CN104109347A - Halogen-free thermosetting resin composition, prepreg and laminated plate - Google Patents
Halogen-free thermosetting resin composition, prepreg and laminated plate Download PDFInfo
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- CN104109347A CN104109347A CN201410232136.5A CN201410232136A CN104109347A CN 104109347 A CN104109347 A CN 104109347A CN 201410232136 A CN201410232136 A CN 201410232136A CN 104109347 A CN104109347 A CN 104109347A
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- halogen
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Abstract
The invention discloses a halogen-free thermosetting resin composition, a prepreg and a laminated plate. The halogen-free thermosetting resin composition comprises, by solid weight, 30-50 parts of epoxy resin, 5-40 parts of modified polyphenyl ether resin, 15-50 parts of phosphorus-containing active ester and 0-20 parts of a strengthening agent. The halogen-free thermosetting resin composition is a halogen-free flame-retardant low-dielectric constant resin composition and utilizes the phosphorus-containing active ester as a fire retardant. Through use of the phosphorus-containing active ester, the problem of resin water absorption rate increasing because of use of a phosphorus-containing epoxy resin, phosphorus-containing phenolic resin or phosphate as a fire retardant is solved. Through use of a proper amount of the modified polyphenyl ether resin, excellent dielectric constant is obtained. The halogen-free thermosetting resin composition can be used in the halogen-free high-speed high-performance printed wiring board field.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of halogen-free resin composition and use prepreg and the veneer sheet of its making, can be applicable to the fields such as high density interconnect integrated antenna package.
Background technology
For a long time, epoxy resin, owing to having the comprehensive advantages such as starting material wide material sources, processibility is good, cost is lower, has obtained application in a large number and widely in FR-4 veneer sheet.But, along with the high-speed high frequency of information processing in recent years and information transmission, veneer sheet used for printed circuit is had higher requirement aspect dielectric properties.In simple terms, laminate sheet material need possess low specific inductivity and dielectric loss, delay, distortion and the loss of signal when reducing high-speed transfer, and interference between signal.But common epoxy resin specific inductivity and dielectric loss are higher, are difficult to meet the application of high frequency aspect.Polyphenylene oxide is a kind of high performance resin, due to the good symmetry of its molecular chain, less Intermolecular Forces and higher aryl ratio, make it have excellent dielectric characteristics, i.e. low specific inductivity and dielectric loss, can meet the requirement of frequency applications to dielectric material performance well.Meanwhile, polyphenylene oxide also has the impelling strength of higher second-order transition temperature, low water absorption and excellence etc., in high frequency laminate sheet material, has broad application prospects.
Simultaneously, along with the progressively intensification of environmental pollution, the living environment going from bad to worse, the theme of " environmental protection " is rooted in the hearts of the people gradually, therefore, in copper-clad plate industry, green halogen-free board is developed the main direction of development in recent years especially, and the main technological route that has been applied to halogen-free flameproof of phosphonium flame retardant.At present, the phosphorus flame retardant extensively adopting on copper-clad plate market: be mainly divided into two kinds of response type and addition types.Response type is mainly DOPO compounds, taking phosphorous epoxy resin, phosphorus containing phenolic resin as main, phosphorus content is between 2-10%, but, in practical application, find, adopt phosphorous epoxy resin as matrix resin or adopt the resin combination that phosphorus containing phenolic resin is epoxy curing agent, it has larger water-intake rate and higher specific inductivity, and the humidity resistance of its sheet material of making decreases; Addition type is mainly phosphine nitrile and phosphate compounds, the flame retarding efficiency relative response type of additive flame retardant is on the low side, need to adding more phosphorus content, just to reach UL 94V-0 level fire-retardant, simultaneously, because of its lower fusing point (generally lower than 150 DEG C), in the course of processing of veneer sheet, easily " migration " is to the surface of sheet material.
