U.S. patent application number 10/077716 was filed with the patent office on 2002-12-19 for flame retardant resin material and flame retardant resin composition.
This patent application is currently assigned to NEC CORPORATION. Invention is credited to Iji, Masatoshi, Kiuchi, Yukihiro, Soyama, Makoto.
Application Number | 20020193552 10/077716 |
Document ID | / |
Family ID | 27309163 |
Filed Date | 2002-12-19 |
United States Patent
Application |
20020193552 |
Kind Code |
A1 |
Kiuchi, Yukihiro ; et
al. |
December 19, 2002 |
Flame retardant resin material and flame retardant resin
composition
Abstract
The present invention provides a flame retardant phenol resin
material which includes a phenol condensate, wherein a
poly-aromatic compound obtained by a reaction of phenols (A) to
aromatics (B) except for phenols and a heterocyclic compound (C)
including nitrogen as heteroatom are condensed via aldehydes (D),
and also provides a flame retardant epoxy resin material which
includes an epoxy resin obtained by glycidyl-etherification of at
least a part of phenolic hydroxyl groups of a poly-aromatic
compound obtained by a reaction of phenols (A) to aromatics (B)
except for phenols and a heterocyclic compound (C) including
nitrogen as heteroatom are condensed via aldehydes (D).
Inventors: |
Kiuchi, Yukihiro; (Tokyo,
JP) ; Iji, Masatoshi; (Tokyo, JP) ; Soyama,
Makoto; (Tokyo, JP) |
Correspondence
Address: |
YOUNG & THOMPSON
745 SOUTH 23RD STREET 2ND FLOOR
ARLINGTON
VA
22202
|
Assignee: |
NEC CORPORATION
7-1, SHIBA 5-CHOME, MINATO-KU
TOKYO
JP
|
Family ID: |
27309163 |
Appl. No.: |
10/077716 |
Filed: |
February 19, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10077716 |
Feb 19, 2002 |
|
|
|
09461197 |
Dec 15, 1999 |
|
|
|
6392003 |
|
|
|
|
Current U.S.
Class: |
528/163 |
Current CPC
Class: |
Y10T 428/31942 20150401;
Y10S 428/901 20130101; C08L 61/34 20130101; C08G 14/10 20130101;
C08G 59/08 20130101; H05K 1/0346 20130101 |
Class at
Publication: |
528/163 |
International
Class: |
C08G 008/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 15, 1998 |
JP |
10-356165 |
Apr 7, 1999 |
JP |
11-100186 |
Nov 19, 1999 |
JP |
11-329693 |
Claims
What is claimed:
1. The flame retardant phenol resin material, comprising: A phenol
condensate, wherein a poly-aromatic compound obtained be a
condensation reaction of phenols (A) to aromatics (B) except for
phenols and a heterocyclic compound (C) including nitrogen as a
heteroatom are condensed via aldehydes (D), wherein said aromatics
(B) are represented by the following chemical formula
(1),XH.sub.2C--R.sub.1--CH.sub.2X (1)wherein R.sub.1 is any one of
biphenyl derivatives, phenylene derivatives, naphthalene
derivatives, biphenylene derivatives, fluorine derivatives,
bis-phenol fluorine derivatives, and X is any one of halogen atoms,
hydroxyl groups and alkoxyl groups having not larger than 10 carbon
atoms, wherein said flame retardant material further comprises at
least a flame retardant phenol resin material, and said flame
retardant material further comprises an aromatic thermosetting
resin comprising aromatic rings on a main chain skeleton.
2. The flame retardant resin composition as claimed in claim 1,
wherein said aromatic thermosetting resin comprises an epoxy resin
having a novolak structure.
3. The flame retardant resin composition as claimed in claim 1,
wherein said aromatic thermosetting resin comprises a phenol resin
having a novolak structure.
4. The flame retardant resin composition as claimed in claim 1,
wherein said aromatic thermosetting resin comprises a phenol
aralkyl epoxy resin having aromatic rings on a novolak-structured
main chain.
5. The flame retardant resin composition as claimed in claim 4,
wherein said phenol aralkyl epoxy resin has at least any one of
biphenyl derivatives and phenylene derivatives on said
novolak-structured main chain.
6. The flame retardant resin composition as claimed in claim 1,
wherein said aromatic thermosetting resin comprises a phenol
aralkyl phenol resin having aromatic rings on a novolak-structure
main chain.
7. The flame retardant resin composition as claimed in claim 6,
wherein said phenol aralkyl phenol resin has at least any one of
biphenyl derivatives and phenylene derivatives on said
novolak-structure main chain.
8. A flame retardant phenol resin material, comprising: A phenol
condensate, wherein a poly-aromatic compound obtained by a
condensation reaction of phenols (A) to aromatics (B) except for
phenols and a heterocyclic compound (C) including nitrogen as a
heteroatom are condensed via aldehydes (D), wherein said aromatics
(B) are represented by the following chemical formula
(1),XH.sub.2C--R.sub.1--CH.sub.2X (1)wherein R.sub.1 is any one of
biphenyl derivatives, phenylene derivatives, naphthalene
derivatives, biphenylene derivatives, fluorine derivatives,
bis-phenol fluorine derivatives, and X is any one of halogen atoms,
hydroxyl groups and alkoxyl groups having not larger than 10 carbon
atoms, said flame retardant material further comprises at least a
flame retardant phenol resin material, and said flame retardant
material further comprises an aromatic thermosetting resin
comprising aromatic rings on a main chain skeleton.
9. A flame retardant epoxy resin material, comprising: an epoxy
resin obtained by glycidyl-etherification of at least a part of
phenolic hydroxyl groups of a poly-aromatic compound obtained by a
condensation reaction of phenols (A) to aromatics (B) except for
phenols and a heterocyclic compound (C) including nitrogen as
heteroatom via aldehydes (D).
10. The flame retardant epoxy resin material as claimed in claim 9,
wherein said aromatics (B) are represented by the following
chemical formula (1)XH.sub.2C--R.sub.1--CH.sub.2X (1)where R.sub.1
is any one of biphenyl derivatives, phenylene derivatives,
naphthalene derivatives, biphenylene derivatives, fluorine
derivatives, bis-phenol fluorine derivatives, and X is any one of
halogen atoms, hydroxyl groups and alkoxyl groups having not larger
than 10 carbon atoms.
11. The flame retardant epoxy resin material as claimed in claim
10, wherein said R.sub.1 is any one of biphenyl derivatives and
phenylene derivatives.
12. The flame retardant epoxy resin material as claimed in claim 9,
wherein said heterocyclic compound (C) is triazines.
13. The flame retardant epoxy resin material as claimed in claim
12, wherein said triazines include compounds having at least one
amino group.
14. The flame retardant epoxy resin material as claimed in claim
12, wherein said triazines are at least one compound selected from
the groups consisting of melamine, acetoguanamine and
benzoguanamine.
15. A flame retardant resin composition, comprising: at least a
flame retardant epoxy resin material as claimed in claim 9.
16. The flame retardant resin composition as claimed in claim 15,
further including an aromatic thermosetting resin having aromatic
rings on a main chain skeleton.
17. The flame retardant resin composition as claimed in claim 16,
wherein said aromatic thermosetting resin comprises an epoxy resin
having a novolak structure.
18. The flame retardant resin composition as claimed in claim 16,
wherein said aromatic thermosetting resin comprises a phenol resin
having a novolak structure.
19. The flame retardant resin composition as claimed in claim 16,
wherein said aromatic thermosetting resin comprises a phenol
aralkyl epoxy resin having aromatic rings on a novolak-structured
main chain.
20. The flame retardant resin composition as claimed in claim 19,
wherein said phenol aralkyl epoxy resin has at least any one of
biphenyl derivatives and phenylene derivatives on said
novolak-structured main chain.
21. The flame retardant resin composition as claimed in claim 16,
wherein said aromatic thermosetting resin comprises a phenol
aralkyl phenol resin aromatic rings on a novolak-structured main
chain.
22. The flame retardant resin composition as claimed in claim 21,
wherein said phenol aralkyl phenol resin has at least any one of
biphenyl derivatives and phenylene derivatives on said
novolak-structured main chain.
23. The flame retardant resin composition as claimed in claim 15,
further including an aromatic thermoplastic resin having aromatic
rings on a main chain skeleton.
24. A semiconductor device having a sealing resin which comprises a
flame retardant resin composition as claimed in claim 15.
25. A printed wiring board having an insulator which comprises a
flame retardant resin composition as claimed in claim 15.
26. A molding material comprising a flame retardant resin
composition as claimed in claim 15.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a flame retardant resin
material and a flame retardant resin composition, and more
particularly to a flame retardant resin material and a flame
retardant resin composition which are improved in flame retardancy,
thermal stability or thermal decomposition resistance, and moisture
resistance.
[0002] In order to prevent flame, it is required that resin
compositions has a flame retardancy. Usually, halogen flame
retardants are used as flame retardants whilst antimony trioxide is
used as a co-flame retardant co-used along with the flame
retardant. The halogen flame retardants generate harmful halogen
substances typically dioxins. The antimony trioxide as the co-flame
retardant has a chronic toxicity. For those reasons, the above
substances raise a problem in safety in fire or waste disposal.
Phosphoric flame retardants such as red phosphorus and ester
phosphate are effective to avoid the above problem. Those
phosphoric flame retardants provide influences to moisture
resistance of the resin compositions. Particularly, insulators for
electronic components are required to have a high reliability .
Those phosphoric flame retardants are problem in use for the
insulators for electronic components.
[0003] On the other hand, epoxy resin compositions are superior in
mechanical properties, adhesive property, chemical resistance
property, heat resistance and insulating properties, for which
reason the epoxy resin compositions are used in various fields in
adhesive, coating materials, laminated plates, molding materials
and injection materials. In case of the epoxy resin compositions,
halogen flame retardants are used as flame retardants whilst
antimony trioxide is used as a co-flame retardant. If the flame
retardant and the co-flame retardant are used for the epoxy resin
composition, problems in not only safety but also corrosion of
metals are raised. If those epoxy resin compositions are used as
insulators for the electronic components, corrosion resistance to
interconnections under high temperature is lowered, whereby
reliability of the electronic device is deteriorated. For this
reason, it had been required to develop other epoxy resin
compositions free from the halogen flame retardant and antimony
trioxide.
[0004] It was investigated to improve the flame retardancy of the
resin material by introducing a triazine ring into a molecular
structure of an epoxy resin or a phenol resin. In Japanese
laid-open patent publication No. 8-311142, it is disclosed that
mixtures of phenols with compounds having triazine rings and with
aldehydes or phenol condensates such as phenol triazine resins are
used as a hardening agent for the epoxy resin compositions. In
Japanese laid-open patent publication No. 10-279657, it is
disclosed that a phenol triazine epoxy resin obtained by
glycidyl-etherification of the above described phenol triazine
resin is used as a main component of the epoxy resin
composition.
[0005] There is, however, the following problem in introducing the
triazine rings into the molecular structures of the epoxy resins
and the phenol resins.
[0006] The flame retardancy of the resin compositions including the
phenol triazine resins and the phenol triazine epoxy resins is
exhibited due to a flame reducing mechanism by flame resistant
gases which contain, as a main component, nitrogen compounds
generated by decomposition of triazines. If in order to emphasize
the flame reducing effect, a content of nitrogen in the resin
composition is increased, then the resistance to the thermal
decomposition of the resin composition is deteriorated, whereby the
flame retardancy is thus deteriorated. Since triazines have
hydrophilicity, the increase in content of the triazines (nitrogen)
in the resin composition causes a remarkable reduction in moisture
resistance.
[0007] Consequently, it is difficult to further improve the flame
retardancy of the resin composition by introducing nitrogen
compounds into the molecular structure of the resin
composition.
[0008] In the above circumstances, it had been required to develop
a novel flame retardant resin material and a novel flame retardant
resin composition free from the above problems.
SUMMARY OF THE INVENTION
[0009] Accordingly, it is an object of the present invention to
provide a novel flame retardant resin material free from the above
problems.
[0010] It is a further object of the present invention to provide a
novel flame retardant resin material having a high frame
retardancy.
[0011] It is a still further object of the present invention to
provide a novel flame retardant resin material having a high
thermal stability or a high thermal decomposition resistance.
[0012] It is yet a further object of the present invention to
provide a novel flame retardant resin material having a high
moisture resistance.
[0013] It is further more of the present invention to provide a
novel flame retardant resin composition free from the above
problems.
[0014] It is moreover object of the present invention to provide a
novel flame retardant resin composition having a high frame
retardancy.
[0015] It is another object of the present invention to provide a
novel flame retardant resin composition having a high thermal
stability or a high thermal decomposition resistance.
[0016] It is still another object of the present invention to
provide a novel flame retardant resin composition having a high
moisture resistance.
[0017] The present invention provides a flame retardant phenol
resin material which includes a phenol condensate, wherein a
poly-aromatic compound obtained by a reaction of phenols (A) to
aromatics (B) except for phenols and a heterocyclic compound (C)
including nitrogen as heteroatom are condensed via aldehydes
(D).
[0018] The present invention also provides a flame retardant epoxy
resin material which includes an epoxy resin obtained by
glycidyl-etherification of at least a part of phenolic hydroxyl
groups of a poly-aromatic compound obtained by a reaction of
phenols (A) to aromatics (B) except for phenols and a heterocyclic
compound (C) including nitrogen as heteroatom are condensed via
aldehydes (D).
[0019] The present invention also provides a flame retardant resin
composition including a flame retardant phenol resin material which
includes a phenol condensate, wherein a poly-aromatic compound
obtained by a reaction of phenols (A) to aromatics (B) except for
phenols and a heterocyclic compound (C) including nitrogen as
heteroatom are condensed via aldehydes (D).
[0020] The present invention also provides a flame retardant resin
composition including a flame retardant epoxy resin material which
includes an epoxy resin obtained by glycidyl-etherification of at
least a part of phenolic hydroxyl groups of a poly-aromatic
compound obtained by a reaction of phenols (A) to aromatics (B)
except for phenols and a heterocyclic compound (C) including
nitrogen as heteroatom are condensed via aldehydes (D).
[0021] The above and other objects, features and advantages of the
present invention will be apparent from the following
descriptions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Preferred embodiments according to the present invention
will be described in detail with reference to the accompanying
drawings.
[0023] FIG. 1A is a schematic view illustrative of a flame
retardant mechanism of a flame retardant resin composition having a
foam layer free of nitrogen based frame reducing gas.
[0024] FIG. 1B is a schematic view illustrative of a flame
retardant mechanism of a flame retardant resin composition having a
foam layer filled with nitrogen based frame reducing gas.
