CN103228697B - High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board - Google Patents
High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board Download PDFInfo
- Publication number
- CN103228697B CN103228697B CN201180056296.3A CN201180056296A CN103228697B CN 103228697 B CN103228697 B CN 103228697B CN 201180056296 A CN201180056296 A CN 201180056296A CN 103228697 B CN103228697 B CN 103228697B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- phosphorus compound
- formula
- compound
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
The purpose is to provide the following: an epoxy resin composition capable of maintaining flame retardancy without containing a halogenated flame retardant in the epoxy resin composition, being heat-resistant for lead-free soldering, and with which it is possible to obtain a substrate that maintains excellent plating adhesion; a prepreg obtained from the composition; and a metal-clad laminate and a printed wiring board on which a resin insulating layer is formed from the composition. The epoxy resin composition contains a phosphorus-modified phenolic curing agent and an epoxy compound, the epoxy resin composition being characterized in that the phosphorus-modified phenolic curing agent contains a phosphorus compound and a compound represented by formula (I) (In the formula, R represents a hydroxyl group or a O-methyl group, and n represents an integer of 2 or greater), and by the phosphorus compound being bonded to the aliphatic carbon in the compound represented by formula (I).
Description
Technical field
The present invention relates to a kind of composition epoxy resin in fact not containing halogen, be particularly suitable for use as the composition epoxy resin of the insulating material as printed circuit board etc.And, the invention still further relates to the prepreg, metal-coated laminated board and the printed-wiring board (PWB) that use this composition epoxy resin.
Background technology
Composition epoxy resin is used as printed wiring panel material widely because having excellent cementability, electrical insulating property and resistance to chemical reagents etc.
But, because epoxy resin compares shortage flame retardant resistance, therefore in the composition epoxy resin of printed-wiring board (PWB), be generally mixed with as the halogenated flame retardants such as bromide fire retardant and the high halogenated flame retardant of the effect as the imparting flame retardant resistance of the Halogen epoxy resin such as tetrabromo-bisphenol type epoxy resin etc.But the cured article of this kind of Halogen composition epoxy resin likely generates the objectionable impuritiess such as hydrogen halide when burning, and therefore has and causes dysgenic shortcoming to human body or physical environment.
In order to eliminate this shortcoming, such as, there will be a known and use the epoxy resin being mixed with phosphorus compound to replace the scheme (such as patent documentation 1) of halogenated flame retardant.
In addition, as the flame-retarded method of this kind of halogen-free material and the phosphorus compound that can be mixed in resin combination, there will be a known addition type phosphorus compound and response type phosphorus compound up to now.Such as, the resin combination (such as patent documentation 2) using phenoxy group phosphazo alkene is there will be a known as addition type phosphorus compound, in addition, the resin combination (such as patent documentation 3) using response type phosphazo ene compound is there will be a known as response type phosphorus compound.
Patent documentation 1: No. 2007-326929, Japanese Laid-Open Patent Publication
Patent documentation 2: No. 2008-56820, Japanese Laid-Open Patent Publication
Patent documentation 3: No. 2006-36736, Japanese Laid-Open Patent Publication
Summary of the invention
But, use the resin combination of addition type phosphorus compound to there is the problems such as second-order transition temperature (Tg) decline and moisture absorption poor heat resistance, on the other hand, use the resin combination of response type phosphorus compound to there is the problem of poor fire.
In recent years, the high quality for material resin requires to improve, thus has higher reliability and the halogen-free material with high Tg and high moisture absorption thermotolerance is looked forward to.
So, the object of the present invention is to provide a kind of halogen, there is high Tg and the composition epoxy resin that the base material that the reliability of excellent moisture absorption thermotolerance is high is shown can be obtained; A kind of prepreg, a kind of metal-coated laminated board and printed-wiring board (PWB) using said composition formation resin insulating barrier using said composition to obtain.
The present inventor conducts in-depth research to solve the problem, and found that to utilize following scheme can solve the problem.
That is: composition epoxy resin of the present invention, comprises P Modification phenols curing agent and epoxy compounds, the compound that described P Modification phenols curing agent comprises phosphorus compound and represented by following formula (I),
In formula, R is hydroxyl or O-methyl, and n represents the integer of more than 2,
Aliphatic carbon atom bonding in described phosphorus compound and the described compound represented by formula (I).
