CN100590168C - Composite epoxy type electron packaging material and preparation method thereof - Google Patents
Composite epoxy type electron packaging material and preparation method thereof Download PDFInfo
- Publication number
- CN100590168C CN100590168C CN200710027674A CN200710027674A CN100590168C CN 100590168 C CN100590168 C CN 100590168C CN 200710027674 A CN200710027674 A CN 200710027674A CN 200710027674 A CN200710027674 A CN 200710027674A CN 100590168 C CN100590168 C CN 100590168C
- Authority
- CN
- China
- Prior art keywords
- naphthalenediol
- component
- epoxy resin
- epoxy
- bisphenol
- 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.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a compound epoxy electric encapsulation material and its producing method. The inventive epoxy electric encapsulation material contains X and Y constituents; in which, said Xconstituent is composed of following components by weight: 100 shares of epoxide resin, 0-20 shares of epoxy alkyl organic silicon coupling agent, 0-200 shares of inorganic silicon dioxide filling; said Y constituent is composed of following components by weight: 0-40 shares of naphthalenediol, 0-40 shares of formaldehyde condensate of naphthalenediol, 1-30 shares of reactive phosphorus containedflame retardent, 5-50 shares of curing agent, aminomethane organic silicon coupling agent, in which the dose of naphthalenediol and the formaldehyde condensate of naphthalenediol are not simultaneously zero. The inventive compound epoxy electric encapsulation material has a high heat resistance, a low moisture absorption and an environment-friendly flame retardancy.
Description
Technical field
The present invention relates to that a kind of tool is heat-resisting, the composite epoxy type electron packaging material of the contour performance of environmental protection flame retardant and preparation method thereof.
Background technology
Resins, epoxy has excellent physical and mechanical properties and electric property, is widely used in coating, tackiness agent, electronic package material etc.Resins, epoxy is one of its most important purposes as electronic package material.The present age, development of electronic technology was particularly had higher requirement to its thermotolerance, wet fastness, environmental protection flame retardant and mechanical property aspect to the performance of Resins, epoxy.At present both at home and abroad as the Resins, epoxy of electronic polymer material the most frequently used mainly be dihydroxyphenyl propane or F type Resins, epoxy and novolac epoxy.Bisphenol A-type and bisphenol f type epoxy resin have good physical strength, electrical insulating property etc., but also exist thermotolerance deficiency, water absorbability to cross high technical vulnerability, can not satisfy the performance requriements of hyundai electronics industry to polymer materials.Novolac epoxy has advantages such as good, the difficult combustion of mechanical strength height, electrical insulation capability, but exist hard and crisp, and poor heat resistance, shortcoming that water-absorbent is high.Another key property of epoxy type electron packaging material is its flame retardant resistance.In order to give this resinoid flame retardant resistance, generally adopt halogenide, for example the epoxy bromide.Though halogenide has good flame retardant resistance, they can form deleterious halogenide such as hydrogen halide, many bromines dibenzodioxine and furans because of decomposition, cause problem of environmental pollution etc.Therefore, all be to replace halogenide at present both at home and abroad, to reach the purpose of environmental protection flame retardant with phosphonium flame retardant.
Summary of the invention
Purpose of the present invention is the above-mentioned shortcoming and defect that overcomes existing electronic package material, and a kind of thermotolerance height, water-absorbent is low and environmental protection flame retardant is good composite epoxy type electron packaging material and preparation method thereof are provided.
Composite epoxy type electron packaging material provided by the present invention comprises X component and Y component; Wherein, described X component is made up of the component of following weight part:
100 parts of Resins, epoxy, 0～20 part of oxirane base class organo-silicon coupling agent, 0～200 part of inorganic silicon dioxide filler;
Described Y component is made up of the component of following weight part:
0～40 part of the formaldehyde condensation products of 0～40 part of naphthalenediol, naphthalenediol, 1～30 part of response type phosphonium flame retardant, 5～50 parts in solidifying agent, 0～10 part of aminoalkyl class organo-silicon coupling agent, wherein, the formaldehyde condensation products consumption of naphthalenediol, naphthalenediol is not 0 simultaneously;
Wherein: the Resins, epoxy in the described X component is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy or the phosphorous epoxy resin; Wherein said phosphorous epoxy resin is the basic phenyl phosphate ester of two (3-Racemic glycidol oxygen) phenylphosphine oxides or two (3-Racemic glycidol); The molecular weight of the basic phenyl phosphate ester of described two (3-Racemic glycidol oxygen) phenylphosphine oxides or two (3-Racemic glycidol) is 150～2000; Described novolac epoxy is linear o-cresol formaldehyde epoxy resin or linear phenolic epoxy resin;
Oxirane base class organo-silicon coupling agent in the described X component is γ-glycidoxy Trimethoxy silane or methyl (γ-glycidoxy) diethoxy silane;
Inorganic silicon dioxide filler fineness in the described X component is selected from 50～3000 orders, is preferably 500～800 orders.