DISCLOSURE OF THE INVENTION
[0025] The first present invention provides a flame retardant
phenol resin material which includes a phenol condensate, wherein a
poly-aromatic compound obtained by a condensation reaction of
phenols (A) to aromatics (B) except for phenols and a heterocyclic
compound (C) including nitrogen as heteroatom are condensed via
aldehydes (D).
[0026] It is preferable that the aromatics (B) are represented by
the following chemical formula (1),
XH.sub.2C--R.sub.1--CH.sub.2X (1)
[0027] where R.sub.1 is any one of biphenyl derivatives, phenylene
derivatives, naphthalene derivatives, biphenylene derivatives,
fluorene derivatives, bis-phenol fluorene derivatives, and X is any
one of halogen atoms, hydroxyl groups and alkoxyl groups having not
larger than 10 carbon atoms.
[0028] It is further preferable that the R.sub.1 is any one of
biphenyl derivatives and phenylene derivatives.
[0029] It is also preferable that the heterocyclic compound (C) is
triazines.
[0030] It is further preferable that the triazines include
compounds having at least one amino group.
[0031] It is also preferable that the triazines are at least one
compound selected from the groups consisting of melamine,
acetoguanamine and benzoguanamine.
[0032] The second present invention provides a flame retardant
resin composition which includes at least a flame retardant phenol
resin material of the first present invention.
[0033] It is preferable to further include an aromatic
thermosetting resin having aromatic rings on a main chain
skeleton.
[0034] It is further preferable that the aromatic thermosetting
resin comprises an epoxy resin having a novolak structure.
[0035] It is also preferable that the aromatic thermosetting resin
comprises a phenol resin having a novolak structure.
[0036] It is also preferable that the aromatic thermosetting resin
comprises a phenol aralkyl epoxy resin having aromatic rings on a
novolak-structured main chain.
[0037] It is further preferable that the phenol aralkyl epoxy resin
has at least any one of biphenyl derivatives and phenylene
derivatives on the novolak-structured main chain.
[0038] It is also preferable that the aromatic thermosetting resin
comprises a phenol aralkyl phenol resin having aromatic rings on a
novolak-structured main chain.
[0039] It is further preferable that the phenol aralkyl phenol
resin has at least any one of biphenyl derivatives and phenylene
derivatives on the novolak-structured main chain.
[0040] It is also preferable to further include an aromatic
thermoplastic resin having aromatic rings on a main chain
skeleton.
[0041] The third present invention provides a semiconductor device
having a sealing resin which comprises a flame retardant resin
composition of the second present invention.
[0042] The fourth present invention provides a printed wiring board
having an insulator which comprises a flame retardant resin
composition of the second present invention.
[0043] The fifth present invention provides a molding material
comprising a flame retardant resin composition of the second
present invention.
[0044] The sixth present invention provides a flame retardant epoxy
resin material which includes an epoxy resin obtained by
glycidyl-etherification of at least a part of phenolic hydroxyl
groups of a poly-aromatic compound obtained by a condensation
reaction of phenols (A) to aromatics (B) except for phenols and a
heterocyclic compound (C) including nitrogen as heteroatom via
aldehydes (D).
[0045] It is preferable that the aromatics (B) are represented by
the following chemical formula (1),
XH.sub.2C--R.sub.1--CH.sub.2X (1)
[0046] where R.sub.1 is any one of biphenyl derivatives, phenylene
derivatives, naphthalene derivatives, biphenylene derivatives,
fluorene derivatives, bis-phenol fluorene derivatives, and X is any
one of halogen atoms, hydroxyl groups and alkoxyl groups having not
larger than 10 carbon atoms.
[0047] It is further preferable that the R.sub.1 is any one of
biphenyl derivatives and phenylene derivatives.
[0048] It is also preferable that the heterocyclic compound (C) is
triazines.
[0049] It is further preferable that the triazines include
compounds having at least one amino group.
[0050] It is also preferable that the triazines are at least one
compound selected from the groups consisting of melamine,
acetoguanamine and benzoguanamine.
[0051] The seventh present invention provides a flame retardant
resin composition which includes at least a flame retardant epoxy
resin material of the sixth present invention.
[0052] It is preferable to further include an aromatic
thermosetting resin having aromatic rings on a main chain
skeleton.
[0053] It is further preferable that the aromatic thermosetting
resin comprises an epoxy resin having a novolak structure.
[0054] It is also preferable that the aromatic thermosetting resin
comprises a phenol resin having a novolak structure.
[0055] It is also preferable that the aromatic thermosetting resin
comprises a phenol aralkyl epoxy resin having aromatic rings on a
novolak-structured main chain.
[0056] It is further preferable that the phenol aralkyl epoxy resin
has at least any one of biphenyl derivatives and phenylene
derivatives on the novolak-structured main chain.
[0057] It is also preferable that the aromatic thermosetting resin
comprises a phenol aralkyl phenol resin having aromatic rings on a
novolak-structured main chain.
[0058] It is further preferable that the phenol aralkyl phenol
resin has at least any one of biphenyl derivatives and phenylene
derivatives on the novolak-structured main chain.
[0059] It is also preferable to further include an aromatic
thermoplastic resin having aromatic rings on a main chain
skeleton.
[0060] The eighth present invention provides a semiconductor device
having a sealing resin which comprises a flame retardant resin
composition of the seventh present invention.
[0061] The ninth present invention provides a printed wiring board
having an insulator which comprises a flame retardant resin
composition of the seventh present invention.
[0062] The tenth present invention provides a molding material
comprising a flame retardant resin composition of the seventh
present invention.
[0063] Accordingly, the present invention provides a flame
retardant phenol resin material which includes a phenol condensate,
wherein a poly-aromatic compound obtained by a reaction of phenols
(A) to aromatics (B) except for phenols and a heterocyclic compound
(C) including nitrogen as heteroatom are condensed via aldehydes
(D).
[0064] The present invention also provides a flame retardant epoxy
resin material which includes an epoxy resin obtained by
glycidyl-etherification of at least a part of phenolic hydroxyl
groups of a poly-aromatic compound obtained by a reaction of
phenols (A) to aromatics (B) except for phenols and a heterocyclic
compound (C) including nitrogen as heteroatom are condensed via
aldehydes (D).
[0065] The present invention also provides a flame retardant resin
composition including a flame retardant phenol resin material which
includes a phenol condensate, wherein a poly-aromatic compound
obtained by a reaction of phenols (A) to aromatics (B) except for
phenols and a heterocyclic compound (C) including nitrogen as
heteroatom are condensed via aldehydes (D).
[0066] The present invention also provides a flame retardant resin
composition including a flame retardant epoxy resin material which
includes an epoxy resin obtained by glycidyl-etherification of at
least a part of phenolic hydroxyl groups of a poly-aromatic
compound obtained by a reaction of phenols (A) to aromatics (B)
except for phenols and a heterocyclic compound (C) including
nitrogen as heteroatom are condensed via aldehydes (D).
[0067] The above flame retardant resin compositions may include an
aromatic thermosetting resin having an aromatic ring in a main
chain skeleton.
[0068] The above flame retardant resin compositions may include an
aromatic thermoplastic resin having an aromatic ring in a main
chain skeleton.
[0069] The present invention also provides a semiconductor device
using a sealing resin which comprises the above flame retardant
resin composition.
[0070] The present invention also provides an electronic or
electric component having a semiconductor device using a sealing
resin which comprises the above flame retardant resin
composition.
[0071] The present invention also provides a printed wiring board
using an insulator material which comprises the above flame
retardant resin composition.
[0072] The present invention also provides a molding material
comprising a flame retardant thermosetting resin which comprises
the above flame retardant resin composition.
[0073] The present invention also provides a molding material
comprising a flame retardant thermoplastic resin which comprises
the above flame retardant resin composition.
[0074] In this specification, "flame retardant phenol resin
material" is defined to be a phenol resin material, wherein a
phenol condensate having the above structure is optionally mixed
with other phenol resins. "flame retardant epoxy resin material" is
defined to be an epoxy resin material, wherein an epoxy resin
having the above structure is optionally mixed with other epoxy
resins. "frame retardant resin composition" includes the above
flame retardant phenol resin materials and/or the above flame
retardant epoxy resin materials which may optionally be mixed with
fillers, flame retardants such as metal hydroxides, phosphoric
compounds except for halogen compounds or other additives.
[0075] The flame retardant phenol resin materials and the flame
retardant epoxy resin materials in accordance with the present
invention will hereinafter be referred to as "flame retardant resin
materials". The flame retardant resin material has the aromatics
(B) and the heterocyclic compound (C) in its condensate, for which
reason the flame retardant resin material is superior in flame
retardancy as compared to the conventional flame retardant resin
materials.
[0076] If, in accordance with the prior art, the flame retardant
resin material having molecular skeletons introduced with the
heterocyclic compound (C) including nitrogen atoms as the
heteroatom therein is added into the resin composition, then
nitrogen based flame resistant gases are generated by ignition,
whereby the flame resistant gases are dispersed to an atmosphere
and an insufficient flame retarding effect is obtained. It is
necessary for obtaining a sufficient flame retarding effect to
generate a large amount of the nitrogen based flame resistant
gases. The source of the nitrogen based flame resistant gases is
triazine ring. If the content of the triazine rings in the resin
composition is increased, then the thermal stability or the
resistance to the thermal decomposition is deteriorated, whereby
the flame retardancy is deteriorated and the moisture resistance
and other properties are also deteriorated.
[0077] In accordance with the present invention, the flame
retardant resin material having both the aromatics (B) and the
heterocyclic compound (C) in the condensate is added to the resin
composition to exhibit a novel flame retarding mechanism different
from the conventional technique.
[0078] The novel flame retarding mechanism will hereinafter be
described by taking an example of a thermosetting resin including
the flame retardant resin material.
[0079] The flame retardant resin material in accordance with the
present invention includes aromatics (B). The flame retardant resin
composition including the flame retardant resin material is low in
bridge density in thermosetting resin composition, for which reason
decomposition gases generated by ignition of the resin composition
expends a surface of the resin composition to form a foam layer.
The addition of the above flame retardant resin composition causes
this foam layer to include phenols superior in thermal stability or
thermal decomposition resistance and aromatic derivatives or
poly-aromatics, whereby the resin composition has a high hot
strength which suppress foam-breaking. Oxygen or heat are shielded
by this foam layer, whereby a high flame retarding effect can be
obtained.
[0080] In addition to the aromatics (B), the heterocyclic compound
(C) is introduced into the molecular skeletons of the flame
retardant resin composition in order to not only prevent the
spreading fire but also cause the foam layer to reduce the fire for
obtaining a higher flame retardancy. Namely, the flame retardant
resin composition in accordance with the present invention includes
the heterocyclic compound (C). The nitrogen based flame resistant
gases are generated in ignition. A part of the generated gases is
diffused into the atmosphere whilst the remaining part thereof
fills the foam layer. The foam layer filled with the nitrogen based
flame resistant gases not only prevents the spreading fire but also
reducing the fire. This mechanism will be described with reference
to the drawing. FIG. 1A is a schematic view illustrative of a flame
retardant mechanism of a flame retardant resin composition having a
foam layer free of nitrogen based frame reducing gas. A left side
edge of a resin product 1 is burned or fired and a fire face 3 is
made spread toward a foam layer 2 which prevents the fire spread.
If the fire face 3 is made close to the foam layer 2, some of forms
are broken, whereby it is no longer possible to prevent the fire
spread. FIG. 1B is a schematic view illustrative of a flame
retardant mechanism of a flame retardant resin composition having a
foam layer filled with nitrogen based frame reducing gas. A left
side edge of a resin product 1' is burned or fired and a fire face
3' is made spread toward a foam layer 2 which reduces the fire. If
the fire face 3 is made close to the foam layer 2, some of forms
are broken, whereby the nitrogen based gases 4 are injected to the
fire, and the fire is reduced by the nitrogen based gases. Namely,
the foam layer 2' serves as a reservoir layer for reserving the
nitrogen based flame reducing gases 4' which are capable of fire
extinction. The thermosetting resin composition including the flame
retardant resin material exhibits the higher flame retardancy than
that of the conventional resin composition. It is also possible to
cause a high multiplier effect in flame retardancy by the flame
retardant resin material to a resin composition having a base
material of an aromatic thermosetting resin having aromatic rings
on the main chain skeleton, for example, an epoxy resin containing
a novolak structure and/or an epoxy resin composition having a base
material of an epoxy resin containing a novolak structure,
particularly a phenol aralkyl type epoxy resin having aromatic
rings on a novolak-structured main chain skeleton and/or a phenol
aralkyl type phenol resin having aromatic rings on a
novolak-structured main chain skeleton. The aromatic thermosetting
resin having the aromatic rings on the main chain skeleton is high
in thermal stability and shows a high compatibility with the flame
retardant resin material, whereby a uniform and stable foam layer
can be obtained in ignition. Particularly, an extremely stable foam
layer can be obtained by using an epoxy resin containing a novolak
structure and/or an epoxy resin composition having a base material
of an epoxy resin containing a novolak structure, particularly a
phenol aralkyl type epoxy resin having aromatic rings on a
novolak-structured main chain skeleton and/or a phenol aralkyl type
phenol resin having aromatic rings on a novolak-structured main
chain skeleton.
[0081] The flame retardant resin material in accordance with the
present invention has both the aromatics (B) and the heterocyclic
compound (C) in the same condensate so that the resin composition
containing the flame retardant resin material has a high flame
retardancy and a high moisture resistance. If, differently from the
present invention, the resin composition having a molecular
skeleton introduced with the aromatics (B) and a different
molecular skeleton introduced with the heterocyclic compound (C)
does not have both a high flame retardancy and a high moisture
resistance. For example, a resin composition having a phenol
biphenyl aralkyl epoxy resin having a biphenyl group on the
molecular skeleton and a phenol resin having triazine rings does
not have a sufficiently high flame retardancy and moisture
resistance. The high flame retardancy and the high moisture
resistance shown by the flame retardant resin material of the
present invention can be obtained by introducing the aromatics (B)
which are superior in both the thermal stability or resistance to
the thermal decomposition and the hydrophobicity. Addition of the
resin composition with the flame retardant resin material having
the aromatics (B) and the heterocyclic compound (C) in the same
condensate in accordance with the present invention results in
improvements in both the flame retardancy and the moisture
resistance.
[0082] The above descriptions about the flame retardancy mechanism
of the flame retardant resin material have been made by taking, as
one example, the thermosetting resin composition. The above novel
flame retardant resin material is, of course, applicable to
thermoplastic resin composition to obtain such the high flame
retardancy. Similarly to the above described thermosetting resin
composition, the thermoplastic resin composition containing the
flame retardant resin material of the present invention causes a
foam layer to be formed in ignition, wherein the foam layer is
superior in thermal stability or resistance to the thermal
decomposition, whereby the thermoplastic resin composition exhibits
a high flame retardancy. The thermoplastic resin composition
containing the flame retardant resin material having both the
aromatics (B) and the heterocyclic compound (C) in the same
condensate provides the large effects. The combination of the
aromatics in the flame retardant resin material is compatible with
the aromatic rings, for which reason the aromatic thermoplastic
resin composition having the aromatic rings on the main chain
skeleton is preferable in view of improvement in the flame
retardancy.