According to the present invention, do not comprise halogenated flame retardant and can maintain flame retardant resistance even if can provide yet and there is high Tg, and the composition epoxy resin that the base material that the reliability of excellent moisture absorption thermotolerance is high is shown can be obtained.And, the use prepreg that described composition obtains can be provided and use described composition to form metal-coated laminated board and the printed-wiring board (PWB) of resin insulating barrier.
Embodiment
(composition epoxy resin)
First illustrate, composition epoxy resin of the present invention comprises P Modification phenols curing agent and epoxy compounds as its basic comprising.
The compound that P Modification phenols curing agent used in the present invention contains phosphorus compound and represented by following formula (I), and the aliphatic carbon atom bonding in described phosphorus compound and the described compound represented by formula (I).
In formula, R is hydroxyl or O-methyl, and n represents the integer of more than 2.
As the phosphorus compound being used in P Modification phenols curing agent involved in the present invention, as long as have phosphorous skeleton, and with the aliphatic carbon atom bonding in the described compound represented by formula (I), then can be not particularly limited.Specifically, the phospho hetero phenanthrene class etc. of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (following, to be sometimes referred to as HCA) or derivatives thereof etc. can be enumerated, wherein, the HCA represented by following formula (II) is preferably used to be used as phosphorus compound.
By using this kind of P Modification phenols curing agent, epoxy resin of the present invention can possess the moisture absorption thermotolerance of flame retardant resistance, high Tg and excellence, can be suitable as the material of various base material.
And in P Modification phenols curing agent of the present invention, the aliphatic carbon atom bonding in described phosphorus compound and the described compound represented by formula (I), the aliphatic carbon atom of this bonding is preferably placed at molecular end.As mentioned above, because phosphorus atom is positioned at the end of compound scaffold, therefore, the problem that the general flame retardant resistance caused by response type phosphorus compound reduces can not be there is, reliably can maintain high flame retardant.
In addition, the phosphorus compound being contained in P Modification phenols curing agent all with the aliphatic carbon atom bonding in the described compound represented by formula (I) for desirable, but the ratio of the phosphorus compound of non-bonding in P Modification phenols curing agent is advisable at below 3 quality %.In addition, in the organic composition of composition epoxy resin involved in the present invention, be advisable at below 1 quality % with the ratio of the phosphorus compound of the non-bonding of aliphatic carbon atom in the described compound represented by formula (I).
In addition, the hydroxyl equivalent of P Modification phenols curing agent used in the present invention is preferably about 150 ~ 300, further preferred 150 ~ 250 scope.
P Modification phenols curing agent as above can use commercially available product, such as, can use EXB9000, EXB9005 etc. that Di Aisheng Co., Ltd. (DIC Corporation) manufactures.
In addition, containing of the described P Modification phenols curing agent in composition epoxy resin of the present invention is proportional, is generally 0.1 ~ 90 quality % in composition epoxy resin total amount, is preferably 0.1 ~ 80 quality %.
Secondly explanation, as the epoxy compounds being contained in epoxy resin of the present invention, in the scope not hindering effect of the present invention, then be not particularly limited, all epoxy resin can be used within the scope of this, such as, be preferably used in the epoxy compounds in a molecule with plural epoxy group(ing).
As concrete example, such as can enumerate the epoxy resin of cresol novolak type epoxy resin (cresol novolac epoxy resins, cresolnovolac epoxy resin), bisphenol f type epoxy resin, novolac epoxy resin (phenol novolac epoxyresin), dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, aralkyl phenol aldehyde type epoxy resin (phenol alkyl epoxy resin) etc.These both may be used singly or in combination of two or more.In addition, in these epoxy resin, particularly preferably use as phenol aldehyde type epoxy resins such as cresol novolak type epoxy resins.
In addition, the preferred average out to about 150 ~ 300 of epoxy equivalent (weight) of the epoxy compounds of epoxy resin of the present invention is contained in.
In addition, containing of the epoxy compounds in composition epoxy resin of the present invention is proportional, in composition epoxy resin total amount, be preferably 0.1 ~ 90 quality %, more preferably 20 ~ 90 quality %.