Naphthalenediol in the described Y component is 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol or 2,2 '-dihydroxyl-1,1 '-dinaphthalene;
Response type phosphonium flame retardant in the described Y component is 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound, phenolic varnish, two (3-aminophenyl) phenyl phosphine oxide or three (3-amine phenyl) phosphine oxide;
Solidifying agent in the described Y component is arylamine class solidifying agent, dicyandiamide class solidifying agent or phenolic solidifying agent; Wherein said arylamine class solidifying agent is diaminodiphenyl-methane, diaminodiphenylsulfone(DDS) or mphenylenediamine, and described dicyandiamide class solidifying agent is a dicyandiamide, and described phenolic solidifying agent is linear phenolic resin or resol;
Aminoalkyl class organo-silicon coupling agent in the described Y component is γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane or anilinomethyl trimethoxy silane.
A kind of composite epoxy type electron packaging material of the present invention, the preferred weight ratio of described X component and Y component is 100: 10～100.
A kind of composite epoxy type electron packaging material of the present invention, the Resins, epoxy in the wherein said X component preferably is made up of following parts by weight of component:
0～100 part of bisphenol A type epoxy resin, 0～100 part of bisphenol f type epoxy resin, 0～100 part of novolac epoxy, 5～50 parts of phosphorous epoxy resins, wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy consumption are not 0 simultaneously;
Wherein: the oxirane value of described bisphenol A type epoxy resin is preferably 0.01～0.58mol/100g, more preferably 0.40～0.54mol/100g;
The oxirane value of described bisphenol f type epoxy resin is preferably 0.40～0.80mol/100g, and molecular weight is preferably 312～2500, and oxirane value is 0.47～0.63mol/100g more preferably;
The oxirane value of described novolac epoxy is preferably 0.40～0.80mol/100g, more preferably 0.47～0.57mol/100g.
A kind of composite epoxy type electron packaging material of the present invention, the oxirane value of wherein said linear o-cresol formaldehyde epoxy resin or linear phenolic epoxy resin is preferably 0.40～0.80mol/100g, and molecular weight is preferably 200～3000.
The preparation method of a kind of composite epoxy type electron packaging material provided by the present invention may further comprise the steps:
(1) preparation of X component:
It is compound at 50～100 ℃ to take off the row material by weight: 0～100 part of bisphenol A type epoxy resin, 0～100 part of bisphenol f type epoxy resin, 0～100 part of novolac epoxy, 5～50 parts of phosphorous epoxy resins, 1～5 part of oxirane base class organo-silicon coupling agent, 0～200 part of inorganic silicon dioxide filler; Wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy consumption can not be 0 simultaneously;
(2) preparation of Y component:
It is compound at 20～100 ℃ to take off the row material by weight: 0～40 part of the formaldehyde condensation products of 0～40 part of naphthalenediol, naphthalenediol, 1～30 part of response type phosphonium flame retardant, 5～50 parts in solidifying agent, 1～5 part of aminoalkyl class organo-silicon coupling agent; Wherein, the formaldehyde condensation products consumption of naphthalenediol, naphthalenediol can not be 0 simultaneously;
(3) be that 100: 10～100 ratio is compound by weight with X component and Y component, solidified 0.5～1.5 hour down at 85 ℃～95 ℃ then, solidified 1.5～2.5 hours down at 110 ℃～130 ℃ again, solidified 1.5～2.5 hours down at 140 ℃～160 ℃ then, solidify 1.5～2.5 hours promptly down at 170 ℃～190 ℃ at last.
The present invention also provides the formaldehyde condensation products of naphthalenediol used in a kind of composite epoxy type electron packaging material.The formaldehyde condensation products of described naphthalenediol has following structural:
Wherein R=-OH or
Wherein: m=0～100.
The present invention also provides a kind of preparation method of formaldehyde condensation products of above-mentioned naphthalenediol; may further comprise the steps: under the nitrogen protection; under the nitrogen protection; get 100 parts of naphthalenediols by weight, 37% 200～400 parts of 20～40 parts of formalins, solvent MIBK, catalyzer p-methyl benzenesulfonic acid are 0.2%～0.8% of naphthalenediol quality; above-mentioned substance is mixed; under 110 ℃～120 ℃, react after 5～6 hours, promptly get the formaldehyde condensation products of naphthalenediol through washing, desolventizing.
Wherein, described naphthalenediol is preferred 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 2,2 '-dihydroxyl-1, one or several in 1 '-dinaphthalene.
Below by form beneficial effect of the present invention is described:
Table 1: the one-tenth of composite epoxy type electron packaging material of the present invention is grouped into and performance
| X component (parts by weight) | Y component (parts by weight) | Tensile strength (Mpa) | The temperature of thermal weight loss 50%, (℃) | Flame retardant resistance limiting oxygen index(LOI) (LOI) | Water-intake rate (%) |
| 100 parts | Fill a prescription 1 18 parts | 59.5 | 385 | 21.2 | 1.28 |
| 100 parts | Fill a prescription 2 25 parts | 54.6 | 391 | 27.6 | 0.96 |
| 100 parts | Fill a prescription 3 30 parts | 55.7 | 393 | 26.8 | 0.92 |
| 100 parts | Fill a prescription 4 24 parts | 52.6 | 396 | 27.4 | 0.87 |
Annotate: 1, tensile strength is tested with reference to method shown in the GB1040-79;
2, thermal weight loss is tested with reference to method shown in the GB13021-91;
3, flame retardant resistance is tested with reference to method shown in the GB2406-80;
4, water-absorbent is tested with reference to method shown in the GB1034-86.