[0083] In accordance with the present invention, phenols (A) are
not limited provided that an aromatic compound having a hydroxyl
group. For example, there are available as the phenols (A) phenol,
naphthols such as .alpha.-naphthol and .beta.-naphthol, bisphenol
fluorene type phenol, alkyl phenols such as cresol, xylenol, ethyl
phenol, butyl phenol, nonyl phenol, and octyl phenol, polyhydric
phenols such as bis-phenol A, bis-phenol F, bis-phenol S, resorcin
and catechol, phenyl phenol, and amino phenol. Those phenols may be
used alone or in combination.
[0084] In accordance with the present invention, the aromatics (B)
comprises one or more aromatic compounds except for the above
described phenols (A). The aromatics (B) are not limited provided
that the aromatics (B) are chemically reacted and bonded with the
phenols (A). It is preferable that the aromatics (B) are
represented by the following chemical formula (1).
XH.sub.2C--R.sub.1--CH.sub.2X (1)
[0085] where R.sub.1 is any one of biphenyl derivatives, phenylene
derivatives, naphthalene derivatives, biphenylene derivatives,
fluorene derivatives, bis-phenol fluorene derivatives, and
anthracene derivatives, and X is any one of halogen atoms, hydroxyl
groups and alkoxyl groups having not larger than 10 carbon
atoms.
[0086] The biphenyl derivatives means a divalent group derived from
substitutional or unsubstitutional biphenyl. The substitutional
biphenyl may be, for example, hydrocarbon groups having a
chain-structure including unsaturated bonds of 1-6 carbon atoms
such as allyl groups, and alkyl groups of 1-6 carbon atoms.
[0087] The phenylene derivatives means a divalent group derived
from substitutional or unsubstitutional phenylene. The
substitutional phenylene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon atoms.
The phenylene derivatives include divalent groups derived from
diphenyl ether, divalent groups derived from bis-phenol A, divalent
groups derived from bis-phenol F, and divalent groups derived from
bis-phenol S.
[0088] The naphthalene derivatives means a divalent group derived
from substitutional or unsubstitutional naphthalene. The
substitutional naphthalene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0089] The biphenylene derivatives means a divalent group derived
from substitutional or unsubstitutional biphenylene. The
substitutional biphenylene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0090] The fluorene derivatives means a divalent group derived from
substitutional or unsubstitutional fluorene. The substitutional
fluorene may be, for example, hydrocarbon groups having a
chain-structure including unsaturated bonds of 1-6 carbon atoms
such as allyl groups, and alkyl groups of 1-6 carbon atoms.
[0091] The bis-phenol fluorene derivatives means a divalent group
derived from substitutional or unsubstitutional bis-phenol
fluorene. The substitutional bis-phenol fluorene may be, for
example, hydrocarbon groups having a chain-structure including
unsaturated bonds of 1-6 carbon atoms such as allyl groups, and
alkyl groups of 1-6 carbon atoms.
[0092] The anthracene derivatives means a divalent group derived
from substitutional or unsubstitutional anthracene. The
substitutional anthracene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0093] It is preferable that R.sub.1 is any one of biphenyl
derivatives, phenylene derivatives, whereby a thermosetting resin
composition having a low bridge density can be obtained. A foam
layer in a form of rubber which is superior in thermal
decomposition resistance is formed in ignition. Biphenyl and
derivatives thereof as well as phenylene and derivatives thereof
are superior in hydrophobicity, for which reason introduction of
them causes a great improvement in moisture resistance of the resin
composition.
[0094] The aromatics (B) are not limited provided that the
aromatics (B) are chemically reacted and bonded with the phenols
(A). The aromatics (B) may be a compound represented by the
following general formula (1). 1
[0095] where a hydrogen atom bonded to a carbon atom of methylene
chain (--CH.sub.2--) is substituted with other substituent (R').
This substituent (R') may be, for example, a hydrocarbon group
having 1-10 carbon atoms and/or an alkoxyl group having 1-10 carbon
atoms as well as polymers based on other hydrocarbons.
[0096] In accordance with the present invention, heterocyclic
compound (C) including nitrogen as heteroatom serves as a source of
flame reducing gas. The heterocyclic compound (C) includes one or
more nitrogen atoms, and optionally may further include other atoms
such as sulfur as heteroatom. It is particularly preferable that
the heterocyclic compound (C) including nitrogen as heteroatom is
triazines. The triazines means compounds having one or more
triazine rings to effectively discharge flame reducing nitrogen
based gases.
[0097] It is preferable that the triazines have at least one amino
group so that the triazines and the poly-aromatics obtained by
reaction of the phenols (A) with the aromatics (B) except for
phenols may easily condensed via the aldehydes (D).
[0098] It is preferable that the triazines are represented by the
following general formulae (2) and (3) so as to effectively
discharge flame reducing nitrogen based gases. 2
[0099] where each of R.sub.2, R.sub.3, and R.sub.4 is any one of
amino groups, phenyl groups, alkyl groups having 1-12 carbon atoms,
hydroxyl groups, hydroxyl alkyl groups, ether groups, ester groups,
carboxyl groups, unsaturated hydrocarbon groups, cyano groups,
thiol groups, halogen atoms. It is preferable that if R.sub.2,
R.sub.3, and R.sub.4 are substituted with alkyl groups, the number
of alkyl groups in the formula is not more than 2 and others are
the above reactive functional groups. 3
[0100] where each of R.sub.5, R.sub.6, and R.sub.7 is any one of
hydrogen atom, alkyl groups having 1-12 carbon atoms, phenyl
groups, hydroxyl groups, hydroxyl alkyl groups, ester groups,
carboxyl groups, unsaturated hydrocarbon groups, cyano groups,
halogen atoms. It is preferable that if R.sub.5, R.sub.6, and
R.sub.7 are substituted with alkyl groups, the number of alkyl
groups in the formula is not more than 2 and others are the above
reactive functional groups.
[0101] As described above, it is preferable that at least one of
R.sub.2, R.sub.3, and R.sub.4 is amino groups. The compounds
represented by the general formula (2) may be, for example, the
triazine derivatives such as benzoguanamine, acetoguanamine and
melamine, cyanuric acid derivatives such as cyanuric acid, methyl
cyanurate, ethyl cyanurate, acetyl cyanurate, cyanuric chloride. It
is more preferable that the triazine derivative is benzoguanamine
(the following general formula (4)), acetoguanamine(the following
general formula (5)), melamine (the following general formula (6)).
Benzoguanamine is most preferable because this compound makes the
heterocyclic compound (C) easy to be compatible with the
poly-aromatics obtained by the reaction of the phenols (A) with the
aromatics (B) except for phenols and with the aldehydes (D),
resulting in an efficient reaction and improvement in moisture
resistance of the flame retardant resin material. 4
[0102] It is also preferable that at least one of is R.sub.5,
R.sub.6, and R.sub.7 is hydrogen atom. The compounds represented by
the general formula (3) may be, for example, isocyanuric acid
derivatives such as isocyanuric acid, methyl isocyanurate, methyl
isocyanurate, ethyl isocyanurate, allyl isocyanurate,
2-hydroxyethyl isocyanurate, 2-carboxylethyl isocyanurate,
isocyanuric chloride. It is most preferable that all of R.sub.5,
R.sub.6, and R.sub.7 are hydrogen atoms. The cyanuric acid
represented in the general formula (2) as tautomer of those
compounds is also preferable.
[0103] The compounds of the general formulae (2) and (3) may be
used alone or in combination.
[0104] In accordance with the present invention, the aldehydes (D)
are not limited but formaldehyde is preferable as being convenient
in use. Typical sources are, for example, formalin and
paraformaldehyde.
[0105] The flame retardant phenol resin material of the present
invention includes a phenol condensate in which the components (A),
(B), (C) and (D) are condensed. The flame retardant epoxy resin
material of the present invention includes an epoxy resin, wherein
the phenol condensate is glycidyl-etherificated.
[0106] It is preferable that an epoxy resin is contained in the
flame retardant phenol resin material of the present invention to
obtain a resin composition superior in flame retardancy, mixing
stability, thermal stability and moisture resistance and other
properties, wherein the phenol condensate of the present invention
serves as a thermosetting agent for the epoxy resin
composition.
[0107] Similarly, it is also preferable that a thermosetting agent
for epoxy resin is included in the flame retardant epoxy resin
material of the present invention to obtain a resin composition
superior in flame retardancy, mixing stability, thermal stability
and moisture resistance and other properties.
[0108] The flame retardant resin material of the present invention
is particularly effective for flame retardation of the epoxy resin
composition. The epoxy resin and the epoxy resin thermosetting
agent serve as the base materials of the epoxy resin composition
including the flame retardant resin material of the present
invention. As the epoxy resin and the epoxy resin thermosetting
agent, an epoxy resin containing a novolak structure and a phenol
resin containing a novolak structure are preferable. Particularly,
a phenol aralkyl type epoxy resin having aromatic rings on the
novolak-structured main chain skeleton and a phenol aralkyl type
phenol resin having aromatic rings on the novolak-structured main
chain skeleton are further preferable. As the phenol aralkyl type
epoxy resin and the phenol aralkyl type phenol resin, there is used
for the base material of the epoxy resin, at least any one of
phenolbiphenylaralkyl epoxy resin, phenolbiphenylaralkyl phenol
resin, phenolphenylenearalkyl epoxy resin, phenolphenylenearalkyl
phenol resin, phenoldiphenylaralkyl epoxy resin,
phenoldiphenylaralkyl phenol resin, naphtholaralkyl epoxy resin,
naphtholaralkyl phenol resin, phenolanthracenearalkyl epoxy resin,
and phenolanthracenearalkyl phenol resin.
[0109] The co-use of the flame retardant resin material of the
present invention along with epoxy resin and/or the thermosetting
material for the epoxy resin is effective to provide a suitable
resin composition for a sealing resin of semiconductor device and
insulator for printed board.
[0110] The flame retardant resin material of the present invention
is also effective for flame retardation of other resin compositions
than the epoxy resin composition. Particularly, the flame retardant
resin material of the present invention may be well compatible and
uniformly dispersed. The flame retardant resin material of the
present invention is effective for the aromatic thermosetting
resins having the aromatic rings on the main chain skeleton, for
example, phenol resins and resin compositions having polyester as
the base material and for the aromatic thermoplastic resins having
the aromatic rings on the main chain skeleton, for example,
polycarbonate, polystyrene, co-polymer (AB) of acrylonitrile and
styrene, co-polymer (ABS) of acrylonitrile, butadiene and styrene,
polyphenylene ether, polybutylene terephthalate, nylon, and resin
compositions having a base material of polymer alloy comprising at
least two of them. The flame retardant resin material of the
present invention is also effective for resin compositions having a
base material of olefins, and optionally together with dispersing
agent for obtaining a higher flame retardancy.
[0111] The flame retardant phenol resin material of the present
invention uses the specific-structured condensate which includes
the above components (A), (B), (C) and (D) in one molecule, for
which reason there is no limitation to molecular weight. As the
phenol condensate, plural types of the substances different in
molecular weight may be included in the condensate.
[0112] The flame retardant epoxy resin material of the present
invention also uses the specific-structured condensate which
includes the above components (A), (B), (C) and (D) in one
molecule, for which reason there is no limitation to molecular
weight. As the epoxy resin, plural types of the substances
different in molecular weight may be included in the
condensate.
[0113] The flame retardant resin composition of the present
invention may include any one of the flame retardant phenol resin
material and the flame retardant epoxy resin material or include
the both. The flame retardant resin composition of the present
invention may further preferably include the aromatic thermosetting
resin having aromatic rings on the main chain skeleton or the
aromatic thermoplastic resin having aromatic rings on the main
chain skeleton. It is particularly preferable that the flame
retardant resin composition of the present invention may further
include the above aromatic thermosetting resin. Those resins have
good compatibility with the flame retardant resin material of the
present invention, for which reason a uniform and extremely stable
foam layer can be obtained in ignition to cause a remarkable flame
retardancy. Particularly, if the above aromatic thermosetting resin
comprises an epoxy resin containing a novolak structure and/or a
phenol resin containing a novolak structure, for example, if the
above aromatic thermosetting resin comprises a phenol aralkyl type
epoxy resin having aromatic rings on a novolak-structured main
chain skeleton and/or a phenol aralkyl type phenol resin having
aromatic rings on a novolak-structured main chain skeleton, then
more remarkable effect of flame retardation can be obtained. It is
preferable that the above phenol aralkyl type epoxy resin includes
biphenyl derivatives and/or phenylene derivatives on the main chain
skeleton. It is preferable that those aromatic thermosetting resins
are used as the base material in the resin composition, to cause a
multiplier effect in the flame retardation.
[0114] A typical method of preparing the phenol condensate in
accordance with the present invention will be described even other
methods may be available.
[0115] The phenols (A) are reacted with the aromatics (B) under an
acidic catalyst to cause a condensation reaction to form a
condensate represented by the following general formula (7). The
above condensation reaction is made under the conditions that a
molar ratio of the phenols (A) to the aromatics (B) is ranged from
0.3:1 to 20:1, preferably from 0.4:1 to 15:1. 5
[0116] where "n" is 0.0 to 10, preferably 0.0 to 3.0, and more
preferably 0.0 to 1.0, R.sub.0--OH is any one of phenol
derivatives, naphthol derivatives, derivatives of poly-phenol such
as bis-phenol fluorene derivatives, bis-phenol A, bis-phenol phenol
F, bis-phenol S, resorcin, and catechol, and derivatives of alkyl
phenols.
[0117] R.sub.1 is any one of biphenyl derivatives, phenylene
derivatives, naphthalene derivatives, biphenylene derivatives,
fluorene derivatives, bis-phenol fluorene derivatives, and
anthracene derivatives.
[0118] The biphenyl derivatives means a divalent group derived from
substitutional or unsubstitutional biphenyl. The substitutional
biphenyl may be, for example, hydrocarbon groups having a
chain-structure including unsaturated bonds of 1-6 carbon atoms
such as allyl groups, and alkyl groups of 1-6 carbon atoms.
[0119] The phenylene derivatives means a divalent group derived
from substitutional or unsubstitutional phenylene. The
substitutional phenylene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon atoms.
The phenylene derivatives include divalent groups derived from
diphenyl ether, divalent groups derived from bis-phenol A, divalent
groups derived from bis-phenol F, and divalent groups derived from
bis-phenol S.