In addition, except above-mentioned required composition, composition epoxy resin of the present invention can also comprise the curing catalyst for promoting curing reaction.As curing catalyst, as long as the material of the curing reaction of above-mentioned epoxy resin ingredient and P Modification phenols curing agent can be promoted, can use without particular limitation.Specifically, such as can enumerate: as imidazoles such as glyoxal ethyline, cyanoethyl imidazoles; As metallic soaps such as zinc octoate, copper naphthenate, cobalt naphthenates; As organo phosphorous compoundss such as triphenylphosphines; As amine compound such as triethylamines; As bases such as 1,8-diazabicyclo [5.4.0] hendecene-7 grade etc.These both may be used singly or in combination of two or more.
When in the present invention containing curing catalyst, preferred consolidation promotor is about 0.01 ~ 2 quality % in composition epoxy resin total amount.
In addition, in order to improve rigidity, composition epoxy resin of the present invention can also comprise filler.Can mineral filler be used as filler, can enumerate particularly: silicon oxide powder; As the powder of the metal hydrate such as aluminium hydroxide, magnesium hydroxide; The clay mineral such as talcum, clay powder etc., these fillers, except can be used alone, also can be used together multiple.This kind of filler, preferably relative to composition epoxy resin total amount, mixes 0.1 ~ 250 quality %.
Composition epoxy resin of the present invention can also comprise other additive, such as fire retardant, flame retardant, leveling agent, tinting material etc. as required in the scope not undermining effect of the present invention.
Composition epoxy resin of the present invention is usually prepared to varnish shape and uses.This kind of varnish is such as prepared by following method.
That is: each composition of above-mentioned composition epoxy resin is added in organic solvent, add inorganic filler etc. as required, then use ball mill, ball mill, stirrer, mixer etc. to disperse equably, mix, thus varnish shape can be prepared into.
As described organic solvent, be then not particularly limited, such as, can enumerate: as benzene, toluene etc. are aromatic hydrocarbon based; As amidess such as DMFs (DMF); As the ketone such as acetone, methylethylketone; As the alcohols such as methyl alcohol, ethanol; Cellosolve class etc.These both may be used singly or in combination of two or more.
(prepreg)
Above-mentioned varnish shape composition epoxy resin obtains containing being immersed in fibrous substrate by prepreg of the present invention.
Specifically, such as, first, medium by fibrous substrate being impregnated in described varnish shape resin, and make varnish shape resin impregnated in fibrous substrate.Impregnation can utilize dipping (dipping), coating etc. to carry out.Also repeatedly repeatedly impregnation can be carried out as required.In addition, the different multiple solution of composition, concentration now also can be used repeatedly to carry out impregnation, be finally adjusted to required composition and amount of resin.
Although be not particularly limited as described fibrous substrate, preferably use sheet-like fiber base material, such as, can use woven (cloth) or non-woven fabrics, aromatic poly amide cloth, mylar and the paper etc. of the inorganic fibres such as glass.In addition, for the thickness of base material, thickness generally can be used to be the base material of 0.02 ~ 0.2mm.
Thereafter, by containing the base material heat drying under the heating condition of specifying (at such as 100 ~ 180 DEG C 3 ~ 10 minutes) being soaked with varnish shape composition epoxy resin, except desolventizing, and by resinous principle semicure (B rank), obtained prepreg.Amount of resin now in prepreg is preferably 30 ~ 80 quality % relative to prepreg total amount.
(metal-coated laminated board)
As the method using prepreg obtained as described above to manufacture metal-coated laminated board, following method can be enumerated, that is: by one or more pieces overlaps by described prepreg, and surface and the tinsel such as the two sides of lower surface or one side overlap Copper Foil thereon, heating and pressurizing shaping carried out to it and makes its lamination integration, thus making the layered product of two sides clad with metal foil or one side clad with metal foil.Heating and pressurizing condition suitably can set according to the kind etc. of the resin combination of the thickness of the veneer sheet that will manufacture, prepreg, such as, temperature can be set to 150 ~ 250 DEG C, pressure is set to 1 ~ 5Pa, will be set to 30 ~ 240 minutes the time.
(multilayer printed circuit board)
Carry out etching and processing etc. by the tinsel on the surface to the layered product made as described above and form circuit, thus the printed-wiring board (PWB) being formed with the conductive pattern as circuit on the surface of layered product can be obtained.
The printed-wiring board (PWB) so obtained is excellent in the thermotolerance corresponding to lead-free solder, and, even if not containing halogenated flame retardant, also possess enough flame retardant resistances.
Below, embodiment is utilized to carry out more specific description to the present invention.In addition, the present invention is not by any restriction of following embodiment.
Embodiment
First, the starting material illustrating and use in the present embodiment are gathered.