The condition of cure of listed composite epoxy type electron packaging material is in the table 1: 90 ℃ solidified 1 hour earlier, solidified 2 hours at 120 ℃ then, and 150 ℃ solidified 2 hours, and last 180 ℃ solidified 2 hours.
X component prescription is in the table 1:
Bisphenol A type epoxy resin (oxirane value is 0.45mol/100g): 70 parts
Novolac epoxy (oxirane value is 0.47mol/100g): 30 parts
Inorganic silicon dioxide filler: 100 parts
γ one glycidoxy Trimethoxy silane organo-silicon coupling agent: 0.5 part
Y component prescription 1 is in the table 1:
Diaminodiphenyl-methane: 22.6 parts
γ-An Bingjisanyiyangjiguiwan organo-silicon coupling agent: 3 parts
Y component prescription 2 is in the table 1:
2,7-naphthalenediol: 10 parts
9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound: 15 parts
Diaminodiphenyl-methane: 20.4 parts
γ-An Bingjisanyiyangjiguiwan organo-silicon coupling agent: 3 parts
Y component prescription 3 is in the table 1:
2, the formaldehyde condensation products of 7-naphthalenediol: 15 parts
10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound:
24 parts
Diaminodiphenyl-methane: 19.4 parts
γ-An Bingjisanyiyangjiguiwan organo-silicon coupling agent: 3 parts
Y component prescription 4 is in the table 1:
1,6-naphthalenediol: 9 parts
9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound: 16 parts
Diaminodiphenyl-methane: 20.7 parts
γ-An Bingjisanyiyangjiguiwan organo-silicon coupling agent: 3 parts
Every performance from the listed composite epoxy type electron packaging material of the present invention of table 1, the Y component contains the prescription of reactive phosphonium flame retardant, the flame retardant resistance limiting oxygen index(LOI) is significantly improved, and illustrates that the adding of reactive flame retardant has improved the flame retardant properties of epoxy resin cured product really.In addition, containing 2,7-naphthalenediol, 1,6-naphthalenediol, 2, the prescription of 7-naphthalenediol formaldehyde condensation products, resistance toheat and low water absorbable can all be greatly increased, and have demonstrated fully technology of the present invention and have improved effect, have reached that the invention tool is heat-resisting, the purpose of the composite epoxy type electron packaging material of the contour performance of environmental protection flame retardant.
Table 2: composite epoxy type electron packaging material of the present invention become to be grouped into and performance
| X component (parts by weight) | Y component (parts by weight) | Tensile strength (Mpa) | The temperature of thermal weight loss 50%, (℃) | Flame retardant resistance limiting oxygen index(LOI) (LOI) | Water-intake rate (%) |
| Fill a prescription 1 100 | Fill a prescription 1 19 | 53.6 | 393 | 21.5 | 1.08 |
| Fill a prescription 1 100 | Fill a prescription 2 19 | 59.7 | 396 | 22.7 | 0.93 |
| Fill a prescription 2 100 | Fill a prescription 2 19 | 58.3 | 398 | 27.1 | 0.91 |
| Fill a prescription 2 100 | Fill a prescription 3 27 | 57.8 | 401 | 29.2 | 0.92 |
The condition of cure of listed composite epoxy type electron packaging material is in the table 2: 90 ℃ solidified 1 hour earlier, solidified 2 hours at 120 ℃ then, and 150 ℃ solidified 2 hours, and last 180 ℃ solidified 2 hours.
X component prescription 1 is in the table 2:
Bisphenol A type epoxy resin (oxirane value is 0.51mol/100g): 80 parts
Novolac epoxy (oxirane value is 0.43mol/100g): 20 parts
Inorganic silicon dioxide filler: 100 parts
X component prescription 2 is in the table 2:
Bisphenol A type epoxy resin (oxirane value is 0.51mol/100g): 80 parts
Novolac epoxy (oxirane value is 0.43mol/100g): 20 parts
Phosphorous epoxy resin: 8 parts
Inorganic silicon dioxide filler: 100 parts
Y component prescription 1 is in the table 2:
2,7-naphthalenediol: 10 parts
Diaminodiphenylsulfone(DDS): 27.6 parts
Y component prescription 2 is in the table 2:
2,7-naphthalenediol: 10 parts
Diaminodiphenylsulfone(DDS): 27.6 parts
Anilinomethyl triethoxysilane organo-silicon coupling agent: 3 parts
Y component prescription 3 is in the table 2:
2,7-naphthalenediol: 10 parts
Diaminodiphenylsulfone(DDS): 27.6 parts
Anilinomethyl triethoxysilane: 3 parts
9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound: 16 parts
Every performance from the listed composite epoxy type electron packaging material of the present invention of table 2, the adding of organo-silicon coupling agent, under the situation that contains the inorganic silicon dioxide filler, help improving the performance of the mechanical property, thermotolerance, water-intake rate etc. of composite epoxy type electron packaging material.Obviously, the adding of organo-silicon coupling agent by the bonding action of coupling agent functional group, has increased the bonding action between Resins, epoxy and the inorganic silicon dioxide filler, helps to improve every performance of composite epoxy type electron packaging material.Simultaneously, we can see in the X component and introduce phosphorous epoxy resin, can play the effect that improves the composite epoxy type electron packaging material flame retardant properties equally.When X component and Y component are introduced phosphorus element-containing simultaneously, flame retardant effect the best.Therefore the present invention introduces phosphorus element-containing by adopting phosphorous epoxy resin and response type phosphonium flame retardant, has both reached the purpose of environment-friendly flame retardant, keeps even improved other performance of electronic package material again.
