CN1167495A - Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same - Google Patents
Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same Download PDFInfo
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- CN1167495A CN1167495A CN 95196516 CN95196516A CN1167495A CN 1167495 A CN1167495 A CN 1167495A CN 95196516 CN95196516 CN 95196516 CN 95196516 A CN95196516 A CN 95196516A CN 1167495 A CN1167495 A CN 1167495A
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Abstract
A halogen-free flame-retardant epoxy resin composition containing: a bisphenol A epoxy resin; a novolak epoxy resin, a phenol resin curative; a cure accelerator; and an inorganic filler. Cocondensate resin formed among phenol, guanamine and aldehyde compounds, still preferably a phenol resin contianing phosphorus and nitrogen atoms. It is also possible to use a curative comprising a combination of (C-1) the cocondensate resin with (C-2) a reactive phosphoric ester.
Description
Technical field
The present invention relates to composition epoxy resin and contain the prepreg and the laminated plate of this resin combination; Specifically, the present invention relates to the halogen free flame retardant composition epoxy resin and contain the prepreg of this resin combination, and laminated plate, copper foil laminate, the printed-wiring board (PWB) made with this prepreg.
Technical background
In recent years, along with the extensive concern of worldwide environmental problem, human safety problem, reduce electric, electronic product hazardness, improving its security and requiring increases day by day, simultaneously, also begins its flame retardant resistance of requirement.Not only require the difficult combustion of electrical and electronic product, and require to reduce the generation of obnoxious flavour and smog.Past, the printed-wiring board (PWB) of assembling electrical and electronic product normally has the substrate of being made by epoxy glass, and as wherein used Resins, epoxy, typically use the brominated epoxy resin of the bromine that has contained the fire retardant effect, particularly tetrabromo-bisphenol type Resins, epoxy.
Though this brominated epoxy resin has excellent flame-retardant performance, produce deleterious hydrogen halide (hydrogen bromide) gas during burning, thereby the use that is under an embargo.For this reason, the someone develops the non-halogen fire retardant that is mixed in ordinary epoxy resin, as the composition of nitrogenous compound, P contained compound, inorganics etc. (as No. the 1st, 112,139, English Patent; Japanese kokai publication hei 2-269730 number).But these additives of composing pre-flame retardant resistance have following point: the sclerosis to Resins, epoxy has detrimentally affect, reduces the wet fastness of hardening composition, or the dipping in the woven fiber glass of reduction composition etc.
In view of the above problems, the object of the present invention is to provide a kind of not halogen-containing, good flame-retardance is arranged and overcomes the composition epoxy resin of former technical disadvantages.
Laminated plate, copper foil laminate and printed-wiring board (PWB) that another object of the present invention is to provide prepreg with this resin impregnation, makes with this prepreg.
Summary of the invention
The present invention is in first embodiment, a kind of flame-retardant epoxy resin omposition of halogen is provided, said composition is mixed with (A) bisphenol A type epoxy resin, (B) phenolic resin varnish type epoxy resin, (D) hardening accelerator and (E) inorganic filler, in order to compose pre-said composition flame retardant resistance, so the nitrogenous resol that is mixed in said composition is as solidifying agent (C).
Nitrogenous resol also can be the amino phenol urea formaldehyde, but is the cocondensation resin of oxybenzene compound/guanamines compound/aldehyde cpd in a preferred embodiment of the invention.
The present invention is in second embodiment, a kind of flame-retardant epoxy resin omposition of halogen is provided, said composition is mixed with (A) bisphenol A type epoxy resin, (B) phenolic resin varnish type epoxy resin, (D) hardening accelerator and (E) inorganic filler, in order to compose pre-said composition flame retardant resistance, the resol of be mixed in said composition nitrogen atom and phosphorus atom is as solidifying agent (C).
The used resol that contains phosphorus atom and nitrogen-atoms is the reaction product of oxybenzene compound, guanamines compound, aldehyde cpd and active phosphate preferably.
The present invention provides a kind of flame-retardant epoxy resin omposition of halogen in the 3rd embodiment, said composition contains the cocondensation resin, (D) hardening accelerator of (A) bisphenol A type epoxy resin, (B) phenolic resin varnish type epoxy resin, (C-1) active phosphate, (C-2) oxybenzene compound/guanamines compound/aldehyde cpd and (E) inorganic filler.
