CN104877134A - Halogen-free flame-retardant polyimide resin composition and prepreg and laminate made with same - Google Patents
Halogen-free flame-retardant polyimide resin composition and prepreg and laminate made with same Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant polyimide resin composition, comprising, by weight, bismaleimide a, composite allyl compound b, and phosphorous compound c. A preparing method of the halogen-free flame-retardant polyimide resin composition includes: heating the bismaleimide, the composite allyl compound and the phosphorous compound in a reaction flask for reaction, with the composite allyl compound being composed of first allyl compound and second allyl compound. The first allyl compound is made from one or any of diallyl bisphenol A, diallyl bisphenol S, allyl phenoxy resin, and diallyl diphenyl ether. The second allyl compound is made from one or any of diallyl bisphenol A diglycidyl ether, diallyl bisphenol S diglycidyl ether, diallyl diphenyl ether diglycidyl ether. A laminate made from the halogen-free flame-retardant polyimide resin composition has the advantages of high resistance, high toughness, low water absorption rate, and excellent dielectric property and flame retardance.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of halogen-free flameproof polyimide resin composition and the prepreg using it to make and veneer sheet.
Background technology
Along with the development in electronic unit multifunction, high performance, high reliability and environmental protection direction, must improve the thermotolerance of sheet material, to meet the harsh complete processing of Pb-free coating and repeatedly pressing, the thermotolerance of traditional FR-4 material can not meet the demands far away.
Bimaleimide resin is the compound that a class has double activated end group, can crosslinking curing under the effect of heating or catalyzer, there is excellent thermotolerance, humidity resistance, dielectric properties, good mechanical property and dimensional stability, be therefore widely used in numerous high-technology fields such as aerospace, electronic apparatus, communications and transportation as High-performance adhesive, resin matrix for advanced composite materials body, insullac etc.But the shortcoming such as there is monomer solubility difference due to bimaleimide resin and cured article fragility is large, when being applied to copper-clad plate field, needs to carry out modification to it.
At present, conventional method of modifying adopts aromatic diamine compounds or allylic compound to carry out modification to it, destroys crystalline texture, improve solvability and toughness etc. by chain extension.Aromatic diamine compounds realizes the modification to bismaleimides by Michael reaction, and modified product all has improvement to a certain degree in solvability, toughness; But aromatic diamine toxicity is comparatively large, and the product of modification can only be dissolved in high bp polar solvent (as DMF, NMP etc.), and it still exists larger room for promotion in toughness, cohesiveness simultaneously.And the modified product of allylic cpd (is soluble in low boiling point solvent in toughness, cohesiveness, solvability, as PM, butanone, acetone etc.) all comparatively aromatic diamine compounds have further improvement, be one of method of current bi-maleimide modified main employing; At present, conventional allylic compound, as allyl group dihydroxyphenyl propane, allyl group bisphenol S, phenol type allyl group phenolic aldehyde, allyl phenol oxygen, aryl allyl alkylphenol etc., but, often attend to one thing and lose sight of another in thermotolerance, water-intake rate, dielectric properties, incendivity, toughness with the bimaleimide resin of these allylic cpd modifications.In addition, the fire-retardant problem of modified product is not resolved.
For the problems referred to above, what the application of solution fire-retardant problem was maximum at present is halogen based compound, but halogen based compound can produce the carcinogenic substance such as dioxin, furans and corrosive gases as fire retardant in the process of burning, works the mischief to human health and ecotope.Therefore, at present the phosphonium flame retardant that adopts substitutes halogenated flame retardant more, but due to addition type fire retardant can very big low reduction sheet material performance and there is the risk of migration precipitation, therefore, the phosphonium flame retardant of response type is subject to the extensive concern of researchist in recent years.Such as, a kind of DOPO of employing and BMI is disclosed and the method for flame-retarded resin is prepared in allylic cpd reaction in Chinese invention patent 201010270929.8, there is good flame retardant effect, but the toughness of the stability in storage of its prepolymer and cured article still needs to improve.In addition, fire-retardant polyimide resin composition disclosing a kind of halogen-free phosphorus-containing and preparation method thereof in Chinese invention patent 201110239153.8, employing single stage method is obtained by reacting, improve the stability in storage of resin combination and the toughness of cured article, but its bisphenol A type epoxy resin self thermotolerance of adding is extremely low, causes the thermotolerance of the bimaleimide resin composition obtained to reduce.