[0120] The naphthalene derivatives means a divalent group derived
from substitutional or unsubstitutional naphthalene. The
substitutional naphthalene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0121] The biphenylene derivatives means a divalent group derived
from substitutional or unsubstitutional biphenylene. The
substitutional biphenylene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0122] The fluorene derivatives means a divalent group derived from
substitutional or unsubstitutional fluorene. The substitutional
fluorene may be, for example, hydrocarbon groups having a
chain-structure including unsaturated bonds of 1-6 carbon atoms
such as allyl groups, and alkyl groups of 1-6 carbon atoms.
[0123] The bis-phenol fluorene derivatives means a divalent group
derived from substitutional or unsubstitutional bis-phenol
fluorene. The substitutional bis-phenol fluorene may be, for
example, hydrocarbon groups having a chain-structure including
unsaturated bonds of 1-6 carbon atoms such as allyl groups, and
alkyl groups of 1-6 carbon atoms.
[0124] The anthracene derivatives means a divalent group derived
from substitutional or unsubstitutional anthracene. The
substitutional anthracene may be, for example, hydrocarbon groups
having a chain-structure including unsaturated bonds of 1-6 carbon
atoms such as allyl groups, and alkyl groups of 1-6 carbon
atoms.
[0125] The condensate represented in the above general formula (7)
may, for example, be substances represented by the following
formulae (8) through (18), but should not limited to those
substances. 6
[0126] In the above condensation reaction, acidic catalysts are
used. Various types of the acidic catalysts may be used, for
example, organic or inorganic acids such as p-toluenesulfonate,
sulfuric acid, hydrochloric acid, oxalic acid, Lewis acids such as
boron trifluoride, aluminum chloric anhydride, and zinc chloride,
particularly, p-toluenesulfonate, sulfuric acid, hydrochloric acid
are preferable. There is no limitation to the amount in use of
those acidic catalyst but 0.1-30% by weight is preferable.
[0127] The above condensation reaction may be made in the absence
of or in the presence of organic solvents. Available organic
solvents may, for example, be methyl cellosolve, ethyl cellosolve,
toluene, xylene, methylisobutylketone, The amount in use of the
organic solvent is normally 50-300% by weight, preferably 100-250%
by weight to a total weight of the source materials. A reaction
temperature is normally 40-180.degree. C. A reaction time is
normally 1-10 hours. Those organic solvents may be used alone or in
combination. A water and an alcohol generated during the reaction
may preferably be removed by use of fractional distillation tube to
promote the reaction.
[0128] After the reaction, a water cleaning treatment is carried
out until a cleaning solution pH value becomes 3-7, preferably 5-7.
For the water cleaning treatment, there may be used, as
neutralization agents, basic substances, for example, alkali metal
hydroxide such as sodium hydroxide and potassium hydroxide, alkali
earth metal hydroxide such as calcium hydroxide and magnesium
hydroxide, ammonia, sodium dihydrogenphosphate, and organic amines
such as diethylene triamine, triethylene tetraamine, aniline and
phenylene diamine. The water cleaning treatment may be carried out
by the normal method. For example, the reaction mixture is added
with a water solved with the above neutralization agents to repeat
separating extraction operation.
[0129] After the neutralization treatment, the solvent and
unreacted substances are removed under a low pressure at a heated
condition to cause a condensation of the product to form a
condensate represented by the above general formula (7).
[0130] The condensate typically represented by the above general
formula (7), heterocyclic compound (C) having nitrogen as
heteroatom and the aldehydes (D) are reacted under conditions of
4-10 pH, preferable 5-9 pH. The condensate typically represented by
the above general formula (7) is condensed with the heterocyclic
compound (C) having nitrogen as heteroatom via the aldehydes (D) to
form a phenol condensate. This condensation reaction may be made
with or without catalyst. The kinds of catalysts are not limited
but basic catalyst is preferable.
[0131] The available basic catalysts may, for example, be alkali
metal hydroxide such as sodium hydroxide and potassium hydroxide,
alkali earth metal hydroxide such as barium hydroxide, and oxides
of those alkali metal hydroxide and alkali earth metal hydroxide,
ammonia, primary, secondary ternary amines,
hexamethylenetetraamine, and sodium carbonate. If the phenol resin
of the present invention is used as the thermosetting agent to the
epoxy resin compositions for electric or electronic devices, it is
preferable to use amines to avoid that inorganic substances as
metal resides as the residual catalyst.
[0132] There is no limitation to the sequences of the reactions. It
is possible that the condensate represented by the above general
formula (7) is reacted with the aldehydes (D) before the
heterocyclic compound (C) having nitrogen as heteroatom is added
thereto. It is also possible that the heterocyclic compound (C)
having nitrogen as heteroatom is reacted with the aldehydes (D)
before the condensate represented by the above general formula (7)
is then added thereto. It is also possible that the condensate
represented by the above general formula (7), the heterocyclic
compound (C) and the aldehydes (D) are concurrently added to case
the reaction. A molar ratio of the condensate represented by the
above general formula (7) to the heterocyclic compound (C) and the
aldehydes (D) is not limited but preferably 1:(0.1-10):(0.1-10),
and more preferably 1:(0.2-5):(0.2-5).
[0133] In view of control the reaction, it is also possible the
reaction is made in the presence of various solvents. There is no
limitation to the kinds of the solvents but available solvents may,
for example, be acetone, methyl ethylketone, toluene, xylene,
methyl isobutylketone, ethyl acetate,
ethyleneglycolmonomethylether, N,N'-dimethylformamide, methanol and
ethanol. Those solvents may be used alone or in combination.
[0134] The neutralization and water cleaning may, if any be carried
out to remove impurities such as salts. If, however, amines are
used as the catalyst, there is no need to carry out these
processes. After the reaction, unreacted substances and the used
catalysts are removed by the normal methods such as distillation
under atmospheric pressure or in vacuum. It is necessary to carry
out a heat treatment at 120.degree. C. for obtain the resin
substantially free of unreacted aldehydes and methylol groups. A
heat treatment at a temperature below 120.degree. C. is incapable
of complete disappearance of the methylol groups. The heat
treatment at above 120.degree. C. for a sufficient time period is
capable of complete disappearance of the methylol groups. The heat
treatment at above 150.degree. C. is preferable. At this high
temperature, a distillation may preferably be carried out in
accordance with the method of obtaining the novolak resins together
with heating the same.
[0135] The phenol condensate of the present invention is useable
for the flame retardant of the resin composition or the
thermosetting agent. Examples of the phenol condensate of the
present invention are represented by the following general formulae
(19) through (30). 7
[0136] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 8
[0137] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 9
[0138] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 10
[0139] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 11
[0140] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 12
[0141] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 13
[0142] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 14
[0143] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 15
[0144] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 16
[0145] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 17
[0146] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 18
[0147] where R8 is any one of phenyl groups, alkyl groups of 1-12
carbon atoms, amino groups, hydroxyl groups, hydroxylalkyl groups,
ether groups, ester groups, carboxyl groups, unsaturated
hydrocarbon groups, thiol groups, and cyano groups, and "n" is
0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m" is
1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0.
[0148] The flame retardant resin material including the phenol
condensate may be used for the frame retardant to the resin
composition or the thermosetting agent in combination with other
phenol resins or amine compounds. The available phenol resins in
combination are not limited but may, for example, be
phenolbiphenylaralkyl resins, phenolphenylenearalkyl resins,
phenoldiphenylaralkyl resins, naphthalene-containing phenol resins
such as naphtholaralkyl resins, phenoltriazine resins, at least one
or combination of biphenyl-4,4'-dihydroxyether, and
3,3',5,5'-tetramethyl biphenyl-4,4'-dihydroxyethr,
tetraphenyrolethane, trisphenyrolethane, phenol novolak resins,
cresol novolak resins, bis-phenol A resin, bis-phenol F resin,
bis-phenol S resin, polyphenol resin, aliphatic ester phenol resin,
cyclic aliphatic ester phenol resin, and ether ester phenol resin.
Available amine compounds in combination are not limited but may,
for example, be diamino diphenylmethane, diethylene triamine, and
diaminodiphenylsulfone. Those phenol resins and the amine resins
may be used alone or in combination. Phenolbiphenylaralkyl resins,
phenolphenylenearalkyl resins, phenoldiphenylaralkyl resins, and
naphtholaralkyl resins are particularly preferable.
[0149] The flame retardant epoxy resin material of the present
invention will subsequently be described. The epoxy resin contained
in the flame retardant epoxy resin material can be obtained by
glycidyl-etherification of the phenol hydroxyl groups of the flame
retardant phenol resin materials with use of any compounds which
are not limited but allow glycidyl-etherification. For example,
epihalohydrin such as epichlorohydrin. Glycidyl-etherification of
substantially all parts of the phenolic hydroxyl groups makes it
easy to produce the resin composition which is superior in thermal
stability or thermal decomposition resistance and the moisture
resistance. Other method than the glycidyl-etherification, for
example, epoxidation to the phenolic hydroxyl group of the flame
retardant resin material may be available by use of other compound
including epoxy group.
[0150] In order for the glycidyl-etherification of the phenolic
hydroxyl groups, it is possible that the phenol condensate is
solved and mixed with an excess epihalohydrin such as
epichlorohydrin and epibromehydrine and then an alkali metal
hydroxide such as potassium hydroxide before and concurrently a
reaction is caused at 20-120.degree. C. for 1-10 hours.
[0151] The alkali metal hydroxide may be used in liquid state. In
this case, the alkali metal hydroxide solution is continuously
added into the reaction system and concurrently water and
epihalohydrin are continuously removed under low pressure or
atmospheric pressure prior to further separation to remove water
whilst to return epihalohydrin to the reaction system.
[0152] A solution mixture of the phenol condensate and
epihalohydrin may be added with a catalyst of quaternary ammonium
salt such as tetramethylammoniumchloride,
tetramethylammoniumbromide, and trimethylbenzylammoniumchloride for
causing a reaction at 50-150.degree. C. for 1-5 hours to obtain a
halohydrin ether before a solid or a liquid of the alkali metal
hydroxide is then added to cause a further reaction at
20-120.degree. C. for 1-10 hours to form dehydrohalogenation. A
molar ratio in use of the quaternary ammonium salt to hydroxyl
groups of the phenol condensate of the present invention is
normally 1-10 g, preferably 2-8 g.
[0153] Normally, a molar ratio in use of epihalohydrin to the
hydroxyl groups of the phenol condensate of the present invention
is normally 1-20 mol, preferably 2-10 mol. A molar ratio in use of
alkali metal hydroxide to the hydroxyl groups of the phenol
condensate of the present invention is normally 0.8-1.5 mol,
preferably 0.9-1.1 mol. In order to promote the reaction, it is
also possible to add alcohols such as methanol and ethanol, aprotic
polar solvents dimethylsulfone and dimethylsulfoxide. An amount in
use of alcohols to epihalohydrin is normally 2-20% by weight,
preferably 4-15% by weight. An amount in use of aprotic polar
solvents to epihalohydrin is normally 5-100% by weight, preferably
10-90% by weight.
[0154] Either after the reacted product of the
glycidyl-etherification is cleaned with water or without water
cleaning, epihalohydrin and the used solvents are removed at
110-250.degree. C. under pressure of not higher than 10 mmHg. In
order to obtain the epoxy resin with reduced hydrolytic halogen,
the epoxy resin is dissolved into a solvent such as toluene and
methylisobutylketone and then an alkali metal hydroxide such as
sodium hydroxide and potassium hydroxide to cause a ring-closing
reaction. In this case, a molar ratio in use of alkali metal
hydroxide to the hydroxyl groups of the phenol condensate of the
present invention used for the glycidyl-etherification is normally
0.01-0.3 mol, preferably 0.05-0.2 mol. A reaction temperature is
normally 50-120.degree. C., and the reaction time is 0.5-2
hours.
[0155] After the reaction, the salt is removed with filtration or
water cleaning before the solvent such as toluene and
isobutylketone is then removed to obtain the epoxy resin having the
flame retardant epoxy resin material of the present invention.
[0156] Some examples of the above epoxy resins are represented by
the following general formulae (31)-(42). 19
[0157] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 20
[0158] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 21
[0159] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 22
[0160] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 23
[0161] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 24
[0162] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 25
[0163] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 26
[0164] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 27
[0165] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 28
[0166] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0. 29
[0167] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and
"m/i" is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0.
30
[0168] where G is glycidyl group, R8 is any one of phenyl groups,
alkyl groups of 1-12 carbon atoms, amino groups, hydroxyl groups,
hydroxylalkyl groups, ether groups, ester groups, carboxyl groups,
unsaturated hydrocarbon groups, thiol groups, and cyano groups, and
"n" is 0.0-10, preferably 0.0-3.0, more preferably 0.0-1.0, and "m"
is 1.0-10, preferably 1.0-5.0, more preferably 1.0-2.0.
[0169] The flame retardant resin material including the epoxy resin
may be used for the frame retardant to the resin composition or the
base material of the epoxy resin composition in combination with
other phenol resins or amine compounds. The available epoxy resins
in combination are not limited but may, for example, be
phenolbiphenylaralkyl epoxy resins, phenolphenylenearalkyl epoxy
resins, phenoldiphenyletheraralkyl resins, naphthalene-containing
epoxy resins such as naphtholaralkyl epoxy resins, phenoltriazine
resins, phenolanthracenearalkyl epoxy resins, bisphenol fluorene
epoxy resins, phenoltriazine epoxy resins, at least one or
combination of biphenyl-4,4'-diglycidylether, and
3,3',5,5'-tetramethyl biphenyl-4,4'-diglycidylether,
tetraphenyrolethane epoxy resins, trisphenyrolethane epoxy resins,
phenol novolak epoxy resins, cresol novolak epoxy resins,
bis-phenol A epoxy resin, bis-phenol F epoxy resin, bis-phenol S
epoxy resin, polyphenol epoxy resin, aliphatic ester epoxy resin,
cyclic aliphatic ester epoxy resin, and ether ester epoxy resin.
Available amine compounds in combination are not limited but may,
for example, be glycidyl amine compounds such as diamino
diphenylmethane, diethylene triamine, and diaminodiphenylsulfone.
Those epoxy resins may be used alone or in combination.
Phenolbiphenylaralkyl epoxy resins, phenolphenylenearalkyl epoxy
resins, phenoldiphenyletheraralkyl epoxy resins, and
naphtholaralkyl epoxy resins are particularly preferable.
[0170] A weight-average molecular weight of the phenol condensate
included in the flame retardant phenol resin material of the
present invention is not limited but may, for example, be
300-10000. A weight-average molecular weight of the epoxy resin
included in the flame retardant epoxy resin material of the present
invention is not limited but may, for example, be 300-10000.
[0171] It is preferable that the flame retardant resin material of
the present invention is substantially free of unreacted
formaldehydes and methylol groups to improve mixing stability with
the epoxy resin or thermosetting agent in use as the base material
or thermosetting agent.