In sum, the composite epoxy type electron packaging material that the present invention obtains has better toughness, thermotolerance, environmental protection flame retardant, lower advantageous properties such as water-intake rate.In addition, present method technology is simple relatively, and cost is cheap relatively, helps large-scale popularization and uses and industrialization.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1 composite epoxy type electron packaging material of the present invention and preparation method thereof
(1) preparation of X component:
By weight in that to take off the row material compound at 50～100 ℃: 0～100 part of bisphenol A type epoxy resin, bisphenol f type epoxy resin: 0～100 part, 0～100 part of novolac epoxy, 5～50 parts of phosphorous epoxy resins, 1～5 part of oxirane base class organo-silicon coupling agent, 0～200 part of inorganic silicon dioxide filler; Wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy consumption can not be 0 simultaneously;
(2) preparation of Y component:
By weight in that to take off the row material down compound at 20～100 ℃: 0～40 part of the formaldehyde condensation products of 0～40 part of naphthalenediol, naphthalenediol, 1～30 part of response type phosphonium flame retardant, 5～50 parts in solidifying agent, 1～5 part of aminoalkyl class organo-silicon coupling agent; Wherein, the formaldehyde condensation products consumption of naphthalenediol, naphthalenediol can not be 0 simultaneously;
(3) be that 100: 10～100 ratio is compound by weight with X component and Y component, solidified 0.5～1.5 hour down at 85 ℃～95 ℃ then, solidified 1.5～2.5 hours down at 110 ℃～130 ℃ again, solidified 1.5～2.5 hours down at 140 ℃～160 ℃ then, solidify 1.5～2.5 hours promptly down at 170 ℃～190 ℃ at last.
Formaldehyde condensation products of embodiment 2 naphthalenediols and preparation method thereof
Under the nitrogen protection; get 100 parts of naphthalenediols, 37% 20～40 parts of formalins, solvent MIBK200～400 part by weight, the catalyzer p-methyl benzenesulfonic acid is 0.2%～0.8% of a naphthalenediol quality; above-mentioned substance is mixed; under 110 ℃～120 ℃; react after 5～6 hours, promptly get the formaldehyde condensation products of naphthalenediol through washing, desolventizing.
Embodiment 3 composite epoxy type electron packaging material of the present invention and preparations thereof
Get 70g bisphenol A type epoxy resin (oxirane value is 0.54mol/100g), contain two (3-Racemic glycidol oxygen) phenylphosphine oxide after mixing under 70 ℃ of situations with 20g novolac epoxy (oxirane value is 0.47mol/100g) and 10g, adding 5g γ-glycidoxy Trimethoxy silane, 100g silica filler (fineness 500 orders) stir under 80 ℃ again, get the X component;
Get 12g 2,6-naphthalenediol, 24g three (3-amine phenyl) phosphine oxide, 5g γ-An Bingjisanyiyangjiguiwan and 23.6g diaminodiphenyl-methane under 80 ℃, mix the Y component;
Above-mentioned X, Y component are mixed, solidified 1.5 hours down, solidified 2.5 hours down at 110 ℃ again, solidified 2.5 hours down at 140 ℃ then, solidify 2.5 hours promptly down at 170 ℃ at last at 85 ℃.The tensile strength that records the composite epoxy type electron packaging material of gained is 53.2MPa, and the temperature of thermal weight loss 50% is 391 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 27.3, and water-intake rate is 0.90%.
Embodiment 4 composite epoxy type electron packaging material of the present invention and preparations thereof
Under the nitrogen protection; in being housed, the four-hole round-bottomed flask of agitator, thermometer, reflux condensing tube adds 1; 5-naphthalenediol 100g; 37% formalin 37.2g; MIBK 300ml, p-methyl benzenesulfonic acid 0.5g; keep reaction after 5 hours at 116 ℃, promptly get 1, the formaldehyde condensation products of 5-naphthalenediol through washing, desolventizing.
Get 80g bisphenol A type epoxy resin (oxirane value is 0.51mol/100g), contain the basic phenyl phosphate ester of two (3-Racemic glycidols) after mixing under 80 ℃ of situations with 15g bisphenol f type epoxy resin (oxirane value is 0.54mol/100g), 5g, stir down at 90 ℃ again with 4g methyl (γ-glycidoxy) diethoxy silane, 80g silica filler (fineness 800 orders), must the X component;
Get 15g 1, the formaldehyde condensation products of 5-naphthalenediol, 16g 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 5g anilinomethyl triethoxysilane and 27.4g diaminodiphenylsulfone(DDS) under 100 ℃, mix the Y component;
Above-mentioned X, Y component are mixed, solidified 0.5 hour down, solidified 1.5 hours down at 130 ℃ again, solidified 1.5 hours down at 160 ℃ then, solidify 2.5 hours promptly down at 170 ℃ at last at 95 ℃.The tensile strength that records the composite epoxy type electron packaging material of gained is 58.9MPa, and the temperature of thermal weight loss 50% is 401 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 27.9, and water-intake rate is 0.89%.
