CN101591471B - Resin composition for processing halogen-free copper foil base plate materials - Google Patents
Resin composition for processing halogen-free copper foil base plate materials Download PDFInfo
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- CN101591471B CN101591471B CN2008101001330A CN200810100133A CN101591471B CN 101591471 B CN101591471 B CN 101591471B CN 2008101001330 A CN2008101001330 A CN 2008101001330A CN 200810100133 A CN200810100133 A CN 200810100133A CN 101591471 B CN101591471 B CN 101591471B
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Abstract
The invention provides a resin composition for processing halogen-free copper foil base plate materials, which contains azo-cycle-containing resin materials and phosphorus-containing epoxy resin materials. Proper amount of inorganic flame-resistant filling agent is added to ensure that the base plate materials can pass a UL 94V-0 flame-resistant test and ensure that the heat resistance, the dimensional stability and the Z-shaft expansion efficiency of the halogen-free copper foil base plate materials are superior to those of common halogen-containing copper foil base plate materials and can pass an anti-CAF test and a lead-free solder process to meet the standard.
Description
Technical field
The present invention is a kind of resin combination of handling the halogen-free copper foil tellite material and preparation method thereof, refers to a kind of tool thermotolerance, substrate size stability and the Z-axle coefficient of expansion improve, the while is had environmental protection again halogen-free copper foil tellite material and preparation method especially.
Background technology
The copper foil base plate materials of general FR-4, its ignition-proof element is based on bromine, but emits and stench because of it has a large amount of black smokes when burning, and discharge objectionable impurities, therefore, environmental consciousness come back now, the demand of halogen-free copper foil base plate materials also grows with each passing day;
Modal on the market halogen-free copper foil base plate materials, it mainly is to comprise with phosphorus resin or phosphorus stiffening agent collocation inorganic additives, nitrogen resin collocation inorganic additives or directly use a large amount of inorganic additivess for main or utilize phosphorus nitrogen to take advantage of the material of effect altogether, it has the TaiWan, China patent announcement to get permission bulletin for No. 293831 and No. 322507, so can disengage the deleterious composition of aquatic animals and plants because of phosphide, it very easily produces ecology and destroys, real do not have a feature of environmental protection, in addition, the material of high content of phosphorus, then have the characteristic of easy suction again, and but described characteristic often increases many puzzlements on the circuit board making, and its machinery, and the reliability electrically, also less than traditional F R-4;
Therefore, the low-phosphorous halogen-free copper foil base plate materials of special exploitation, and the making of circuit card, because line-spacing and pitch-row densification day by day, its requirement to sheet material is also more rigorous, to guarantee that circuit card is operated when using under stricter high temperature, high humidity and high voltage environment, still have good machinery and electrically on reliability; Therefore, the halogen substrate of being developed also will have the advantage of Anti-CAF (anti-glass electric leakage), and printed circuit board (PCB) product development direction trend environmental requirement, in the technology of scolding tin, also plant by original tin splicer, change lead-free process into, also therefore make printed circuit board (PCB) be increased to 250～270 ℃ by 220 ℃, so the stable on heating requirement of copper clad laminate also show important in the processing temperature of SMT technology;
Therefore, for satisfying the requirement of market, develop this material especially and form and manufacturing technology halogen-free copper foil base plate materials;
This case contriver is urgently to think to be improved innovation in view of the every shortcoming of above-mentioned existing system institute's deutero-, and after concentrating on studies through taking great pains to attain one's goal for many years and testing, and successfully the prescription of this case copper foil base plate materials is finished in research and development finally.
Summary of the invention
Main purpose of the present invention provides a kind of resin combination of handling halogen-free copper foil base plate materials, it comprises resin material and the phosphorous epoxy resin material that contains azo-cycle at least, and adds suitable inorganic fire-retarded weighting agent and make the flame resistivity test that baseplate material can be by UL 94V-0.
Secondary objective of the present invention provides a kind of resin combination of handling halogen-free copper foil base plate materials, its can improve dimensional stability, all more general halogen-containing copper foil base plate materials of the Z-axle coefficient of expansion of thermotolerance, substrate good, have the feature of environmental protection and anti-glass electric leakage (Anti-CAF) test and Pb-free solder technology simultaneously again concurrently and all reach standard.
Illustrate
Fig. 1 is the nitrogenous resinous molecular structure figure of the present invention;
Fig. 2 is the synoptic diagram of Anti CAF test data of the present invention;
Fig. 3 is the synoptic diagram of lead-free process test condition of the present invention (IR Reflow condition);
Fig. 4 is the test data of the present invention and general brominated FR-4 material behavior;
Fig. 5 is a phosphinylidyne biphenol compound structure iron of the present invention.