The present invention also provides the prepreg with the flame-retardant epoxy resin omposition dipping of the invention described above halogen; With the laminated plate made from this prepreg, copper foil laminate and printed-wiring board (PWB).
Implement the preferred embodiments of the invention
Describe the present invention below in detail.
Composition epoxy resin of the present invention as composition (A), contains bisphenol A type epoxy resin.As everyone knows, bisphenol A type epoxy resin is the reaction product of dihydroxyphenyl propane and epoxy chloropropane etc.The epoxy equivalent (weight) number of used bisphenol A type epoxy resin is usually more than 170 among the present invention.If equivalents surpasses 1000, the dipping reduction of the composition of gained in woven fiber glass, this is not that we are desirable.Commercially available bisphenol A type epoxy resin generally is the EPIKOTE series of Japanese Yuka Shell company and the ARALDITE series plastics of Ciba Geigy company.This bisphenol A type epoxy resin can the independent or two or more uses that are mixed.
The composition of composition epoxy resin of the present invention (B) is a phenolic resin varnish type epoxy resin.As everyone knows, phenolic resin varnish type epoxy resin is the Resins, epoxy that epoxy chloropropane reacts in novolac resin and obtains.Novolac resin is in the presence of an acidic catalyst, the resin that phenols and formaldehyde generation condensation obtain.As by producing the phenols of novolac resin, can use phenol, ortho-cresol, dihydroxyphenyl propane etc. with formaldehyde reaction.Be used for phenolic resin varnish type epoxy resin of the present invention, softening temperature is 70 ℃-130 ℃, and optimum range is 80 ℃-100 ℃.This class phenolic resin varnish type epoxy resin for example, changes into company and big Japanese INK chemical industrial company provides by Japanese Dongdu.Phenolic resin varnish type epoxy resin can the independent or two or more uses that are mixed.
The composition that composition epoxy resin of the present invention contains (C) is the resol of nitrogen atom in the molecule, as stiffening agent and be used for composing pre-resin combination flame retardant resistance.Self-evident, resol is the reaction product of aldehydes such as phenols and formaldehyde.Contained nitrogen may reside in all sites of resol in the resol of nitrogen atom, and for example, this nitrogen can be provided by the nuclear substituted amino of phenol.For example, the resol of nitrogen atom also comprises the amino phenol urea formaldehyde.
But in a preferred embodiment of the invention, the resol of nitrogen atom is the cocondensation resin of phenolic compound, guanamines compound and formolation compound.
This cocondensation resin is to exist down at acid catalyst (for example, oxalic acid, P-toluenesulphonic acids), phenolic compound, aldehyde cpd and guanamines compound is reacted prepare.In the case, the mol ratio of aldehyde cpd and phenolic compound is less than 1.0, and optimum range is below the 0.5-1.0, with respect to 1 grade of amino (NH of guanamines
2) with 1 mole of aldehyde cpd (for example: 1 mole of trimeric cyanamide with 3 moles of formaldehyde, 1 mole of benzoguanamine 2 moles of formaldehyde).
As used oxybenzene compound, specifiable have phenol, Resorcinol, an alkylphenol (ortho-cresol, xylenol etc.).
Aldehyde compound is preferably selected formaldehyde for use.
The structural formula of expression guanamines compound is:
(in the formula, R represents alkyl such as amino, phenyl or methyl).Generally select the specifiable example as the guanamines compound such as trimeric cyanamide, benzoguanamine, methyl guanamines for use.This guanamines compound can the independent or two or more uses that are mixed.
When using the resol of above-mentioned nitrogen atom, because itself and following weighting agent synergy can obtain effect of sufficient aspect the flame retardant resistance of raising resin as stiffening agent.But, when using composition epoxy resin of the present invention to produce epoxy glass copper foil laminate, printed-wiring board (PWB),,, preferably select the resol of nitrogen atom in the molecule, phosphorus atom for use as solidifying agent for improving tracking index.
The resol of nitrogen atom and phosphorus atom can be produced by phenolic compound, guanamines compound, aldehyde cpd and active phosphate reaction.
Phenolic compound, guanamines compound, aldehyde cpd consumption are by the aforementioned cocondensation resin time institute certainty ratio of producing in this reaction; The active phosphate consumption is dosed in the ratio of the corresponding 2 moles of aldehyde of its each free hydroxyl group.
