thereby, it is possible to the coating that makes powder coating.If use level is few
In above-mentioned lower limit, then the flatness reduction of film sometimes, on the other hand, if more than above-mentioned higher limit, sometimes in conduct
Curing process after application causes so-called sunburner when burning till(タレ)Or tip(トガリ)Etc bad order.
As the packing material used in the present invention, calcium carbonate, calcium sulfate, barium sulfate, aluminium hydroxide, hydroxide can be enumerated
Magnesium, aluminum oxide, crystallization or fused silica, surface treated silica, talcum, kaolin, clay, mica, dolomite, silicon
Lime stone, glass fibre, bead, zircon, titanium compound, molybdenum compound etc..These can be used alone, can also multiple combinations
Use.Wherein preferred molten silica.
Relative to the gross mass of epoxy resin powder coating, the use level of packing material is preferably the matter of 50 mass %~80
Measure %, the mass % of more preferably 50 mass %~70.Become good thereby, it is possible to the coating that makes powder coating.If coordinated
Amount is less than above-mentioned lower limit, then causes the apparent bad existing of so-called sunburner or tip etc when burning till sometimes
As making the mechanical strength of film also not enough.On the other hand, if more than the flatness reduction of above-mentioned higher limit, sometimes film.
In addition, being not particularly limited as the particle diameter of packing material, generally, it is preferred to be used as average grain diameter using 5~30 μm.
Thereby, it is possible to assign good mobility to powder coating, more improve coating, and then also it is for the mechanical strength of film
It is optimal.
As the laser colour former used in the present invention, metal salt compound is used.As metal salt compound, it can enumerate
The nickel compounds such as lactic acid nickel, nickelous hypophosphite, nickel formate, the copper compound such as copper carbonate, cupric oxalate, the zirconium compounds, lead such as zirconium silicate
Compound etc..These multiple alone or in combination can be used.Wherein, the metallic salt chemical combination in addition to lead compound is preferably used
Thing, more preferably using copper compound or zirconium compounds.Thereby, it is possible to assign sufficient color emissivity with less amount of addition, and
Mitigation carrying capacity of environment can be realized.
The use level of laser colour former is more preferably relative to the gross mass of powder coating, preferably 0.5~20 mass %
0.5~10 mass %.If use level is less than above-mentioned lower limit, color emissivity is not enough sometimes, on the other hand, if more than above-mentioned
Higher limit, then cause being greatly lowered for moisture-proof.
In order to assign sufficient anti-flammability, the preferred phosphorus content of phosphate flame retardant used in the present invention is high and in room temperature
Under be solid-state phosphate flame retardant, such as can enumerate triphenyl or aromatic condensation type phosphate.
Relative to the quality of the epoxy resin used, containing ratio of the phosphate flame retardant preferably with synthesis phosphorus composition is 1
~3 mass %, more preferably with synthesis 2~2.5 mass %.If phosphorus containing ratio is less than above-mentioned lower limit, it can not be filled sometimes
The anti-flammability divided, even if more than above-mentioned higher limit, also not finding the effect for improving anti-flammability imparting more than it sometimes.Separately
Outside, phosphate flame retardant is coordinated by way of with as the phosphorus composition in above range, obtained powder can be improved and applied
The mechanical strengths such as the heat-resisting cyclicity of material.
More than the Tg of Flame resistance epoxy resin powder paint of the invention containing mentioned component thermal coefficient of expansion is 10
×10-5/ DEG C below.The Flame resistance epoxy resin powder paint of the present invention, because more than Tg thermal coefficient of expansion is 10 × 10-5/
Below DEG C, the mechanical strengths such as heat-resisting cyclicity can be improved.The reason is still not clear, but it is believed that being due to and electronic unit
The reason for difference of thermal coefficient of expansion diminishes.
In addition, the lower limit of more than the Tg of the Flame resistance epoxy resin powder paint of present invention thermal coefficient of expansion is without spy
Do not limit, usually 8.5 × 10-5/ DEG C more than, preferably 5 × 10-5/ DEG C more than.