Therefore, how obtaining the copper-clad plate material of flame retardant resistance, thermotolerance, high tenacity, low water absorption, superior dielectric performance and the flame retardant resistance integrating excellent, is one of this area technical problem urgently to be resolved hurrily.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of halogen-free flameproof polyimide resin composition and the prepreg using it to make and veneer sheet.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of halogen-free flameproof polyimide resin composition, with solid weight meter, comprising:
(a) bismaleimides: 100 parts;
(b) compound allylic cpd: 40 ~ 160 parts;
(c) P contained compound: 1 ~ 75 part;
Wherein, described compound allylic cpd is made up of first kind allylic cpd and Equations of The Second Kind allylic cpd, and the mass ratio of first kind allylic cpd and Equations of The Second Kind allylic cpd is 0 ~ 99:1 ~ 100;
Described first kind allylic cpd is selected from one or more in diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, diallyl phenyl ether;
Described Equations of The Second Kind allylic cpd is selected from one or more in diallyl bisphenol diglycidylether, diallyl bisphenol-S diglycidyl ether, diallyl phenyl ether diglycidylether.
Above, the preparation method of above-mentioned halogen-free flameproof polyimide resin composition is as follows: get bismaleimides, compound allylic cpd and P contained compound in reaction flask, reacting by heating, can obtain described halogen-free flameproof polyimide resin composition.
Preferably, get bismaleimides, compound allylic cpd and P contained compound in reaction flask, be heated to 120 ~ 160 DEG C, reaction 10 ~ 150min, can obtain described halogen-free flameproof polyimide resin composition.
The chemical structural formula of described diallyl bisphenol diglycidylether is:
The chemical structural formula of described diallyl bisphenol-S diglycidyl ether is:
The chemical structural formula of described diallyl phenyl ether diglycidylether is:
Mineral filler can also be contained in described resin combination.It is one or more in silicon-dioxide, aluminium hydroxide, Bao Mushi, magnesium hydroxide, talcum, kaolin, aluminum oxide, zinc borate, polytetrafluorethylepowder powder that described mineral filler is selected from mineral filler.Described silicon-dioxide can be spherical, crystal type or fusion.Preferably, mineral filler is carry out surface-treated mineral filler with silane coupling agent.The preferred end group of described silane coupling agent contains double bond or epoxide group.By above-mentioned coupling agent carry out surface-treated mineral filler be added into resin combination time, because the double bond/epoxide group of coupling agent and modified bismaleimide prepolymer have excellent com-patibilising effect, the viscosity of full tree oil/fat composition is made to rise slowly, the dispersiveness of filler in resin combination is better, efficiently solve the unmanageable problem of reaction between resin Composition because viscosity is large, improve the surface smoothness of prepreg.
Phosphorus content in described halogen-free flameproof polyimide resin composition accounts for 0.5 ~ 2.5% of polyimide resin composition gross weight.In addition, research finds: when system phosphorus content is too low, does not fire-retardantly reach V-0 rank; And when system phosphorus content is too high, thermotolerance (Tg, Td and T300 etc.) can be caused to decline, water-intake rate rises.
The Equations of The Second Kind allylic cpd that the present invention adopts contains epoxide group, improve solvability and the stability in storage of modified bismaleimide prepolymer, allyl group in its structure can be polymerized with the double bond in bismaleimides, the epoxide group introduced can carry out ring-opening reaction with the active group (P-H or N-H) in P contained compound, residual epoxide group as active end group occur when heating further autohemagglutination or with other resin Composition copolymerization in formula, the introducing of epoxide group improves the cross-linking density of cured article; Meanwhile, due to a large amount of ehter bonds formed after epoxide group open loop, improve the toughness of cured article.
In technique scheme, described bismaleimides is selected from 4,4 '-diphenyl methane dimaleimide, 4,4 '-Diphenyl Ether Bismaleimide, 4,4 '-hexichol sec.-propyl bismaleimides, 4, one or more in 4 '-sulfobenzide bismaleimides.
Preferably, the mass ratio of described first kind allylic cpd and Equations of The Second Kind allylic cpd is 20 ~ 60:40 ~ 80.
In technique scheme, described P contained compound is selected from one or more in P contained compound A, P contained compound B, P contained compound C, P contained compound D, P contained compound E;
The chemical formula of described P contained compound A is:
The chemical formula of described P contained compound B is:
The chemical formula of described P contained compound C is:
The chemical formula of described P contained compound D is:
The chemical formula of described P contained compound E is:
The present invention asks to protect a kind of prepreg adopting above-mentioned resin combination to make simultaneously, and above-mentioned resin combination dissolution with solvents is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding after strongthener baking, described prepreg can be obtained.