For example, produce the method for the resol of nitrogen atom and phosphorus atom, a kind of is the single stage method that phenolic compound, guanamines compound, aldehyde cpd and active phosphate one are reacted; Another kind is the cocondensation resin for preparing phenolic compound, guanamines compound, aldehyde cpd in advance, and then itself and aldehyde and active phosphate one is reacted produce the two-step approach of the resol that contains phosphorus atom and nitrogen-atoms.Phenolic compound, guanamines compound, aldehyde cpd and active phosphate are all dosed according to the above ratio in these two kinds of methods.When producing above-mentioned cocondensation resin in advance, this moment used aldehyde amount and back together the condensation resins total amount of reacting used aldehyde amount decide by aforementioned ratio.
Used active phosphate is the product of 3 molecule phenolic compound and 1 molecule triclosan oxidation phosphorus reaction.At least 1 has 2 hydroxyls in the 3 molecule phenolic compound.For example Resorcinol, pyrogaelol can be used as the example of the phenolic compound with 2 above hydroxyls.The active phosphate structural formula that is used for the present invention is:
(in the formula: a+b+c=3; A=1,2 or 3; B=0,1 or 2; C=0,1 or 2; N is 1 or 2; R
1, R
2, R
3, R
4And R
5Be hydrogen atom or alkyl such as methyl, at least one in the middle of these is alkyl).The resorcyl diphenyl phosphoester that for example has Japan's aginomoto (strain) to provide, its trade name are RDP.
Can take phenolic compound/guanamines compound/aldehyde cpd cocondensation resin and active phosphate to sneak in the Resins, epoxy to substitute the method that is mixed again and reacts after the pre-reaction as independent component respectively in addition.In this case, active phosphate (composition C-1) is respectively 5-30% (wt), 70-95% (wt) with the consumption of phenolic compound/guanamines compound/aldehyde cpd cocondensation resin (composition C-2), and when the former used quantity not sufficient 5%, tracking index was bad, surpass at 30% o'clock, wet fastness reduces.
Hardening accelerator (D) contained in composition epoxy resin of the present invention is the curing catalyst that is generally used for promoting epoxy resin cure, imidazolium compoundss such as 2-ethyl-4-methylimidazole commonly used and 1 benzyl 2 methyl imidazole.The use that can separately or be mixed of these curing catalysts.The consumption of curing catalyst in promoting epoxy resin cure should lack fully.
Inorganic filler (composition E) contained in the composition epoxy resin of the present invention is composed the additional flame retardant resistance of pre-resin combination, thermotolerance, wet fastness.The weighting agent that is used for the present invention comprises that independent or two or more being mixed all can as talcum, silicon-dioxide, alundum, aluminium hydroxide, magnesium hydroxide etc.
In no-halogen type flame-retardant epoxy resin omposition of the present invention, account for the 5-50 weight part of composition A+B+C+D+E gross weight as the inorganic filler optimum amount of composition (E).During quantity not sufficient 5 weight parts of composition (E), can not get excellent flame-retardant performance, thermotolerance, wet fastness, and the amount of composition (E) is when surpassing 50 weight parts, the viscosity of gained resin combination increases, and causes being easy to generate the phenomenons such as laminated plate uneven thickness that are coated with spot, the space is arranged, obtain on the base materials such as glass non-woven fabrics, glass woven.
In composition epoxy resin of the present invention, resin solid state component [composition (A)+(B)+(C)+(D)] consumption preferably accounts for the 50-95 weight % of composition (A)+(B)+(C)+(D)+(E) gross weight.Wherein composition (D) consumption is a spot of as mentioned above, for example accounts for 0.01～1 weight % and gets final product.
Resins, epoxy composition [composition (A)+(B)] is pressed the corresponding 0.8-1.2 equivalent of per 1 equivalent hydroxyl in all resins composition with resol composition (C) [or situation of composition (C-1)+(C-2)], and preferred 0.95-1.05 equivalent epoxy group(ing) is come proportioning.Resins, epoxy composition consumption is about 51-80% of the resinous principle gross weight of all resins composition in this case.
Composition (A) consumption is preferably the 60-95 weight % of (A)+(B) gross weight.