< solidifying agent >
P Modification phenols curing agent 1: Di Aisheng Co., Ltd. manufactures, " EXB9000 " (hydroxyl equivalent 207)
P Modification phenols curing agent 2: Di Aisheng Co., Ltd. manufactures, " EXB9005 " (hydroxyl equivalent 167)
Phenols curing agent: Di Aisheng Co., Ltd. manufactures, " TD-2090 " (hydroxyl equivalent 105)
< phosphorus compound >
Phenoxy group phosphazo alkene (addition type phosphorus compound): Otsuka Chemical Co., Ltd manufactures, " SPB-100 "
Phospho hetero phenanthrene (HCA): Sanko Co., Ltd. manufactures, " HCA "
Response type phosphazo alkene: Otsuka Chemical Co., Ltd manufactures, " SPH-100 " (hydroxyl equivalent 250)
< epoxy compounds >
Cresol novolac epoxy compound: Di Aisheng Co., Ltd. manufactures, " N-690 " (cresol novolak epoxy, epoxy equivalent (weight) 215)
P Modification epoxy resin: Toto Kasei KK manufactures, " FX289 " (epoxy equivalent (weight) 318)
< filler >
Aluminium hydroxide: Sumitomo Chemical Co manufactures, " CL-303 "
Dissolve silicon oxide: Co., Ltd.'s refined all agates manufacture, " SC-2500-SEJ "
< curing catalyst >
Imidazoles: Shikoku Chem manufactures, " 2E4MZ "
(embodiment 1 ~ 4 and comparative example 1 ~ 5)
Except mixing composition (mass parts) shown in table 1, also add methylethylketone and be used as solvent, prepared embodiment 1 ~ 4 that solids component is 50 ~ 70 quality % and the epoxy resin varnish involved by comparative example 1 ~ 5.
Secondly, woven fiber glass (2116 of Asahi Kasei Electronics Materials Co., Ltd's manufacture) is immersed in above-mentioned each resinous varnish, by resinous varnish containing being dipped into after in woven fiber glass, heat drying 3 ~ 5 minutes at 150 ~ 170 DEG C, by removing desolventizing and making resinous principle semicure (B rank), thus make prepreg.Now, the amount of resin in prepreg is set to 45 ~ 55 quality % relative to prepreg total amount.
And, by overlapping for manufactured prepreg 8, thick 12 μm of its both sides configuration Copper Foil (JTCLPZ that Nippon Mining and Metals Co., Ltd manufactures) and as by laminate, at temperature 220 DEG C, pressure 30kg/cm
2condition under heating, pressurization 240 minutes, obtained the copper clad laminate being bonded with Copper Foil, thick 0.8mm on two sides thus.
The prepreg obtained as described above and copper clad laminate are used as evaluation sample, utilizes method shown below, carried out the evaluation of second-order transition temperature (Tg), PCT solder heat resistance and flame retardant resistance.These results are shown in Table 1.
[second-order transition temperature (Tg)]
The visco-elasticity spectrometer " DMS100 " using Seiko instrument Co., Ltd. to manufacture determines the Tg of veneer sheet.Now, in a flexural mode frequency be set to 10Hz and carried out Measurement of Dynamic Viscoelasticity, illustrating that great temperature is as Tg using under the condition of heat-up rate 5 DEG C/min from tan δ during room temperature to 280 DEG C.
[PCT solder heat resistance]
After the Copper Foil on the surface of removing copper clad laminate, cut out the test piece of long 50mm, wide 50mm.This test piece is put into 121 DEG C, 2 normal atmosphere, humidity 100% pressure kettle test (PCT) machine in 4 hours and 6 hours.Test piece after dropping into be impregnated of 20 seconds in the solder bath of 260 DEG C, if 3 samples all do not have the white angle of white edge (measling) and do not bubble, then be evaluated as zero, if two in 3 samples do not have the white angle of white edge and do not have to bubble and remaining one has the white angle of white edge or foaming, then be evaluated as △, if two or more has the white angle of white edge or foaming in 3 samples, be then evaluated as ×.
[flame retardant resistance]
After the Copper Foil of removing copper clad laminate, cut out the test piece of long 127mm, wide 12.7mm.Then, according to the combustion test method of " plastic material combustion testing (the Test forFlammability of Plastic Materials) UL 94 " of Underwriters Laboratories (Underwriters Laboratories), combustion test is carried out to this test piece, and has judged.