Embodiment 5 composite epoxy type electron packaging material of the present invention and preparations thereof
Get 80g bisphenol A type epoxy resin (oxirane value is 0.44mol/100g), with 5g novolac epoxy (oxirane value is 0.57mol/100g), 15g two (3-Racemic glycidol oxygen) phenylphosphine oxide after mixing under 75 ℃ of situations, again 90 ℃ down and 2g γ-glycidoxy Trimethoxy silane, silica filler 120g stir, be combined into the X component;
Get 8g 2,3-naphthalenediol, 30g two (3-aminophenyl) phenyl phosphine oxide, 3g anilinomethyl trimethoxy silane and 9.0g dicyandiamide (DICY) stir into uniform Y component at 100 ℃;
Above-mentioned X, Y component are mixed, solidified 1 hour down, solidified 2 hours down at 120 ℃ again, solidified 2 hours down at 150 ℃ then, solidify 2 hours promptly down at 180 ℃ at last at 90 ℃.The tensile strength that records the composite epoxy type electron packaging material of gained is 52.6MPa, and the temperature of thermal weight loss 50% is 391 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 23.4, and water-intake rate is 0.95%.
Embodiment 6 composite epoxy type electron packaging material of the present invention and preparations thereof
Under the nitrogen protection, in being housed, the four-hole round-bottomed flask of agitator, thermometer, reflux condensing tube adds 2,2 '-dihydroxyl-1,1 '-dinaphthalene 100g, 37% formalin 20.8g, MIBK250ml, p-methyl benzenesulfonic acid 0.5g, 116 ℃, keep reaction after 6 hours, promptly get 2 through washing, desolventizing, 2 '-dihydroxyl-1, the formaldehyde condensation products of 1 '-dinaphthalene;
Get 70g bisphenol A type epoxy resin (oxirane value is 0.54mol/100g), with 10g bisphenol f type epoxy resin (oxirane value is 0.51mol/100g), 20g two (3-Racemic glycidol oxygen) phenylphosphine oxide after mixing under 100 ℃ of situations, stir and be combined into the X component with 5g methyl (γ-glycidoxy) diethoxy silane, 100g silica filler (fineness 100 orders);
20g 2,2 '-dihydroxyl-1, the formaldehyde condensation products of 1 '-dinaphthalene, 19g 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide compound, 2g anilinomethyl triethoxysilane and 25.5g diaminodiphenyl-methane (DDM) are under 20 ℃, and uniform mixing gets the Y component;
Above-mentioned X, Y component are mixed, solidified 1.2 hours down, solidified 1.8 hours down at 125 ℃ again, solidified 2.2 hours down at 155 ℃ then, solidify 2 hours promptly down at 185 ℃ at last at 88 ℃.The tensile strength that records the composite epoxy type electron packaging material of gained is 57.1MPa, and the temperature of thermal weight loss 50% is 407 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 29.6, and water-intake rate is 0.87%.
The formaldehyde condensation products and the preparation thereof of embodiment 7 naphthalenediols
Under the nitrogen protection; in being housed, the four-hole round-bottomed flask of agitator, thermometer, reflux condensing tube adds 2; 7-naphthalenediol 100g, 37% formalin 37.2g, solvent MIBK 350mL, catalyzer p-methyl benzenesulfonic acid 0.5g; under 116 ℃; react after 6 hours; promptly get 2, the formaldehyde condensation products of 7-naphthalenediol through washing, desolventizing.
Formaldehyde condensation products of embodiment 8 naphthalenediols and preparation method thereof
Under the nitrogen protection; in being housed, the four-hole round-bottomed flask of agitator, thermometer, reflux condensing tube adds 1; 7-naphthalenediol 100g, 37% formalin 37.2g, solvent MIBK 300mL, catalyzer p-methyl benzenesulfonic acid 0.5g; under 110 ℃; react after 5 hours; promptly get 1, the formaldehyde condensation products of 7-naphthalenediol through washing, desolventizing.
The formaldehyde condensation products and the preparation thereof of embodiment 9 naphthalenediols
Under the nitrogen protection; in being housed, the four-hole round-bottomed flask of agitator, thermometer, reflux condensing tube adds 2; 6-naphthalenediol 100g, 37% formalin 25.0g, MIBK400ml, p-methyl benzenesulfonic acid 0.5g; 120 ℃; keep reaction after 5 hours; promptly get 2, the formaldehyde condensation products of 6-naphthalenediol through washing, desolventizing.
Embodiment 10 composite epoxy type electron packaging materials of the present invention and preparation method thereof
Get 95g bisphenol A type epoxy resin (oxirane value is 0.40mol/100g) and contain the basic phenyl phosphate ester of two (3-Racemic glycidols) after mixing under 60 ℃, add 1g γ-glycidoxy Trimethoxy silane down at 80 ℃ again, be combined into the X component with 5g;
Get 5g 1,6-naphthalenediol, 1g three (3-amine phenyl) phosphine oxide, 1g γ-An Bingjisanyiyangjiguiwan and 26.0g diaminodiphenyl-methane (DDM) obtain the Y component at 50 ℃ of following uniform mixing;
After above-mentioned X, Y component mixed, solidified 1 hour down at 90 ℃ then, solidified 2 hours down at 120 ℃ again, solidified 2 hours down at 150 ℃ then, solidify 2 hours down promptly at 180 ℃ at last.The tensile strength that records the composite epoxy type electron packaging material of gained is 58.5MPa, and the temperature of thermal weight loss 50% is 389 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 22.3, and water-intake rate is 1.19%.