In the present invention, nitrogen atom content is generally the 1-10 weight % of composition epoxy resin total amount, preferred 4-7 weight %, and phosphorus atom content is 0.5-3 weight %, is preferably 0.8-1.5 weight %.By above-mentioned content be mixed composition (C) or composition (C-1) and (C-2) good flame retardant resistance and tracking index can be arranged.
The usual way of producing prepreg of the present invention is as follows: with the composition epoxy resin of suitable organic solvent such as monomethyl propylene glycol dilution the invention described above, coating or dipping are as the sintered glass base material of glass non-woven fabrics or glass woven etc. then, and reheat gets final product.Zhi Bei prepreg can be used for the manufacturing copper foil laminated plate like this.The method of producing the epoxy glass copper foil laminate is as follows: this prepreg of laminated multi-layer, the Copper Foil that then superposes on the single or double of rhythmo structure heats it, pressurizeing just can obtain the epoxy glass copper foil laminate then under usual conditions.If just obtain the normal stack plate without Copper Foil.It is as follows to produce multiple-plate usual way: on copper foil laminate (inner plating), optionally etch is handled Copper Foil to form the loop, lamination prepreg and Copper Foil at least one surface of inner plating then, with it at for example 170 ℃, 40kg/cm
2The heating, the pressurization that kept under the condition of pressure 90 minutes get final product.The universal method of producing printed-wiring board (PWB) is as follows: after forming through hole on copper foil laminate or the multi-ply wood, carry out the through hole spray treatment, then form required loop.
With specific embodiment the present invention is described below.
Produce embodiment A
In the mixture that 56 weight (wt) part benzoguanamine, 300wt part 37% formlinata aquae concentratac, 367wt part phenol are formed, add 0.1wt part oxalic acid, again with the mixture decompression dehydration after reacting 2 hours under 80 ℃ that obtains.Add methyl ethyl ketone in the reaction product that obtains, adjusting resin solid state component (phenol/benzoguanamine/formaldehyde cocondensation resin) content is 70wt weight %.Nitrogen content is 4wt% in the cocondensation resin that obtains.
Produce Embodiment B
Under 80 ℃, make the mixture reaction 30 minutes that 18wt part trimeric cyanamide, 28wt part benzoguanamine, 50wt part 37% formlinata aquae concentratac form.In this reaction mixture, add 367wt part phenol, 250wt part 37% formlinata aquae concentratac then, add 0.1 part of oxalic acid again.The reaction mixture that obtains reacted 2 hours down in 80 ℃ again, then decompression dehydration.Add methyl ethyl ketone in the reaction product that obtains, adjusting resin solid state component (phenol/trimeric cyanamide/benzoguanamine/formaldehyde cocondensation resin) content is 70wt%.Nitrogen content is 4wt% in the cocondensation resin that obtains.
Produce Embodiment C:
In the mixture that 50 weight part benzoguanamines, 214 weight parts, 37% formlinata aquae concentratac, 248 weight part phenol and 36 weight part RDP (aginomoto company of Japan makes, the resorcyl diphenyl phosphoester) form, add 0.1 weight part oxalic acid.Descend reaction after 2 hours at 80 ℃ this reaction mixture, decompression dehydration.Add methyl ethyl ketone in the reaction product that obtains, adjusting resin solid state component (phosphorus sex change benzoguanamine/phenol/formaldehyde cocondensation resin) is 70wt%.Nitrogen content is 4wt% in the resin that obtains, and phosphorus content is 1wt%.
Produce embodiment D
Under the reaction conditions identical with Embodiment C, the reaction mixture that 92.5 weight part benzoguanamines, 218 weight parts, 37% formlinata aquae concentratac, 212 weight part phenol and 115 weight part RDP are formed reacts, and obtains the resol of nitrogen atom and phosphorus atom.Nitrogen content is 8wt% in this resin, and phosphorus content is 2wt%.
Embodiment 1
To 260 weight part bisphenol A type epoxy resin EPIKOTE 1001 (oiling Shell corporate systems, epoxy equivalent (weight) several 456, resin solid state component 70wt%), (Dongdu changes into corporate system to 65 weight part methoxycresol phenolic resin varnish YDCN-704P, epoxy equivalent (weight) several 210, solid state component 70wt%), 128 weight parts are produced the nitrogen atom that routine C obtains and the resol of phosphorus atom, add monomethyl propylene glycol solvent (PGM) in the mixture that 175 weight part aluminium hydroxides and 0.1 weight part 2-ethyl-4-methylimidazole are formed, make the epoxy resin varnish that the resin solid state component is 65wt%.