One or more in described solvent selected from acetone, butanone, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
Described strongthener can adopt glass-fiber-fabric, as D glass-fiber-fabric, E glass-fiber-fabric, NE glass-fiber-fabric, S glass-fiber-fabric and T glass-fiber-fabric.Here the thickness of glass-fiber-fabric is not particularly limited, but for producing the veneer sheet of thickness 0.03 ~ 0.20mm, general use fibrillation cloth, flat fabric.In addition, in order to improve the interface cohesion of resin and glass-fiber-fabric, glass-fiber-fabric generally all needs to carry out chemical treatment, and main method is coupling agent treatment, coupling agent used as epoxy silane, aminosilane, vinyl silanes etc.
Described prepreg be temperature at 100 ~ 200 DEG C, the time be under 1 ~ 10min dry preparation obtain.
The present invention asks to protect a kind of veneer sheet adopting above-mentioned resin combination to make simultaneously; tinsel is covered with by the single or double of above-mentioned prepreg at one; or after at least 2 are superposed by above-mentioned prepreg; tinsel is covered with at its single or double; in 0.2 ~ 2MPa pressure and 180 ~ 250 DEG C of temperatures systems 2 ~ 4 hours, described veneer sheet can be obtained.
The quantity of described prepreg determines according to the laminate thickness of customer requirement, available one or more.Described tinsel can be Copper Foil, and can be also aluminium foil, thickness be not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention adopts the compound allylic cpd that is made up of first kind allylic cpd and Equations of The Second Kind allylic cpd as the properties-correcting agent of bimaleimide resin, the Bismaleimide prepolymer be obtained by reacting has higher reactive behavior, good solubility and stability in storage, good toughness after solidification, stripping strength is high, water-intake rate is low, specific inductivity is low and maintain the excellent heat resistance of bismaleimides, the flame retardant resistance that the veneer sheet collection obtained is excellent, thermotolerance, high tenacity, low water absorption, superior dielectric performance and flame retardant resistance are in one, the requirement of high-precision electronic baseplate material can be met, there is realistic meaning energetically,
2. halogen-free flameproof polyimide resin composition stability in storage of the present invention is good, reactive behavior is high, it is fire-retardant that the copper-clad plate using it to make can realize Halogen V-0, there is good toughness and stripping strength, maintain the thermotolerance of bismaleimides excellence simultaneously, achieve significant effect, can be applicable to high temperature resistant anti-aging, the field such as integrated antenna package, high-speed high frequency, have broad application prospects.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment one:
Get 4,4 '-diphenyl methane dimaleimide 100g, diallyl bisphenol diglycidylether 70g (epoxy equivalent (weight) 256g/eq), P contained compound (A) 20g puts into 500mL reaction flask, oil bath is used slowly to be heated to 120 ~ 160 DEG C and to react 30min under keeping agitation condition, obtain the polyimide resin composition of halogen-free flameproof, after having reacted, be cooled to room temperature.
Embodiment two:
Get 4,4 '-Diphenyl Ether Bismaleimide 30g, 4,4 '-diphenyl methane dimaleimide 90g, diallyl bisphenol 40g, diallyl bisphenol diglycidylether 20g (epoxy equivalent (weight) 220g/eq), P contained compound (A) 23g puts into 500mL reaction flask, uses oil bath be slowly heated to 120 ~ 160 DEG C and react 50min under keeping agitation condition, obtain the polyimide resin composition of halogen-free flameproof, after having reacted, be cooled to room temperature.
Embodiment three:
Get 4,4 '-Diphenyl Ether Bismaleimide 125g, allyl phenoxy resin 20g, diallyl bisphenol diglycidylether 50g (epoxy equivalent (weight) 215g/eq), P contained compound (B) 30g puts into 500mL reaction flask, oil bath is used slowly to be heated to 120 ~ 160 DEG C and to react 60min under keeping agitation condition, obtain the polyimide resin composition of halogen-free flameproof, after having reacted, be cooled to room temperature.
Embodiment four:
Get 4,4 '-hexichol sec.-propyl bismaleimides 100g, allyl phenol urea formaldehyde 30g, diallyl bisphenol diglycidylether 30g (epoxy equivalent (weight) 250g/eq), P contained compound (C) 7g puts into 500mL reaction flask, oil bath is used slowly to be heated to 130 ~ 150 DEG C and to react 45min under keeping agitation condition, obtain the polyimide resin composition of halogen-free flameproof, after having reacted, be cooled to room temperature.