Embodiment
For the effect that makes things convenient for simple and direct understanding other features of the present invention and advantage and reached can more manifest, with conjunction with figs. of the present invention, be described in detail as follows now:
All herein content " part " numbers that relates to each composition all refer to " weight part ".
The present invention is a kind of resin combination of handling halogen-free copper foil base plate materials and preparation method thereof, and the composition of wherein said processing halogen-free copper foil base plate materials comprises:
Nitrogenous resin (Benzoxazine): nitrogen content is 5～50%, and molecular weight is 500～10000, and its molecular structure sees also shown in Figure 1.
Not halogen-containing isocyanic ester based epoxy resin: not halogen-containing isocyanic ester based epoxy resin is isocyanate modified epoxy resin (Isocyanate modified Epoxy).
Phosphorous epoxy resin: (phosphorous epoxy resin is tool P contained compound DOPO:9 to the phosphorous epoxy resin that uses, the Resins, epoxy of 10-dihydro-9-oxa-10-phosphaphan-threne 10 oxide structures, structural formula such as accompanying drawing five), its phosphorus content is 1～20%, epoxy equivalent (weight) (Epoxy Equivalent Weight, EEW) be 200～1000, hydrolyzable chloride content is less than 500ppm
Stiffening agent: the stiffening agent of use can be amine type hardeners (amine) or phenols (phenol) stiffening agent; The amine type hardeners of using (amine), its molecular weight is 80～1000, contains 1 reactive with active hydrogen base in the molecular structure at least, its usage quantity is 2～30 parts; And, then be 20～70 parts if with phenols (phenol) stiffening agent, be benchmark with 100 parts epoxy compoundss, as the polymerizing agent (curing agent) of polymerization sclerous reaction.
Catalyzer: the catalyzer of use is a heterocyclic amine as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 3,5-dimethylphenyl amine (Benyl dimethylamine) etc.
Inorganic fire-retarded weighting material, it comprises:
Nitrogenous phosphorated material (Ammonium Polyphosate or Melamine Pyrophosphate), nitrogen content is 5～50%, and phosphorus is 1～20%, and particle diameter is 1～100um.
Phosphorous particle (Phosphorus particle), phosphorus content is 1～20%, particle diameter is 1～100um.
Aluminium hydroxide (Al (OH) 3), aluminium sesquioxide (Al2O3), magnesium hydroxide (Mg (OH) 2), magnesium oxide inorganic additives such as (MgO), particle diameter is 1～100um.
Nano grade inorganic silicon-dioxide, particle diameter are 1～500nm
Dispersion agent: use dispersion agent to be silane coupling agent (Silane), comprise aminosilane coupling agent (amino-silane) and epoxy radicals silicone hydride coupler (epoxy-silane).
Thinner: can use acetone (Acetone), methylethylketone (MEK), pimelinketone (cyclohexanol), 1-methoxyl group-2-propyl alcohol (PM), acetate 1-methoxyl group-2-propyl alcohol ester (PMA)
Wherein:
Described nitrogenous resin when exposing laminated thing at flame or high temperature to the open air, generates flame-retardant layer with slow burning, and the nitrogen content that its use contains the azo-cycle resin material is 5～50%, and molecular weight is 500～10000, and usage quantity is 100 parts; Wherein if nitrogen content surpasses 50% reactivity that influences material few in 5% no fire-retardant effect; And if its molecular weight then has the excessive phenomenon of gummosis less than 70, and if molecular weight then has the phenomenon of moistening (wetting) state meeting variation of resin and glass interfascicular greater than 10000.
Described not halogen-containing isocyanic ester based epoxy resin, be to carry out crosslinked with stiffening agent, and form stable reticulated structure, make it to have good anti-bubble, so selected not halogen-containing polyurethanes epoxy resin: not halogen-containing polyurethanes epoxy resin is Isocyanate modified epoxy, its epoxy equivalent (weight) of Resins, epoxy (Epoxy Equivalent Weight, EEW) be 200～1500, usage quantity is 5～30 parts, wherein epoxy equivalent (weight) has the excessive phenomenon of gummosis if height is understood variation to 1500 moistening (wetting) states that have resin and glass interfascicular if be low to moderate 200.Wherein hydrolyzable chloride content must be less than 500ppm, if greater than 500ppm, then can influence the carrying out of sclerous reaction, usage quantity if less than 5 parts then to no effect, surpass 30 parts of then right property of influence resistance.