(result)
According to the result of table 1, the veneer sheet of embodiments of the invention 1 ~ 4 all has high Tg, and, even if do not use halogenated flame retardant, also show excellent flame retardant resistance.And the multilayer board of each embodiment all illustrates good PCT solder heat resistance.
In addition, embodiment 4 also added phospho hetero phenanthrene (HCA) on the basis of embodiment 1, phosphorus compound due to bonding non-in the organic composition of resin combination is more than 1 quality %, therefore, PCT solder heat resistance compared with embodiment 1 ~ 3 slightly poor.
On the other hand, replace P Modification phenols curing agent involved in the present invention and employ the veneer sheet of the comparative example 1 of the phenoxy group phosphazo alkene (addition type phosphorus compound) of phenols curing agent and 20 mass parts and do not employ in the veneer sheet of comparative example 2 of P Modification epoxy resin containing phenols curing agent involved in the present invention as epoxy resin, observed the decline of Tg.About this point, the addition of phenoxy group phosphazo alkene is set to the comparative example 4 of the half of comparative example 1, although rise Tg, is reduction of flame retardant resistance.
In addition, replace P Modification phenols curing agent involved in the present invention and employ the comparative example 3 of the phospho hetero phenanthrene of phenols curing agent and 15 mass parts, showing the result that PCT solder heat resistance is deteriorated.
In addition, replace P Modification phenols curing agent involved in the present invention and employ the test piece of the comparative example 5 of phenols curing agent and response type phosphazo alkene (response type phosphorus compound), being completely burned in combustion test.
According to these results, showing according to using composition epoxy resin involved in the present invention, can halogen be obtained and there is all excellent prepreg of high Tg, moisture absorption thermotolerance and flame retardant resistance, metal-coated laminated board and printed-wiring board (PWB).
As described above, the composition epoxy resin involved by an embodiment of the present invention comprises P Modification phenols curing agent and epoxy compounds, the compound that described P Modification phenols curing agent comprises phosphorus compound and represented by following formula (I),
In formula, R is hydroxyl or O-methyl, and n represents the integer of more than 2, the aliphatic carbon atom bonding in described phosphorus compound and the described compound represented by formula (I).By using described composition epoxy resin, the addition type phosphorus compound of the resin combination being used in halogen up to now and the shortcoming of response type phosphorus compound can be suppressed, and then obtain there is the high base material of the reliability of high Tg, moisture absorption thermotolerance and flame retardant resistance.
In addition, the phosphorus compound that preferably represented by following formula (II) of described phosphorus compound.
The epoxy resin utilizing this kind to form and the base material that is shaped has high Tg, and there is more excellent moisture absorption thermotolerance and flame retardant resistance.
In addition, preferred: in described P Modification phenols curing agent, to be below 3 quality % with the described phosphorus compound of the described non-bonding of compound represented by formula (I).Form according to this kind, high flame retardant and moisture absorption thermotolerance can be realized more reliably.
In addition, preferred: in the organic composition of described composition epoxy resin, to be below 1 quality % with the described phosphorus compound of the described non-bonding of compound represented by formula (I).Form according to this kind, high flame retardant and moisture absorption thermotolerance can be realized more reliably.
In addition, in described P Modification phenols curing agent, when the aliphatic carbon atom bonding of the molecular end of described phosphorus compound and the described compound represented by formula (I), higher flame retardant resistance can be guaranteed.
In addition, the prepreg involved by another embodiment of the present invention is by making described composition epoxy resin containing to be immersed in fibrous substrate and to make it dry and obtained prepreg.By using this kind of prepreg, there is high Tg and excellent moisture absorption thermotolerance even if can obtain and containing halogenated flame retardant, not there is the high metal-coated laminated board of the reliability of sufficient flame retardant resistance and printed-wiring board (PWB) yet.
Metal-coated laminated board involved by another embodiment of the present invention, be by by metal foil laminated in described prepreg, and to be shaped and obtained metal-coated laminated board through heating and pressurizing.
In addition, the printed-wiring board (PWB) involved by the another embodiment of the present invention is by removing tinsel to form circuit and obtained printed-wiring board (PWB) from the local, surface of described metal-coated laminated board.