Embodiment 11 composite epoxy type electron packaging materials of the present invention and preparation method thereof
Get 50g bisphenol A type epoxy resin (oxirane value is 0.51mol/100g), the basic phenyl phosphate ester of 50g two (3-Racemic glycidol) is after mixing under 70 ℃ of situations, add 5g methyl (γ-glycidoxy) diethoxy silane, 200g silica filler (fineness 1500 orders) down at 90 ℃ again, be combined into the X component;
Get 40g2,7-naphthalenediol, 10g two (3-aminophenyl) phenyl phosphine oxide, 5g anilinomethyl trimethoxy silane and 12.0g dicyandiamide be the compound Y component that obtains under 60 ℃;
Above-mentioned X, Y component are mixed, solidified 1 hour down at 90 ℃ then, solidified 2 hours down at 120 ℃ again, solidified 2 hours down at 150 ℃ then, solidify 2 hours promptly down at 180 ℃ at last.The tensile strength that records the composite epoxy type electron packaging material of gained is 59.8MPa, and the temperature of thermal weight loss 50% is 405 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 29.2, and water-intake rate is 0.87%.
Embodiment 12 composite epoxy type electron packaging materials of the present invention and preparation method thereof
Get 60g bisphenol A type epoxy resin (oxirane value is 0.44mol/100g), with 25g novolac epoxy (oxirane value is 0.55mol/100g), 15g two (3-Racemic glycidol oxygen) phenylphosphine oxide after mixing under 60 ℃ of situations, add 4g γ-glycidoxy Trimethoxy silane, 150g silica filler (fineness 900 orders) down at 90 ℃ again, be combined into the X component;
Get 16g1,5-naphthalenediol, 7g phenolic varnish phosphine oxide, 3g γ-An Bingjisanjiayangjiguiwan and 26.5g diaminodiphenylsulfone(DDS) DDS be the compound Y component that obtains under 90 ℃;
Above-mentioned X, Y component are mixed, solidified 0.8 hour down at 87 ℃ then, solidified 1.5 hours down at 115 ℃ again, solidified 1.8 hours down at 145 ℃ then, solidify 2 hours promptly down at 180 ℃ at last.The tensile strength that records the composite epoxy type electron packaging material of gained is 57.6MPa, and the temperature of thermal weight loss 50% is 392 ℃, and flame retardant resistance limiting oxygen index(LOI) (LOI) is 27.8, and water-intake rate is 0.91%.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1, a kind of composite epoxy type electron packaging material is characterized in that, comprises X component and Y component; Wherein, described X component is made up of the component of following weight part:
100 parts of Resins, epoxy, 0～20 part of oxirane base class organo-silicon coupling agent, 0～200 part of inorganic silicon dioxide filler;
Described Y component is made up of the component of following weight part:
0～40 part of the formaldehyde condensation products of 0～40 part of naphthalenediol, naphthalenediol, 1～30 part of response type phosphonium flame retardant, 5～50 parts in solidifying agent, 0～10 part of aminoalkyl class organo-silicon coupling agent, wherein, the formaldehyde condensation products consumption of naphthalenediol, naphthalenediol is not 0 simultaneously;
Wherein: the Resins, epoxy in the described X component is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy or the phosphorous epoxy resin; Wherein said phosphorous epoxy resin is the basic phenyl phosphate ester of two (3-Racemic glycidol oxygen) phenylphosphine oxides or two (3-Racemic glycidol); The molecular weight of the basic phenyl phosphate ester of described two (3-Racemic glycidol oxygen) phenylphosphine oxides or two (3-Racemic glycidol) is 150～2000; Described novolac epoxy is linear o-cresol formaldehyde epoxy resin or linear phenolic epoxy resin;
Oxirane base class organo-silicon coupling agent in the described X component is γ-glycidoxy Trimethoxy silane or methyl (γ-glycidoxy) diethoxy silane;
Inorganic silicon dioxide filler fineness in the described X component is 50～3000 orders;
Naphthalenediol in the described Y component is 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 2,2 '-dihydroxyl-1, one or several in 1 '-dinaphthalene;
Response type phosphonium flame retardant in the described Y component is 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound, phenolic varnish phosphine oxide, two (3-aminophenyl) phenyl phosphine oxide or three (3-amine phenyl) phosphine oxide;
Solidifying agent in the described Y component is arylamine class solidifying agent, dicyandiamide class solidifying agent or phenolic solidifying agent; Wherein said arylamine class solidifying agent is diaminodiphenyl-methane, diaminodiphenylsulfone(DDS) or mphenylenediamine, and described dicyandiamide class solidifying agent is a dicyandiamide, and described phenolic solidifying agent is linear phenolic resin or resol;
Aminoalkyl class organo-silicon coupling agent in the described Y component is γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane or anilinomethyl trimethoxy silane.
2, a kind of composite epoxy type electron packaging material according to claim 1 is characterized in that, the weight ratio of described X component and Y component is 100: 10～100.