Described phosphorous epoxy resin, be when exposing laminated thing to the open air at flame or high temperature, generate flame-retardant layer with slow burning, after being soaked in nonwoven glass cloth, form the laminated thing of difficult combustion to form varnish, what make has a heat-resisting and anti-bubble of good welds, its best phosphorus content scope is 1～20%, (Epoxy Equivalent Weight is 200～1000 EEW) to epoxy equivalent (weight), and usage quantity is 20～70 parts; Wherein epoxy equivalent (weight) has the excessive phenomenon of gummosis if height is understood variation at 1000 moistening (wetting) states that have resin and glass interfascicular if hang down 200; If the hydrolyzable chloride content of described phosphorous epoxy resin then can influence the carrying out of sclerous reaction greater than 500ppm again; And hang down at 20 parts when usage quantity, then flame retardant effect is not obvious, and is high at 70 parts, and then the water-absorbent of substrate becomes big.
The stiffening agent that carries out the polymerization sclerous reaction with epoxy compounds can be amine type hardeners (amine), its molecular weight is 80～1000, at least contain 1 reactive with active hydrogen base in the molecular structure, its usage quantity is 2～30 parts, and at room temperature can not react, it carries out temperature of reaction and must therefore can store for a long time more than 170 ℃.
Its consumption of the reaction of amine type hardeners and epoxy compounds is that per 100 parts of epoxy compoundss add 2～30 parts, if be low to moderate 2.0 parts, then if the hardenability deficiency of polyreaction high to 30 parts, then the phenomenon that stiffening agent is separated out can occur; If with phenolic hardeners, then its molecular weight is 100～1000g/mol., and its molecular structure contains a reactive with active hydrogen base at least; The reaction consumption of phenolic hardeners and epoxy compounds is that per 100 parts of epoxy compoundss add 20～70 parts, if low to 20 parts, then if the hardenability deficiency of polyreaction high to 70 parts, the excessive phenomenon of gummosis then can occur.
Described catalyzer is a heterocyclic amine, as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 3,5-dimethylphenyl amine (Benyl dimethylamine) etc., the characteristic of heterocyclic amine is for reducing temperature of reaction, if do not use heterocyclic amine, then sclerous reaction just begins about 170 ℃, if use then sclerous reaction just generation about 120 ℃ of heterocyclic amine, usage quantity is 0.01～1.0 part, wherein usage quantity Ruo Taigao then makes reactivity too fast, influences the storage time, and if consumption is too little, then to no effect.
Described inorganic fire-retarded weighting material, wherein nitrogenous phosphorated material is nitrogenous phosphorated particle, nitrogen content is 5～50%, phosphorus is 1～20%, particle diameter is 1～100um, and addition is 0～30 part, and its purpose is in the flame retardant resistance of strengthening baseplate material, usage quantity is if surpass 30 parts, and then the thermotolerance of substrate can obvious variation.
Described phosphorous particle, phosphorus content are 1～20%, and particle diameter is 1～100um, and addition is 0～30 part, and purpose is in the flame retardant resistance of strengthening baseplate material, and usage quantity is if surpass 30 parts, and then the thermotolerance of substrate can obvious variation.
Described aluminium hydroxide (Al (OH) 3), aluminium sesquioxide (Al2O3), magnesium hydroxide (Mg (OH) 2), the selection of magnesium oxide fire-retardant additives such as (MgO) is not to influence raw-material characteristic, and it is main reaching the target that will improve, and usage quantity is 0～100 part, if usage quantity is too high, then make too thickness of rubber water, and influence moistening (wetting) of itself and woven fiber glass; If consumption is too little, then to no effect.
Described nano grade inorganic silicon-dioxide, not influencing raw-material characteristic, and to reach the target that will improve be main, usage quantity is 0～30 part, if usage quantity is too high, then makes too thickness of rubber water, influence moistening (wetting) of itself and woven fiber glass, consumption is too little, then to no effect.
For described inorganic additive is uniformly dispersed in Resins, epoxy, the present invention adds dispersion agent, its dispersion agent that uses is silane coupling agent, comprise aminosilane coupling agent (amino-silane) or epoxy radicals silicone hydride coupler (epoxy-silane), be used for improving the combination stability between inorganics and nonwoven glass cloth, and reach finely dispersed purpose, and this type of coupler heavy metal free exists, can not cause detrimentally affect to human body, usage quantity is 0.1～5.0 part, if usage quantity is too high, then add fast response, influence the storage time, consumption is too little, then to no effect.