Embodiment 2
Produce in the mixture that resol, 150 weight part aluminium hydroxides and the 0.1 weight part 2-ethyl-4-methylimidazole of nitrogen atom that embodiment D obtains and phosphorus atom form to 260 weight part bisphenol A type epoxy resin EPIKOTE, 1001,65 weight part methoxycresol phenolic resin varnish YDCN-704P, 184 weight parts and to add PGM, make the epoxy resin varnish that the resin solid state component is 65wt%.
Embodiment 3
Produce in the mixture that resol, 150 weight part aluminium hydroxides and the 0.1 weight part 2-ethyl-4-methylimidazole of nitrogen atom that Embodiment C obtains and phosphorus atom form to 260 weight part bisphenol A type epoxy resin EPIKOTE, 1001,65 weight part methoxycresol phenolic resin varnish YDCN-704P, 206 weight parts and to add PGM, make the epoxy resin varnish that solid state component is 65wt%.
Embodiment 4
Produce in the mixture that cocondensation resin, 200 weight part aluminium hydroxides and 0.1 weight part 2-ethyl-4-methylimidazole that embodiment A obtains form to 260 weight part bisphenol A type epoxy resin EPIKOTE, 1001,65 weight part methoxycresol phenolic resin varnish YDCN-704P, 105 weight parts and to add PGM, make the epoxy resin varnish that the resin solid state component is 65wt%.
Embodiment 5
In the mixture that cocondensation resin, 30 weight part RDP, 175 weight part aluminium hydroxides and 0.1 weight part 2-ethyl-4-methylimidazole that 260 weight part bisphenol A type epoxy resin EPIKOTE, 1001,65 weight part methoxycresol phenolic resin varnish YDCN-704P, 105 weight parts manufacturing embodiment A make are formed, add PGM, make the epoxy resin varnish that the resin solid state component is 65wt%.
Comparative example 1
To 283 weight part brominated epoxy resins (big Japanese INK chemical industry society system, epoxy equivalent (weight) several 490, solid state component 75wt%), 34 weight part methoxycresol phenolic resin varnish YDCN-704P, 92 weight part bisphenol A-type resol (big Japanese INK chemical industrial company system, hydroxyl value 118, solid-state component 70wt%), add PGM in the mixture formed of 130 weight part aluminium hydroxides and 0.1 part of 2-ethyl-4-methylimidazole, make the epoxy resin varnish that the resin solid state component is 65wt%.
Comparative example 2
Add N in the mixture that used brominated epoxy resin, 43 weight part methoxycresol phenolic resin varnish YDCN-704P, 7.5 weight part Dyhard RU 100s, 130 weight part aluminium hydroxides and 0.1 weight part 2-ethyl-4-methylimidazole formed in 360 weight part comparative examples 1, dinethylformamide makes the epoxy resin varnish that the resin solid state component is 65wt%.
Epoxy resin varnish difference continuously coating or dipping glass non-woven fabrics or woven fiber glass with embodiment 1-5 and comparative example 1-2 obtain obtain prepreg 160 ℃ of following dryings.With 8 prepreg laminations that so obtain, then stack thickness is the Copper Foil of 18 μ m on two surfaces of this laminated plate, at 170 ℃ temperature, 40kg/cm
2Pressure heating down, pressurization 90 minutes, obtaining thickness is the 1.6mm copper foil laminate.
With the flame retardant resistance of the copper foil laminate that obtains, tracking index, insulation strength, initial stage with peel off intensity, thermotolerance, wet fastness through the Copper Foil after long-term and measure.The result is as shown in table 1.