Therefore, the application of above-mentioned phosphor-containing flame-proof technology, often can not meet the requirement of the resin composition formula design of the humidity resistance of low-k, excellence, seek new halogen-free flame retardants, prepare the copper-clad plate that has halogen-free flameproof and high heat resistance, low-k concurrently, become one of direction of copper-clad plate future development.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of halogen-free thermosetting resin composite and uses prepreg and the veneer sheet of its making, with flame retardant properties, thermotolerance, the dielectric properties of improving layer pressing plate, reduces water-intake rate.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of halogen-free thermosetting resin composite, adds up to 100 parts in solid weight, comprising:
(a) epoxy resin: 30 ~ 50 parts;
(b) modified polyphenylene ether resin: 5 ~ 40 parts;
(c) phosphorous active ester: 15 ~ 50 parts;
(d) strengthening agent: 0 ~ 20 part.
In technique scheme, described epoxy resin is selected from: the mixture of one or more of bisphenol A epoxide resin, bisphenol F epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
In technique scheme, the structural formula of described phosphorous active ester compound is,
，
In formula, R1 is methyl, ethyl or the tertiary butyl;
Y is H or CH
3;
Z is
or
, wherein R is phenyl, naphthyl or C
1～C
5alkyl;
N is 1～10 integer;
X is:
,
,
or
.
The preparation method of above-mentioned active ester compound, by phosphorus compound and p-Hydroxybenzaldehyde, adds the H of 50～70% mass concentrations
2sO
4in, heating at 90～130 DEG C, condensing reflux 3～8hr, then reaction product is passed through to 3～10 alcohol washes, under the vacuum condition of 95～105 DEG C, dry 3～6hr, obtains pre-product; Above-mentioned gained pre-product is dissolved in aromatic series organic solution, add phenylformic acid or naphthyl, benzene alkylbenzoic acid compound, under the temperature condition of 100～120 DEG C, add catalyzer, condensing reflux 2～8hr, after washing, under the vacuum condition of 95～105 DEG C, be dried 3～6hr, obtain required phosphorous active ester compound, esterification yield is 65～85%; Wherein, described phosphorus compound is selected from 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, 10-(2,5-dihydroxyl naphthyl) one or more mixture in the phospho hetero phenanthrene compound such as-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound or 10-(2,5-dihydroxybiphenyl base)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound.
Described aromatic organic solvent can be selected from toluene, dimethylbenzene, ethylbenzene, isopropyl benzene.
Described catalyzer is AlCl
3.
Further technical scheme, in described phosphorous active ester compound, in mass, phosphorus content is 5.2～7.2%.
In technique scheme, described phosphorous active ester content is preferably 20-40 part.
In technique scheme, described modified polyphenylene ether resin is at least one in phenol modified polyphenylene ether resin or epoxide modified polyphenylene oxide resin, and its number-average molecular weight is 500 ~ 5000, and its content is preferably 10-30 part.
In technique scheme, described strengthening agent is one or more in Dyhard RU 100, diaminodiphenylmethane, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, and its content is preferably 0-10 part.
Further technical scheme, contains curing catalyst, and described curing catalyst is selected from one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole and triphenylphosphine, and consumption is weight epoxy 0.01 ~ 3%.
Further technical scheme, contains mineral filler, and the consumption of described mineral filler is 0～35% of resin combination solid total mass; Described mineral filler is one or more the mixture in aluminium hydroxide, magnesium hydroxide, wollastonite, fine silica powder, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide, zinc borate, zinc molybdate.Particle diameter is 0.3～20 μ m, preferentially selects 0.5～5 μ m.Above-mentioned mineral filler can directly drop into or previously prepared fillers dispersed liquid or make lotion and drop in resin combination.
The prepreg that adopts above-mentioned halogen-free resin composition to make, makes glue by halogen-free resin composition by dissolution with solvents, then strongthener is immersed in above-mentioned glue; By the strongthener heat drying after dipping, obtain described prepreg.
Described solvent is selected from one or more the mixture in acetone, butanone, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or without woven fabrics.
Adopt above-mentioned prepreg, be covered with tinsel at single or double, hot compacting, obtains described veneer sheet.