Its principle of selecting for use of described thinner is for containing when being dipped on the woven fiber glass, and behind 60～190 ℃ of following exsiccant, do not remain in the material, as using acetone (Acetone), methylethylketone (MEK), pimelinketone (cyclohexanol), 1-methoxyl group-2-propyl alcohol (PM), acetate-1-methoxyl group-2-propyl diester (PMA).
Embodiments of the invention can utilize the cylinder coating machine that slurry is coated on the glasscloth, are a polymeric substrate behind the dry through.
Glass tansition temperature, thermotolerance, thermal stresses test are interconnected and (the The Institute for Interconnecting and Packaging Electronic Circuits of encapsulation association of electronic circuit with the test specification of the Z axle coefficient of expansion, IPC) IPC-TM-650 detection method, wherein the test specification of glass transfer temperature is IPC-TM-650.2.4.25C and 24C detection method, and the test specification of the Z axle coefficient of expansion is the IPC-TM-650.2.4.41 detection method; Stable on heating test specification is the IPC-TM-650.2.4.24.1 detection method; Thermal shock test is put into tin stove pull-up after 20 seconds of 288 ℃ again for test piece being put into 2 normal atmosphere, 121 ℃ following 1 hour of hot and humid environment, repeats the action 5 times that this immerses pull-up; Specific inductivity and dissipation loss are according to the IPC-TM-650.2.5.5.3 detection method; The water absorbability of substrate is according to the IPC-TM-650.2.6.2.1 detection method; Anti-glass leakage current characteristic test is with Japanese Industrial Standards (Japan Industrial Standard, the standard of JIS-Z3284 JIS).Testing method is that substrate is 85 ℃ of temperature, relative humidity is under 85% the environment, feed the direct current of 100V, detection in the hole to hole (pitch-row 0.7mm, aperture 0.3mm) and the resistance value of Line To Line (line length 100 μ m, line-spacing 100 μ m) test event less than time (seeing also shown in Figure 3) of 108ohm.The test condition of lead-free process is to contain copper base with 5, size is 290*210mm, behind IR RefloW 3 times (seeing also shown in Figure 3),, observe and contain copper base and whether have copper face to peel off or the phenomenon of plate bursting with Solder dip/288 ℃/20sec/5 time test.
The present invention provides a kind of resin combination of handling halogen-free copper foil base plate materials, and its technology is as follows:
It is that 50 parts phosphorous epoxy resin and 100 parts are contained azo-cycle resin (Benzoxazine), and 10 parts of polyurethanes epoxy resin tools and 35 parts stiffening agent and 0.1 part catalyzer, and 3 parts phosphorous weighting material, and 3 parts nanometer grade silica, after at room temperature mixing 60 minutes, add 30 parts of 40 parts in inorganic filler aluminium hydroxide (Al (OH) 3) and 1.5 parts of dispersion agents and thinners again by agitator.
With aforesaid formulation 30～45 ℃ down stir 120 minutes after, again the varnish shape thing of institute's furnishing is immersed on 7628 the woven fiber glass on the drum-type impregnation machine varnish being contained.
Aforementioned woven fiber glass through impregnation is carried out pressing with the thickness (39mil) of 7628*5 at the Copper Foil of outermost layer two sides and each 1oz respectively, again the substrate after the pressing is carried out Characteristics Detection.
Please consult shown in Figure 4 again, test data by described test data and general brominated F-4 copper clad laminate can be found, the present invention really can be by the flame resistivity test of UL 94V-0, and make dimensional stability, the good person of all more general halogen-containing copper foil base plate materials of the Z-axle coefficient of expansion of thermotolerance, substrate, and possess again can be by anti-glass electric leakage (Anti-CAF) test and Pb-free solder technology.
For making the present invention more show its progressive and practicality, hereby as follows with one comparative analysis of existing do:
Existing disappearance
1, when burning, have a large amount of black smokes and emit and stench, and the suitable harmful substance of emitting.
2, ecology is produced destruction.
3, do not have a feature of environmental protection.
Advantage of the present invention
1, heavy metal free exists, and can not cause detrimentally affect to human body.
2, improve combination stability between inorganics and nonwoven glass cloth.
3, tool environmental protection.
4, thermotolerance is good.
5, the dimensional stability of substrate is good.
6, the Z-axle coefficient of expansion is good.
7, can be by anti-glass electric leakage (Anti-CAF) test and Pb-free solder technology, conformance with standard.