[0172] An unreacted unifunctional phenol monomer included in the
flame retardant resin material of the present invention is
preferably not more than 3% by weight in order to improve the
mixing stability and particularly improve thermal stability and
moisture resistance of the epoxy resin composition.
[0173] The unreacted unifunctional phenol monomer means a phenol
monomer including only one phenolic hydroxyl group which may be
reacted with epoxy groups.
[0174] The flame retardant resin composition of the present
invention includes the flame retardant phenol resin material and/or
the flame retardant epoxy resin material. It is possible to add
those resin materials alone or in combination. It is also possible
to prepare a mixture of flame retardant phenol resin material and
the flame retardant epoxy resin material to add the mixture. It is
also possible to prepare a mixture of flame retardant phenol resin
material and the flame retardant epoxy resin material for
subsequent semi-thermosetting and thermosetting the mixture and
then grinding the same for adding the powders.
[0175] In accordance with the present invention, a total content
(X) of the phenol condensate and the epoxy resin obtained by the
glycidyl-etherification of the phenol condensate is preferably in
the range of 0.1% by weight to 45% by weight, particularly
preferable 0.3% by weight to 30% by weight, where X=(b/a)100, "a"
is a total weight of the resin component of the resin composition,
"b" is a total weight of the phenol condensate and the epoxy resin
obtained by the glycidyl-etherification of the phenol
condensate.
[0176] If the total weight is less than 0.1% by weight, then an
amount of flame reducing gas of nitrogen based gas is insufficient
for reducing the fire or flame. If the total weight is less than
45% by weight, it is possible that the obtained flame retardancy is
insufficient, and also possible that a concentration of the
heterocyclic compound having nitrogen as heteroatom in the resin
composition is so high as reducing the moisture resistance.
[0177] The epoxy resin and the thermosetting agent for the epoxy
resin may be contained in the flame retardant resin composition of
the present invention. A ratio (OH/Ep) of a total number (Ep) of
epoxy groups in the epoxy resin to a total number (OH) of hydroxyl
groups in the thermosetting agent is preferably in the range of 0.7
to 2.5 in order to improve the flame retardancy of the resin. If
the ratio (OH/Ep) is less than 0.7, then a generated amount of a
flammable component such as allylalcohol is increased due to
residual epoxy resin residing on a bridge structure which has been
formed by the thermosetting agent and the epoxy resin, thereby
preventing improvement in the flame retardancy. If the ratio
(OH/Ep) is more than 2.5, then the bridge density is too low to
harden the epoxy resin composition, whereby the thermal stability
and the solidity are insufficient.
[0178] The flame retardant resin composition of the present
invention may optionally include various additives such as filler
and hardening promoter.
[0179] Available fillers are not limited but may, for example, be
fused silica powders, crystal silica powders, alumina powders,
silicon nitride, glass fibers, carbon fibers, and aramid fibers or
aromatic polyamide fibers. Those fillers may be used alone or in
mixture.
[0180] Available hardening promoters may be promoters for hardening
the epoxy resin and the hardening agent, for example, triphenyl
phosphine, 2-methylimidazol, and 1,8-diazabicyclo(5,4,0)undecyne-7.
Those hardening promoters may be used alone or in mixture.
[0181] Other available additives may, for example, be coloring
materials such as carbon black, silane coupling agents such as
.gamma.-glycidexypropyl trimethoxysilane, low stress components
such as silicone oils and silicone rubbers, natural waxes,
synthetic waxes, higher fatty acids, and metal salts thereof, mold
release agents such as paraffin. Further, if any, other flame
retardants may be co-used which comprises at least one selected
from the groups of phosphorus compounds such as red phosphorus and
ester phosphate, metal hydroxide such as magnesium, aluminum, zinc,
boron, calcium, nickel, cobalt, tin, copper, iron, and
titanium.
[0182] The metal oxides may be co-used provided that the flame
retardancy is improved by co-use of the metal oxide and the resin
material. A composite metal hydroxide of the metal hydroxide and
the metal oxide may be used to improve the flame retardancy. The
necessary amount in addition of the above flame retardant is small
because the flame retardant includes the flame retardant phenol
resin martial and/or the flame retardant epoxy resin martial,
whereby any deterioration in moisture resistance and other
properties are suppressed.
[0183] The thermosetting resin composition including the flame
retardant resin material of the present invention may be produced
by previously admixing by ribbon blender or Henschel mixer and
subsequent mixing with use of heating roller or kneader or
subsequent dissolving the same into an organic solvent. After the
organic solvent and moisture are if any removed before a transfer
molding press or a heating press is used under predetermined
conditions to heat the resin composition so as to cause a bridge
reaction for hardening the resin composition, whereby the hard
resin composition having a high flame retardancy can be
obtained.
[0184] Semiconductor devices using the sealing material of the
epoxy resin composition including the flame retardant resin
material of the present invention are also superior in high flame
retardancy, thermal stability or thermal decomposition resistance
and moisture resistance. For example, a semiconductor device is
mounted on a die pad of a lead frame for wire-bonding before
sealing the semiconductor device with a resin composition including
the flame retardant resin material of the present invention. The
above epoxy resin composition may be applied to a lead on chip
resin-sealed semiconductor device, and a ball grid array
resin-sealed semiconductor device. The above epoxy resin
composition may also be applied to the sealing resin for various
types of electric and electronic devices including semiconductor
devices.
[0185] The above epoxy resin composition including the flame
retardant resin material of the present invention may be used as an
insulator for a printed wiring board including glass fibers for
improvements in flame retardancy, thermal stability or thermal
decomposition resistance and moisture resistance. The above epoxy
resin composition including the flame retardant resin material of
the present invention may further be used as molding materials,
cast materials, adhesives, coloring materials for improvements in
flame retardancy, thermal stability or thermal decomposition
resistance and moisture resistance.
[0186] The above thermoplastic resin composition including the
flame retardant resin material of the present invention may be
produced by extruders such as a uniaxial extruder, a biaxial
extruder, a stone grinder type extruder. After the moisture is if
any removed before an injection molding machine or a heating press
is used under predetermined conditions to form the thermoplastic
resin composition having a high flame retardancy.
[0187] Examples of the present invention and comparative examples
will hereinafter be described, wherein a filler is used which
comprises a molten spherical silica particles which has an average
particle diameter of 16 micrometers and a specific surface area of
1.9 m.sup.2/g measured by BET method, wherein particles having
diameters of not less than 75 micrometers are 0.5% by weight.
[0188] Silane coupling agent is used which comprises
N-phenyl-.gamma.-aminopropyltrimethoxysilane (KBM573) which is
commercially available from Shin-Etsu Chemical Industries Co.
EXAMPLE 1
[0189] A flask was attached with a temperature gage, a dripping
funnel, a cooling tube, a fractionating column and a stirrer. 99
parts by weight (1.05 mol) of phenol and 121 parts by weight (0.5
mol) of a compound represented by the following general formula
(43) were entered into the flask. At room temperature, a stirring
is made with nitrogen blowing. 0.5 parts by weight (0.0026 mol) of
p-toluene sulfonic acid (1-hydrate) was gradually added into the
flask with attention to heat generation and without rising
temperature of the solution to over 50.degree. C. In oil bath, a
heating was made to rise the temperature up to 120.degree. C. so
that, by use of the fractionating column, methanol was extracted
before a reaction is allowed for 5 hours. After the reaction, 500
ml of methylisobutylketone was added and then an organic layer was
transferred into a separating funnel for subsequent water cleaning
which is continued until the cleaning solution becomes neutral. The
used solvent and unreacted unifunctional phenol were removed from
the organic layer with heating and under a low pressure, thereby
obtaining a condensate (E) represented by the following formula
(44). 31
[0190] where "n" is 0.0 to 1.0.
EXAMPLE 2
[0191] 81.3 parts by weight (0.22 mol) of the condensate (E)
obtained in Example 1 was added with 26.4 parts by weight (0.22
mol) of melamine, 8.1 parts by weight (0.11 mol) of 41.5 wt.
%-formaldehyde solution and 0.2 parts by weight (0.01 mol) of 25
wt. %-ammonium solution for gradually rising the temperature up to
100.degree. C. with attention to heat generation. A reaction was
made at 100.degree. C. for 5 hours before further rising the
temperature up to 180.degree. C. for 2 hours under an atmospheric
pressure with water removal. Subsequently, unreacted substances
were then removed under a low pressure to obtain a phenol
condensate (P1) having a nitrogen content of 8% by weight and a
hydroxyl groups equivalent of 252 as well as having a softening
point of 95.degree. C. The obtained phenol condensate (P1) is
represented in the following general formula (45). 32
[0192] where "n" is 0.0 to 1.0, and "m" is 1.0 to 2.0.
EXAMPLE 3
[0193] 25 parts by weight (0.05 mol) of the phenol condensate (P1)
obtained in Example 2 was added with 50 parts by weight (0.54 mol)
of epichlorohydrin to rise the temperature up to 105.degree. C. for
dissolution thereof. Further, 20 parts by weight (0.1 mol) of 20
wt. %-sodium hydroxide solution was dropped for 3 hours for placing
the solution statically for 30 minutes to cause a static separation
before a lower layer or a water layer was removed.
[0194] Subsequently, the excess epichlorohydrin was distillated and
recycled. 20 parts by weight (2 mol) of methylisobutylketone was
added and dissolved. 0.5 parts by weight (0.0025 mol) of 20 wt.
%-sodium hydroxide solution was added for placing the solution at
70.degree. C. for 3 hours to cause a static separation before a
lower layer or a water layer was removed. The reminder was then
cleaned with 200 parts by weight of a distilled water. A volatile
component was removed by distillation to obtain an epoxy resin
(EP1) having a nitrogen content of 6% by weight and an epoxy
equivalent of 308 as well as having a softening point of 75.degree.
C. and including hydrolytic chlorine of not more than 400 ppm. The
obtained epoxy resin (EP1) is represented in the following general
formula (46). 33
[0195] where "n" is 0.0 to 1.0, and "m" is 1.0 to 2.0.
EXAMPLE 4
[0196] A flask was attached with a temperature gage, a dripping
funnel, a cooling tube, a fractionating column and a stirrer. 99
parts by weight (1.05 mol) of phenol and 83 parts by weight (0.5
mol) of a compound represented by the following general formula
(47) were entered into the flask. At room temperature, a stirring
is made with nitrogen blowing. 0.5 parts by weight (0.0026 mol) of
p-toluene sulfonic acid (1-hydrate) was gradually added into the
flask with attention to heat generation and without rising
temperature of the solution to over 50.degree. C. In oil bath, a
heating was made to rise the temperature up to 120.degree. C. so
that, by use of the fractionating column, methanol was extracted
before a reaction is allowed for 5 hours. After the reaction, 500
ml of methylisobutylketone was added and then an organic layer was
transferred into a separating funnel for subsequent water cleaning
which is continued until the cleaning solution becomes neutral. The
used solvent and unreacted unifunctional phenol were removed from
the organic layer with heating and under a low pressure, thereby
obtaining a condensate (F) represented by the following formula
(48). 34
[0197] where "n" is 0.0 to 1.0.
EXAMPLE 5
[0198] 63.8 parts by weight (0.22 mol) of the condensate (F)
obtained in Example 4 was added with 26.4 parts by weight (0.22
mol) of melamine, 8.1 parts by weight (0.11 mol) of 41.5 wt.
%-formaldehyde solution and 0.2 parts by weight (0.01 mol) of 25
wt. %-ammonium solution for gradually rising the temperature up to
100.degree. C. with attention to heat generation. A reaction was
made at 100.degree. C. for 5 hours before further rising the
temperature up to 180.degree. C. for 2 hours under an atmospheric
pressure with water removal. Subsequently, unreacted substances
were then removed under a low pressure to obtain a phenol
condensate (P2) having a nitrogen content of 8% by weight and a
hydroxyl group equivalent of 245 as well as having a softening
point of 92.degree. C. The obtained phenol condensate (P2) is
represented in the following general formula (49). 35
[0199] where "n" is 0.0 to 1.0, and "m" is 1.0 to 2.0.
EXAMPLE 6
[0200] 25 parts by weight (0.05 mol) of the phenol condensate (P2)
obtained in Example 5 was added with 50 parts by weight (0.54 mol)
of epichlorohydrin to rise the temperature up to 105.degree. C. for
dissolution thereof. Further, 20 parts by weight (0.1 mol) of 20
wt. %-sodium hydroxide solution was dropped for 3 hours for placing
the solution statically for 30 minutes to cause a static separation
before a lower layer or a water layer was removed.
[0201] Subsequently, the excess epichlorohydrin was distillated and
recycled. 20 parts by weight (1.2 mol) of methylisobutylketone was
added and dissolved. 0.5 parts by weight (0.0025 mol) of 20 wt.
%-sodium hydroxide solution was added for placing the solution at
70.degree. C. for 3 hours to cause a static separation before a
lower layer or a water layer was removed. The reminder was then
cleaned with 200 parts by weight of a distilled water. A volatile
component was removed by distillation to obtain an epoxy resin
(EP2) having a nitrogen content of 6% by weight and an epoxy
equivalent of 270 as well as having a softening point of 69.degree.
C. and including hydrolytic chlorine of not more than 400 ppm. The
obtained epoxy resin (EP2) is represented in the following general
formula (50). 36
[0202] where G is glycidyl group, "n" is 0.0 to 1.0, and "m" is 1.0
to 2.0.
[0203] Epoxy resins and thermosetting agents used in the following
examples and comparative examples are represented in the following
general formulae (51) through (60) and thermoplastic resins used in
the following examples and comparative examples are shown.
[0204] (Phenolbiphenylaralkyl Epoxy Resin (Epoxy Resin 1)) 37
[0205] where "G" is glycidyl groups, "n"=0.0 to 10, softening point
is 57.degree. C., epoxy equivalent is 270.
[0206] (Phenolbiphenylaralkyl Resin (Phenol Resin 1)) 38
[0207] where "n"=0.0 to 10, softening point is 120.degree. C.,
hydroxyl group equivalent is 208.
[0208] (Phenolphenylenearalkyl Epoxy Resin (Epoxy Resin 2)) 39
[0209] where "G" is glycidyl groups, "n"=0.0 to 10, softening point
is 55.degree. C., epoxy equivalent is 238.
[0210] (Phenolphenylenearalkyl Resin (Phenol Resin 2)) 40
[0211] where "n"=0.0 to 10, softening point is 83.degree. C.,
hydroxyl group equivalent is 175.
[0212] (2-Functional Biphenyl Epoxy Resin (Epoxy Resin 3)) 41
[0213] where melting point is 111.degree. C., epoxy equivalent is
170.