The quantity of prepreg is to determine according to the veneer sheet thickness of customer requirement, available one or more.Described tinsel, can be Copper Foil, can be also aluminium foil, and their thickness is not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention has designed a kind of resin combination of the halogen-free flameproof low-k taking phosphorous active ester as fire retardant, the application of phosphorous active ester, avoid because of after introducing phosphorous epoxy resin or phosphorus containing phenolic resin or phosphoric acid ester and introducing as fire retardant the rising of resin water-intake rate;
2. in the present invention, introduce appropriate modified polyphenylene ether resin simultaneously, can obtain and there is more excellent specific inductivity, be more conducive to it and be applied to the contour performance printed circuit board of Halogen high speed field.
Brief description of the drawings
Fig. 1 be synthesis example one product nmr spectrum (
13c);
Fig. 2 be synthesis example one product nmr spectrum (
1h).
Embodiment
Below in conjunction with embodiment, the invention will be further described:
First carry out the synthetic of raw material.
Synthesis example one:
The preparation 1 of phosphorous active ester compound:
Weigh 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound of 0.6mol and the p-Hydroxybenzaldehyde of 0.6mol, add the H of 65% mass concentration
2sO
4, condensing reflux 3～5hr under 100 DEG C of heating conditions, then this mixture is passed through to 4～6 alcohol washes, obtain pre-product; Above-mentioned gained pre-product is dissolved in toluene solution, add 0.2mol phenylformic acid, under the temperature condition of 120 DEG C, add the catalyzer (AlCl of 0.05mol
3), condensing reflux 4hr, then, after washing for several times, under the vacuum condition of 105 DEG C, dry 4hr, obtains required phosphorous active ester compound, and esterification yield is 70～80%, and the phosphorous active ester compound that phosphorus content is 6.4%, is designated as C1, and concrete structure is as follows:
X=
, Y=H, Z=
, R is phenyl, R1=CH
3, n is 3 ~ 5.
The nmr spectrum of above-mentioned product (
13c) as shown in Figure 1,165ppm place peak position is stronger, shows to contain in resin the activated ester composition of tool, nmr spectrum (
1h) as shown in Figure 2,7-8ppm is mainly corresponding peak position on phenyl ring, and 3-4ppm is mainly DOPO and CH
2the corresponding peak position that is connected, this synthetic compound of above explanation meets the constitutional features of phosphorous active ester compound.
The preparation 2 of phosphorous active ester compound:
Weigh the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of 0.6mol and the p-Hydroxybenzaldehyde of 0.6mol, add the H of 65% mass concentration
2sO
4, condensing reflux 3～5hr under 105 DEG C of heating conditions, then this mixture is passed through to 4～8 alcohol washes, obtain pre-product; Above-mentioned gained pre-product is dissolved in toluene solution, add 0.2mol phenylformic acid, under the temperature condition of 120 DEG C, add the catalyzer (AlCl of 0.05mol
3), condensing reflux 4hr, then, after washing for several times, under the vacuum condition of 105 DEG C, dry 4hr, obtains required phosphorous active ester compound, and esterification yield is 75～85%, and the phosphorous active ester compound that phosphorus content is 7.2%, is designated as C2, and concrete structure is as follows:
X=
, Y=H, Z=
, R is phenyl, R1=CH
3, n is 3 ~ 5.
Embodiment:
According to weight ratio shown in table 1, epoxy resin, modified polyphenylene ether resin, phosphorous active ester compound, curing catalyst and mineral filler and solvent are joined in mixed glue still, controlling glue solids content is 65%, stir, and slaking 8hr, resin combination composition glue liquid made; Then woven fiber glass is immersed in above-mentioned resin combination composition glue liquid; Then the woven fiber glass after dipping is formed to prepreg after 155 ~ 175 DEG C of baking 4 ~ 7min; Prepreg is cut to after certain size 8 prepregs stacks are formed to folded structures, respectively place up and down an electrolytic copper foil at folded structure, send into pressing in vacuum press, program is 150 DEG C/60min+200 DEG C/120min, makes veneer sheet.