More than explanation is just illustrative for the purpose of the present invention; and nonrestrictive, those of ordinary skills understand, under the situation of the spirit and scope that do not break away from claim and limited; can make many modifications, variation or equivalence, but all will fall into protection scope of the present invention in.
Claims (4)
1. resin combination of handling halogen-free copper foil base plate materials, its composition comprises at least:
A kind of nitrogenous resin, its structure is suc as formula shown in the I: using nitrogen content is 5～50%, and molecular weight is 500～10000, and usage quantity is 100 parts;
Not halogen-containing polyurethanes epoxy resin: not halogen-containing polyurethanes epoxy resin is an isocyanate modified epoxy resin;
Phosphorous epoxy resin: generate flame-retardant layer with slow burning when high temperature, phosphorus content is 1～20%, and epoxy equivalent (weight) is 200～1000, and hydrolyzable chloride content is less than 500ppm, and usage quantity is 20～70 parts;
Stiffening agent: carry out the polymerization sclerous reaction with described epoxy compounds, the stiffening agent that uses is amine type hardeners, and its molecular weight is 80～1000, contains 1 reactive with active hydrogen base in the molecular structure at least, and its usage quantity is 2～30 parts;
Catalyzer: reduce temperature of reaction, the catalyzer that uses is heterocyclic amine, and usage quantity is 0.01～1.0 part;
Inorganic fire-retarded weighting material: the flame retardant resistance of strengthening baseplate material;
Dispersion agent: described inorganic additive is uniformly dispersed in described Resins, epoxy, and usage quantity is 0.1～5.0 part;
Thinner: can use acetone, methylethylketone, pimelinketone, 1-methoxyl group-2-propyl alcohol, acetate-1-methoxyl group-2-propyl diester.
2. the resin combination of processing halogen-free copper foil base plate materials according to claim 1, it is characterized in that: described stiffening agent is a phenolic hardeners, its molecular weight is 100～1000, contains 1 reactive with active hydrogen base in its molecular structure at least, and its usage quantity is 20～70 parts.
3. the resin combination of processing halogen-free copper foil base plate materials according to claim 1 is characterized in that: described inorganic fire-retarded weighting material comprises at least:
Nitrogenous phosphorous weighting material is nitrogenous phosphorated particle, and nitrogen content is 5～50%, and phosphorus is 1～20%, and particle diameter is 1～100um, and addition is 0～30 part;
Phosphorous weighting material is the phosphorated particle, and phosphorus content is 1～20%, and particle diameter is 1～100um, and addition is 0～30 part;
Aluminium hydroxide, aluminium sesquioxide, magnesium hydroxide, the fire-retardant additive of magnesium oxide, usage quantity is 0～100 part;
Nano grade inorganic silicon-dioxide, usage quantity are 0～30 part.
4. the resin combination of processing halogen-free copper foil base plate materials according to claim 1 is characterized in that: dispersion agent is a silane coupling agent, comprises aminosilane coupling agent and epoxy radicals silicone hydride coupler.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775734A (en) * | 2012-08-15 | 2012-11-14 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg prepared by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102134377B (en) * | 2010-01-26 | 2014-10-08 | 台燿科技股份有限公司 | Electronic material composition |
| CN102399414A (en) * | 2010-09-08 | 2012-04-04 | 联茂电子股份有限公司 | Resin composition, dielectric structure containing the resin composition and preparation method of the dielectric structure containing the resin composition |
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| CN1119444A (en) * | 1993-03-15 | 1996-03-27 | 西门子公司 | Epoxy resin mixtures |
| CN1272424A (en) * | 1999-04-29 | 2000-11-08 | 北京化工大学 | Composite base laminated board covered with copper foil and its production method |
| CN1488672A (en) * | 2003-08-01 | 2004-04-14 | 广州宏昌电子材料工业有限公司 | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same |
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Patent Citations (3)
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|---|---|---|---|---|
| CN1119444A (en) * | 1993-03-15 | 1996-03-27 | 西门子公司 | Epoxy resin mixtures |
| CN1272424A (en) * | 1999-04-29 | 2000-11-08 | 北京化工大学 | Composite base laminated board covered with copper foil and its production method |
| CN1488672A (en) * | 2003-08-01 | 2004-04-14 | 广州宏昌电子材料工业有限公司 | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same |
Non-Patent Citations (2)
| Title |
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| JP特开2004-43699A 2004.02.12 |
| JP特开2007-326929A 2007.12.20 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775734A (en) * | 2012-08-15 | 2012-11-14 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg prepared by using same |
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