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
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- 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
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- Prior art keywords
- naphthalenediol
- component
- epoxy resin
- epoxy
- bisphenol
- Prior art date
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Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 88
- 239000005022 packaging material Substances 0.000 title claims description 47
- 239000002131 composite material Substances 0.000 title claims description 46
- 238000002360 preparation method Methods 0.000 title claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000003822 epoxy resin Substances 0.000 claims abstract description 67
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 67
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 69
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 35
- 239000003063 flame retardant Substances 0.000 claims description 35
- 239000007859 condensation product Substances 0.000 claims description 32
- 229920003986 novolac Polymers 0.000 claims description 24
- 229930185605 Bisphenol Natural products 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 15
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 13
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical group C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- -1 phenyl phosphate ester Chemical class 0.000 claims description 9
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 claims description 8
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical class O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 6
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 5
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CEPVQEBPYKXKAM-UHFFFAOYSA-N NC=1C=C(C=CC1)P(C1=CC=CC=C1)=O Chemical compound NC=1C=C(C=CC1)P(C1=CC=CC=C1)=O CEPVQEBPYKXKAM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 4
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 claims description 4
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 claims description 4
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 4
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical group C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 3
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005538 encapsulation Methods 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 230000004580 weight loss Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XFVUECRWXACELC-UHFFFAOYSA-N trimethyl oxiran-2-ylmethyl silicate Chemical compound CO[Si](OC)(OC)OCC1CO1 XFVUECRWXACELC-UHFFFAOYSA-N 0.000 description 1
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.
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