Table 1
| Composition character | Embodiment | Comparative example | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????1 | ????2 | ||
| Flame retardant resistance *1 | ???V-1 | ???V-0 | ???V-0 | ???V-0 | ???V-0 | ???V-0 | ???V-0 | |
| Tracking index *2 | ???300V | ???600V | ???600V | ???200V | ???600V | ???200V | ???200V | |
| Insulation strength *3 | ???5.0 | ???2.0 | ???0.75 | ???5.0 | ???3.0 | ???2.0 | ???2.0 | |
| The Copper Foil stripping strength *4 | Initial stage | ???1.50 | ???1.60 | ???1.65 | ???1.60 | ???1.55 | ???1.50 | ???1.60 |
| For a long time | ???1.45 | ???1.60 | ???1.60 | ???1.60 | ???1.50 | ???0.90 | ???0.95 | |
| Thermotolerance *5 | 5 minutes | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| 10 minutes | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | |
| 15 minutes | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | |
| 20 minutes | ????◎ | ????◎ | ????◎ | ????◎ | ????○ | ????○ | ????△ | |
| Wet fastness *6 | Condition A | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| Condition B | ????◎ | ????◎ | ????○ | ????◎ | ????△ | ????◎ | ????○ | |
*1: measure according to UL94 flame retardant resistance experimental standard.
*2: according to the IEC-PB112 standard test.
*3: according to the JIS-C-6481 standard test.Unit: Ω (* 10
13).
*4: according to the JIS-C-6481 standard test.Unit: KN/m.
*5: by time suspended sample shown in the table, observation has or not expansion in 260 ℃ of tin soldering liquids.Press following standard rating:
◎ ... do not have and expand; Zero ... demi-inflation;
△ ... the most of expansion; * ... all expand.
*6 after handling under condition A (boiling 6 hours) or the condition B (placing 2 atmospheric water vapour under 120 ℃ 7 hours), flooded for 30 seconds in 260 ℃ tin soldering liquid.Observation has or not expansion, presses following standard rating:
◎ ... do not have and expand; Zero ... demi-inflation;
△ ... the most of expansion; * ... all expand.
Embodiment 6
With the epoxy resin varnish product continuously coating that obtains among the embodiment 2 or dipping glass non-woven fabrics or glass woven, make prepreg 160 ℃ of following dryings.With 8 prepreg laminations that so obtain, and at 170 ℃, 40kg/cm
2Pressure keeps heating in 90 minutes, pressurization down, makes the glass epoxide laminated plate.By preceding method it is measured flame retardant resistance, tracking index, insulation strength, wet fastness.The result is as follows.
Flame retardant resistance: V-0
Tracking index: 600V
Insulation strength: 2.0 Ω
Wet fastness: condition A: ◎
Condition B: ◎
Embodiment 7
Equally make prepreg with embodiment 6, this prepreg of lamination, and at its two-sided stack thickness Copper Foil that is 35 μ m, same heating and pressurizing is made the inner plating of thickness of slab 0.8mm.At the above-mentioned prepreg of the two-sided lamination of this inner plating, the thick 18 μ m Copper Foils of stack on it, same heating and pressurizing is made thickness of slab 1.6mm multi-ply wood.After handling this multi-ply wood under the condition A, measure its wet fastness, do not observe swelling by preceding method.
In sum, the invention provides a kind of not halogen-containing composition epoxy resin, it has good flame retardant resistance, and is used to make all excellent epoxy glass copper foil laminate of thermotolerance, wet fastness, tracking index.This epoxy glass copper foil laminate can be made the good printed-wiring board (PWB) of various characteristics.
Claims (20)
1. the flame-retardant epoxy resin omposition of halogen, said composition contains:
(A) bisphenol A type epoxy resin;
(B) phenolic resin varnish type epoxy resin;
(C) stiffening agent is the resol of nitrogen atom;
(D) hardening accelerator;
(E) inorganic filler.
2. according to the described resin combination of claim 1, wherein the resol of nitrogen atom is the cocondensation resin of phenolic compound, guanamines compound and aldehyde cpd.
3. according to claim 1 or 2 described compositions, wherein the epoxy equivalent (weight) number of bisphenol A type epoxy resin is 170-1000.
4. the flame-retardant epoxy resin omposition of halogen, said composition contains
(A) bisphenol A type epoxy resin;
(B) phenolic resin varnish type epoxy resin;
(C) stiffening agent is the resol of nitrogen atom and phosphorus atom;
(D) hardening accelerator;
(E) inorganic filler.
5. according to the described composition of claim 4, wherein the resol of nitrogen atom and phosphorus atom is the reaction product of active phosphate, phenolic compound, guanamines compound and aldehyde cpd.