Claims (6)
1. a composition epoxy resin, it is characterized in that: comprise P Modification phenols curing agent and epoxy compounds, the compound that described P Modification phenols curing agent comprises phosphorus compound and represented by following formula (I), and in the compound that following formula (I) represents, at least one R is hydroxyl and at least one R is O-methyl
In formula, R is hydroxyl or O-methyl, and n represents the integer of more than 2,
Described phosphorus compound is the phosphorus compound represented by following formula (II),
The aliphatic carbon atom bonding of the molecular end of described phosphorus compound and the described compound represented by formula (I).
2. composition epoxy resin according to claim 1, is characterized in that:
In described P Modification phenols curing agent, be below 3 quality % with the described phosphorus compound of the described non-bonding of compound represented by formula (I).
3. composition epoxy resin according to claim 1 and 2, is characterized in that:
In the organic composition of described composition epoxy resin, be below 1 quality % with the described phosphorus compound of the described non-bonding of compound represented by formula (I).
4. a prepreg, is characterized in that, is impregnated in fibrous substrate by composition epoxy resin as claimed any one in claims 1 to 3 and obtains.
5. a metal-coated laminated board, is characterized in that, by metal foil laminated in prepreg as claimed in claim 4, and be shaped through heating and pressurizing and obtain.
6. a printed-wiring board (PWB), is characterized in that, removes tinsel obtain to form circuit from the local, surface of metal-coated laminated board as claimed in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-261146 | 2010-11-24 | ||
| JP2010261146A JP5909693B2 (en) | 2010-11-24 | 2010-11-24 | High heat resistant epoxy resin composition, prepreg, metal-clad laminate and printed wiring board |
| PCT/JP2011/006387 WO2012070202A1 (en) | 2010-11-24 | 2011-11-16 | High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103228697A CN103228697A (en) | 2013-07-31 |
| CN103228697B true CN103228697B (en) | 2015-04-29 |
Family
ID=46145573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180056296.3A Active CN103228697B (en) | 2010-11-24 | 2011-11-16 | High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5909693B2 (en) |
| CN (1) | CN103228697B (en) |
| TW (1) | TWI441868B (en) |
| WO (1) | WO2012070202A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6770793B2 (en) * | 2015-08-19 | 2020-10-21 | 日鉄ケミカル＆マテリアル株式会社 | Flame-retardant epoxy resin composition and its cured product |
| EP3520584A1 (en) * | 2016-09-27 | 2019-08-07 | AT & S Austria Technologie & Systemtechnik Aktiengesellschaft | Flame retardant structure for component carrier |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616949A (en) * | 2007-02-23 | 2009-12-30 | 松下电工株式会社 | Composition epoxy resin, prepreg, laminated wood and printing distributing board |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3721950B2 (en) * | 2000-06-06 | 2005-11-30 | 松下電工株式会社 | Epoxy resin composition, prepreg, multilayer printed wiring board |
| JP2002138096A (en) * | 2000-10-27 | 2002-05-14 | Dainippon Ink & Chem Inc | Phenol compound including phosphorus, manufacturing method therefor, and epoxy resin composition using the same |
| JP4830748B2 (en) * | 2006-09-20 | 2011-12-07 | パナソニック電工株式会社 | Flame retardant epoxy resin composition, resin film, prepreg and multilayer printed wiring board |
| US20100261837A1 (en) * | 2007-11-29 | 2010-10-14 | Dow Global Technologies Inc. | Dimethylformamide-free formulations using dicyanadiamide as curing agent for thermosetting epoxy resins |
| US8288003B2 (en) * | 2009-03-18 | 2012-10-16 | Dic Corporation | Method for producing phosphorus-containing phenolic compound, novel phosphorus-containing phenol, curable resin composition, cured product of the same, printed wiring board, and semiconductor sealing material |
| JP4953039B2 (en) * | 2010-02-18 | 2012-06-13 | Ｄｉｃ株式会社 | Phosphorus atom-containing oligomer, production method thereof, curable resin composition, cured product thereof, and printed wiring board |
| WO2011132406A1 (en) * | 2010-04-20 | 2011-10-27 | パナソニック株式会社 | See-through display and head-up display |
| WO2011132408A1 (en) * | 2010-04-23 | 2011-10-27 | パナソニック電工株式会社 | Epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board |