Embodiment five:
Get 4,4 '-sulfobenzide bismaleimides 110g, diallyl bisphenol S 10g, diallyl bisphenol diglycidylether 70g (epoxy equivalent (weight) 225g/eq), P contained compound (E) 21g puts into 500mL reaction flask, oil bath is used slowly to be heated to 130 ~ 150 DEG C and to react 30min under keeping agitation condition, obtain the polyimide resin composition of halogen-free flameproof, after having reacted, be cooled to room temperature.
Comparative example one:
Get 4,4 '-diphenyl methane dimaleimide 100g, allyl group dihydroxyphenyl propane 70g, P contained compound (A) 20g, put into 500mL reaction flask, oil bath is used slowly to be heated to 130 ~ 150 DEG C and to react 50min under keeping agitation condition, obtain modified quartz sand, after having reacted, be cooled to room temperature.
Comparative example two:
Get 4,4 '-diphenyl methane dimaleimide 150g, allyl group dihydroxyphenyl propane 100g, bisphenol A type epoxy resin 15g, ring-type phenoxy phosphazene compound 33g (Fushimi Pharmaceutical Co., Ltd, FP-100), put into 500mL reaction flask, use oil bath is slowly heated to 130 ~ 150 DEG C and under keeping agitation condition, reaction obtains modified quartz sand in 3 hours, is cooled to room temperature after having reacted.
Comparative example three:
Get 4,4 '-diphenyl methane dimaleimide 100g, allyl group phenolic aldehyde diglycidylether 70g (epoxy equivalent (weight) 250g/eq), P contained compound (A) 20g, put into 500mL reaction flask, use oil bath to be slowly heated to 130 ~ 150 DEG C and react under keeping agitation condition and obtain modified quartz sand in 3 hours, after having reacted, be cooled to room temperature.
One, prepreg makes:
Get the resin combination of 100g above-described embodiment one to five preparation, add proper amount of acetone and dissolve, after stirring, obtain glue.Choose 300 × 450mm, smooth bright and clean 7628E-glass-fiber-fabric, evenly the above-mentioned glue of coating, toast 5min at 165 DEG C in an oven and obtain a series of 5 groups of prepregs.
It is the same that comparative example one to three gained modified quartz sand prepares prepreg method.
Two, copper-clad plate makes:
Get above-mentioned gained prepreg, each group gets 8,8 is cut out the semicure superposition of deflashing, encloses the Copper Foil of 35 microns up and down, is placed in thermocompressor compacting and obtains 7 groups of copper-clad plates.Wherein, employing staged (heating up step by step and boosting) program compacting, be specially: temperature, 15min rises to 150 DEG C from room temperature and keeps 30min, and then 5min is raised to 180 DEG C of maintenances 2hr, last 10min and is raised to 230 DEG C of maintenance 2.0hr; 30min; Pressure, 1min rises to 0.6Mpa pressurize 30min, and then 1min rises to 1.0Mpa pressurize 1hr, and last 1min rises to 2Mpa pressurize 3.0hr57min; Post-treatment condition: 220 DEG C/4hr.
Conventionally performance test is carried out to the copper-clad plate of above-mentioned gained 8 groups of embodiments and comparative example, the results are shown in Table 1.
The fundamental property of copper-clad plate prepared by table 1 embodiment and comparative example
Partial test method of the present invention is specific as follows:
Humidity resistance: adopt pressure cooker gluten substitute, sheet material after 180 minutes through pressure cooker (0.105MPA) 121 DEG C of continuously cookings, immerses in 288 DEG C of scolding tin and observes layering, bubble time;
Impelling strength: adopt 5512 Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.If the cross pattern after sheet material impacts is clear and elongated, illustrate that the toughness of sheet material is better; On the contrary, cross pattern is fuzzy or do not have cross pattern, and the poor toughness of sheet material is described, fragility is large, specifically can be divided into excellent, good, in, differ from four grades;
Stability in storage: be dissolved in acetone solvent by solids content 55% by resin combination, leaves standstill one week after sealing, observes whether have resin layering, precipitation.
As can be seen from Table 1, compared with comparative example one, the advantages such as resin combination obtained by the present invention has that stability in storage is good, the high and water-intake rate of good toughness, stripping strength is low after solidification.
Compared with documents two, sheet material obtained by the present invention has more excellent thermotolerance (Tg, Td and T300).