[0214] (Cresol Novolak Epoxy Resin (Epoxy Resin 4)) 42
[0215] where "n"=0.0 to 10, softening point is 68.degree. C., epoxy
equivalent is 194.
[0216] (Phenoltriazine Epoxy Resin) 43
[0217] where "G" is glycidyl groups, "n"=0.0 to 10, "m"=1.0 to 10,
softening point is 65.degree. C., epoxy equivalent is 220, nitrogen
content is 6% by weight.
[0218] (Phenoltriazine Resin) 44
[0219] where "n"=0.0 to 10, "m"=1.0 to 10, softening point is
90.degree. C., hydroxyl group equivalent is 124, nitrogen content
is 8% by weight.
[0220] (Phenol Benzoguanamine Resin) 45
[0221] where "n"=0.0 to 10, "m"=1.0 to 10, softening point is
105.degree. C., hydroxyl group equivalent is 220, nitrogen content
is 19% by weight.
[0222] (Phenol Benzoguanamine Epoxy Resin) 46
[0223] where "G" is glycidyl groups, "n"=0.0 to 10, "m"=1.0 to 10,
softening point is 80.degree. C., epoxy equivalent is 276, nitrogen
content is 15% by weight.
[0224] (Thermoplastic Resin Composition 1)
[0225] acrylonitrile butadiene styrene copolymer: Sumitomo Chemical
A & L GA-704, hereinafter referred to as "ABS".
[0226] (Thermoplastic Resin Composition 2)
[0227] polystyrene resin: Shin-Nitetsu Sumitomo Chemical H-65,
hereinafter referred to as "PS".
EXAMPLE 7
[0228] At ordinary temperature, there were previously admixed 11.2
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 7.5 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of the above phenol condensate (P1)
obtained in Example 2, 79.0% by weight of fused spherical silica
powders, 0.4% by weight of carbon black, 0.1% by weight of silane
coupling agent, 0.2% by weight of carnauba wax, 0.2% by weight of
triphenyl phosphine (T.T.P). Thereafter, the admixture was made on
a roll of 100.degree. C. for about 5 minutes and then the mixture
was cooled and crushed to form the resin composition.
[0229] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 8
[0230] At ordinary temperature, there were previously admixed 10.0
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.7 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of the above epoxy resin (EP1) obtained in
Example 3, 79.0% by weight of fused spherical silica powders, 0.4%
by weight of carbon black, 0.1% by weight of silane coupling agent,
0.2% by weight of carnauba wax, 0.2% by weight of triphenyl
phosphine (T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0231] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 9
[0232] At ordinary temperature, there were previously admixed 5.99
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 4.94 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.17% by weight of the above phenol resin (P1) obtained
in Example 2, 88.4% by weight of fused spherical silica powders,
0.2% by weight of carbon black, 0.1% by weight of silane coupling
agent, 0.1% by weight of carnauba wax, 0.1% by weight of triphenyl
phosphine (T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0233] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 10
[0234] At ordinary temperature, there were previously admixed 11.2
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 7.5 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of the above phenol condensate (P2), 79.0%
by weight of fused spherical silica powders, 0.4% by weight of
carbon black, 0.1% by weight of silane coupling agent, 0.2% by
weight of carnauba wax, 0.2% by weight of triphenyl phosphine
(T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0235] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 11
[0236] At ordinary temperature, there were previously admixed 10.0
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.7 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of the above epoxy resin (EP2), 79.0% by
weight of fused spherical silica powders, 0.4% by weight of carbon
black, 0.1% by weight of silane coupling agent, 0.2% by weight of
carnauba wax, 0.2% by weight of triphenyl phosphine (T.T.P).
Thereafter, the admixture was made on a roll of 100.degree. C. for
about 5 minutes and then the mixture was cooled and crushed to form
the resin composition.
[0237] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 12
[0238] At ordinary temperature, there were previously admixed 11.4
parts by weight of phenolphenylenearalkyl epoxy resin (epoxy resin
2), 7.3 parts by weight of phenolphenylenearalkyl resin (phenol
resin 2), 1.4% by weight of the above phenol condensate (P2), 79.0%
by weight of fused spherical silica powders, 0.4% by weight of
carbon black, 0.1% by weight of silane coupling agent, 0.2% by
weight of carnauba wax, 0.2% by weight of triphenyl phosphine
(T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0239] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
EXAMPLE 13
[0240] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 10.0% by weight of the above
phenol condensate (P1), 89.5% by weight of the above ABS
(thermoplastic resin 1), 0.5% by weight of polytetrafluoroethylene
(PTFE) to form a resin composition. This resin composition was
dried at 120.degree. C. for 3 hours before press-molding is carried
out at 200.degree. C. for 1 minute to form a flat plate having a
thickness of 3.2 millimeters.
EXAMPLE 14
[0241] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 10.0% by weight of the above
phenol condensate (P1), 89.5% by weight of the above PS
(thermoplastic resin 2), 0.5% by weight of polytetrafluoroethylene
(PTFE) to form a resin composition. This resin composition was
dried at 120.degree. C. for 3 hours before press-molding is carried
out at 200.degree. C. for 1 minute to form a flat plate having a
thickness of 3.2 millimeters.
[0242] The molded test plates obtained in Examples 7-14 were
evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance.
[0243] Flame Retardancy Examination:
[0244] The sample plate has a size of 127 mm in length, 12.7 in
width and 1.6 or 3.2 mm in thickness. The plate was held by a
sample holder (clamp) so that a longitudinal direction of the plate
is vertical to the ground. An opposite edge of the plate to the
clamp was exposed to a flame by a burner for 10 seconds before the
burner was made far from the plate so as to measure a after-flame
time during which the flame resides on the plate after the burner
had been made far from the plate (first after-flame time=F1). After
the flame had disappeared, then the plate was again exposed to a
flame by the burner for 10 seconds before the burner was made far
from the plate so as to measure a after-flame time (second
after-flame time=F2). This examination was made to five samples of
each type of the plates for evaluation on the flame retardancy.
There are four flame retardancy criterions.
[0245] Highest Criterion (UL94 V-0)
[0246] .SIGMA.F.ltoreq.50 seconds (.SIGMA.F=total time of
individual after-flame times of five plates)/Fmax.ltoreq.10 seconds
(Fmax=longest one of two after-flame times F1 and F2./No drip
(drip=drip of a melt part of the plate due to flame)/Flame does not
reach the clamp.
[0247] High Criterion (UL94 V-1)
[0248] .SIGMA.F.ltoreq.250 seconds (.SIGMA.F=total time of
individual after-flame times of five plates)/Fmax.ltoreq.30 seconds
(Fmax=longest one of two after-flame times F1 and F2./No drip
(drip=drip of a melt part of the plate due to flame)/Flame does not
reach the clamp.
[0249] Low Criterion (UL94 V-2)
[0250] .SIGMA.F.ltoreq.250 seconds (.SIGMA.F=total time of
individual after-flame times of five plates)/Fmax.ltoreq.30 seconds
(Fmax=longest one of two after-flame times F1 and F2./drip
(drip=drip of a melt part of the plate due to flame)/Flame does not
reach the clamp.
[0251] Lowest Criterion (UL94 V-2)
[0252] .SIGMA.F>250 seconds (.SIGMA.F=total time of individual
after-flame times of five plates)/Fmax>30 seconds (Fmax=longest
one of two after-flame times F1 and F2./Drip (drip =drip of a melt
part of the plate due to flame)/Flame does reach the clamp.
[0253] Boiled Water Absorption Coefficient Examination:
[0254] The resin composition in Example 7 were formed in a
disk-shape of 50 millimeters in diameter and 3 millimeters in
thickness. The disk-shaped resin composition was dipped into a
boiled water at 100.degree. C. for 24 hours. The boiled water
absorption coefficient (% by weight) was found on the basis of
variation in weight of the disk-shaped resin composition between
after and before the disk-shaped resin composition was dipped into
the boiled water. Results of evaluations on the boiled water
absorption coefficient are shown on below Table 1.
[0255] Thermal Stability (Thermal Decomposition Resistance)
Examination:
[0256] The plate of the flame retardation test of Example 7 was
crushed to form 10 g of powders of 80 micrometers in powder size.
The powder was heated at a temperature rising rate of 200.degree.
C./min in an air with a flow rate of 200 ml/min. When 5 wt. %
reduction was confirmed, the temperature was measured. Results of
evaluations on the thermal stability are shown on below Table
1.
[0257] Moisture Resistance Examination:
[0258] A silicon chip of 3.0 millimeters in longitudinal length,
3.5 millimeters in horizontal length and 3.5 millimeters in
thickness was prepared, wherein aluminum wirings with a width of 10
micrometers are provided at a pitch of 10 micrometers, and the
aluminum wirings have expanding square parts of 70 micrometers
squares on pads. The chip was mounted on a 16 pins DIP 42-aloy
frame so that gold wirings of 20 micrometers were wire-bonded
directly on the pads of the chip. Thereafter, the single plunger
type transfer molding machine was used to seal the chip with the
above tablet of Example 7 under conditions of previous heat
temperature of 85.degree. C., injection time of 15 seconds,
injection pressure (effective pressure) of 100 kg/cm.sup.2, molding
temperature of 175.degree. C., molding time of 120 seconds, thereby
forming a 16 pins DIP type semiconductor device of 18 millimeters
in longitudinal length, 5 millimeters in horizontal length and 3
millimeters in thickness. The semiconductor device was then
subjected to the thermosetting process at 175.degree. C. for 4
hours to form the moisture resistance test sample.
[0259] Tens of the above semiconductor device were subjected to a
pressure cooker bias test (PCBT) under condition of 20V voltage
application. When open defective rate becomes 20% or two
semiconductor devices become defective, the time was measured as
index of the moisture resistance. Long defective generation time
means high moisture resistance. Results of evaluations on the
moisture resistance are shown on below Table 1.
1 TABLE 1 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 Ex.12 Ex.13 Ex.14
phenolbiphenylaralkyl epoxy resin (epoxy resin 1) 11.2 10.0 5.99
11.2 10 -- -- -- phenolbiphenylaralkyl resin (phenol resin 1) 7.5
8.7 4.94 7.5 8.7 -- -- -- phenolphenylenearalkyl epoxy resin (epoxy
resin 2) -- -- -- -- -- 11.4 -- -- phenolphenylenearalkyl resin
(phenol resin 2) -- -- -- -- -- 7.3 -- -- 2-functional biphenyl
epoxy resin (epoxy resin 3) -- -- -- -- -- -- -- -- cresol novolak
epoxy resin (epoxy resin 4) -- -- -- -- -- -- -- --
phenolbiphenyltriazine epoxy resin -- 1.4 -- -- -- -- -- -- (epoxy
resin (PE1).N6wt. %) (7.0/0.56) phenolbiphenyltriazine resin 1.4 --
1.7 -- -- -- 10.0 10.0 (phenol condensate (P1),N8wt. %) (7.0/0.56)
(1.5/0.12) (10/0.8) (10/0.8) phenolphenylenetriazine epoxy resin --
-- -- -- 1.4 -- -- -- (epoxy resin (PE2).N6wt. %) (7.0/0.42)
phenolphenylenetriazine resin -- -- -- 1.4 -- 1.4 -- -- (phenol
condensate (P2).N8wt. %) (7.0/0.56) (7.0/0.56)
phenolbiphenylbenzoguanamine epoxy resin -- -- -- -- -- -- -- --
(epoxy resin (PE3),N9wt. %) phenolbiphenylbenzoguanamine resin --
-- -- -- -- -- -- -- (phenol condensate (P3).N10wt. %)
phenolphenylenebenzoguanamine epoxy resin -- -- -- -- -- -- -- --
(epoxy resin (PE4).N8wt, %) phenolphenylenebenzoguanamine resin --
-- -- -- -- -- -- -- (phenol condensate (P4).N10wt. %)
phenoltriazine epoxy resin (N6wt. %) -- -- -- -- -- -- -- --
phenoltriazine resin (N8wt. %) -- -- -- -- -- -- -- --
phenolbenzoguanamine epoxy resin (N15wt. %) -- -- -- -- -- -- -- --
phenolbenzoguanamine resin (N19wt. %) -- -- -- -- -- -- -- -- ABS
(thermoplastic resin 1) -- -- -- -- -- -- 89.5 -- PS (thermoplastic
resin 2) -- -- -- -- -- -- -- 89.5 fused spherical silica 79.0 79.0
88.4 79.0 79.0 79.0 -- -- carbon black 0.4 0.4 0.2 0.4 0.4 0.4 --
-- silane coupling agent 0.1 0.1 0.1 0.1 0.1 0.1 -- -- carnauba wax
0.2 0.2 0.1 0.2 0.2 0.2 -- -- triphenylphosphine (T.P.P.) 0.2 0.2
0.1 0.2 0.2 0.2 -- -- polytetorafluoroethylene (PTFE) -- -- -- --
-- -- 0.5 0.5 UL94 criterion V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-1 (total
time of after-flame times) 7 9 20 15 16 19 105 130 boiled water
absorption coefficient par 24 hours 0.19 0.19 0.13 0.20 0.21 0.22
un- un- % by weight examined examined thermal decomposition
resistance 610 604 725 600 595 580 un- un- (temperature at 5wt. %
reduction) .degree. C. examined examined moisture-resistance (time
period for 450 450 470 440 440 430 un- un- 20% defects) Time
examined examined (A/B): A = percent by weight of the present resin
to the total amount of resins. B = percent by weight of nitrogen
atoms to the total amount of resins. Epoxy resin and phenol resin
of the present invention
COMPARATIVE EXAMPLE 1
[0260] At ordinary temperature, there were previously admixed 11.9
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 6.8 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of phenoltriazine resin having nitrogen
content of 8% by weight, 79.0% by weight of fused spherical silica
powders, 0.4% by weight of carbon black, 0.1% by weight of silane
coupling agent, 0.2% by weight of carnauba wax, 0.2% by weight of
triphenyl phosphine (T.T.P). Thereafter, the admixture was made on
a roll of 100.degree. C. for about 5 minutes and then the mixture
was cooled and crushed to form the resin composition.
[0261] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0262] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 2
[0263] At ordinary temperature, there were previously admixed 9.8
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.9 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.4% by weight of phenoltriazine epoxy resin having
nitrogen content of 6% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of carnauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0264] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0265] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 3
[0266] At ordinary temperature, there were previously admixed 6.07
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 4.86 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 0.17% by weight of phenoltriazine resin having nitrogen
content of 8% by weight, 88.4% by weight of fused spherical silica
powders, 0.2% by weight of carbon black, 0.1% by weight of silane
coupling agent, 0.1% by weight of carnauba wax, 0.1% by weight of
triphenyl phosphine (T.T.P). Thereafter, the admixture was made on
a roll of 100.degree. C. for about 5 minutes and then the mixture
was cooled and crushed to form the resin composition.