Herein, above-mentioned more than Tg thermal coefficient of expansion is to utilize thermo-mechanical analysis according to JIS C 2161(TMA)Method is surveyed
Fixed value, represents the average value of the thermal coefficient of expansion in the region of Tg~160 DEG C.
In addition, the above-mentioned Tg of the epoxy resin powder coating of the present invention be preferably less than 100 DEG C, be more preferably 95 DEG C with
Under.It is below above-mentioned higher limit, so that the stress for improving epoxy resin powder coating relaxes ability, as a result, can be with by Tg
Improve the heat-resisting cyclicity of epoxy resin powder coating.In addition, the Tg of the epoxy resin powder coating of present invention lower limit does not have
It is particularly limited to, usually more than 60 DEG C.
In addition, the epoxy resin powder coating of the present invention is preferably according to the moduluses of elasticity in static bending determined of JIS K 6911
1.0×104More than MPa.It is more than above-mentioned lower limit, so as to further improve resistance to thermal cycle by the modulus of elasticity in static bending
The mechanical strengths such as property.In addition, the higher limit of the modulus of elasticity in static bending of the epoxy resin powder coating of the present invention is not particularly limited,
Usually 1.3 × 104Below MPa.
The powder coating of the present invention, in addition to composition described above is coordinated, can coordinate as needed pigment, levelling agent,
The additives such as coupling agent, defoamer.In addition, organic siliconresin, melmac etc. can also be used in order to improve anti-flammability
Resin with cyanurate ring skeleton, or the non-halogen such as Firebrake ZB, expansile graphite anti-flammability auxiliary agent.
The Flame resistance epoxy resin powder paint of the present invention can be by suitably selecting above-mentioned each composition and suitably adjusting
The use level of each composition and obtain.
The method that powder coating is manufactured in the present invention is not particularly limited, and can use general method.It is used as an example
Son, after can the material composition that coordinate into regulation ratio of components be sufficiently mixed uniformly using blender, is kneaded with extruder, twin shaft
Machine etc. carries out melting mixing, is ground into appropriate granularity followed by pulverizer and is classified and obtains.
Although being not particularly limited, the epoxy resin powder coating of the present invention can perform well in such as ceramic condenser
The packaging film of the electric components such as device, electronic unit.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to following embodiment.
By the use level shown in table 1(Mass parts)Material composition mixed using blender, after melting mixing, utilize crushing
Machine is crushed, and the epoxy resin powder coating that particle mean size is 40~60 μm is made.By obtained powder coating for following projects
Evaluated.Show the result in following table.
1. epoxy resin
Bisphenol A type epoxy resin:Mitsubishi Chemical Ind's system, " EPIKOTE 1003 "(Epoxide equivalent 720)
Brominated epoxy resin:Chemical company of Nippon Steel system, " EPO TOHTO YDB-400 "(Epoxide equivalent 400)
2. curing agent
·BTDA:Benzophenone tetracarboxylic anhydride
·TMA:Trimellitic anhydride
3. curing accelerator
·TPP:Triphenylphosphine
4. packing material
Fused silica:The gloomy company system of dragon, " RD-8 "(15 μm of average grain diameter)
5. pigment
White pigments(Titanium oxide):Stone originates in industry company system, " TTO-55 "
Blue pigment(Cyanines are blue):Sumitomo chemical company system, " CYANINE BLUE-GH "
6. additive
Silane coupler:GE Toshiba Silicones systems, " A-187 "
Levelling agent:Surface Specialties company systems, MODAFLOW POWDER
7. fire retardant
Phosphate:Big eight chemical company system, " PX-200 "(The mass % of phosphorus containing ratio 8.9)
Antimony trioxide
8. laser colour former
Nickelous hypophosphite
Copper compound
Zirconium compounds
9. ion capturing agent
Hydrotalcite:Coordinate chemical industrial company's system, " DHT-4A "
(Test method)
1. gelation time:According to JIS C 2161, determined with 165 DEG C of hot plates.
2. flame retardant test:Experiment plate thickness is set to 0.8mm, determined according to UL94 methods.