Compared with documents three (adopting allyl group novolac glycidyl ethers separately), sheet material obtained by the present invention has the advantages such as the low and specific inductivity of good toughness, water-intake rate after solidification is low.Cause primarily of two aspects with the difference of documents three: first, because the rigid radical density in resol main framing structure is comparatively large and without rotatable group, cause its cured article toughness poor; On the other hand, allyl group phenolic aldehyde is due to steric effect in the process of etherificate, and the etherificate and not easily reacting completely of the hydroxyl in the middle of molecule, cause remaining hydroxyl groups in cured article, and hydroxyl belongs to polar group, easily causes that cured article water-intake rate is large and specific inductivity is higher.
In sum, the veneer sheet obtained by the present invention integrates excellent flame retardant resistance, thermotolerance, high tenacity, low water absorption, superior dielectric performance and flame retardant resistance, can be applicable to high temperature resistant anti-aging, the field such as integrated antenna package, high-speed high frequency.
Above embodiment, not the content of composition of the present invention is imposed any restrictions, every above embodiment is done according to technical spirit of the present invention or composition composition or content any trickle amendment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. a halogen-free flameproof polyimide resin composition, is characterized in that, with solid weight meter, comprising:
(a) bismaleimides: 100 parts;
(b) compound allylic cpd: 40 ~ 160 parts;
(c) P contained compound: 1 ~ 75 part;
Wherein, described compound allylic cpd is made up of first kind allylic cpd and Equations of The Second Kind allylic cpd, and the mass ratio of first kind allylic cpd and Equations of The Second Kind allylic cpd is 0 ~ 99:1 ~ 100;
Described first kind allylic cpd is selected from one or more in diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, diallyl phenyl ether;
Described Equations of The Second Kind allylic cpd is selected from one or more in diallyl bisphenol diglycidylether, diallyl bisphenol-S diglycidyl ether, diallyl phenyl ether diglycidylether.
2. resin combination according to claim 1, it is characterized in that: described bismaleimides is selected from 4,4 '-diphenyl methane dimaleimide, 4,4 '-Diphenyl Ether Bismaleimide, 4,4 '-hexichol sec.-propyl bismaleimides, 4, one or more in 4 '-sulfobenzide bismaleimides.
3. resin combination according to claim 1, is characterized in that: the mass ratio of described first kind allylic cpd and Equations of The Second Kind allylic cpd is 20 ~ 60:40 ~ 80.
4. resin combination according to claim 1, is characterized in that: the content of described compound allylic cpd is 60 ~ 120 parts.
5. resin combination according to claim 1, is characterized in that: described P contained compound is selected from one or more in P contained compound A, P contained compound B, P contained compound C, P contained compound D, P contained compound E;
The chemical formula of described P contained compound A is:
The chemical formula of described P contained compound B is:
The chemical formula of described P contained compound C is:
The chemical formula of described P contained compound D is:
The chemical formula of described P contained compound E is:
6. the prepreg adopting resin combination as claimed in claim 1 to make, is characterized in that: resin combination dissolution with solvents according to claim 1 is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding after strongthener baking, described prepreg can be obtained.
7. the veneer sheet adopting resin combination as claimed in claim 1 to make, it is characterized in that: be covered with tinsel at one by the single or double of prepreg according to claim 6, or after at least 2 are superposed by prepreg according to claim 6, tinsel is covered with at its single or double, in 0.2 ~ 2MPa pressure and 180 ~ 250 DEG C of temperatures systems 2 ~ 4 hours, described veneer sheet can be obtained.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017088745A (en) * | 2015-11-11 | 2017-05-25 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil clad laminate, resin sheet and printed wiring board |
| JP2017095599A (en) * | 2015-11-25 | 2017-06-01 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
| WO2018025921A1 (en) * | 2016-08-05 | 2018-02-08 | 日本化薬株式会社 | Maleimide resin composition, prepreg, cured product of same and semiconductor device |
| WO2019019463A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg made therefrom, copper clad laminate and high-frequency circuit board |