3, a kind of composite epoxy type electron packaging material according to claim 1 is characterized in that, the Resins, epoxy in the described X component is made up of following parts by weight of component:
0～100 part of bisphenol A type epoxy resin, 0～100 part of bisphenol f type epoxy resin, 0～100 part of novolac epoxy, 5～50 parts of phosphorous epoxy resins, wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy consumption are not 0 simultaneously;
Wherein: the oxirane value of described bisphenol A type epoxy resin is 0.01～0.58mol/100g;
The oxirane value of described bisphenol f type epoxy resin is 0.40～0.80mol/100g;
The oxirane value of described novolac epoxy is 0.40～0.80mol/100g.
4, a kind of composite epoxy type electron packaging material according to claim 3 is characterized in that, the oxirane value of described bisphenol A type epoxy resin is 0.40～0.54mol/100g.
5, a kind of composite epoxy type electron packaging material according to claim 3 is characterized in that, the oxirane value of described bisphenol f type epoxy resin is 0.47～0.63mol/100g, and molecular weight is 312～2500.
6, a kind of composite epoxy type electron packaging material according to claim 1 is characterized in that, the oxirane value of described linear o-cresol formaldehyde epoxy resin or linear phenolic epoxy resin is 0.40～0.80mol/100g; The molecular weight of described linear o-cresol formaldehyde epoxy resin or linear phenolic epoxy resin is 200～3000.
7, a kind of composite epoxy type electron packaging material according to claim 1 is characterized in that, the formaldehyde condensation products of the naphthalenediol in the described Y component is the compound with following structural:
Wherein R=-OH or
Wherein: m=0～100.
8, the preparation method of the described a kind of composite epoxy type electron packaging material of claim 1 is characterized in that, may further comprise the steps:
(1) preparation of X component:
It is compound at 50～100 ℃ to take off the row material by weight: 0～100 part of bisphenol A type epoxy resin, 0～100 part of bisphenol f type epoxy resin, 0～100 part of novolac epoxy, 5～50 parts of phosphorous epoxy resins, 1～5 part of oxirane base class organo-silicon coupling agent, 0～200 part of inorganic silicon dioxide filler; Wherein, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy consumption can not be 0 simultaneously;
(2) preparation of Y component:
It is compound down at 20～100 ℃ to take off the row material by weight: 0～40 part of the formaldehyde condensation products of 0～40 part of naphthalenediol, naphthalenediol, 1～30 part of response type phosphonium flame retardant, 5～50 parts in solidifying agent, 1～5 part of aminoalkyl class organo-silicon coupling agent; Wherein, the formaldehyde condensation products consumption of naphthalenediol, naphthalenediol can not be 0 simultaneously;
(3) be that 100: 10～100 ratio is compound by weight with X component and Y component, solidified 0.5～1.5 hour down at 85 ℃～95 ℃ then, solidified 1.5～2.5 hours down at 110 ℃～130 ℃ again, solidified 1.5～2.5 hours down at 140 ℃～160 ℃ then, solidify 1.5～2.5 hours promptly down at 170 ℃～190 ℃ at last.
9, the preparation method of composite epoxy type electron packaging material according to claim 8 is characterized in that, the formaldehyde condensation products of described naphthalenediol has following structural formula:
Wherein R=-OH or
Wherein: m=0～100.
10, the preparation method of composite epoxy type electron packaging material according to claim 9; it is characterized in that; the preparation method of the formaldehyde condensation products of described naphthalenediol may further comprise the steps: under the nitrogen protection; get 100 parts of naphthalenediols by weight, 37% 200～400 parts of 20～40 parts of formalins, solvent MIBK, catalyzer p-methyl benzenesulfonic acid are 0.2%～0.8% of naphthalenediol quality; above-mentioned substance is mixed; under 110～120 ℃; react after 5～6 hours, promptly get the formaldehyde condensation products of naphthalenediol through washing, desolventizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710027674A CN100590168C (en) | 2007-04-24 | 2007-04-24 | Composite epoxy type electron packaging material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710027674A CN100590168C (en) | 2007-04-24 | 2007-04-24 | Composite epoxy type electron packaging material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101054508A CN101054508A (en) | 2007-10-17 |
| CN100590168C true CN100590168C (en) | 2010-02-17 |
Family
ID=38794567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710027674A Expired - Fee Related CN100590168C (en) | 2007-04-24 | 2007-04-24 | Composite epoxy type electron packaging material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100590168C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100567393C (en) * | 2008-03-20 | 2009-12-09 | 江南大学 | A kind of surface modified spherical SiO 2The preparation method of particulate epoxy resin composite material |
| CN101250318B (en) * | 2008-03-25 | 2011-07-20 | 中国科学院广州化学研究所 | Epoxy radical material for printing circuit copper clad laminate and preparation method thereof |
| CN101638481B (en) * | 2009-06-23 | 2012-02-01 | 中国科学院广州化学研究所 | Polyphenyl methoxylsilane and preparation method and application thereof |
| JP5488326B2 (en) * | 2009-09-01 | 2014-05-14 | 信越化学工業株式会社 | White thermosetting silicone epoxy hybrid resin composition for optical semiconductor device, method for producing the same, pre-mold package and LED device |