Comparative example
According to weight ratio shown in table 1, each component and solvent are joined in mixed glue still, controlling glue solids content is 65%, stir, and slaking 8hr, make resin combination composition glue liquid; Then woven fiber glass is immersed in above-mentioned resin combination composition glue liquid; Then the woven fiber glass after dipping is formed to prepreg after 165 DEG C of baking 5min; Prepreg is cut to after certain size 8 prepregs stacks are formed to folded structures, respectively place up and down an electrolytic copper foil at folded structure, send into pressing in vacuum press, program is 150 DEG C/60min+200 DEG C/120min, makes veneer sheet.
Table 1 composite formula
A component: epoxy resin
A1: biphenyl type epoxy resin;
A2: dicyclopentadiene type epoxy resin;
B component: modified polyphenylene ether resin
B1: phenol modified polyphenylene ether resin, number-average molecular weight is 1000-2000;
B2: epoxide modified polyphenylene oxide resin, number-average molecular weight is 1500-4000; ;
C component: active ester
C1, C2: phosphorous active ester, prepared by synthesis example one;
C3: without phosphorus active ester, Japanese DIC company, HPC8000-65T;
D component: other P contained compounds
D1: phosphorous epoxy resin, CHIN YEE PE-315, phosphorus content 3.5%wt;
D2: phosphorus containing phenolic resin, Dow 92741 phosphorus content 9.2%wt;
E component: strengthening agent
E1: Dyhard RU 100;
E2: diaminodiphenylsulfone(DDS);
F component: curing catalyst, dimethyl-tetraethyl-imidazoles;
G component: mineral filler, silicon-dioxide, 0.5 ~ 5 micron of particle diameter.
Table 2 is respectively the performance test that embodiment mono-to five and comparative example one to four are carried out, and result is as shown in the table:
The laminate properties data of table 2 embodiment and comparative example
In table, the testing method of each performance is as follows:
(1) second-order transition temperature (Tg):
According to dsc, measure according to the DSC method of IPC-TM-650 2.4.25 defined.
(2) stripping strength (PS):
According to " after the thermal stresses " experiment condition in IPC-TM-650 2.4.8 method, the stripping strength of test metal cap rock.
(3) wicking thermotolerance:
Use the two sides band copper sample of 50 × 50mm, immerses in the scolding tin of 288 DEG C, record the time of sample layering foaming.
(4) wicking thermotolerance after moist processing:
The base material sample of 3 100 × 100mm is kept after 3hr in 121 DEG C, the pressure cooking treatment unit of 105Kpa, immerse 2min in the solder bath of 288 DEG C, observe sample whether the phenomenons such as layering bubbling occur, 3 all there is not layering bubbling and are designated as 3/3,2 there is not layering bubbling and are designated as 2/3,1 there is not layering bubbling and is designated as 1/3,0 and layering bubbling does not occur is designated as 0/3.
(5) heat decomposition temperature Td:
Measure according to IPC-TM-650 2.4.26 method.
(6) specific inductivity:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the specific inductivity under 1GHz.
(7) dielectric loss angle tangent:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the dielectric loss factor under 1GHz.
(8) drop impact toughness (veneer sheet fragility):
Use Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.
The judge that toughness is good and bad: cross bar is clear, illustrates that the toughness of product is better, and with character, ☆ represents; Cross bar is fuzzy, illustrates that the poor toughness of product, fragility are large, and with character, ◎ represents; Cross bar readability illustrates that toughness of products is general between clear and fuzzy, and with character, ◇ represents.
(9) resistance to flame (flame retardancy):
Measure according to UL94 method.
From upper table data, synthetic phosphorous active ester in the present invention's design is incorporated in resin combination, avoid resin system because of after introducing phosphorous epoxy resin or phosphorus containing phenolic resin and introducing as fire retardant (comparative example), the rising of resin water-intake rate, simultaneously, improve the humidity resistance of cyanate ester resin system, and there is lower dielectric properties constant and dielectric loss tangent value, can meet high frequency requirement.