[0267] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0268] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 4
[0269] At ordinary temperature, there were previously admixed 6.0
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 5.1 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 88.4% by weight of fused spherical silica powders, 0.2%
by weight of carbon black, 0.1% by weight of silane coupling agent,
0.1% by weight of carnauba wax, 0.1% by weight of triphenyl
phosphine (T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0270] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0271] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 5
[0272] At ordinary temperature, there were previously admixed 11.9
parts by weight of phenolphenylenearalkyl epoxy resin (epoxy resin
2), 6.8 parts by weight of phenolphenylenearalkyl resin (phenol
resin 2), 1.4% by weight of phenoltriazine resin having nitrogen
content of 8% by weight, 79.0% by weight of fused spherical silica
powders, 0.4% by weight of carbon black, 0.1% by weight of silane
coupling agent, 0.1% by weight of carnauba wax, 0.1% by weight of
triphenyl phosphine (T.T.P). Thereafter, the admixture was made on
a roll of 100.degree. C. for about 5 minutes and then the mixture
was cooled and crushed to form the resin composition.
[0273] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm2, a molding temperature
of 175.degree. C., a molding time of 120 seconds in accordance with
the UL94 flame retardation regulation. Subsequently, thermosetting
process was carried out at 175.degree. C. for 6 hours to form a
flame retardant test sample plate.
[0274] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 6
[0275] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 99.5% by weight of the above
ABS (thermoplastic resin 1), 0.5% by weight of
polytetrafluoroethylene (PTFE) to form a resin composition. This
resin composition was dried at 120.degree. C. for 3 hours before
press-molding is carried out at 200.degree. C. for 1 minute to form
a flat plate having a thickness of 3.2 millimeters.
[0276] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 7
[0277] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 10.0% by weight of
phenoltriazine resin having nitrogen content of 8% by weight, 89.5%
by weight of the above ABS (thermoplastic resin 1), 0.5% by weight
of polytetrafluoroethylene (PTFE) to form a resin composition. This
resin composition was dried at 120.degree. C. for 3 hours before
press-molding is carried out at 200.degree. C. for 1 minute to form
a flat plate having a thickness of 3.2 millimeters.
[0278] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
COMPARATIVE EXAMPLE 8
[0279] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 99.5% by weight of the above
PS (thermoplastic resin 2), 0.5% by weight of
polytetrafluoroethylene (PTFE) to form a resin composition. This
resin composition was dried at 120.degree. C. for 3 hours before
press-molding is carried out at 200.degree. C. for 1 minute to form
a flat plate having a thickness of 3.2 millimeters.
[0280] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
2.
2 TABLE 2 Com.Ex.1 Com.Ex.2 Com.Ex.3 Com.Ex.4 Com.Ex.5 Com.Ex.6
Com.Ex.7 Com.Ex.8 phenolbiphenylaralkyl epoxy resin (epoxy resin 1)
11.9 9.8 6.07 6.0 -- -- -- -- phenolbiphenylaralkyl resin (phenol
resin 1) 6.8 8.9 4.86 5.1 -- -- -- -- phenolphenylenearalkyl epoxy
resin (epoxy resin 2) -- -- -- -- 11.9 -- -- --
phenolphenylenearalkyl resin (phenol resin 2) -- -- -- -- 6.8 -- --
-- 2-functional biphenyl epoxy resin (epoxy resin 3) -- -- -- -- --
-- -- -- cresol novolak epoxy resin (epoxy resin 4) -- -- -- -- --
-- -- -- phenolbiphenyltriazine epoxy resin -- -- -- -- -- --
(epoxy resin (PE1).N6wt. %) phenolbiphenyltriazine resin - -- -- --
-- -- -- -- (phenol condensate (P1),N8wt. %)
phenolphenylenetriazine epoxy resin -- -- -- -- -- -- -- -- (epoxy
resin (PE2).N6wt. %) phenolphenylenetriazine resin -- -- -- -- --
-- -- -- (phenol condensate (P2).N8wt. %)
phenolbiphenylbenzoguanamine epoxy resin -- -- -- -- -- -- -- --
(epoxy resin (PE3),N9wt. %) phenolbiphenylbenzoguanamine resin --
-- -- -- -- -- -- -- (phenol condensate (P3).N10wt. %)
phenolphenylenebenzoguanamine epoxy resin -- -- -- -- -- -- -- --
(epoxy resin (PE4).N8wt, %) phenolphenylenebenzoguanamine resin --
-- -- -- -- -- -- -- (phenol condensate (P4).N10wt. %)
phenoltriazine epoxy resin (N6wt. %) -- 1.4 -- -- -- -- -- --
(7.0/0.42) phenoltriazine resin (N8wt. %) 1.4 -- 0.17 -- 1.4 --
10.0 -- (7.0/0.56) (1.5/0.12) (7.0/0.56) (10.0/0.8)
phenolbenzoguanamine epoxy resin (N15wt. %) -- -- -- -- -- -- -- --
phenolbenzoguanamine resin (N19wt. %) -- -- -- -- -- -- -- -- ABS
(thermoplastic resin 1) -- -- -- -- -- 99.5 89.5 -- PS
(thermoplastic resin 2) -- -- -- -- -- -- -- 99.5 fused spherical
silica 79.0 79.0 88.4 88.4 79.0 -- -- -- carbon black 0.4 0.4 0.2
0.4 0.4 -- -- -- silane coupling agent 0.1 0.1 0.1 0.1 0.1 -- -- --
carnauba wax 0.2 0.2 0.1 0.1 0.1 -- -- -- triphenylphosphine
(T.P.P.) 0.2 0.2 0.1 0.1 0.1 -- -- -- polytetorafluoroethylene
(PTFE) -- -- -- -- -- 0.5 0.5 0.5 UL94 criterion V-0 V-0 V-0 V-0
V-0 NOT V-2 V-1 NOT V-2 (total time of after-flame times) 29 31 37
43 34 >250 150 >250 boiled water absorption coefficient par
24 hours 0.25 0.26 0.18 0.12 0.29 un- un- un- % by weight examined
examined examined thermal decomposition resistance 563 550 670 660
545 un- un- un- (temperature at 5wt. % reduction) .degree. C.
examined examined examined moisture-resistance (time period for 400
400 410 460 385 un- un- un- 20% defects) Time examined examined
examined (A/B): A = percent by weight of the present resin to the
total amount of resins. B = percent by weight of nitrogen atoms to
the total amount of resins. Epoxy resin and phenol resin of the
present invention
EXAMPLE 15
[0281] 274.7 parts by weight (0.5 mol) of the condensate (E)
obtained in Example 1 was added with 93.85 parts by weight (0.5
mol) of benzoguanamine, 52.7 parts by weight (0.65 mol) of 37 wt.
%-formaldehyde solution and 0.879 parts by weight (0.015 mol) of 29
wt. %-ammonium solution for gradually rising the temperature up to
100.degree. C. with attention to heat generation. A reaction was
made at 100.degree. C. for 5 hours before further rising the
temperature up to 180.degree. C. for 2 hours under an atmospheric
pressure with water removal. Subsequently, unreacted substances
were then removed under a low pressure to obtain a phenol
condensate (P3) having a nitrogen content of 10% by weight and a
hydroxyl groups equivalent of 260 as well as having a softening
point of 120.degree. C. The obtained phenol condensate (P3) is
represented in the following general formula (61). 47
[0282] where "n" is 0.0 to 1.0, and "m" is 1.0 to 2.0.
EXAMPLE 16
[0283] 25 parts by weight (0.05 mol) of the phenol condensate (P3)
obtained in Example 15 was added with 50 parts by weight (0.54 mol)
of epichlorohydrin to rise the temperature up to 115.degree. C. for
dissolution thereof. Further, 20 parts by weight (0.1 mol) of 20
wt. %-sodium hydroxide solution was dropped for 3 hours for placing
the solution statically for 30 minutes to cause a static separation
before a lower layer or a water layer was removed.
[0284] Subsequently, the excess epichlorohydrin was distillated and
recycled. 20 parts by weight (2 mol) of methylisobutylketone was
added and dissolved. 0.5 parts by weight (0.0025 mol) of 20 wt.
%-sodium hydroxide solution was added for placing the solution at
70.degree. C. for 3 hours to cause a static separation before a
lower layer or a water layer was removed. The reminder was then
cleaned with 200 parts by weight of a distilled water. A volatile
component was removed by distillation to obtain an epoxy resin
(EP3) having a nitrogen content of 9% by weight and an epoxy
equivalent of 316 as well as having a softening point of 80.degree.
C. and including hydrolytic chlorine of not more than 400 ppm. The
obtained epoxy resin (EP3) is represented in the following general
formula (62). 48
[0285] where G is glycidyl group, "n" is 0.0 to 1.0, and "m" is 1.0
to 2.0.
EXAMPLE 17
[0286] 403.4 parts by weight (0.5 mol) of the condensate (F)
obtained in Example 4 was added with 93.85 parts by weight (0.5
mol) of benzoguanamine, 52.7 parts by weight (0.65 mol) of 37 wt.
%-formaldehyde solution and 0.879 parts by weight (0.015 mol) of 29
wt. %-ammonium solution for gradually rising the temperature up to
100.degree. C. with attention to heat generation. A reaction was
made at 100.degree. C. for 5 hours before further rising the
temperature up to 180.degree. C. for 2 hours under an atmospheric
pressure with water removal. Subsequently, unreacted substances
were then removed under a low pressure to obtain a phenol
condensate (P4) having a nitrogen content of 10% by weight and a
hydroxyl groups equivalent of 226 as well as having a softening
point of 110.degree. C. The obtained phenol condensate (P4) is
represented in the following general formula (63). 49
[0287] where "n" is 0.0 to 1.0, and "m" is 1.0 to 2.0.
EXAMPLE 18
[0288] 25 parts by weight (0.05 mol) of the phenol condensate (P4)
obtained in Example 17 was added with 50 parts by weight (0.54 mol)
of epichlorohydrin to rise the temperature up to 115.degree. C. for
dissolution thereof. Further, 20 parts by weight (0.1 mol) of 20
wt. %-sodium hydroxide solution was dropped for 3 hours for placing
the solution statically for 30 minutes to cause a static separation
before a lower layer or a water layer was removed.
[0289] Subsequently, the excess epichlorohydrin was distillated and
recycled. 20 parts by weight (1.2 mol) of methylisobutylketone was
added and dissolved. 0.5 parts by weight (0.0025 mol) of 20 wt.
%-sodium hydroxide solution was added for placing the solution at
70.degree. C. for 3 hours to cause a static separation before a
lower layer or a water layer was removed. The reminder was then
cleaned with 200 parts by weight of a distilled water. A volatile
component was removed by distillation to obtain an epoxy resin
(EP4) having a nitrogen content of 8% by weight and an epoxy
equivalent of 284 as well as having a softening point of 75.degree.
C. and including hydrolytic chlorine of not more than 400 ppm. The
obtained epoxy resin (EP4) is represented in the following general
formula (64). 50
[0290] where G is glycidyl group, "n" is 0.0 to 1.0, and "m" is 1.0
to 2.0.
EXAMPLE 19
[0291] At ordinary temperature, there were previously admixed 11.23
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 7.74 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.13% by weight of the above phenol condensate (P3)
having a nitrogen content of 10% by weight, 79.0% by weight of
fused spherical silica powders, 0.4% by weight of carbon black,
0.1% by weight of silane coupling agent, 0.2% by weight of carnauba
wax, 0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0292] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0293] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 20
[0294] At ordinary temperature, there were previously admixed 10.47
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.69 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 0.94% by weight of the above epoxy resin (EP3) having a
nitrogen content of 9% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of carnauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0295] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0296] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 21
[0297] At ordinary temperature, there were previously admixed 10.32
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.72 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.06% by weight of the above epoxy resin (EP4) having a
nitrogen content of 8% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of carnauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0298] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0299] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 22
[0300] At ordinary temperature, there were previously admixed 11.43
parts by weight of phenolphenylenearalkyl epoxy resin (epoxy resin
2), 7.54 parts by weight of phenolphenylenearalkyl resin (phenol
resin 2), 1.13% by weight of the above phenol condensate (P4)
having a nitrogen content of 10% by weight, 79.0% by weight of
fused spherical silica powders, 0.4% by weight of carbon black,
0.1% by weight of silane coupling agent, 0.2% by weight of carnauba
wax, 0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0301] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0302] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 23
[0303] At ordinary temperature, there were previously admixed 8.94
parts by weight of 2-functional biphenyl epoxy resin (epoxy resin
3), 10.03 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 1.13% by weight of the above phenol condensate (P3)
having a nitrogen content of 10% by weight, 79.0% by weight of
fused spherical silica powders, 0.4% by weight of carbon black,
0.1% by weight of silane coupling agent, 0.2% by weight of carnauba
wax, 0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0304] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0305] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 24
[0306] At ordinary temperature, there were previously admixed 5.62
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 3.86 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 4.63 parts by weight of phenolphenylenearalkyl resin
(phenol resin 2), 4.86 parts by weight of 2-functional biphenyl
epoxy resin (epoxy resin 3), 1.13% by weight of the above phenol
condensate (P3) having a nitrogen content of 10% by weight, 79.0%
by weight of fused spherical silica powders, 0.4% by weight of
carbon black, 0.1% by weight of silane coupling agent, 0.2% by
weight of carnauba wax, 0.2% by weight of triphenyl phosphine
(T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0307] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0308] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 25
[0309] At ordinary temperature, there were previously admixed 5.61
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 3.87 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 4.30 parts by weight of phenolphenylenearalkyl resin
(phenol resin 2), 5.19 parts by weight of cresol novolak epoxy
resin (epoxy resin 4), 1.13% by weight of the above phenol
condensate (P3) having a nitrogen content of 10% by weight, 79.0%
by weight of fused spherical silica powders, 0.4% by weight of
carbon black, 0.1% by weight of silane coupling agent, 0.2% by
weight of camauba wax, 0.2% by weight of triphenyl phosphine
(T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0310] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0311] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 26
[0312] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 8.0% by weight of the above
phenol condensate (P3) having a nitrogen content of 10% by weight,
91.5% by weight of the above ABS (thermoplastic resin 1), 0.5% by
weight of polytetrafluoroethylene (PTFE) to form a resin
composition. This resin composition was dried at 120.degree. C. for
3 hours before press-molding is carried out at 200.degree. C. for 1
minute to form a flat plate having a thickness of 3.2
millimeters.
[0313] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
EXAMPLE 27
[0314] At a temperature of 220.degree. C., on a stone grinding
extruder, there were fused and admixed 8.0% by weight of the above
phenol condensate (P3) having a nitrogen content of 10% by weight,
91.5% by weight of the above PS (thermoplastic resin 2), 0.5% by
weight of polytetrafluoroethylene (PTFE) to form a resin
composition. This resin composition was dried at 120.degree. C. for
3 hours before press-molding is carried out at 200.degree. C. for 1
minute to form a flat plate having a thickness of 3.2
millimeters.