6. according to the described composition of claim 5, wherein active phosphate is represented with following structural:
(a+b+c=3 in the formula; A=1,2 or 3; B=0,1 or 2; C=0,1 or 2; N=1 or 2; R
1, R
2, R
3, R
4And R
5Respectively be hydrogen atom or alkyl, wherein having one at least is alkyl).
7. the flame-retardant epoxy resin omposition of halogen, said composition contains:
(A) bisphenol A type epoxy resin;
(B) phenolic resin varnish type epoxy resin;
(C-1) active phosphate;
(C-2) the cocondensation resin of resol/guanamines compound/aldehyde cpd;
(D) hardening accelerator;
(E) inorganic filler.
8. according to the described composition of claim 7, wherein active phosphate (C-1) is represented with following structural:
(a+b+c=3 in the formula; A=1,2 or 3; B=0,1 or 2; C=0,1 or 2; N=1 or 2; R
1, R
2, R
3, R
4And R
5Respectively be hydrogen atom or alkyl, wherein having one at least is alkyl).
9. prepreg, it contains the glass baseplate of each described composition epoxy resin dipping among the useful claim 1-3.
10. prepreg, it comprises the glass baseplate with each described composition epoxy resin dipping among the claim 4-6.
11. a prepreg, it comprises the glass baseplate with claim 7 or 8 described composition epoxy resin dippings.
12. a laminated plate, it is that the described prepreg of superimposed many claims 9 forms by this composition epoxy resin sclerosis.
13. a laminated plate, it is to be solidified by this composition epoxy resin, and the described prepreg of superimposed many claims 10 forms.
14. a laminated plate, it is to be solidified by this composition epoxy resin, and the described prepreg of superimposed many claims 11 forms.
15. a copper foil laminate, this copper foil laminate are equipped with substrate that the described prepreg of this composition epoxy resin hardened claim 9 makes and the Copper Foil of fitting on the single face at least of this substrate.
16. a copper foil laminate, this copper foil laminate are equipped with substrate that the described prepreg of this composition epoxy resin hardened claim 10 makes and the Copper Foil of fitting on the single face at least of this substrate.
17. a copper foil laminate, this copper foil laminate are equipped with substrate that the described prepreg of this composition epoxy resin hardened claim 11 makes and the Copper Foil of fitting on the single face at least of this substrate.
18. a printed-wiring board (PWB), this printed-wiring board (PWB) are equipped with substrate that the prepreg of this composition epoxy resin hardened claim 9 makes and the line layer that forms on the single face at least of this substrate.
19. a printed-wiring board (PWB), this printed-wiring board (PWB) are equipped with substrate that the prepreg of this composition epoxy resin hardened claim 10 makes and the line layer that forms on the single face at least of this substrate.
20. a printed-wiring board (PWB), this printed-wiring board (PWB) are equipped with substrate that the prepreg of this composition epoxy resin hardened claim 11 makes and the line layer that forms on the single face at least of this substrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95196516A CN1073127C (en) | 1995-09-29 | 1995-09-29 | Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95196516A CN1073127C (en) | 1995-09-29 | 1995-09-29 | Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
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| CN1167495A true CN1167495A (en) | 1997-12-10 |
| CN1073127C CN1073127C (en) | 2001-10-17 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005070990A1 (en) * | 2004-01-12 | 2005-08-04 | Taizhou Repow Chemical And Material Institute Co., Ltd | An epoxy resin curing agent containing elemental phosphorus and the method for preparing the same |
| CN100341938C (en) * | 2000-07-18 | 2007-10-10 | 京瓷化成株式会社 | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board |
| CN100345921C (en) * | 2004-03-24 | 2007-10-31 | 中央硝子株式会社 | Coating material and mirror coated therewith |
| CN100365035C (en) * | 2000-08-18 | 2008-01-30 | 长春人造树脂厂股份有限公司 | Phosphorous polymer having phenolic structure and its use |