Claims (8)
1. a halogen-free thermosetting resin composite, adds up to 100 parts in solid weight, comprising:
(a) epoxy resin: 30 ~ 50 parts;
(b) modified polyphenylene ether resin: 5 ~ 40 parts;
(c) phosphorous active ester: 15 ~ 50 parts;
(d) strengthening agent: 0 ~ 20 part.
2. halogen-free thermosetting resin composite according to claim 1, is characterized in that: described epoxy resin is selected from: the mixture of one or more of bisphenol A epoxide resin, bisphenol F epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
3. according to the halogen-free thermosetting resin composite described in claim 1, it is characterized in that: the structural formula of described phosphorous active ester compound is,
，
In formula, R1 is methyl, ethyl or the tertiary butyl;
Y is H or CH
3;
Z is
or
, wherein R is phenyl, naphthyl or C
1～C
5alkyl;
N is 1～10 integer;
X is:
,
,
or
.
4. according to the halogen-free thermosetting resin composite described in claim 3, it is characterized in that: in described phosphorous active ester compound, in mass, phosphorus content is 5.2～7.2%.
5. according to the halogen-free thermosetting resin composite described in claim 1, it is characterized in that: described modified polyphenylene ether resin is at least one in phenol modified polyphenylene ether resin or epoxide modified polyphenylene oxide resin, and its number-average molecular weight is 500 ~ 5000.
6. according to the halogen-free thermosetting resin composite described in claim 1, it is characterized in that: described strengthening agent is one or more in Dyhard RU 100, diaminodiphenylmethane, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide.
7. one kind adopts the prepreg that halogen-free thermosetting resin composite is made as described in claim 1, it is characterized in that: halogen-free thermosetting resin composite claimed in claim 1 dissolution with solvents is made to glue, then strongthener is immersed in above-mentioned glue; By the strongthener heat drying after dipping, obtain described prepreg.
8. adopt the veneer sheet that halogen-free thermosetting resin composite is made as described in claim 1, it is characterized in that: the single or double at least one the prepreg being obtained by claim 7 is covered with tinsel, hot compacting, obtains described veneer sheet.
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| CN105017723A (en) * | 2015-06-26 | 2015-11-04 | 四川东材科技集团股份有限公司 | Insulation stressed member used for extra-high voltage direct current power transmission and transformation, and preparation method thereof |
| US9738774B2 (en) | 2015-02-19 | 2017-08-22 | Icl-Ip America Inc. | Flame retardant for epoxy resin containing phosphonate and phosphinate functionality |
| WO2018031103A1 (en) | 2016-08-11 | 2018-02-15 | Icl-Ip America Inc. | Curable epoxy composition |
| CN107759977A (en) * | 2017-09-20 | 2018-03-06 | 苏州巨峰新材料科技有限公司 | Copper-clad plate modified epoxy base prepreg and preparation method thereof |
| CN109735086A (en) * | 2019-01-08 | 2019-05-10 | 苏州生益科技有限公司 | A kind of high frequency resin prepolymer and high frequency resin composition, prepreg, laminate and interlayer dielectric using its preparation |
| WO2019127992A1 (en) * | 2017-12-29 | 2019-07-04 | 洛阳尖端技术研究院 | Prepreg, composite material, and preparation methods therefor and uses thereof |
| CN115028967A (en) * | 2022-07-13 | 2022-09-09 | 山东金宝电子股份有限公司 | Resin composition and manufacturing method of high-frequency high-speed copper-clad plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9738774B2 (en) | 2015-02-19 | 2017-08-22 | Icl-Ip America Inc. | Flame retardant for epoxy resin containing phosphonate and phosphinate functionality |
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| CN115028967A (en) * | 2022-07-13 | 2022-09-09 | 山东金宝电子股份有限公司 | Resin composition and manufacturing method of high-frequency high-speed copper-clad plate |
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