| WO2019019483A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Intrinsic flame-retardant resin with low polarity, and preparation method therefor and use thereof |
| CN109929109A (en) * | 2019-03-19 | 2019-06-25 | 武汉理工大学 | A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof |
| WO2020108334A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminate prepared using same |
| CN115873251A (en) * | 2022-12-27 | 2023-03-31 | 苏州生益科技有限公司 | Modified maleimide prepolymer, preparation method thereof and resin composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473900A (en) * | 1977-11-25 | 1979-06-13 | Mitsubishi Gas Chem Co Inc | Curable resin composition |
| WO2000071614A1 (en) * | 1999-05-21 | 2000-11-30 | Miguel Albert Capote | High performance cyanate-bismaleimide-epoxy resin compositions for printed circuits and encapsulants |
| CN101974156A (en) * | 2010-09-03 | 2011-02-16 | 苏州生益科技有限公司 | Halogen-free flam retardant prepolymer, preparation method thereof and application of halogen-free flam retardant prepolymer in copper clad laminate (CCL) |
| CN102276837A (en) * | 2011-08-19 | 2011-12-14 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
| CN103524739A (en) * | 2013-10-09 | 2014-01-22 | 胶州市精细化工有限公司 | Allyl/epoxy etherified phenolic aldehyde modified bismaleimide resin and preparation method thereof |
| CN104194269A (en) * | 2014-08-31 | 2014-12-10 | 海安南京大学高新技术研究院 | Reversible repair functional matrix resin for pultrusion and preparation method of matrix resin |
| JP2015086343A (en) * | 2013-11-01 | 2015-05-07 | 京セラケミカル株式会社 | Thermosetting type resin composition for adhesively bonding semiconductor and semiconductor device using the same |
-
2015
- 2015-05-28 CN CN201510282770.4A patent/CN104877134B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473900A (en) * | 1977-11-25 | 1979-06-13 | Mitsubishi Gas Chem Co Inc | Curable resin composition |
| WO2000071614A1 (en) * | 1999-05-21 | 2000-11-30 | Miguel Albert Capote | High performance cyanate-bismaleimide-epoxy resin compositions for printed circuits and encapsulants |
| CN101974156A (en) * | 2010-09-03 | 2011-02-16 | 苏州生益科技有限公司 | Halogen-free flam retardant prepolymer, preparation method thereof and application of halogen-free flam retardant prepolymer in copper clad laminate (CCL) |
| CN102276837A (en) * | 2011-08-19 | 2011-12-14 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
| CN103524739A (en) * | 2013-10-09 | 2014-01-22 | 胶州市精细化工有限公司 | Allyl/epoxy etherified phenolic aldehyde modified bismaleimide resin and preparation method thereof |
| JP2015086343A (en) * | 2013-11-01 | 2015-05-07 | 京セラケミカル株式会社 | Thermosetting type resin composition for adhesively bonding semiconductor and semiconductor device using the same |
| CN104194269A (en) * | 2014-08-31 | 2014-12-10 | 海安南京大学高新技术研究院 | Reversible repair functional matrix resin for pultrusion and preparation method of matrix resin |
Non-Patent Citations (1)
| Title |
|---|
| 张雪平 等: "共固化剂DADE 改性BDM/BCE高性能树脂体系的研究", 《绝缘材料》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017088745A (en) * | 2015-11-11 | 2017-05-25 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil clad laminate, resin sheet and printed wiring board |
| JP2017095599A (en) * | 2015-11-25 | 2017-06-01 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
| WO2018025921A1 (en) * | 2016-08-05 | 2018-02-08 | 日本化薬株式会社 | Maleimide resin composition, prepreg, cured product of same and semiconductor device |
| CN109563344A (en) * | 2016-08-05 | 2019-04-02 | 日本化药株式会社 | Maleimide resin composition, prepreg, its hardening thing and semiconductor device |
| JPWO2018025921A1 (en) * | 2016-08-05 | 2019-06-20 | 日本化薬株式会社 | Maleimide resin composition, prepreg, cured product thereof and semiconductor device |
| WO2019019463A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg made therefrom, copper clad laminate and high-frequency circuit board |
| WO2019019483A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Intrinsic flame-retardant resin with low polarity, and preparation method therefor and use thereof |
| KR20200016346A (en) * | 2017-07-26 | 2020-02-14 | 셍기 테크놀로지 코. 엘티디. | Low polar intrinsic flame retardant resin and its manufacturing method and application |
| KR102292464B1 (en) | 2017-07-26 | 2021-08-23 | 셍기 테크놀로지 코. 엘티디. | Low polarity intrinsic flame retardant resin and its manufacturing method and application |
| WO2020108334A1 (en) * | 2018-11-28 | 2020-06-04 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminate prepared using same |
| CN109929109A (en) * | 2019-03-19 | 2019-06-25 | 武汉理工大学 | A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof |
| CN115873251A (en) * | 2022-12-27 | 2023-03-31 | 苏州生益科技有限公司 | Modified maleimide prepolymer, preparation method thereof and resin composition |
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