| CN102382421B (en) * | 2011-09-16 | 2015-06-24 | 汕头市骏码凯撒有限公司 | Liquid epoxy resin packaging material and preparation method thereof |
| CN102643593B (en) * | 2012-04-19 | 2014-04-02 | 东华大学 | Epoxy-tetramine resin system coating and preparation method thereof |
| CN103601401B (en) * | 2013-11-25 | 2015-07-15 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| CN104177782B (en) * | 2014-08-27 | 2017-11-03 | 广东生益科技股份有限公司 | A kind of resin combination and its copper-clad plate of making |
| BE1022462B1 (en) * | 2014-09-12 | 2016-04-07 | Techspace Aero S.A. | LOW AXIAL TURBOMACHINE COMPRESSOR COMPRESSOR CASING |
| CN104974475A (en) * | 2015-07-15 | 2015-10-14 | 龚灿锋 | Chip packaging material for computer |
| CN112210193A (en) * | 2020-11-26 | 2021-01-12 | 武汉市三选科技有限公司 | High-glossiness epoxy plastic packaging material chip protection film and preparation method thereof |
| CN113512389B (en) * | 2021-08-03 | 2022-09-20 | 威盛亚（上海）有限公司 | Water-based environment-friendly binder for producing fire-resistant decorative material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321179A (en) * | 1999-09-06 | 2001-11-07 | 住友电木株式会社 | Epoxy resin composition and semiconductor device |
| US6338903B1 (en) * | 1998-11-02 | 2002-01-15 | Fujitsu Limited | Resin composition for semiconductor encapsulation, method and apparatus for producing the composition, as well as semiconductor device using the composition |
| CN1560106A (en) * | 2004-03-10 | 2005-01-05 | 中国科学院广州化学研究所 | Modified epoxy resin by organic silicon and its electronic packag material and preparation process thereof |
| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
| CN1796455A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院广州化学研究所 | Epoxidation silicon oil modified three kinds of composite material of epoxy resin |
-
2007
- 2007-04-24 CN CN200710027674A patent/CN100590168C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6338903B1 (en) * | 1998-11-02 | 2002-01-15 | Fujitsu Limited | Resin composition for semiconductor encapsulation, method and apparatus for producing the composition, as well as semiconductor device using the composition |
| CN1321179A (en) * | 1999-09-06 | 2001-11-07 | 住友电木株式会社 | Epoxy resin composition and semiconductor device |
| CN1560106A (en) * | 2004-03-10 | 2005-01-05 | 中国科学院广州化学研究所 | Modified epoxy resin by organic silicon and its electronic packag material and preparation process thereof |
| CN1796455A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院广州化学研究所 | Epoxidation silicon oil modified three kinds of composite material of epoxy resin |
| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101054508A (en) | 2007-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590168C (en) | Composite epoxy type electron packaging material and preparation method thereof | |
| CN103180366B (en) | Cyanate esters, curable resin composition containing cyanate esters and cured article thereof | |
| CN102666637B (en) | Toughened epoxy resin formulations | |
| CN104024337B (en) | Silane-containing compositions, hardening resin composition and sealing material | |
| CN103992621B (en) | A kind of compositions of thermosetting resin and use its prepreg made and veneer sheet | |
| CN103289326B (en) | For the halogen-free flame retardant epoxy resin composition of potting compound | |
| CN108997714B (en) | Reactive flame retardant for epoxy resin and flame-retardant epoxy resin thereof | |
| CN102407630A (en) | Halogen-free flame-retardant phenolic epoxy glass cloth laminate and preparation method thereof | |
| JP2016204626A (en) | Composition, epoxy resin curing agent, epoxy resin composition, heat curable composition, cured article, semiconductor device and interlayer insulation material | |
| JP2007326956A (en) | Prepreg, laminate, and printed circuit board comprising the same | |
| JPH04227922A (en) | Resin which can form flame-retardant and heat-resistant resin when cured, and manufacture and use thereof | |
| CN102666649A (en) | Epoxy resin compositions | |
| JP3468291B2 (en) | Alkoxy group-containing silane-modified phenolic resin, resin composition, epoxy resin curing agent, and organic / inorganic hybrid. | |
| JP6620981B2 (en) | Thermosetting molding material, method for producing the same, and semiconductor sealing material | |
| CN102834429A (en) | Phosphorus-containing epoxy resin | |
| CN102666636B (en) | Hydroxyl-functional polyester's resin | |
| CN105339362B (en) | Compound containing phenolic hydroxyl group, phenolic resin, solidification compound, its solidfied material, semiconductor-encapsulating material and tellite | |
| CN103102471B (en) | Phosphorus containing phenolic resin and its manufacture method, the resin combination, solidfied material | |
| KR102477271B1 (en) | Thermosetting resin composition with high toughness and flame retardant | |
| JP4560928B2 (en) | Epoxy resin composition for interposer, prepreg, and copper-clad laminate using the same | |
| JP3484403B2 (en) | Phosphorus-containing flame-retardant epoxy resin and method for producing the same | |
| CN113242873B (en) | Sealing composition and semiconductor device | |
| CN115894937B (en) | High-strength silicone resin and preparation method thereof | |
| WO2006004118A1 (en) | Thermosetting resin composition, boric acid-modified triazine structure-containing novolac resin, and method for producing same | |
| CN110218445A (en) | A kind of high-toughness halogen-free cyanate composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100217 Termination date: 20140424 |