Stock material or miscellaneous articles – Composite – Of epoxy ether
Reexamination Certificate
2000-10-12
2003-02-25
Dawson, Robert (Department: 1712)
Stock material or miscellaneous articles
Composite
Of epoxy ether
C528S099000, C525S523000
Reexamination Certificate
active
06524709
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a new type of phosphorus containing epoxy resin compositions with flame retardant and a resin sheet resin clad metal foil prepreg laminated board multi layer board used for an electric circuit board containing said epoxy resin.
2. Description of the Prior Art
To copper clad laminates, which are in use for electronic or electric apparatus and devices, the measures such as fire prevention or retardation are strongly required. Therefore, halogenated epoxy resins that have flame retardance are usually in use for copper clad laminates. Especially, among halogen group of atoms, by introducing bromine into epoxy resin, an excellent flame resistance can be provided to the epoxy resin and its cured product that has highly reactive epoxy groups and characteristics can be obtained, therefore, the halogenated epoxy resins, especially brominated epoxy resins are known to useful material for electronic or electric devices. However, when these halogenated epoxy resin are used at high temperatures for a long term, they can be dissociated to form halogen compounds such as hydrogen halogenide and halogen, and subsequently might be a danger to occurring corrosion problem for wires, and such actual accidents have been already reported. Furthermore, it is pointed out that toxic chemical substances such as dioxin and hydrogen halogenide could be formed to incur a serious environmental problem when used parts of electric and (or) electronic devices are calcined. This indicates that use of halogen containing flame retardant could result in such environmental problem. Considering the present situation of epoxy resin composition, the research to develop a new epoxy resin composition substitute for halogenated epoxy resins is highly required. Under the current situation, the development and commercialization of a flame retardant epoxy resin not containing any halogen and a copper clad laminated for printed wiring applications using that said flame retardant epoxy resin can be said as a subject to meet the current requirement of the era.
BRIEF ILLUSTRATION OF THE INVENTION
The inventors of this invention have studied intensively to develop a new type of flame retardant epoxy resins not containing any halogen and a copper clad laminate for printed wiring applications using said flame retardant epoxy resin, and aimed a basic theory of flame retardance by phosphorus and phosphorus compound disclosed in pages 49, 52-59 of “Flame Retardation of Polymer” (published by Taiseisha, 1989, Tokyo, Japan. Hitoshi Nishizawa). And the inventors of this invention have found that the new flame retardant phosphorus containing epoxy resin composition that said basic theory is applicable to can be obtained only by the use of a specific organic phosphorus compound, and furthermore, the resin compositions obtained by containing specific epoxy resin as an essential component indicate an excellent flame retardance, and physical properties of its cured products are suitable for printed wiring applications. Thus, we accomplished the present invention.
As disclosed in EP0806429A2, the flame retardant epoxy resin not using any halogen, which is a phosphorus containing organic compounds with epoxy groups, which are prepared from organic phosphorus compounds and epoxy resins have been investigated; however, when bifunctional epoxy resins are used as starting material, the concentration of epoxy group, which is a reactive functional group, will become lower, and lowering of heat resistance of the hardened epoxy resin is pointed out as a problem. Furthermore, for example, the viscosity of a phosphorus containing epoxy resin obtained from organic phosphorus compounds and epoxy resins, which has been disclosed in JP4-11662A, is too high to use it hence, it is required to decrease in actual viscosity by adding another liquid epoxy resin with lower viscosity. Therefore, generally the epoxy resin compositions using this kind of epoxy resin has a problem that the phosphorus content will be lowered in the composition. An epoxy resin containing phosphorus disclosed in JP11-166035A can be obtained from an organic phosphorus compound and epoxy resins, however, this has a problem to decrease in heat resistance and adhesion.
The present invention is aimed to solve the above mentioned problem, and the a im of this invention is to provide a flame retardant epoxy resin composition that contains phosphorus and epoxy groups having excellent flame retardance, heat resistance and adhesion which is useful for printed wiring applications, including a resin sheet, resin clad copper (RCC), prepreg, copper clad laminate and build-up wiring board.
DETAILED DESCRIPTION OF THE INVENTION
That is, the important point of this invention is a phosphorus containing epoxy resin compositions, comprising an epoxy resin composition (a) in which a phosphorus containing epoxy resin (A) and a hardener are contained, wherein the said phosphorus containing epoxy resin (A) is a phosphorus containing resin compositions prepared by reacting phosphorus containing organic compounds (B) obtained by the reaction in the range of molar ratio of 1.01 to 2 moles of organic phosphorus compounds (b) having one active hydrogen atom bonded to phosphorus atom with 1 mole of quinone compounds, with at least one kind of epoxy resins (C) selected from the group composed of general formula 1, general formula 2 or general formula 3 so as the content of the said epoxy resins (C) to be from 20 to 45 wt. %,
The other composition of this invention, using of novolac type epoxy resins for such as kind of epoxy resin (C) and the above mentioned epoxy resin (A) is prepared by reacting phosphorus containing organic compounds (B) obtained by the reaction in the range of molar ratio of greater than 0 mole to smaller than 1 mole of quinone compounds with 1 mole of organic phosphorus compounds (b) having one active hydrogen atom bonded to phosphorus atom, with novolac type epoxy resin so as content of the said epoxy resin (C) to be more than 20 wt. %. Furthermore, the another important point of this invention is a flame retardant epoxy resin composition containing a phosphorus with epoxy resin characterized by using the said phosphorus containing epoxy resin compositions and total content of phosphorus in whole resin composition is in the range of 0.5 to 4 wt. %.
wherein R
1
is a hydrogen atom and/or a phenyl group, m is an integer including
wherein R
2
is a hydrogen atom and/or a phenyl group, n is an integer including 0,
wherein R
3
is a hydrogen atom and/or a phenyl group, I is an integer including 0,
and, X is —CH
2
—, —O—, —CO—, —SO
2
—, —S—, —CH(C
6
H
5
)—, —C(C
6
H
5
)
2
—, not existing function group or chemical formula 4.
other important applications of the present invention are resin sheet, resin clad copper, prepreg to be impregnated into and coated to the sheet type inorganic and organic substrate and resin sheet thereof and printed wiring board build-up printed wiring one obtained with heating and curing the said prepreg.
The present invention will be illustrated more in detail.
As illustrative examples of quinone compounds for present invention, 1,4-benzoquinone, 1,2-benzoquinone or 1,4-naphtoquinone can be mentioned. These of quinone compounds can be used alone or can be used together with, in addition, not intended to be limited to them.
As illustrative example of an organic phosphorus compound (b) having one active hydrogen atom bonded to phosphorus atom of present invention, 3,4,5,6,-dibenzo-1,2-oxaphosphane-2-oxide (abbreviated to HCA, a product of Sanko Chemicals Co., Ltd. Osaka, Japan), diphenylphosphineoxide or others can be mentioned. These of organic phosphorus compounds (b) can be used alone or can be used together with, in addition, not intended to be limited to them.
The reaction of quinone compounds with organic phosphorus compounds (b) having one active hydrogen atom bonded to phosphorus atom can be carried out, for example, by the methods disclosed in JP5-214068A, Zh. Obshch. Khim. 42(11)
Asano Chiaki
Gunji Masao
Ihara Kiyoaki
Ishihara Kazuo
Kakiuchi Hidetaka
Dawson Robert
Feely Michael J
Matsushita Electric Works LTD
Sherman & Shalloway
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