3. glass transition temperature(Tg):According to JIS C 2161, determined with TMA methods.
4. thermal coefficient of expansion(Below Tg ,/DEG C):According to JIS C 2161, determined with TMA methods, and calculate 30 DEG C~Tg's
The average value of thermal coefficient of expansion in region.
5. thermal coefficient of expansion(More than Tg ,/DEG C):According to JIS C 2161, determined with TMA methods, and calculate Tg~160 DEG C
The average value of thermal coefficient of expansion in region.
6. bending strength(MPa):According to JIS K 6911, determined with bending strength.
7. heat-resisting cyclicityUse with more than thickness 0.75mm
The electronic unit of powder body coating is carried out, the presence or absence of crack is confirmed.
8. heat-resisting cyclicityUse with more than thickness 0.75mm
The electronic unit of powder body coating is carried out, the presence or absence of crack is confirmed.
9. the modulus of elasticity in static bending(MPa):The modulus of elasticity in static bending is determined according to JIS K 6911.
Table 1
More than the Tg of the epoxy resin powder coating of embodiment thermal coefficient of expansion is 10 × 10-5/ DEG C below.It is such
Epoxy resin powder coating existsThermal cycling test in, possess 2500 with
On heat-resisting cyclicity; Thermal cycling test in possess more than 1500
Heat-resisting cyclicity, and possess more than 110MPa bending strength and 1.0 × 104More than the MPa modulus of elasticity in static bending.
On the other hand, the powder coating of the comparative example containing brominated epoxy resin, Thermal cycling test in, heat-resisting cyclicity be less than 500; Thermal cycling test in, heat-resisting cyclicity be less than 500.In addition, the split of comparative example is applied
The bending strength of material is less than 110MPa and the modulus of elasticity in static bending is less than 1.0 × 104MPa。
Claims (5)
1. a kind of Flame resistance epoxy resin powder paint, it is characterised in that
It is the epoxy resin powder containing epoxy resin, curing agent, packing material, laser colour former and phosphate flame retardant
Coating,
The packing material includes fused silica,
The thermal coefficient of expansion more than glass transition temperature of the epoxy resin powder coating is 10 × 10-5/ DEG C below,
The glass transition temperature of the epoxy resin powder coating is less than 100 DEG C,
Relative to the quality of the epoxy resin powder coating, the packing material is more than 50 mass %.
2. Flame resistance epoxy resin powder paint as claimed in claim 1, wherein, the laser colour former contains copper compound
Or zirconium compounds.
3. Flame resistance epoxy resin powder paint as claimed in claim 1, wherein, the curing agent contains acid anhydrides.
4. Flame resistance epoxy resin powder paint as claimed in claim 1, wherein, the bending of the epoxy resin powder coating
Modulus of elasticity is 1.0 × 104More than MPa.
5. Flame resistance epoxy resin powder paint as claimed in claim 1, wherein, the epoxy resin powder coating is used for electricity
The packaging film of gas part, electronic unit.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-111065 | 2011-05-18 | ||
JP2011111065 | 2011-05-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102786858A CN102786858A (en) | 2012-11-21 |
CN102786858B true CN102786858B (en) | 2017-09-01 |
Family
ID=47152455
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210154946.4A Active CN102786858B (en) | 2011-05-18 | 2012-05-17 | Flame resistance epoxy resin powder paint |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP5949116B2 (en) |
CN (1) | CN102786858B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6349836B2 (en) * | 2014-03-25 | 2018-07-04 | 住友ベークライト株式会社 | Epoxy resin powder coating for varistor and varistor |
CN103965737A (en) * | 2014-05-09 | 2014-08-06 | 福建万安实业有限公司 | Flame retardant powder coating |
KR102255191B1 (en) | 2016-08-26 | 2021-05-24 | 다이킨 고교 가부시키가이샤 | Powder coatings, laminates and tubes |
CN107629378A (en) * | 2017-11-05 | 2018-01-26 | 包红珠 | A kind of oil plant of gas square diffuser |