| JP5866806B2 (en) * | 2010-05-31 | 2016-02-24 | 日立化成株式会社 | Epoxy resin composition, prepreg using this epoxy resin composition, resin film with support, metal foil-clad laminate and multilayer printed wiring board |
-
2010
- 2010-11-24 JP JP2010261146A patent/JP5909693B2/en active Active
-
2011
- 2011-11-16 CN CN201180056296.3A patent/CN103228697B/en active Active
- 2011-11-16 WO PCT/JP2011/006387 patent/WO2012070202A1/en active Application Filing
- 2011-11-17 TW TW100142050A patent/TWI441868B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616949A (en) * | 2007-02-23 | 2009-12-30 | 松下电工株式会社 | Composition epoxy resin, prepreg, laminated wood and printing distributing board |
Non-Patent Citations (1)
| Title |
|---|
| Flame-retardant epoxy resins from novel phosphorus-containing novolac;Ying Ling Liu;《Polymer》;20010430;第42卷(第8期);3445-3454 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103228697A (en) | 2013-07-31 |
| JP2012111828A (en) | 2012-06-14 |
| TWI441868B (en) | 2014-06-21 |
| JP5909693B2 (en) | 2016-04-27 |
| TW201235401A (en) | 2012-09-01 |
| WO2012070202A1 (en) | 2012-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100228047B1 (en) | Halogen-free flame-retardant epoxy resin composition as well as prepreg and laminate containing the same | |
| CN102858839B (en) | Composition epoxy resin, prepreg, metal-clad and printed wiring board | |
| JP5576930B2 (en) | Epoxy resin composition for prepreg, prepreg, and multilayer printed wiring board | |
| JP3412585B2 (en) | Epoxy resin composition for prepreg used for production of printed wiring board and multilayer printed wiring board, prepreg, multilayer printed wiring board | |
| CN102369227B (en) | Phosphorus-containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| CN102020830B (en) | Halogen-free fire resistance resin composite and application thereof | |
| US20140349090A1 (en) | Low dielectric halogen-free resin composition and circuit board using the same | |
| KR100722900B1 (en) | Thermosetting Resin Composition, and Prepreg, Metal-Clad Laminated Board and Printed Wiring Board Using the Same | |
| JP2006131743A (en) | Thermosetting resin composition and prepreg and metal-clad laminate and printed wiring board using the same | |
| WO2016019595A1 (en) | Epoxy resin composition, and prepreg and copper clad laminate made therefrom | |
| JP5034181B2 (en) | Prepreg and laminate | |
| JP2009051978A (en) | Epoxy resin composition for printed wiring board, prepreg, metal foil clad laminated plate, and multilayer printed wiring board | |
| JP2012241179A (en) | Epoxy resin composition for prepreg, the prepreg, and multilayer printed wiring board | |
| CN105131597A (en) | Halogen-free resin composition and prepreg using halogen-free resin composition and printed circuit laminated board | |
| CN103228697B (en) | High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board | |
| JPH10195178A (en) | Flame-retardant epoxy resin composition, prepreg, laminate and copper-clad printed circuit board | |
| JP2002220435A (en) | Phosphorus-containing epoxy resin composition, prepreg, resin-coated metal foil, adhesive sheet, laminated board and multilayer board, phosphorus-containing epoxy resin varnish for coating, phosphorus-containing epoxy resin sealing material, phosphorus-containing epoxy resin casting material and phosphorus-containing epoxy resin varnish for immersion | |
| JP2002249641A (en) | Epoxy resin composition, resin film, resin-sticking metal foil, prepreg, and laminated sheet | |
| JP2006182991A (en) | Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it | |
| JP4200251B2 (en) | Epoxy resin composition, film, prepreg, laminate | |
| JP2013087253A (en) | Epoxy resin composition, prepreg, metal-clad laminate and printed wiring board | |
| JP3982507B2 (en) | Prepreg and metal-clad laminate | |
| JP2000007897A (en) | Flame-retardant resin composition and prepreg and laminate using the same | |
| JP2002097260A (en) | Hardening agent, having high durability and flame- resistance | |
| JP2002060590A (en) | Epoxy resin composition for imprregnating glass fiber substrate and prepreg, laminated sheet and printed wiring board using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LT Free format text: FORMER OWNER: MATSUSHITA ELECTRIC INDUSTRIAL CO, LTD. Effective date: 20150908 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150908 Address after: Osaka Japan Patentee after: PANASONIC INTELLECTUAL PROPERTY MANAGEMENT Co.,Ltd. Address before: Osaka Japan Patentee before: Matsushita Electric Industrial Co.,Ltd. |