| CN100432144C (en) * | 2005-11-16 | 2008-11-12 | 广东生益科技股份有限公司 | Resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN100497475C (en) * | 2005-11-16 | 2009-06-10 | 广东生益科技股份有限公司 | Halogen-free resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN1621481B (en) * | 2003-10-16 | 2010-05-26 | 日东电工株式会社 | Epoxy resin composition for encapsulating optical semiconductor element and optical semiconductor device using the same |
| CN101302327B (en) * | 2007-05-10 | 2011-05-04 | 广科工业股份有限公司 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
| CN102234409A (en) * | 2010-04-29 | 2011-11-09 | 台燿科技股份有限公司 | Epoxy resin composition and prepreg and printed circuit board (PCB) manufactured therefrom |
| CN101381506B (en) * | 2008-09-26 | 2012-05-30 | 广东生益科技股份有限公司 | Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
| CN102673071A (en) * | 2012-05-22 | 2012-09-19 | 苏州巨峰电气绝缘系统股份有限公司 | Intermediate temperature solidified prepreg and preparation method thereof |
| CN101679602B (en) * | 2007-05-18 | 2013-04-17 | 新日铁住金化学株式会社 | Novel flame-retardant epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product thereof |
| CN103694455A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Blending method of epoxy resin applicable to preparing carbon fiber preimpregnated material by medium-temperature heat melting method |
| CN104404770A (en) * | 2014-12-16 | 2015-03-11 | 山东圣泉新材料股份有限公司 | Amino resin composition for flame-retardant wet curtain and preparation method and application thereof |
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| JPS51129498A (en) * | 1975-04-02 | 1976-11-11 | Hitachi Ltd | Thermosetting resin composition |
| JPS58189219A (en) * | 1982-04-30 | 1983-11-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame retardant for thermosetting resin |
| JPS59106960A (en) * | 1982-12-10 | 1984-06-20 | 東芝ケミカル株式会社 | Manufacture of flame-retarded laminated board |
| EP0459951A3 (en) * | 1990-05-30 | 1993-09-15 | Ciba-Geigy Ag | Char forming nonhalogenated flame retardant epoxy composition |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341938C (en) * | 2000-07-18 | 2007-10-10 | 京瓷化成株式会社 | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board |
| CN100365035C (en) * | 2000-08-18 | 2008-01-30 | 长春人造树脂厂股份有限公司 | Phosphorous polymer having phenolic structure and its use |
| CN1621481B (en) * | 2003-10-16 | 2010-05-26 | 日东电工株式会社 | Epoxy resin composition for encapsulating optical semiconductor element and optical semiconductor device using the same |
| WO2005070990A1 (en) * | 2004-01-12 | 2005-08-04 | Taizhou Repow Chemical And Material Institute Co., Ltd | An epoxy resin curing agent containing elemental phosphorus and the method for preparing the same |
| CN100345921C (en) * | 2004-03-24 | 2007-10-31 | 中央硝子株式会社 | Coating material and mirror coated therewith |
| CN100432144C (en) * | 2005-11-16 | 2008-11-12 | 广东生益科技股份有限公司 | Resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN100497475C (en) * | 2005-11-16 | 2009-06-10 | 广东生益科技股份有限公司 | Halogen-free resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN101302327B (en) * | 2007-05-10 | 2011-05-04 | 广科工业股份有限公司 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
| CN101679602B (en) * | 2007-05-18 | 2013-04-17 | 新日铁住金化学株式会社 | Novel flame-retardant epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product thereof |
| CN101381506B (en) * | 2008-09-26 | 2012-05-30 | 广东生益科技股份有限公司 | Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby |
| CN102234409A (en) * | 2010-04-29 | 2011-11-09 | 台燿科技股份有限公司 | Epoxy resin composition and prepreg and printed circuit board (PCB) manufactured therefrom |
| CN102234409B (en) * | 2010-04-29 | 2015-09-23 | 台燿科技股份有限公司 | Composition epoxy resin and the prepreg made thereof and printed circuit board (PCB) |
| CN102673071A (en) * | 2012-05-22 | 2012-09-19 | 苏州巨峰电气绝缘系统股份有限公司 | Intermediate temperature solidified prepreg and preparation method thereof |
| CN103694455A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Blending method of epoxy resin applicable to preparing carbon fiber preimpregnated material by medium-temperature heat melting method |
| CN103694455B (en) * | 2012-09-28 | 2015-12-02 | 中国石油天然气股份有限公司 | A kind of be applicable in warm molten legal system for the concocting method of the epoxy resin of carbon fiber prepreg |
| CN104404770A (en) * | 2014-12-16 | 2015-03-11 | 山东圣泉新材料股份有限公司 | Amino resin composition for flame-retardant wet curtain and preparation method and application thereof |
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