[0315] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
3.
3 TABLE 3 Ex.19 Ex.20 Ex.21 Ex.22 Ex.23 Ex.24 Ex.25 Ex.28 Ex.27
phenolbiphenylaralkyl epoxy resin 11.23 10.47 10.32 -- -- 5.62 5.61
-- -- (epoxy resin 1) phenolbiphenylaralkyl resin (phenol resin 1)
7.74 8.69 8.72 -- 10.03 3.86 3.87 -- -- phenolphenylenearalkyl
epoxy resin -- -- -- 11.43 -- -- -- -- -- (epoxy resin 2)
phenolphenylenearalkyl resin -- -- -- 7.54 -- 4.63 4.30 -- --
(phenol resin 2) 2-functional biphenyl epoxy resin -- -- -- -- 8.94
4.86 -- -- -- (epoxy resin 3) cresol novolak epoxy resin (epoxy
resin 4) -- -- -- -- -- -- 5.19 -- -- phenolbiphenyltriazine epoxy
resin -- -- -- -- -- -- -- -- -- (epoxy resin (PE1).N6wt. %)
phenolbiphenyltriazine resin -- -- -- -- -- -- -- -- -- (phenol
condensate (P1),N8wt. %) phenolphenylenetriazine epoxy resin -- --
-- -- -- -- -- -- -- (epoxy resin (PE2).N6wt. %)
phenolphenylenetriazine resin -- -- -- -- -- -- -- -- -- (phenol
condensate (P2).N8wt. %) phenolbiphenylbenzoguanamine epoxy resin
-- 0.04 -- -- -- -- -- -- -- (epoxy resin (PE3),N9wt. %) (4.7/0.42)
phenolbiphenylbenzoguanamine resin 1.13 -- -- -- 1.13 1.13 1.13 8.0
8.0 (phenol condensate (P3).N10wt. %) (5.6/0.56) (5.6/0.56)
(5.6/0.56) (5.6/0.56) (8/0.8) (8/0.8) phenolphenylenebenzoguanamine
-- -- 1.08 -- -- -- -- -- -- epoxy resin (5.3/0.42) (epoxy resin
(PE4).N8wt, %) phenolphenylenebenzoguanamine resin -- -- -- 1.13 --
-- -- -- (phenol condensate (P4).N10wt. %) (5.6/0.56)
phenoltriazine epoxy resin (N6wt. %) -- -- -- -- -- -- -- -- --
phenoltriazine resin (N8wt. %) -- -- -- -- -- -- -- -- --
phenolbenzoguanamine epoxy resin -- -- -- -- -- -- -- -- -- (N15wt.
%) phenolbenzoguanamine resin (N19wt. %) -- -- -- -- -- -- -- -- --
ABS (thermoplastic resin 1) -- -- -- -- -- -- -- 91.5 -- PS
(thermoplastic resin 2) -- -- -- -- -- -- -- -- 91.5 fused
spherical silica 79.0 79.0 79.0 79.0 79.0 79.0 79.0 -- -- carbon
black 0.4 0.4 0.4 0.4 0.4 0.4 0.4 -- -- silane coupling agent 0.1
0.1 0.1 0.1 0.1 0.1 0.1 -- -- carnauba wax 0.2 0.2 0.2 0.2 0.2 0.2
0.2 -- -- triphenylphosphine (T.P.P.) 0.2 0.2 0.2 0.2 0.2 0.2 0.2
-- -- polytetorafluoroethylene (PTFE) -- -- -- -- -- -- 0.5 0.5
UL94 criterion V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-1 (total time of
after-flame times) 3 5 12 14 24 11 10 90 110 boiled water
absorption coefficient par 0.16 0.15 0.19 0.20 0.22 0.20 0.14
unexa- unexa- 24 hours % by weight mined mined thermal
decomposition resistance 630 620 610 595 600 595 625.0 unexa-
unexa- (temperature at 5wt. % reduction) .degree. C. mined mined
moisture-resistance (time period for 460 460 450 450 430 440 470.0
unexa- unexa- 20% defects) Time mined mined (A/B): A = percent by
weight of the present resin to the total amount of resins. B =
percent by weight of nitrogen atoms to the total amount of resins.
Epoxy resin and phenol resin of the present invention
COMPARATIVE EXAMPLE 9
[0316] At ordinary temperature, there were previously admixed 11.3
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.18 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 0.59% by weight of phenol benzoguanamine resin having a
nitrogen content of 19% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of carnauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0317] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0318] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 10
[0319] At ordinary temperature, there were previously admixed 10.8
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 8.74 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 0.56% by weight of phenol benzoguanamine epoxy resin
having a nitrogen content of 15% by weight, 79.0% by weight of
fused spherical silica powders, 0.4% by weight of carbon black,
0.1% by weight of silane coupling agent, 0.2% by weight of carnauba
wax, 0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0320] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0321] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 11
[0322] At ordinary temperature, there were previously admixed 11.51
parts by weight of phenolphenylenearalkyl epoxy resin (epoxy resin
2), 8.00 parts by weight of phenolphenylenearalkyl resin (phenol
resin 2), 0.59% by weight of phenol benzoguanamine resin having a
nitrogen content of 19% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of carnauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0323] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0324] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 12
[0325] At ordinary temperature, there were previously admixed 9.03
parts by weight of 2-functional biphenyl epoxy resin (epoxy resin
3), 10.48 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 0.59% by weight of phenol benzoguanamine resin having a
nitrogen content of 19% by weight, 79.0% by weight of fused
spherical silica powders, 0.4% by weight of carbon black, 0.1% by
weight of silane coupling agent, 0.2% by weight of camauba wax,
0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0326] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0327] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 13
[0328] At ordinary temperature, there were previously admixed 5.72
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 4.30 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 4.63 parts by weight of phenolphenylenearalkyl resin
(phenol resin 2), 4.86 parts by weight of 2-functional biphenyl
epoxy resin (epoxy resin 3), 0.59% by weight of phenol
benzoguanamine resin having a nitrogen content of 19% by weight,
79.0% by weight of fused spherical silica powders, 0.4% by weight
of carbon black, 0.1% by weight of silane coupling agent, 0.2% by
weight of camauba wax, 0.2% by weight of triphenyl phosphine
(T.T.P). Thereafter, the admixture was made on a roll of
100.degree. C. for about 5 minutes and then the mixture was cooled
and crushed to form the resin composition.
[0329] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0330] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 14
[0331] At ordinary temperature, there were previously admixed 5.72
parts by weight of phenolbiphenylaralkyl epoxy resin (epoxy resin
1), 4.30 parts by weight of phenolbiphenylaralkyl resin (phenol
resin 1), 4.30 parts by weight of phenolphenylenearalkyl resin
(phenol resin 2), 5.19 parts by weight of cresol novolak epoxy
resin (epoxy resin 4), 0.59% by weight of phenol benzoguanamine
resin having a nitrogen content of 19% by weight, 79.0% by weight
of fused spherical silica powders, 0.4% by weight of carbon black,
0.1% by weight of silane coupling agent, 0.2% by weight of carnauba
wax, 0.2% by weight of triphenyl phosphine (T.T.P). Thereafter, the
admixture was made on a roll of 100.degree. C. for about 5 minutes
and then the mixture was cooled and crushed to form the resin
composition.
[0332] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0333] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
COMPARATIVE EXAMPLE 15
[0334] At ordinary temperature, there were previously admixed 4.2%
by weight of phenol benzoguanamine resin having a nitrogen content
of 19% by weight, 95.3% by weight of the above PS (thermoplastic
resin 2), 0.5% by weight of polytetrafluoroethylene (PTFE).
Thereafter, the admixture was made on a roll of 100.degree. C. for
about 5 minutes and then the mixture was cooled and crushed to form
the resin composition.
[0335] The resin composition was compressed to form a tablet. This
tablet was previously heated at 85.degree. C. for subsequent
molding by use of a single plunger type transfer molding machine
under conditions of an injection time of 15 seconds, an injection
pressure (effective pressure) of 100 kg/cm.sup.2, a molding
temperature of 175.degree. C., a molding time of 120 seconds in
accordance with the UL94 flame retardation regulation.
Subsequently, thermosetting process was carried out at 175.degree.
C. for 6 hours to form a flame retardant test sample plate.
[0336] The molded test plates obtained in this comparative example
was evaluated on flame retardancy, a boiled water absorption
coefficient, a thermal stability and a moisture resistance. Results
of evaluations on the moisture resistance are shown on below Table
4.
4 TABLE 4 Com. Com. Com. Com. Com. Com. Com.Ex.9 Ex.10 Ex.11 Ex.12
Ex.13 Ex.14 Ex.15 phenolbiphenylaralkyl epoxy resin (epoxy resin 1)
11.3 10.8 -- -- 5.72 5.72 -- phenolbiphenylaralkyl resin (phenol
resin 1) 8.18 8.74 -- 10.48 4.30 4.30 -- phenolphenylenearalkyl
epoxy resin (epoxy resin 2) -- -- 11.51 -- -- -- --
phenolphenylenearalkyl resin (phenol resin 2) -- -- 8.00 -- 4.63
4.30 -- 2-functional biphenyl epoxy resin (epoxy resin 3) -- -- --
9.03 4.86 -- -- cresol novolak epoxy resin (epoxy resin 4) -- -- --
-- -- 5.19 -- phenolbiphenyltriazine epoxy resin -- -- -- -- -- --
-- (epoxy resin (PE1).N6wt. %) phenolbiphenyltriazine resin -- --
-- -- -- -- -- (phenol condensate (P1),N8wt. %)
phenolphenylenetriazine epoxy resin -- -- -- -- -- -- -- (epoxy
resin (PE2).N6wt. %) phenolphenylenetriazine resin -- -- -- -- --
-- -- (phenol condensate (P2).N8wt. %) phenolbiphenylbenzoguanamine
epoxy resin -- -- -- -- -- -- -- (epoxy resin (PE3),N9wt. %)
phenolbiphenylbenzoguanamine resin -- -- -- -- -- -- (phenol
condensate (P3).N10wt. %) phenolphenylenebenzoguanamine epoxy resin
-- -- -- -- -- -- -- (epoxy resin (PE4).N8wt, %)
phenolphenylenebenzoguanamine resin -- -- -- -- -- -- -- (phenol
condensate (P4).N10wt. %) phenoltriazine epoxy resin (N6wt. %) --
-- -- -- -- -- -- phenoltriazine resin (N8wt. %) -- -- -- -- -- --
-- phenolbenzoguanamine epoxy resin (N15wt. %) -- 0.56 -- -- -- --
-- (2.8/0.42) phenolbenzoguanamine resin (N19wt. %) 0.59 -- 0.59
0.59 0.59 0.59 0.42 (2.9/0.56) (2.9/0.56) (2.9/0.56) (2.9/0.56)
(2.9/0.56) (4.2/0.8) ABS (thermoplastic resin 1) -- -- -- -- -- --
-- PS (thermoplastic resin 2) -- -- -- -- -- -- 9.53 fused
spherical silica 0.4 0.4 0.4 0.4 0.4 0.4 -- carbon black 0.1 0.1
0.1 0.1 0.1 0.1 -- silane coupling agent 0.2 0.2 0.2 0.2 0.2 0.2 --
carnauba wax 0.2 0.2 0.2 0.2 0.2 0.2 -- triphenylphosphine (T.P.P.)
0.2 0.2 0.2 0.2 0.2 0.2 -- polytetorafluoroethylene (PTFE) -- -- --
-- -- -- 0.5 UL94 criterion V-0 V-0 V-0 V-0 V-0 V-0 V-1 (total time
of after-flame times) 26 28 30 44 31 30 180 boiled water absorption
coefficient par 24 hours 0.23 0.24 0.27 0.32 0.36 0.28 unexa- % by
weight mined thermal decomposition resistance 565 558 555 550 540
560 unexa- (temperature at 5wt. % reduction) .degree. C. mined
moisture-resistance (time period for 410 410 395 380 380 400 unexa-
20% defects) Time mined (A/B): A = percent by weight of the present
resin to the total amount of resins. B = percent by weight of
nitrogen atoms to the total amount of resins. Epoxy resin and
phenol resin of the present invention
[0337] The novel resin compositions having the improved flame
retardant resin materials in Examples 7, 8, 10, 11, 19-21 are
superior in flame retardancy, thermal stability or thermal
decomposition resistance, moisture resistance as compared to the
conventional resin compositions having the conventional flame
retardant resin materials in Comparative Examples 1, 2, 9, 10.
[0338] The novel resin composition having the improved flame
retardant resin material in Example 9 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
compositions having the conventional flame retardant resin
materials in Comparative Examples 3, 4.
[0339] The novel resin compositions having the improved flame
retardant resin materials in Examples 12, 22 are superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
compositions having the conventional flame retardant resin
materials in Comparative Examples 5, 11.
[0340] The novel resin composition having the improved flame
retardant resin material in Example 23 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
composition having the conventional flame retardant resin material
in Comparative Example 12.
[0341] The novel resin composition having the improved flame
retardant resin material in Example 24 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
composition having the conventional flame retardant resin material
in Comparative Example 13.
[0342] The novel resin composition having the improved flame
retardant resin material in Example 25 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
composition having the conventional flame retardant resin material
in Comparative Example 14.
[0343] The novel resin compositions having the improved flame
retardant resin materials in Examples 13, 26 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
compositions having the conventional flame retardant resin
materials in Comparative Examples 6, 7.
[0344] The novel resin compositions having the improved flame
retardant resin materials in Examples 14, 27 is superior in flame
retardancy, thermal stability or thermal decomposition resistance,
moisture resistance as compared to the conventional resin
compositions having the conventional flame retardant resin
materials in Comparative Examples 8, 15.
[0345] The conventional resin compositions include the phenol
resins having triazine rings on the molecular skeletons or include
the epoxy resins having triazine rings on the molecular skeletons.
The other conventional resin compositions include both
phenolbiphenylaralkyl epoxy resins having biphenyl groups on the
molecular skeletons and the phenol resins having triazine rings on
the molecular skeletons. The novel resin compositions include the
flame retardant resin compositions having both the triazine rings
and the aromatic rings on the same molecular skeletons.
[0346] The novel resin compositions are superior in flame
retardancy, thermal stability or thermal decomposition resistance
and moisture resistance as compared to the conventional resin
compositions.
[0347] Whereas modifications of the present invention will be
apparent to a person having ordinary skill in the art, to which the
invention pertains, it is to be understood that embodiments as
shown and described by way of illustrations are by no means
intended to be considered in a limiting sense. Accordingly, it is
to be intended to cover by claims all modifications which fall
within the spirit and scope of the present invention.
* * * * *