CN114230202B (en) * | 2022-01-20 | 2023-08-01 | 漳州市瑞隆达工贸有限公司 | Preparation process of hollow glass |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004292765A (en) * | 2003-03-28 | 2004-10-21 | Sumitomo Bakelite Co Ltd | Flame resistant epoxy resin powder coating material for laser printing |
CN1730548A (en) * | 2004-08-06 | 2006-02-08 | 株式会社日本触媒 | Resin composition, method of its composition, and cured formulation |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5463300A (en) * | 1975-06-23 | 1979-05-22 | Hitachi Ltd | Manufacrure of electric device |
JPS60115619A (en) * | 1983-11-28 | 1985-06-22 | Toray Silicone Co Ltd | Thermosetting epoxy resin composition |
JPS61283671A (en) * | 1985-06-11 | 1986-12-13 | Sumitomo Bakelite Co Ltd | Electrical insulating paint |
JPH0781103B2 (en) * | 1986-01-17 | 1995-08-30 | 日本インシュレーション株式会社 | Fireproof paint |
JPH068380B2 (en) * | 1990-11-16 | 1994-02-02 | 住友ベークライト株式会社 | Epoxy resin composition suitable for carbon dioxide laser printing |
WO2006006593A1 (en) * | 2004-07-13 | 2006-01-19 | Hitachi Chemical Co., Ltd. | Epoxy resin molding material for sealing and electronic component device |
JP5024205B2 (en) * | 2007-07-12 | 2012-09-12 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
CN101148457A (en) * | 2007-11-02 | 2008-03-26 | 湖南大学 | Phosphorus-containing tri-functional group liquid alicyclic epoxy compound and preparation method thereof |
JP5396740B2 (en) * | 2008-05-07 | 2014-01-22 | 日立化成株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
-
2012
- 2012-05-08 JP JP2012106744A patent/JP5949116B2/en active Active
- 2012-05-17 CN CN201210154946.4A patent/CN102786858B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004292765A (en) * | 2003-03-28 | 2004-10-21 | Sumitomo Bakelite Co Ltd | Flame resistant epoxy resin powder coating material for laser printing |
CN1730548A (en) * | 2004-08-06 | 2006-02-08 | 株式会社日本触媒 | Resin composition, method of its composition, and cured formulation |
Also Published As
Publication number | Publication date |
---|---|
CN102786858A (en) | 2012-11-21 |
JP2012255139A (en) | 2012-12-27 |
JP5949116B2 (en) | 2016-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101480178B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same | |
TWI638850B (en) | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device | |
CN102786858B (en) | Flame resistance epoxy resin powder paint | |
TWI403552B (en) | Epoxy resin composition for sealing semiconductor and semiconductor device | |
KR101362887B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
KR101854501B1 (en) | Composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
JP6886770B2 (en) | Epoxy resin composition for sealing semiconductor devices and semiconductor packages sealed using this | |
KR101309820B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same | |
JP5310472B2 (en) | High heat-resistant aluminum hydroxide particles, production method thereof, resin composition containing the particles, and printed wiring board using the resin composition | |
KR101557538B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
KR101309822B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
JP5310471B2 (en) | High heat-resistant aluminum hydroxide particles, production method thereof, resin composition containing the particles, and printed wiring board using the resin composition | |
JP2015183121A (en) | Epoxy resin powder coating for varistor and varistor | |
TWI473856B (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same | |
KR101557537B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
JPH09255812A (en) | Resin composition | |
KR100882332B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same | |
TW200936500A (en) | Silica powder, process for its production and its use | |
JP2697510B2 (en) | Epoxy resin composition for semiconductor encapsulation | |
KR20160028090A (en) | Epoxy resin composition for encapsulating semicondouctor device and semiconductor device encapsulated by using the same | |
JPS5817214B2 (en) | Acid anhydride-based heat-resistant curing agent composition | |
JP2004292765A (en) | Flame resistant epoxy resin powder coating material for laser printing | |
KR100917662B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same | |
JP4622428B2 (en) | Epoxy resin powder coating and manufacturing method thereof | |
KR100882333B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |