U.S. patent application number 10/442268 was filed with the patent office on 2003-11-27 for crosslinked phenoxyphosphazene compounds, flame retardants, flame-retardant resin compositions, and moldings of flame-retardant resins.
This patent application is currently assigned to OTSUKA CHEMICAL CO., LTD.. Invention is credited to Tadao, Yabuhara, Yoichi, Nishioka, Yoshifumi, Nakacho, Yuji, Tada.
Application Number | 20030220515 10/442268 |
Document ID | / |
Family ID | 26371356 |
Filed Date | 2003-11-27 |
United States Patent
Application |
20030220515 |
Kind Code |
A1 |
Yoshifumi, Nakacho ; et
al. |
November 27, 2003 |
Crosslinked phenoxyphosphazene compounds, flame retardants,
flame-retardant resin compositions, and moldings of flame-retardant
resins
Abstract
This invention has an object of providing a flame retardant
which advantageously has a high melting point and a low volatility
and is unlikely to depress the inherent properties of resins. The
flame retardant of the invention is a phosphazene compound
crosslinked with a crosslinking group such as phenylene group, each
of the crosslinking groups being interposed between the two oxygen
groups left after the elimination of phenyl groups from the
phosphazene compound, the amount of the phenyl groups in the
crosslinked compound being 50 to 99.9% based on the total number of
the phenyl groups in the phosphazene compound. The invention also
provides a resin composition containing the flame retardant, and a
molded article of the resin.
Inventors: |
Yoshifumi, Nakacho;
(Barcelona, ES) ; Tadao, Yabuhara; (Tokushima-shi,
JP) ; Yuji, Tada; (Tokushima-shi, JP) ;
Yoichi, Nishioka; (Tokushima-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
WASHINGTON
DC
20037
US
|
Assignee: |
OTSUKA CHEMICAL CO., LTD.
|
Family ID: |
26371356 |
Appl. No.: |
10/442268 |
Filed: |
May 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10442268 |
May 21, 2003 |
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09331013 |
Aug 12, 1999 |
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6596893 |
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09331013 |
Aug 12, 1999 |
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PCT/JP98/02974 |
Jul 2, 1998 |
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Current U.S.
Class: |
558/157 ; 524/86;
564/13 |
Current CPC
Class: |
C08K 5/5399 20130101;
C09K 21/14 20130101; C08G 75/0204 20130101 |
Class at
Publication: |
558/157 ; 564/13;
524/86 |
International
Class: |
C07F 009/02 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 15, 1997 |
JP |
281679/1997 |
Feb 16, 1998 |
JP |
32770/1998 |
Claims
1. A crosslinked phenoxyphosphazene compound characterized in that
at least one phosphazene compound selected from the group
consisting of a cyclic phosphazene compound represented by the
formula (1) 15wherein m is an integer of 3 to 25 and Ph is a phenyl
group and a straight-chain phosphazene compound represented by the
formula (2) 16wherein X is a group --N.dbd.P(OPh).sub.3, or a group
--N.dbd.P(O)OPh, Y is a group --P(OPh).sub.4 or a group
--P(O)(OPh).sub.2, n is an integer of 3 to 1000 and Ph is as
defined above, is crosslinked with at least one crosslinking group
selected from the class consisting of o-phenylene group,
m-phenylene group, p-phenylene group, biphenylene group, and a
group 17wherein A is --C(CH.sub.3).sub.2--, --SO.sub.2--, --S-- or
--O--; wherein each of said crosslinking groups is interposed
between the two oxygen atoms left after the elimination of phenyl
groups from the phosphazene compound; and wherein the amount of the
phenyl groups in the crosslinked compound is 50 to 99.9% based on
the total number of the phenyl groups in said phosphazene compound
represented by the formula (1) and/or said phosphazene compound
represented by the formula (2).
2. A flame retardant comprising a crosslinked phenoxyphosphazene
compound characterized in that at least one phosphazene compound
selected from the group consisting of a cyclic phosphazene compound
represented by the formula (1) 18wherein m is an integer of 3 to 25
and Ph is a phenyl group and a straight-chain phosphazene compound
represented by the formula (2) 19wherein X is a group
--N.dbd.P(OPh).sub.3, or a group --N.dbd.P(O)OPh, Y is a group
--P(OPh).sub.4 or a group --P(O)(OPh).sub.2, n is an integer of 3
to 1000 and Ph is as defined above, is crosslinked with at least
one crosslinking group selected from the class consisting of
o-phenylene group, m-phenylene group, p-phenylene group,
biphenylene group, and a group 20wherein A is
--C(CH.sub.3).sub.2--, --SO.sub.2--, --S-- or --O--; wherein each
of said crosslinking groups is interposed between the two oxygen
atoms left after the elimination of phenyl groups from the
phosphazene compound; and wherein the amount of the phenyl groups
in the crosslinked compound is 50 to 99.9% based on the total
number of the phenyl groups in said phosphazene compound
represented by the formula (1) and/or said phosphazene compound
represented by the formula (2).
3. A flame-retardant resin composition comprising (i) a
thermoplastic resin or a thermosetting resin and (ii) a flame
retardant comprising a crosslinked phenoxyphosphazene compound
characterized in that at least one phosphazene compound selected
from the group consisting of a cyclic phosphazene compound
represented by the formula (1) 21wherein m is an integer of 3 to 25
and Ph is a phenyl group and a straight-chain phosphazene compound
represented by the formula (2) 22wherein X is a group
--N.dbd.P(OPh).sub.3# or a group --N.dbd.P(O)OPh, Y is a group
--P(OPh).sub.4 or a group --P(O)(OPh).sub.2, n is an integer of 3
to 1000 and Ph is as defined above, is crosslinked with at least
one crosslinking group selected from the class consisting of
o-phenylene group, m-phenylene group, p-phenylene group,
biphenylene group, and a group 23wherein A is
--C(CH.sub.3).sub.2--, --SO.sub.2--, --S-- or --O--; wherein each
of said crosslinking groups is interposed between the two oxygen
atoms left after the elimination of phenyl groups from the
phosphazene compound; and wherein the amount of the phenyl groups
in the crosslinked compound is 50 to 99.9% based on the total
number of the phenyl groups in said phosphazene compound
represented by the formula (1) and/or said phosphazene compound
represented by the formula (2), the amount of the flame retardant
(ii) being 0.1 to 100 wt. parts per 100 wt. parts of the resin
(i).
4. The flame-retardant resin composition according to claim 3 which
further contains an inorganic filler in an amount of 0.01 to 50 wt.
parts per 100 wt. parts of the resin (i).
5. The flame-retardant resin composition according to claim 3 which
further contains a halogen-free organic phosphorus compound in an
amount of 0.01 to 50 wt. parts per 100 wt. parts of the resin
(i).
6. The flame-retardant resin composition according to claim 3 which
further contains a fluorine-containing resin in an amount of 0.01
to 2.5 wt. parts per 100 wt. parts of the resin (i).
7. A flame retardant comprising at least one phosphazene compound
selected from the group consisting of a cyclic phosphazene compound
represented by the formula (1) 24wherein m and Ph are as defined
above, and a straight-chain phosphazene compound represented by the
formula (2) 25wherein X, Y, n and Ph are as defined above.
8. A flame-retardant resin composition comprising (i) a
thermoplastic resin or a thermosetting resin, (ii) a flame
retardant comprising at least one phosphazene compound selected
from the group consisting of a cyclic phosphazene compound
represented by the formula (1) 26wherein m and Ph are as defined
above and a straight-chain phosphazene compound represented by the
formula (2) 27wherein X, Y, n and Ph are as defined above, and
(iii) an inorganic filler, the amount of the flame retardant (ii)
being 0.1 to 100 wt. parts per 100 wt. parts of the resin (i) and
the amount of the inorganic filler being 0.01 to 50 wt. parts per
100 wt. parts of the resin (i).
9. A flame-retardant resin composition comprising (i) a
thermoplastic resin or a thermosetting resin, (ii) a flame
retardant comprising at least one phosphazene compound selected
from the group consisting of a cyclic phosphazene compound
represented by the formula (1) 28wherein m and Ph are as defined
above and a straight-chain phosphazene compound represented by the
formula (2) 29wherein X, Y, n and Ph are as defined above, and
(iii) a halogen-free organic phosphorus compound, the amount of the
flame retardant (ii) being 0.1 to 100 wt. parts per 100 wt. parts
of the resin (i) and the amount of the halogen-free organic
phosphorus compound (iii) being 0.1 to 50 wt. parts per 100 wt.
parts of the resin (i).
10. A flame retardant comprising at least one phosphazene compound
selected from the group consisting of a cyclic phosphazene compound
represented by the formula (3). 30wherein m is as defined above,
R.sup.1 is a cyano-substituted phenyl group, R.sup.2 represents an
alkyl group having 1 to 18 carbon atoms, a group 31or a group
32wherein R.sup.3 is a hydrogen atom, cyano group, alkyl group
having 1 to 10 carbon atoms, allyl group or phenyl group; when two
or more R.sup.2 groups exist, the R.sup.2 groups may be the same or
different; and p and q are numbers which fulfil the requirements
that p>O, q.gtoreq.0, and p+q=2, and a straight-chain
phosphazene compound represented by the formula (4) 33wherein n,
R.sup.1, R.sup.2, p and q are as defined above, X' is a group
--P(OR.sup.1).sub.4, a group --P(OR.sup.1).sub.3(OR.sup.2), a group
--P(OR.sup.1).sub.2(OR.sup.2).sub.2, a group
--P(OR.sup.1)(OR.sup.2).sub.- 3, a group --P(OR.sup.2).sub.4, a
group --P(O)(OR.sup.1).sub.2, a group --P(O)(OR.sup.1)(OR.sup.2),
or a group --P(O)(OR.sup.2).sub.2, and Y' is a group
--N.dbd.P(OR.sup.1).sub.3, a group --N.dbd.P(OR.sup.1).sub.2(OR.s-
up.2), a group --N.dbd.P(OR.sup.1)(OR.sup.2).sub.2, a group
--N.dbd.P(OR.sup.2).sub.3, a group --N.dbd.P(O)OR.sup.1 or a group
--N.dbd.P(O)OR.sup.2.
11. The flame retardant according to claim 10, wherein the
phosphazene compound is at least one compound selected from the
group consisting of a cyclic phosphazene compound represented by
the formula (3) wherein R.sup.1 is a cyano-substituted phenyl
group, R.sup.2 represents an alkyl group having 1 to 8 carbon
atoms, a group 34or a group 35wherein R.sup.3 is a hydrogen atom,
alkyl group having 1 to 4 carbon atoms or allyl group, p is 0.3 to
1.7, q is 0.3 to 0.7, and a straight-chain phosphazene compound
represented by the formula (4) wherein R.sup.1 is a
cyano-substituted phenyl group, R.sup.2 represents an alkyl group
having 1 to 8 carbon atoms, a group 36or a group 37wherein R.sup.3
is a hydrogen atom, alkyl group having 1 to 4 carbon atoms or allyl
group, p is 0.3 to 1.7, and q is 0.3 to 0.7.
12. A flame-retardant resin composition comprising (i) a
thermoplastic resin or a thermosetting resin, and (ii) a flame
retardant comprising at least one phosphazene compound selected
from the group consisting of a cyclic phosphazene compound
represented by the formula (3). 38wherein m is as defined above,
R.sup.1 is a cyano-substituted phenyl group, R.sup.2 represents an
alkyl group having 1 to 18 carbon atoms, a group 39or a group
40wherein R.sup.3 is a hydrogen atom, cyano group, alkyl group
having 1 to 10 carbon atoms, allyl group or phenyl group; when two
or more R.sup.2 groups exist, the R.sup.2 groups may be the same or
different; and p and q are numbers which fulfil the requirements
that p>0, q.gtoreq.0, and p+q=2, and a straight-chain
phosphazene compound represented by the formula (4) 41wherein n,
R.sup.1, R.sup.2, p and q are as defined above, X' is a group
--P(OR.sup.1).sub.4, a group --P(OR.sup.1).sub.3(OR.sup.2), a group
--P(OR.sup.1).sub.2(OR.sup.2).sub.- 2, a group
--P(OR.sup.1)(OR.sup.2).sub.3, a group --P(OR.sup.2).sub.4, a group
--P(O)(OR.sup.1).sub.2, a group --P(O)(OR.sup.1)(OR.sup.2), or a
group --P(O)(OR.sup.2).sub.2, and Y' is a group
--N.dbd.P(OR.sup.1).sub.3- , a group
--N.dbd.P(OR.sup.1).sub.2(OR.sup.2), a group
--N.dbd.P(OR.sup.1)(OR.sup.2).sub.2, a group
--N.dbd.P(OR.sup.2).sub.3, a group --N.dbd.P(O)OR.sup.1 or a group
--N.dbd.P(O)OR.sup.2, the amount of the flame retardant (ii) being
0.1 to 100 wt. parts per 100 wt. parts of the resin (i).
13. A flame-retardant resin composition comprising (i) a
thermoplastic resin or a thermosetting resin and (ii) the flame
retardant of claim 11, the amount of the flame retardant (ii) being
0.1 to 100 wt. parts per 100 wt. parts of the resin (i).
14. A flame-retardant resin molded article obtainable by molding
the flame-retardant resin composition as defined in claim 3, 4, 5
or 6.
15. A flame-retardant resin molded article obtainable by molding
the flame-retardant resin composition as defined in claim 8 or
9.
16. A flame-retardant resin molded article obtainable by molding
the flame-retardant resin composition as defined in claim 12 or
13.
17. A method for imparting flame retardancy to a molded article of
thermoplastic resin or thermosetting resin produced using the flame
retardant as defined in claim 2, 7 or 10.
18. Use of the flame-retardant as defined in claim 2, 7 or 10 for
imparting the flame retardancy to a thermoplastic resin or a
thermosetting resin.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to crosslinked
phenoxyphosphazene compounds, flame retardants, flame-retardant
resin compositions and moldings of flame-retardant resins.
BACKGROUND ART
[0002] Plastics are used for applications such as electric and
electronic products, office automation equipment, office equipment
and communications equipment because of their excellent
processability, mechanical properties, appearance and the like. The
resins used in these applications are required to have flame
retardancy for protection against the heat and ignition of internal
parts in devices and appliances.
[0003] In order to impart flame retardancy to thermoplastic resins
or thermosetting resins, a flame retardant is generally added to
the resin prior to molding of the resin. Known as flame retardants
are inorganic hydroxides, organic phosphorus compounds, organic
halogen compounds, halogen-containing organic phosphorus compounds
and the like.
[0004] Among said flame retardants, those having high
flame-retardancy are halogen-containing compounds such as organic
halogen compounds, halogen-containing organic phosphorus compounds
and the like.
[0005] However, these halogen-containing compounds undergo thermal
decomposition during molding of the resin to generate hydrogen
halide, thereby causing corrosion of the metallic mold and
degradation and discoloration of the resin. Another problem is
that, when the resin is burned in a fire or the like, hydrogen
halide and the like are evolved as gases and smokes detrimental to
organisms.
[0006] On the other hand, halogen-free flame retardants are
magnesium hydroxide, aluminum hydroxide and like inorganic
hydroxides and organic phosphorus compounds.
[0007] However, the inorganic hydroxides exhibit flame retardancy
due to water generated by thermal decomposition, and therefore
produce only low flame-retardancy. Consequently, the inorganic
hydroxide must be added in a large amount, but such a large amount
addition entails a disadvantage that the inherent properties of
resins are impaired.
[0008] The organic phosphorus compounds are widely used because
they give relatively high flame-retardancy. Known as typical
organic phosphorus compounds are triphenyl phosphate (TPP),
tricresyl phosphate (TCP) and the like. However, these organic
phosphorus compounds are liquid or low melting solid and thus have
a high volatility, posing problems such as lowering of the molding
temperature of resins, blocking and their migration to the surface
(juicing) during kneading.
[0009] Furthermore, resin compositions containing said organic
phosphorus compound have the drawback of dripping (falling of
molten resin droplets) during burning and spreading of a fire due
to the dripping. Consequently, in order to obtain a rating of V-0
(flaming does not continue for more than a specified period, and
there are no molten resin drips which ignite cotton) in a flame
retardancy test UL-94 (Testing for Flammability of Plastic
Materials for Parts in Devices & Appliances) which is a
standard test for evaluating flame retardancy, by adding an organic
phosphorus compound to a resin, it is necessary to add a
fluorine-containing resin such as polytetrafluoroethylene (PTFE) as
an agent for preventing dripping of molten resin during burning.
However, the fluorine-containing resin contains halogen and evolves
gases harmful to human body during combustion, as stated above.
[0010] In view of the foregoing prior art drawbacks, it is desired
to develop a novel flame retardant which is free of halogen, which
has a high melting point and a low volatility, which would not
impair the inherent properties of resins such as mechanical
properties and processability, which is free from the problems of
inducing blocking and juicing during kneading and which does not
permit dripping during flaming.
DISCLOSURE OF THE INVENTION
[0011] An object of the present invention is to provide a compound
useful as a flame retardant.
[0012] Another object of the invention is to provide a halogen-free
flame retardant.
[0013] A further object of the invention is to provide a flame
retardant which has a high melting point and a low volatility and
which does not impair the inherent properties of resins, such as
mechanical properties and processability.
[0014] A still further object of the invention is to provide a
flame retardant which does not present the problems of blocking and
juicing in kneading.
[0015] Another object of the invention is to provide a flame
retardant which does not induce dripping during burning.
[0016] An additional object of the invention is to provide a flame
retardant which is free from the prior art problems.
[0017] A still further object of the invention is to provide a
flame-retardant resin composition containing the foregoing flame
retardant.
[0018] Another object of the invention is to provide a molded
articles of flame-retardant resin produced by molding said
flame-retardant resin composition.
[0019] Another object of the invention is to provide a method for
imparting flame retardancy to molded articles of resins.
[0020] An additional object of the invention is to provide use of a
phosphazene compound for imparting flame retardancy to resin molded
articles.
[0021] Other features of the present invention will become apparent
from the following description.
[0022] The inventors of the present invention conducted extensive
research to overcome the foregoing prior art problems and found
that certain partly crosslinked phenoxyphosphazene compounds can be
the desired flame retardants. The present invention was completed
based on this novel finding.
[0023] According to the present invention, there is provided a
crosslinked phenoxyphosphazene compound characterized in that at
least one phosphazene compound selected from the group consisting
of a cyclic phosphazene compound represented by the formula (1)
1
[0024] wherein m is an integer of 3 to 25 and Ph is phenyl group
and a straight-chain phosphazene compound represented by the
formula (2) 2
[0025] wherein X represents a group --N.dbd.P(OPh).sub.3 or a group
--N.dbd.P(O)OPh, Y represents a group --P(OPh).sub.4 or a group
--P(O)(OPh).sub.2, and n is an integer of 3 to 1000, and Ph is as
defined above
[0026] is crosslinked with at least one crosslinking group selected
from the group consisting of o-phenylene group, m-phenylene group,
p-phenylene group, biphenylene group, and a group 3
[0027] wherein A is --C(CH.sub.3).sub.2--, --SO.sub.2--, --S-- or
--O--;
[0028] wherein each of said crosslinking groups is interposed
between the two oxygen atoms left after the elimination of phenyl
groups from the phosphazene compound; and
[0029] wherein the amount of the phenyl groups in the crosslinked
compound is 50 to 99.9% based on the total amount of the phenyl
groups in said phosphazene compound represented by the formula (1)
and/or said phosphazene compound represented by the formula
(2).
[0030] According to the present invention, there is also provided a
flame retardant comprising said crosslinked phenoxyphosphazene
compound (this flame retardant will hereinafter be referred to as
"flame retardant A").
[0031] Flame retardant A comprising the crosslinked
phenoxyphosphazene compound of the present invention does not
contain halogen, and therefore does not cause the corrosion of the
mold and degradation and discoloration of the resin due to the
generation of hydrogen halide by thermal decomposition during the
resin molding operation, and does not produce gases and smokes
detrimental to organisms, such as hydrogen halide, when the resin
is burned in a fire or the like. Further, the crosslinked
phenoxyphosphazene compound of the present invention has a low
volatility and does not lower the molding temperature, and is free
from the shortcomings such as blocking or their migration to the
surface (juicing) during kneading, and dripping during burning. The
incorporation of flame retardant A does not impair inherent
properties of resins, such as impact resistance and like mechanical
properties, heat resistance, processability and the like.
[0032] According to the present invention, there are also provided:
(a) a flame-retardant resin composition comprising 100 parts by
weight of a thermoplastic resin or a thermosetting resin and 0.1 to
100 parts by weight of flame retardant A; (b) a flame-retardant
resin composition comprising 100 parts by weight of a thermoplastic
resin or a thermosetting resin, 0.1 to 100 parts by weight of flame
retardant A and 0.01 to 50 parts by weight of an inorganic filler;
(c) a flame-retardant resin composition comprising 100 parts by
weight of a thermoplastic resin or a thermosetting resin, 0.1 to 50
parts by weight of flame retardant A and 0.1 to 50 parts by weight
of an organic phosphorus compound free of halogen; and (d) a
flame-retardant resin composition comprising 100 parts by weight of
a thermoplastic resin, 0.1 to 100 parts by weight of flame
retardant A and 0.01 to 2.5 parts by weight of a
fluorine-containing resin.
[0033] According to the present invention, there are provided
flame-retardant resin molded articles produced by molding any of
flame-retardant resin compositions (a) to (d).
[0034] Furthermore, the inventors of the present invention found
that the foregoing contemplated effects of the invention can be
achieved likewise when using at least one phosphazene compound
selected from the group consisting of the cyclic phosphazene
compound represented by the formula (1) and the straight-chain
phosphazene compound represented by the formula (2) in combination
with an inorganic filler or an organic phosphorus compound free of
halogen.
[0035] According to the present invention, there is provided a
flame retardant comprising at least one phosphazene compound
selected from the group consisting of the cyclic phosphazene
compound represented by the formula (1) and the straight-chain
phosphazene compound represented by the formula (2) (said flame
retardant will hereinafter be referred to as "flame retardant
B").
[0036] According to the present invention, there are also provided:
(e) a flame-retardant resin composition comprising 100 parts by
weight of a thermoplastic resin or a thermosetting resin, 0.1 to
100 parts by weight of flame retardant B and 0.01 to 50 parts by
weight of an inorganic filler; and (f) a flame-retardant resin
composition comprising 100 parts by weight of a thermoplastic resin
or a thermosetting resin, 0.1 to 50 parts by weight of flame
retardant B, and 0.1 to 50 parts by weight of an organic phosphorus
compound free of halogen.
[0037] According to the present invention, there are provided
flame-retardant resin molded articles produced by molding any of
flame-retardant resin compositions (e) and (f).
[0038] The inventors of the present invention also found that the
foregoing contemplated effects of the invention can be achieved
when using, as a flame retardant, at least one phosphazene compound
selected from the group consisting of a cyclic phosphazene compound
represented by the formula (3) and a straight-chain phosphazene
compound represented by the formula (4).
[0039] According to the present invention, there is provided a
flame retardant comprising at least one phosphazene compound
selected from the group consisting of a cyclic phosphazene compound
represented by the formula (3). 4
[0040] wherein m is as defined above, R.sup.1 is a
cyano-substituted phenyl group, R.sup.2 represents an alkyl group
having 1 to 18 carbon atoms, a group 5
[0041] or a group 6
[0042] wherein R.sup.3 is a hydrogen atom, cyano group, alkyl group
having 1 to 10 carbon atoms, allyl group or phenyl group; when two
or more R.sup.2 groups exist, the R.sup.2 groups may be the same or
different; p and q are numbers which fulfil the requirements that
p>0, q.gtoreq.0, and p+q=2, and a straight-chain phosphazene
compound represented by the formula (4) 7
[0043] wherein n, R.sup.1, R.sup.2, p and q are as defined above,
X' represents a group --P(OR.sup.1).sub.4, a group
--P(OR.sup.1).sub.3(OR.su- p.2), a group
--P(OR.sup.1).sub.2(OR.sup.2).sub.2, a group
--P(OR.sup.1)(OR.sup.2).sub.3, a group --P(OR.sup.2).sub.4, a group
--P(O)(OR.sup.1).sub.2, a group --P(O)(OR.sup.1)(OR.sup.2), or a
group --P(O)(OR.sup.2).sub.2, and Y' represents a group
--N.dbd.P(OR.sup.1).sub- .3, a group
--N.dbd.P(OR.sup.1).sub.2(OR.sup.2), a group
--N.dbd.P(OR.sup.1)(OR.sup.2).sub.2, a group
--N.dbd.P(OR.sup.2).sub.3, a group --N.dbd.P(O)OR.sup.1 or a group
--N.dbd.P(O)OR.sup.2 (this flame retardant will hereinafter be
referred to as "flame retardant C").
[0044] According to the present invention, there is provided a
flame-retardant resin composition comprising 100 parts by weight of
a thermoplastic resin or a thermosetting resin and 0.1 to 100 parts
by weight of flame retardant C.
[0045] According to the present invention, there are provided a
flame-retardant resin molded article obtainable by molding said
flame-retardant resin composition.
[0046] According to the present invention, there is also provided a
method for imparting flame retardancy to a resin molded article
using flame retardant A, flame retardant B or flame retardant C.
For example, by incorporating flame retardant A, flame retardant B
or flame retardant C to a resin and molding the mixture, there is
provided a resin molded article having a flame retardancy
imparted.
[0047] According to the present invention, there is provided use of
the phosphazene compounds for imparting flame retardancy to a
resin.
[0048] Crosslinked Phenoxyphosphazene Compounds
[0049] The phenoxyphosphazene compounds of the invention can be
obtained by, for example, reacting dichlorophosphazene oligomers (a
mixture of cyclic dichlorophosphazene oligomers and straight-chain
dichlorophosphazene oligomers) with an alkali metal salt of phenol
and an alkali metal salt of an aromatic dihydroxy compound.
Concerning the dichlorophosphazene oligomers, each of the cyclic
and straight-chain dichlorophosphazene oligomers may be isolated
from the mixture and used singly. The alkali metal salt of the
phenol and the alkali metal salt of the aromatic dihydroxy compound
may be mixed together before being subjected to the reaction.
Alternatively, the alkali metal salt of phenol and the alkali metal
salt of the aromatic dihydroxy compound are consecutively subjected
to the reaction in this order or in the reverse order.
[0050] The dichlorophosphazene oligomer can be produced by known
methods disclosed in, for example, Japanese Unexamined Patent
Publication No. 87427/1982 and Japanese Examined Patent
Publications Nos. 19604/1983, 1363/1986 and 20124/1987. An
exemplary method comprises reacting ammonium chloride and
phosphorus pentachloride (or ammonium chloride, phosphorus
trichloride and chlorine) at about 120 to 130.degree. C. using
chlorobenzene as a solvent, followed by removal of hydrochloric
acid.
[0051] Examples of the alkali metal salts of phenol include Na
salt, K salt and Li salt of phenol. Examples of the alkali metal
salts of aromatic dihydroxy compounds include any of the alkali
metal salts of known compounds having one or more benzene rings and
two hydroxy groups in the molecule. Examples of such alkali metal
salts include alkali metal salts of resorcinol, hydroquinone,
catechol, 4,4'-isopropylidene diphenol (bisphenol-A),
4,4'-sulfonyldiphenol (bisphenol-S), 4,4'-thiodiphenol,
4,4'-oxydiphenol and 4,4'-diphenol. The alkali metal salts are not
limited, but Li salt is preferred. The alkali metal salts of
aromatic dihydroxy compounds may be used either singly or in
combination.
[0052] The alkali metal salt of phenol and the alkali metal salt of
the aromatic dihydroxy compound are used in amounts such that the
combined amount of the two alkali metal salts, relative to the
dichlorophosphazene oligomers, is usually about 1 to 1.5
equivalents (based on the chlorine content of the
dichlorophosphazene oligomers), preferably about 1 to 1.2
equivalents (based on the chlorine content of the
dichlorophosphazene oligomers). The ratio of the two alkali metal
salts (the alkali metal salt of the aromatic dihydroxy compound/the
alkali metal salt of phenol, molar ratio) is not paticularly
limited and can be suitably selected from a wide range, but is
usually about {fraction (1/2000)} to {fraction (1/4)}. Using the
alkali metal salts in the ratio within the above range, the desired
crosslinked phenoxyphsphazene compound of the invention can be
obtained.
[0053] If the ratio is markedly lower than {fraction (1/2000)}, the
resulting crosslinked compound has low effect, and it may become
difficult to achieve the above objects, such as prevention of
dripping of molten resin. On the other hand, if the ratio is much
higher than {fraction (1/4)}, the crosslinking proceeds to an
excess degree and may result in a crosslinked phenoxyphosphazene
compound which is insoluble and infusible and thus has decreased
dispersiblility into resins.
[0054] The reaction of the dichlorophosphazene oligomers with said
two alkali metal salts is carried out at a temperature between room
temperature and about 150.degree. C., in a solvent such as an
aromatic hydrocarbon (e.g., toluene) or a halogenated aromatic
hydrocarbon (e.g., chlorobenzene).
[0055] The terminal groups X and Y in the formula (2) vary in
accordance with the reaction conditions and other factors. If the
reaction is carried out under ordinary conditions, e.g., under mild
conditions in a non-aqueous system, the resulting product will have
a structure wherein X is --N.dbd.P(OPh).sub.3 and Y is
--P(OPh).sub.4. If the reaction is carried out under such
conditions that moisture or an alkali metal hydroxide is present in
the reaction system, or under so severe conditions that a
rearrangement reaction occurs, the resulting product will have a
structure wherein X is --N.dbd.P(OPh).sub.3 and Y is --P(OPh).sub.4
and additionally a structure wherein X is --N.dbd.P(O)OPh and Y is
--P(O)(OPh).sub.2.
[0056] The crosslinked phenoxyphosphazene compound of the invention
is thus obtained. The decomposition temperature of the crosslinked
phenoxyphosphazene compound of the invention is usually in the
range of 250 to 350.degree. C.
[0057] In the above process, if the dichlorophosphazene oligomers
are reacted only with the alkali metal salt of phenol and is not
reacted with the alkali metal salt of the aromatic dihydroxy
compound, a cyclic phosphazene compound of the formula (1) or a
straight-chain phosphazene compound of the formula (2) is produced.
On the other hand, when the alkali metal salt of the aromatic
dihydroxy compound is used in addition to the alkali metal salt of
phenol, there is provided the crosslinked phenoxyphosphazene
compound of the invention, wherein part of the phenyl groups in the
cyclic phosphazene compound of the formula (1) and/or the
straight-chain phosphazene compound of the formula (2) are
substituted by the crosslinking groups.
[0058] The proportion of the phenyl groups of the crosslinked
phenoxyphosphzene compound of the invention is 50 to 99.9%,
preferably 70 to 90%, based on the total amount of the phenyl
groups in the phosphazene compound of the formula (1) and/or
phosphazene compound of the formula (2).
[0059] The crosslinked phenoxyphosphazene compound of the invention
is isolated and purified from the reaction mixture by a
conventional isolation method such as washing, filtration, drying
or the like.
[0060] Flame Retardant
[0061] (a) Flame Retardant A
[0062] Flame retardant A comprises the crosslinked
phenoxyphosphazene compound of the present invention.
[0063] (b) Flame Retardant B
[0064] Flame retardant B will be described below.
[0065] The cyclic phosphazene compounds of the formula (1) and the
straight-chain phosphazene compounds of the formula (2) are known
compounds. These phosphazene compounds are disclosed in, for
example, James E. Mark, Harry R. Allcock, Robert West, "Inorganic
Polymers" Pretice-Hall International, Inc., 1992, pp. 61-140.
[0066] The cyclic phosphazene compound of the formula (1) and the
straight-chain phosphazene compound of the formula (2) can be
produced by, for example, following the above process for producing
the crosslinked phenoxyphosphazene compound except that the alkali
metal salt of the aromatic dihydroxy compound is not used.
[0067] The obtained phosphazene compound is isolated and purified
from the reaction mixture by a conventional isolation method such
as washing, filtration, drying or the like.
[0068] Specific examples of the cyclic phosphazene compounds of the
formula (1) include phosphazene compounds in which phenoxy groups
are substituted in a mixture of cyclic and straight-chain
chlorophosphazenes wherein n is an integer of 3 to 25, e.g.,
hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene and
the like, prepared by reacting ammonium chloride and phosphorus
pentachloride at 120 to 130.degree. C.; and
hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene
and decaphenoxycyclopentaphosphazene and like cyclic phosphazene
compounds obtained by isolating, from the above mixture of
chlorophosphazenes, hexachlorocyclotriphosphazene,
octachlorocyclotetraphosphazene, decachlorocylopentaphosphazene or
the like, and substituting the isolated product by phenoxy
groups.
[0069] Specific examples of the straight-chain phosphazene
compounds of the formula (2) include those obtained by heating
hexachlorocyclotriphosp- hazene to 220 to 250.degree. C. for
ring-opening polymerization and substituting, by phenoxy groups,
the resulting dichlorophosphazene wherein n is an integer of 3 to
1000.
[0070] Among these examples, phosphazene compounds obtained by
substituting, by phenoxy groups, a mixture of cyclic or
straight-chain chlorophosphazenes wherein n is an integer of 3 to
25.
[0071] (c) Flame Retardant C
[0072] Flame retardant C will be described below.
[0073] As the phosphazene compound of the formula (3), preferred
are, for example, cyclic phosphazene compounds wherein R.sup.1 is a
cyano-substituted phenyl group, R.sup.2 is an alkyl group having 1
to 8 carbon atoms, a group 8
[0074] or a group 9
[0075] and R.sup.3 is a hydrogen atom, alkyl group having 1 to 4
carbon atoms or allyl group, p is 0.3 to 1.7, and q is 0.3 to
0.7.
[0076] As the phosphazene compounds represented by the formula (4),
preferred are, for example, straight-chain phosphazene compounds
wherein R.sup.1 is a cyano-substituted phenyl group, R.sup.2 is an
alkyl group having 1 to 8 carbon atoms, a group 10
[0077] or a group 11
[0078] R.sup.3 is a hydrogen atom, alkyl group having 1 to 4 carbon
atoms or allyl group, p is 0.3 to 1.7, and q is 0.3 to 0.7.
[0079] The cyano-substituted phenyl group represented by R.sup.1
is, for example, 2-cyanophenyl, 3-cyanophenyl or 4-cyanophenyl
group, and so on.
[0080] More specifically, the phosphazene compounds represented by
the formulas (3) and (4) include cyclic phosphazene compounds or
straight-chain phosphazene compounds, such as cyclotriphosphazene,
cyclotetraphosphazene and cyclopentaphosphazene, each substituted
by both cyanophenoxy and phenoxy groups.
[0081] Specific examples of cyclic phosphazene compounds
substituted by both cyanophenoxy and phenoxy groups include
monocyanophenoxypentaphenoxy- cyclotriphosphazene,
dicyanophenoxytetraphenoxycyclotriphosphazene,
tricyanophenoxytriphenoxycyclotriphosphazene,
tetracyanophenoxydiphenoxyc- yclotriphosphazene,
pentacyanophenoxymonophenoxycyclotriphosphazene and like
cyclotriphosphazene compounds;
monocyanophenoxyheptaphenoxycyclotetr- aphosphazene,
dicyanophenoxyhexaphenoxycyclotetraphosphazene,
tricyanophenoxypentaphenoxycyclotetraphosphazene,
tetracyanophenoxytetrap- henoxycyclotetraphosphazene,
pentacyanophenoxytriphenoxycyclotetraphosphaz- ene,
hexacyanophenoxydiphenoxycyclotetraphosphazene,
heptacyanophenoxymonophenoxycyclotetraphosphazene and like
cyclotetraphosphazene compounds; and cyclopentaphosphazene
compounds substituted by both cyanophenoxy and phenoxy groups.
[0082] Examples of the straight-chain phosphazene compounds include
those substituted by both cyanophenoxy and phenoxy groups.
[0083] These phosphazene compounds may be used singly or in
combination.
[0084] Among the above phosphazene compounds, phosphazene oligomers
(mixtures of cyclic and straight-chain phosphazene oligomers)
substituted by both cyanophenoxy and phenoxy groups are preferred
in view of their production processes and availability.
Particularly preferred are phosphazene oligomers wherein the ratio
of cyanophenoxy group content to the phenoxy group content is 1:7
to 7:1.
[0085] The cyanophenoxy group-containing phosphazene compound (a
phosphazene compound represented by the formula (3) or (4)) of the
present invention can be produced by various processes.
[0086] Usable starting materials for the production of the
cyanophenoxy group-containing phosphazene compound include
hexachlorocyclotriphosphaze- ne, octachlorocyclotetraphosphazene
and like cyclic or straight-chain phosphazene compounds obtained
by, for example, reacting ammonium chloride and phosphorus
pentachloride at 120 to 130.degree. C., as illustrated by the
following Reaction Scheme-1. Solvents usable in this reaction
include tetrachloroethane, chlorobenzene and the like. 12
[0087] wherein n is as defined above.
[0088] Also usable as starting materials are straight-chain
dichlorophosphazenes obtained by isolating
hexachlorocyclotriphosphazene from the mixture of cyclic and
straight-chain phosphazene compounds prepared by the process shown
by Reaction Scheme-1, heating the hexachlorocyclotriphosphazene at
220 to 250.degree. C. for ring-opening polymerization (see Reaction
Scheme-2). 13
[0089] wherein n is as defined above.
[0090] The cyanophenoxy group-containing phosphazene compound of
the invention can be produced by, for example, a process comprising
reacting the cyclic or straight-chain phosphazene compound obtained
above, with a mixture consisting of, in a desired ratio, an alkali
metal salt of a cyanophenol and an alkali metal salt of at least
one member selected from the group consisting of phenols (including
phenols substituted on the aromatic ring by an alkyl group having 1
to 10 carbon atoms, allyl group or phenyl group), naphthols
(including naphthols substituted on the aromatic ring by an alkyl
group having 1 to 10 carbon atoms, allyl group or phenyl group) and
alcohols having 1 to 18 carbon atoms (these will hereinafter be
referred to as "phenolic compound").
[0091] For example, a mixture of a cyanophenol, a phenolic compound
and sodium hydroxide in a desired ratio is subjected to dehydration
reaction to prepare sodium salt of the cyanophenol and sodium salt
of the phenolic compound. This dehydration reaction is performed
merely for removing water, and can be carried out with or without
use of a solvent. The solvent, when used, may be benzene, toluene,
xylene, chlorobenzene or the like. Azeotropic distillation using
such a solvent may increase the dehydration efficiency in some
cases. Subsequently, the cyclic or straight-chain phosphazene
compound obtained above is added to the mixture of sodium salt of
the cyanophenol and sodium salt of the phenolic compound, and the
resulting mixture is subjected to substitution reaction by heating
at 50 to 150.degree. C. for 1 to 24 hours, giving the desired
cyanophenoxy group-containing phosphazene compound. 14
[0092] wherein n is as defined above, and n=a+b+c.
[0093] The desired cyanophenoxy group-containing phosphazene
compound can be obtained by dehydration reaction and substitution
reaction, as described above. From the viewpoint of efficiency of
these reactions, chlorobenzene is selected as the solvent. When
chlorobenzene is used as the solvent, the substitution reaction is
completed by performing the reaction at the reflux temperature of
chlorobenzene for about 12 hours.
[0094] Other production processes can be also employed which
include a process comprising reacting an isolated and purified
cyclic or straight-chain dichlorophosphazene with the alkali metal
salt of a cyanophenol and the alkali metal salt of the phenolic
compound; or a process comprising reacting the dichlorophosphazene
oligomer consecutively with the alkali metal salt of a cyanophenol
and the alkali metal salt of the phenolic compound.
[0095] The cyanophenoxy-containing phosphazene compound obtained
above is isolated and purified from the reaction mixture by a
conventional isolation method such as washing, filtration, drying
or the like.
[0096] Flame-Retardant Resin Composition
[0097] The flame-retardant resin composition of the present
invention comprises a thermoplastic resin or a thermosetting resin,
and flame retardant A, B or C. Hereinafter, the term
"flame-retardant resin composition of the present invention"
collectively refers to the resin compositions containing a
thermoplastic resin or a thermosetting resin as a matrix, unless
otherwise indicated.
[0098] (a) Thermoplastic Resin
[0099] A wide variety of resins known in the art may be used as the
thermoplastic resin for use in the present invention. Such resins
are, for example, polyethylene, polypropylene, polyisoprene,
polyesters (polyethylene terephthalate, polybutylene terephthalate,
etc.), polybutadiene, styrene resin, impact-resistant polystyrene,
acrylonitrile-styrene resin (AS resin),
acrylonitrile-butadiene-styrene resin (ABS resin), methyl
methacrylate-butadiene-styrene resin (MBS resin), methyl
methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin),
acrylonitrile-acrylic rubber-styrene resin (AAS resin),
polymethyl(meth)acrylate, polycarbonate, modified polyphenylene
ether (PPE), polyamide, polyphenylene sulfide, polylmide, polyether
ether ketone, polysulfone, polyarylate, polyether ketone, polyether
nitrile, polythioether sulfone, polyether sulfone,
polybenzimidazol, polycarbodiimide, polyamideimide, polyetherimide,
liquid crystalline polymer, composite plastics and the like.
[0100] Among these thermoplastic resins, polyester, ABS resin,
polycarbonate, modified polyphenylene ether, polyamide, etc., are
preferably used.
[0101] In the present invention, the thermoplastic resins may be
used singly or in combination.
[0102] (b) Thermosetting Resin
[0103] A wide variety of resins known in the art may be used as the
thermosetting resin for use in the present invention. Such
thermosetting resins include polyurethane, phenol resin, melamine
resin, urea resin, unsaturated polyester resin, diallyl phthalate
resin, silicon resin and epoxy resin.
[0104] Among these thermosetting resins, particularly preferable
are polyurethane, phenolic resin, melamine resin, epoxy resin,
etc.
[0105] The epoxy resins are not limited to any specific types and
may be selected from a wide variety of epoxy resins known in the
art. Examples of such epoxy resins include bisphenol-A type epoxy
resin, bisphenol-F type epoxy resin, bisphenol-AD type epoxy resin,
phenol novolac type epoxy resin, cresol novolac type epoxy resin,
cycloaliphatic epoxy resin, glycidyl ester-based resin, glycidyl
amine-based epoxy resin, heterocyclic epoxy resin, urethane
modified epoxy resin and brominated bisphenol-A type epoxy
resin.
[0106] In the present invention, the thermosetting resins may be
used singly or in combination.
[0107] The amount of the flame retardant A, flame retardant B or
flame retardant C relative to the thermoplastic resin or
thermosetting resin is not particularly limited, but is 0.1-100 wt.
parts, preferably 1-50 wt. parts, more preferably 5-30 wt. parts,
based on 100 wt. parts of the thermoplastic resin or thermosetting
resin.
[0108] (c) Inorganic Filler
[0109] The flame-retardant resin composition of the present
invention may contain inorganic fillers to further enhance dripping
preventing effect.
[0110] Conventionally, these inorganic fillers have been used
mainly as reinforcements for improving the mechanical properties of
resins. However, the inventors of the present invention have found
that said flame retardants and inorganic fillers, when both were
present in a resin, act synergistically and therefore are effective
for improving the flame-retardant effects of the flame retardant,
especially dripping preventive effect, as well as the mechanical
properties of the resin.
[0111] When said flame retardant and the inorganic filler are both
present in a resin, the surface layer of the resin becomes dense
and reinforced. This prevents the diffusion of gases formed during
combustion, and induces the formation of a char layer from the
flame retardant, resulting in high flame-retardancy. In particular,
it is essential to use the flame retardant B in combination with
inorganic fillers.
[0112] The inorganic fillers may be known fillers for resins.
Examples of such fillers include mica, kaolin, talc, silica, clay,
barium sulfate, barium carbonate, calcium carbonate, calcium
sulfate, calcium silicate, titanium oxide, glass beads, glass
balloons, glass flakes, glass fibers, fibrous alkali metal
titanates (potassium titanate fibers, etc.), fibrous transition
metal borates (aluminum borate fibers, etc.), fibrous alkaline
earth metal borates (magnesium borate fibers, etc.), zinc oxide
whisker, titanium oxide whisker, magnesium oxide whisker, gypsum
whisker, aluminum silicate (mineralogical name: mullite) whisker,
calcium silicate (mineralogical name: wollastonite) whisker,
silicon carbide whisker, titanium carbide whisker, silicon nitride
whisker, titanium nitride whisker, carbon fibers, alumina fibers,
alumina-silica fibers, zirconia fibers, quartz fibers and the
like.
[0113] Among these inorganic fillers, it is preferred to use
fillers having shape anisotropy such as fibrous fillers, e.g.,
fibrous alkali metal titanates, fibrous transition metal borates,
fibrous alkaline earth metal borates, zinc oxide whisker, titanium
oxide whisker, magnesium oxide whisker, aluminum silicate whisker,
calcium silicate whisker, silicon carbide whisker, titanium carbide
whisker, silicon nitride whisker, titanium nitride whisker, and
mica. More preferable are fibrous alkali metal titanates, fibrous
transition metal borates, fibrous alkaline earth metal borates,
titanium oxide whisker, calcium silicate whisker and the like.
[0114] These inorganic fillers may be used singly or in
combination.
[0115] Among these inorganic fillers, those having shape anisotropy
such as whiskers and mica are preferably used.
[0116] Examples of the potassium titanate fibers among inorganic
fillers include potassium hexatitanate fibers having an average
fiber diameter of about 0.05-2 .mu.m and an average fiber length of
about 1-500 .mu.m, and preferably having an aspect ratio (fiber
length/fiber diameter) of 10 or greater. Among them, potassium
hexatitanate fibers having a pH ranging from 6 to 8.5 are more
preferable. A pH of potassium titanate fibers mentioned herein
refers to a pH, as determined at 20.degree. C., of 1.0 wt. % of an
aqueous suspension of potassium titanate fibers (in deionized
water) which was stirred for 10 minutes. If the pH of the potassium
titanate fibers is much higher than 8.5, physical properties of the
resin and resistance to discoloration with heat may be
disadvantageously decreased. On the other hand, when the pH is far
below 6, the strength of the resulting resin composition is not
effectively increased, and the residual acid may corrode processing
machines and metallic molds. Hence it is not favorable.
[0117] The amount of the inorganic filler relative to the
thermoplastic resin or thermosetting resin is not particularly
limited. In view of a balance of improvements in mechanical
properties and flame retardancy, however, the amount is 0.01-50 wt.
parts, preferably 1-20 wt. parts, based on 100 wt. parts of the
thermoplastic resin or thermosetting resin.
[0118] (d) Organic Phosphorus Compound Free of Halogen
[0119] The flame-retardant resin composition of the present
invention may contain an organic phosphorus compound free of
halogen (hereinafter referred to as "halogen-free organic
phosphorus compounds") to further improve the flame retardancy
thereof.
[0120] It is known that halogen-free organic phosphorus compounds
are capable of improving the flame retardancy of the matrix such as
resins. However, the inventors of the present invention found that
when the specific phosphazene compounds for use in the present
invention is used in combination with the halogen-free organic
phosphorus compound, the flame-retardant effect is significantly
increased due to synergism. The reason for this remarkable effect
still remains to be elucidated. However, it is presumably because
the conjoint use of these two compounds serves to form an expansion
layer along with a char layer on the surface of the resin
composition during combustion, and these layers suppress the
diffusion of decomposition products and heat transfer.
[0121] A wide variety of halogen-free organic phosphorus compounds
known in the art may be used in the present invention. For example,
useful compounds include those disclosed in Japanese Examined
Patent Publication No. 19003/1994, Japanese Unexamined Patent
Publication No. 115262/1990, Japanese Unexamined Patent Publication
No. 1079/1993, Japanese Unexamined Patent Publication No.
322277/1994, the specification of U.S. Pat. No. 5,122,556, etc.
[0122] Specific examples of the halogen-free phosphorus compound
include trimethyl phosphate, triethyl phosphate, tributyl
phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl
phosphate, trixylyl phosphate, cresyl diphenyl phosphate, xylyl
diphenyl phosphate, tolyl dixylyl phosphate, tris(nonylphenyl)
phosphate, (2-ethylhexyl)diphenyl phosphate and like phosphates;
resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate and
like hydroxyl-containing phosphates; resorcinol bis(diphenyl
phosphate), hydroquinone bis(diphenyl phosphate), bisphenol-A
bis(diphenyl phosphate), bisphenol-S bis(diphenyl phosphate),
resorcinol bis(dixylyl phosphate), hydroquinone bis(dixylyl
phosphate), bisphenol-A bis(ditolyl phosphate), biphenol-A
bis(dixylyl phosphate), bisphenol-S bis(dixylyl phosphate) and like
condensed phosphate compounds; and trilauryl phosphine, triphenyl
phosphine, tritolyl phosphine, triphenyl phosphine oxide, tritolyl
phosphine oxide and like phosphines or phosphine oxide
compounds.
[0123] Among these halogen-free organic phosphorus compounds,
preferable are triphenyl phosphate, tricresyl phosphate, trixylyl
phosphate, resorcinol bis(diphenyl phosphate), hydroquinone
bis(diphenyl phosphate), bisphenol-A bis(diphenyl phosphate),
resorcinol bis(dixylyl phosphate), hydroquinone bis(dixylyl
phosphate), bisphenol-A bis(ditolyl phosphate) and like condensed
phosphate compounds; and triphenyl phosphine oxide, tritolyl
phosphine oxide and like phosphine oxide compounds. In particular,
preferable are the compounds such as triphenyl phosphate,
resorcinol bis(diphenyl phosphate), resorcinol bis(dixylyl
phosphate), triphenyl phosphine oxide and the like.
[0124] These halogen-free organic phosphorus compounds may be used
singly or in combination.
[0125] These halogen-free organic phosphorus compounds are more
effective when used in combination with flame retardant A or flame
retardant B.
[0126] The amount of the halogen-free organic phosphorus compound
relative to the thermoplastic resin or thermosetting resin is not
particularly limited. In view of a balance of improvements in
mechanical properties and flame retardancy, however, the amount of
the halogen-free organic phosphorus compound is 0.1-50 wt. parts,
preferably 1-30 wt. parts, based on 100 wt. parts of the
thermoplastic resin or thermosetting resin. The amount of the flame
retardant to be added thereto is 0.1-50 wt. parts, preferably 5-30
wt. parts, based on 100 wt. parts of the thermoplastic resin or
thermosetting resin.
[0127] (e) Fluorine-Containing Resin
[0128] Further, a fluorine-containing resin may be incorporated
into the flame-retardant resin composition of the present invention
containing a thermoplastic resin as a matrix within the range which
does not adversely affect the object of the present invention. The
amount of the fluorine-containing resin to be used is not
particularly limited, but is 0.01-2.5 wt. parts, preferably 0.1-1.2
wt. parts, based on 100 wt. parts of the thermoplastic resins.
[0129] A wide variety of fluorine-containing resins known in the
art may be used in the present invention. The examples include
polytetrafluoroethylene resin (PTFE),
tetrafluoroethylene-hexafluoropropy- lene copolymer resin (FEP),
tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin
(PFA), tetrafluoroethylene-ethylene copolymer resin (ETFE),
polychlorotrifluoroethylene resin (CTFE) and polyvinylidene
fluoride (PVdF). Among these, PTFE is particularly preferable. By
the addition of the fluorine-containing resins, the dripping
preventing effect is produced in a more pronounced manner.
[0130] Fluorine-containing resins are more effective when used in
combination with flame retardant A.
[0131] (f) Other Additives
[0132] The flame-retardant composition of the invention is a resin
composition which does not contain a halogen (e.g., chlorine,
bromine)-containing compound as a flame retardant component but can
produce excellent flame retardant effects. One or more flame
retardant additives conventionally used may be incorporated into
the composition insofar as they do not adversely affect the
excellent effects.
[0133] The flame retardant additive for use is not limited, and
usually any additive that produces flame retardant effects can be
used. Examples of useful flame retardant additives are metal oxides
such as zinc oxide, tin oxide, iron oxide, molybdenum oxide, copper
oxide and manganese dioxide; metal hydroxides such as aluminum
hydroxide, magnesium hydroxide, zirconium hydroxide, oxalic
acid-treated aluminum hydroxide and nickel compound-treated
magnesium hydroxide; alkali metal salts or alkaline earth metal
salts such as sodium carbonate, calcium carbonate, barium carbonate
and sodium alkylsulfonate; organic chlorine compounds or organic
bromine compounds such as chlorinated paraffin,
perchlorocyclopentadecane, tetrabromobisphenol-A; epoxy resins,
bis(tribromophenoxy)ethane and bis(tetrabromophthalimino)ethane;
antimony compounds such as antimony trioxide, antimony tetraoxide,
antimony pentaoxide and sodium antimonate; red phosphorus,
halogen-containing phosphoric ester compounds, halogen-containing
condensed phosphoric ester compounds or phosphonic acid ester
compounds, nitrogen-containing compounds such as melamine, melamine
cyanurate, melamine phosphate, melam, melem, mellon,
succinoguanamine, guanidine sulfamate, ammoninum sulfate, ammonium
phosphate, ammonium polyphosphate and alkylamine phosphate; boron
compounds such as zinc borate, barium methaborate and ammonium
borate; silicon compounds such as silicone polymers and silica; and
thermally expansive graphite.
[0134] These flame retardant additives can be used singly or in
combination.
[0135] Incorporating a trace amount of a Lewis acid into
flame-retardant resin compositions containing flame retardant C of
the invention imparts further improved heat resistance and flame
retardancy to the resin. Useful Lewis acids include a wide variety
of those known, for example, zinc chloride, ferric chloride and the
like. These Lewis acids can be used singly or in combination, and
the amount of the Lewis acid to be incorporated is usually about
0.01 to about 0.6 wt. parts, based on the total weight of the
flame-retardant resin composition.
[0136] Further, one or more conventional resin additives may be
incorporated into the flame-retardant composition of the invention,
insofar as they do not adversely affect the excellent properties.
Examples of useful resin additives include flame retardants other
than the aforementioned ones, dripping inhibitors (dropping
inhibitors), UV absorbers, light stabilizers, antioxidants, light
screens, metal deactivators, quenching agents, heat resistance
stabilizers, lubricants, mold releasing agents, coloring agents,
antistatic agents, antiaging agents, plasticizers, impact strength
improving agents and compatibilizers.
[0137] The UV absorber is a component for absorbing light energy
and releasing the absorbed light energy harmlessly in the form of
heat energy by the transformation thereof into a keto form through
intramolecular proton transfer (in the case of benzophenones and
benzotriazoles) or by cis-trans isomerization (in the case of
cyanoacrylates). Specific examples of UV absorbers include
2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and
5,5'-methylenebis(2-hydroxy-4-methoxyb- enzophenone);
2-(2'-hydroxyphenyl)benzotriazoles such as
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphen- yl)benzotriazole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3'-t-5'-methylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole and
2,2'-(methylenebis(4-t-octyl-6-benzotriazolyl)phenol; benzoates
such as phenylsalicylate, resorcinol monobenzoate,
2,4-di-t-butylphenyl-3',5'-di-- t-butyl-4'-hydroxybenzoate and
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and substituted oxalic
anilide such as 2-ethyl-2'-ethoxy oxalic anilide and
2-ethoxy-4'-dodecyl oxalic anilide; cyanoacrylates such as
ethyl-.alpha.-cyano-.beta.,.beta.-diphenylacrylate and
methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate.
[0138] The light stabilizer is a component for decomposing
hydroperoxides produced by light energy into stable N--O.radical,
N--OR or N--OH, thereby providing light stability. For example,
hindered amine light stabilizers can be used. Specific examples of
light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl-stearate,
1,2,2,6,6-pentamethyl-4-piperid- ylstearate,
2,2,6,6-tetramethyl-4-piperidylbenzoate,
bis(2,2,6,6-tetramethyl-4-piperidylsebacate,
bis(1,2,2,6,6-pentamethyl-4-- piperidyl)-sebacate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-but- ane
tetracarboxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4--
butanetetracarboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl-
)-1,2,3,4-butanetetra-carboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)--
2-butyl-2-(3',5'-di-t-butyl-4-hydroxybenzyl)malonate,
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-piperidinol/diethyl
succinate polycondensate,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibro- moethane
polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexa-
ne/2,4-dichloro-6-t-octylamino-s-triazine polycondensate,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpho-
lino-s-triazine polycondensate, and the like.
[0139] The antioxidant is a component for stabilizing peroxide
radicals, such as hydroperoxy radicals, which are formed upon heat
with molding or light exposure, or for decomposing generated
peroxides, such as hydroperoxides. Examples of antioxidants include
hindered phenol type antioxidants and peroxide decomposers. The
hindered phenol type antioxidant acts as a radical chain-transfer
inhibitor, and the peroxide decomposer decomposes peroxides
generated in the reaction system into a stable alcohol, and
prevents autoxidation.
[0140] Specific examples of hindered phenol type antioxidants
include 2,6-di-t-butyl-4-methylphenol, styrenated phenol,
n-octadecyl-3-(3,5-di-t- -butyl-4-hydroxylphenyl)propionate,
2,2'-methylene bis(4-methyl-6-t-butylp- henol),
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacr-
ylate,
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyla-
crylate, 4,4'-butylidene bis(3-methyl-6-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol), alkylated bisphenol,
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)proprionate]methane,
3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimeth-
ylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like.
[0141] Examples of peroxide decomposers include organic phosphorus
type peroxide decomposers such as tris(nonylphenyl)phosphite,
triphenyl phosphite and tris(2,4-di-t-butylphenyl)phosphite; and
organic thio type peroxide decomposers such as
dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate,
distearyl-3,3'-thiodipropionate,
pentaerythrityltetrakis(3-laurylthiopropionate),
ditridecyl-3,3'-thiodipr- opionate and 2-mercaptobenzimidazole.
[0142] The light screen is a component for preventing light from
penetrating into the bulk of a polymer. Specific examples of light
screens include titanium oxide having a rutile structure
(TiO.sub.2), zinc oxide (ZnO), chromium oxide (Cr.sub.2O.sub.3) and
cerium oxide (CeO.sub.2).
[0143] The metal deactivator is a component for deactivating heavy
metal ions in the resin by forming a chelate compound. Specific
examples of metal deactivators include benzotriazoles and
derivatives thereof (e.g. 1-hydroxybenzotriazole and the like).
[0144] The quenching agent is a component for deactivating
photo-excited hydroperoxides and functional groups such as carbonyl
groups in the polymer due to energy transfer. Useful quenching
agents include organic nickel and the like.
[0145] In order to impart improved antifogging, antifungal,
antimicrobial or like properties, other conventionally known
additives may also be added.
[0146] Production of Flame-Retardant Resin Compositions of the
Invention
[0147] The flame-retardant resin composition of the invention can
be produced by mixing a thermoplastic resin or a thermosetting
resin and the aforementioned frame retardant, optionally toghether
with an inorganic filler, a halogen-free organic phosphorus
compound, a fluorine-containing resin, one or more flame retardant
additives and other additives, in prescribed or proper amounts,
followed by mixing and kneading the mixture by a conventional
method. For example, the mixture of components in the form of
powder, beads, flakes or pellets is kneaded using an extruder,
e.g., a uniaxial extruder or a biaxial extruder, or a kneader,
e.g., Banbury mixer, a pressure kneader or a two-roll mill, giving
a resin composition of the invention. When a liquid needs to be
added, a conventional liquid injection device can be used and the
mixture can be kneaded using the aforementioned extruder, kneader
or the like.
[0148] Flame-Retardant Resin Moldings of the Invention
[0149] The flame-retardant resin composition of the invention can
be molded into flame-retardant resin moldings. For example, the
resin composition can be molded into resin plates, sheets, films,
special shapes or like extrusion moldings of various shapes using a
conventional molding method such as press molding, injection
molding or extrusion molding, or can be molded into a resin plate
of two- or three-layered structure using a coextruder.
[0150] The thus-obtained flame-retardant resin composition and
flame-retardant resin moldings of the invention can find wide
application in various industrial fields, such as electrical,
electronics or telecommunication industries, agriculture, forestry,
fishery, mining, construction, foods, fibers, clothing, medical
services, coal, petroleum, rubber, leather, automobiles, precision
machinery, timber, furniture, printing, musical instruments, and
the like.
[0151] Stated more specifically, the flame-retardant resin
composition and flame-retardant resin moldings of the invention can
be used for business or office automation equipment, such as
printers, personal computers, word processors, keyboards, PDA
(personal digital assistants), telephones, facsimile machines,
copying machines, ECR (electronic cash registers), desktop
electronic calculators, electronic databooks, electronic
dictinaries, cards, holders and stationery; electrical household
appliances and electrical equipment such as washing machines,
refrigerators, cleaners, microwave ovens, lighting equipment, game
machines, irons and kotatsu (low, covered table with a heat source
underneath); audio-visual equipment such as TV, VTR, video cameras,
radio cassette recorders, tape recorders, mini discs, CD players,
speakers and liquid crystal displays; and electric or electronic
parts and telecommunication equipment, such as connectors, relays,
condensers, switches, printed circuit boards, coil bobbins,
semiconductor sealing materials, electric wires, cables,
transformers, deflecting yokes, distribution boards, and clocks and
watches.
[0152] Further, the flame-retardant resin composition and
flame-retardant resin moldings can be widely used for the following
applications: materials for automobiles, vehicles, ships, aircrafts
and constructions, such as seats (e.g., padding, outer materials),
belts, ceiling covering, convertible tops, arm rests, door trims,
rear package trays, carpets, mats, sun visors, wheel covers,
mattress covers, air bags, insulation materials, hangers, hand
straps, electric wire coating materials, electrical insulating
materials, paints, coating materials, overlaying materials, floor
materials, corner walls, deck panels, covers, plywoods, ceiling
boards, partition plates, side walls, carpets, wall papers, wall
covering materials, exterior decorating materials, interior
decorating materials, roofing materials, sound insulating panels,
thermal insulation panels and window materials; and living
necessities and sporting goods such as clothing, curtains, sheets,
plywoods, laminated fiber boards, carpets, entrance mats, seats,
buckets, hoses, containers, glasses, bags, cases, goggles, skies,
rackets, tents and musical instruments.
BEST MODE FOR CARRYING OUT THE INVENTION
[0153] The present invention will be specifically described below
with reference to Synthesis examples, Examples and Comparative
Examples. In the following description, parts and % mean weight
parts and weight %, respectively, unless otherwise specified. In
addition, Ph- means phenyl group and -Ph- means phenylene
group.
SYNTHESIS EXAMPLE 1
Synthesis of Compound A; Phenoxyphosphazene Compound Having
Paraphenylene-crosslinked Structure
[0154] Phenol (2.04 moles, 196 g) and 2.04 moles (82 g) of sodium
hydroxide were subjected to azeotropic dehydration with use of
toluene to prepare about 1200 g of a 20% solution of sodium
phenolate in toluene.
[0155] In parallel with the above reaction, 580 g of a 20% solution
containing 115.9 g of dichlorophosphazene oligomers (a mixture of
58.57% of trimer, 12.26% of tetramer, 11.11% of pentamer and
hexamer, 2.82% of heptamer, 12.04% of octamer and higher oligomers)
in chlorobenzene was placed in a 4-necked, 2-liter flask, and a 10%
solution containing 0.15 mole (18.3 g) of separately prepared
hydroquinone dilithium salt in toluene was added dropwise thereto
with stirring. After the dropwise addition, the mixture was
subjected to a reaction with stirring at 50.degree. C. for 5 hours.
Subsequently, about 1200 g of the previously prepared 20% solution
of sodium phenolate in toluene was added dropwise thereto, and the
resulting mixture was subjected to a reaction with stirring at
100.degree. C. for 8 hours.
[0156] After the reaction was completed, the reaction mixture was
concentrated and poured into 3 liters of a mixture of
water/methanol (1/1 by volume) with stirring, and the mixture was
neutralized with dilute sulfuric acid and filtered. The obtained
product was washed twice with 3 liters of a mixture of
water/methanol (1/1 by volume), separated by filtration, and dried
in a vacuum with heating at 80.degree. C. at a pressure of 20 mmHg
for 11 hours to give 220 g of a pale yellow powder.
[0157] The crosslinked phenoxyphosphazene compound obtained above
did not show a definite melting point, and showed a decomposition
starting temperature of 305.degree. C. as determined by TG/DTA
analysis. It was found from the phosphorus content and CHN
elemental analysis data that approximate composition of this
crosslinked phenoxyphosphazene compound was
[N.dbd.P(--O-p-Ph-O--).sub.0.15(--O-Ph).sub.1.7].
SYNTHESIS EXAMPLE 2
Preparation of Compound B: Phenoxyphosphazene Compound Having
2,2-bis(p-oxyphenyl)propane-crosslinked Structure
[0158] A 86.7 g-quantity of bisphenol-A (0.38 mole) and 460 ml of
tetrahydrofuran (THF) were placed in a 4-necked, 2-liter flask, and
while maintaining the internal temperature at 19.degree. C., 3.5 g
(0.5 mole) of Li metal in the form of cut pieces was added thereto
with stirring. After the completion of the addition, the
temperature was elevated to 61.degree. C. over 1 hour, and the
stirring was continued for 4 hours at 61.degree. C. to 68.degree.
C. After the reaction was completed, the resulting reaction mixture
containing lithium salt of bisphenol-A became a white slurry
form.
[0159] A 215.6 g-quantity of phenol (2.25 moles) and 500 ml of
toluene were placed in a 4-necked, 3-liter flask, and while
maintaining the internal temperature at 25.degree. C., 34.5 g (1.5
moles) of sodium metal in the form of cut pieces was added thereto
with stirring. After completion of the addition, the temperature
was elevated to 77.degree. C. over 4 hours, and the stirring was
continued for 3 hours at 77.degree. C. to 113.degree. C. After the
reaction was completed, the reaction mixture containing sodium
phenolate became a white slurry form.
[0160] A 313.13 g (1.0 mole) quantity of dichlorophosphazene
oligomers (concentration 37.01%, monochlorobenzene solution, a
mixture of 58.57% of trimer, 12.26% of tetramer, 11.11% of pentamer
and hexamer, 2.82% of heptamer, 12.04% of octamer and higher
oligomers) was placed in a 4-necked, 5-liter flask, and while
maintaining the internal temperature at 20.degree. C., the solution
of lithium salt of bisphenol-A was added dropwise thereto over 1
hour with stirring, whereby the content became a pale yellow milk
form. Then, while maintaining the internal temperature at
20.degree. C., the sodium phenolate solution was added dropwise
thereto over 1 hour with strring, whereby the content became a
brown slurry form. After the dropwise addition, the stirring was
continued for 13 hours at 47.degree. C., whereby the content became
a pale brown slurry form.
[0161] After the reaction was completed, the reaction mixture was
concentrated, and the concentrate was washed three times with 3
liters of a 2% NaOH, filtered, washed three times with 3 liters of
a mixture of water/methanol (1/1 by volume), filtered, and
subjected to a vacuum drying with heating at 80.degree. C. at 20
mmHg for 11 hours to give a white powder.
[0162] Yield: 208.67 g
[0163] Yield based on dichlorophosphazene: 86.50%
[0164] The obtained compound had a hydrolyzable chlorine content of
0.93%, a decomposition temperature of 296.0.degree. C., and a 5%
weight loss temperature of 307.7.degree. C. It was found-from the
phosphorus content and CHN elemental analysis data that the
composition of the final product was
[N.dbd.P(--O-Ph-C(CH.sub.3).sub.2-Ph-O--).sub.0.25(--O-Ph).sub.1.50].
SYNTHESIS EXAMPLE 3
Preparation of Compound C: Phenoxyphosphazene Compound Having
m-phenylene-crosslinked Structure
[0165] Following the procedure of Synthesis Example 1 and using
resorcinol in place of hydroquinone, reaction and workup were
carried out, thereby giving a product represented by the formula
[N.dbd.P(--O-m-Ph-O--).sub.0.- 15(--O-Ph).sub.1.7] as a white
powder. This crosslinked phenoxyphosphazene compound did not show a
definite melting point, and showed a decomposition starting
temperature of 300.degree. C. as determined by TG/DTA analysis.
EXAMPLE 1
[0166] A flame-retardant resin composition was prepared by adding
15 parts of Compound A prepared in Synthesis Example 1 and 0.2 part
of PTFE to a resin comprising 75 parts of an aromatic polycarbonate
resin and 25 parts of ABS resin, mixing the components in a mixer,
and melting and kneading the mixture by means of a laboplasto
mill.
[0167] This composition was made into test pieces having a
thickness of 1/8 inch by a heat-press. The test pieces were
evaluated for flame retardancy according to the test method of
UL-94 and the heat distortion temperature thereof was measured
according to ASTM D-648.
[0168] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 108.degree. C. Juicing was not observed
during the molding processing of this resin composition.
EXAMPLE 2
[0169] A flame-retardant resin composition was prepared following
the procedure of Example 1 and using Compound B prepared in
Synthesis Example 2 in place of Compound A. Furthermore, following
the procedure of Example 1, test pieces were prepared therefrom,
and the evaluation of the flame retardancy thereof and measurement
of the heat distortion temperature thereof were carried out.
[0170] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 111.degree. C. Juicing was not observed
during the molding processing of this resin composition.
EXAMPLE 3
[0171] A flame-retardant resin composition was prepared following
the procedure of Example 1 and using Compound C prepared in
Synthesis Example 3 in place of Compound A. Furthermore, following
the procedure of Example 1, test pieces were prepared therefrom,
and the evaluation of the flame retardancy thereof and measurement
of the heat distortion temperature thereof were carried out.
[0172] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 106.degree. C. Juicing was not observed
during the molding processing of this resin composition.
EXAMPLE 4
[0173] A flame-retardant resin composition was prepared in the same
manner as in Example 1 except that PTFE was not added. Furthermore,
following the procedure of Example 1, test pieces were prepared
therefrom, and the evaluation of the flame retardancy thereof and
measurement of the heat distortion temperature thereof were carried
out.
[0174] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 109.degree. C. Juicing was not observed
during the molding processing of this resin composition.
COMPARATIVE EXAMPLE 1
[0175] A resin composition was prepared following the procedure of
Example 1 and using trixylyl phosphate in place of Compound A.
Furthermore, following the procedure of Example 1, test pieces were
prepared therefrom, and the evaluation of the flame retardancy
thereof and measurement of the heat distortion temperature thereof
were carried out.
[0176] As a result, the flame retardancy was V-2, and the heat
distortion temperature was 82.degree. C. Juicing was observed
during the molding processing of this resin composition.
REFERENCE EXAMPLE 1
[0177] Into a flask equipped with a stirrer, a condenser, a
dropping funnel and a thermometer was simultaneously fed 460 g (3
moles) of phosphorus oxychloride, 110 g (2 moles) of resorcinol,
94.1 g (1 mole) of phenol and 9 g of aluminum chloride (catalyst),
and the mixture was subjected to reaction until the temperature
became 150.degree. C., and then 564.6 g (6 moles) of phenol was
added thereto for effecting the reaction. The reaction mixture was
washed with water, and the triphenyl phosphate was distilled off in
a vacuum at a high temperature to give 515 g of a condensed
phosphoric acid diphenyl ester crosslinked by resocinol.
[0178] The condensed phosphoric acid diphenyl ester was a yellow
liquid, had an average molecular weight of 540, a P content of
10.6% and an acid value of 2.2.
COMPARATIVE EXAMPLE 2
[0179] A resin composition was prepared following the procedure of
Example 1 and using the condensed phosphoric acid diphenyl ester
crosslinked by resocinol (prepared in Reference Example 1) in place
of Compound A. Furthermore, following the procedure of Example 1,
test pieces were prepared therefrom, and the evaluation of the
flame retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0180] As a result, the flame retardancy was V-2, and the heat
distortion temperature was 89.degree. C. Juicing was observed
during the molding processing of this resin composition.
COMPARATIVE EXAMPLE 3
[0181] A resin composition was prepared in the same manner as in
Example 1 except that no flame retardant was added. Furthermore,
following the procedure of Example 1, test pieces were prepared
therefrom, and the evaluation of the flame retardancy thereof was
carried out, whereby the test piece burned, exhibiting no flame
retardancy at all. The heat distortion temperature of the test
piece was 111.degree. C.
EXAMPLE 5
[0182] To a resin comprising 70 parts of
poly(2,6-dimethyl-1,4-phenylene)o- xide and 30 parts of
rubber-modified impact resistant polystyrene was added 15 parts of
Compound A, and the components were mixed in a mixer. The mixture
was melted and kneaded by means of laboplasto mill to thereby give
a flame-retardant resin composition.
[0183] This resin composition was made into a test piece having a
thickness of 1/8 inch by a heat-press. The test piece was evaluated
for flame retardancy according to the test method of UL-94 and the
heat distortion temperature thereof was measured according to ASTM
D-648.
[0184] As a result, flame retardancy was V-0, and the heat
distortion temperature was 130.degree. C. Juicing was not observed
during the molding processing of this resin composition.
EXAMPLE 6
[0185] A flame-retardant resin composition was prepared following
the procedure of Example 5 and using Compound B in place of
Compound A. Furthermore, following the procedure of Example 5, test
pieces were prepared therefrom, and the evaluation of the flame
retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0186] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 131.degree. C. Juicing was not observed
during the molding processing of this resin composition.
EXAMPLE 7
[0187] A flame-retardant resin composition was prepared following
the procedure of Example 5 and using Compound C in place of
Compound A. Furthermore, following the procedure of Example 5, test
pieces were prepared therefrom, and the evaluation of the flame
retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0188] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 128.degree. C. Juicing was not observed
during the molding processing of this resin composition.
COMPARATIVE EXAMPLE 4
[0189] A resin composition was prepared following the procedure of
Example 5 and using triphenyl phosphate in place of Compound A.
Furthermore, following the procedure of Example 5, test pieces were
prepared therefrom, and the evaluation of the flame retardancy
thereof and measurement of the heat distortion temperature thereof
were carried out.
[0190] As a result, the flame retardancy was V-2, and the heat
distortion temperature was 110.degree. C. Juicing was observed
during the molding processing of this resin composition.
COMPARATIVE EXAMPLE 5
[0191] A resin composition was prepared following the procedure of
Example 5 and using the condensed phosphoric acid diphenyl ester
crosslinked by resocinol (prepared in Reference Example 1) in place
of Compound A. Furthermore, following the procedure of Example 5,
test pieces were prepared therefrom, and the evaluation of the
flame retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0192] As a result, the flame retardancy was V-2, and the heat
distortion temperature was 115.degree. C. Juicing was observed
during the molding processing of this resin composition.
COMPARATIVE EXAMPLE 6
[0193] A resin composition was prepared in the same manner as in
Example 5 except that no flame retardant was added. Furthermore,
following the procedure of Example 5, test pieces were prepared
therefrom, and the evaluation of the flame retardancy thereof was
carried out, whereby the test piece burned, exhibiting no flame
retardancy at all. The heat distortion temperature of test piece
was 133.degree. C.
EXAMPLE 8
[0194] A varnish was prepared by adding 10 parts of Compound A to
100 parts of bisphenol-A type epoxy resin. A glass cloth was
impregnated with the varnish and the impregnated glass cloth was
dried to prepare a prepreg. Subsequently, a prescribed number of
pieces of the prepregs were laminated on one another and the
laminate was subjected to a heat-press processing at 160.degree. C.
or above to give a glass epoxy board having a thickness of
{fraction (1/16)} inch, which was cut into test pieces of
predetermined size.
[0195] Evaluation of these test pieces for flame retardancy
according to the test method of UL-94 revealed that the flame
retardancy thereof was V-O. Juicing was not observed during the
heat-press processing of this resin composition.
EXAMPLE 9
[0196] Test pieces were prepared following the procedure of Example
8 and using Compound C in place of Compound A, and the evaluation
of the flame retardancy thereof was carried out.
[0197] As a result, the flame retardancy was V-0. Juicing was not
observed during the heat-press processing of this resin
composition.
COMPARATIVE EXAMPLE 7
[0198] Test pieces were prepared following the procedure of Example
8 and using the condensed phosphoric acid diphenyl ester
crosslinked by resocinol (prepared in Reference Example 1) in place
of Compound A, and the evaluation of the flame retardancy thereof
was carried out.
[0199] As a result, the flame retardancy was V-2. Juicing was
observed during the heat-press processing of this resin
composition.
COMPARATIVE EXAMPLE 8
[0200] Test pieces were prepared in the same manner as in Example 8
except that no flame retardant was added, and the evaluation of the
flame retardancy thereof was carried out. The test piece burned,
exhibiting no flame retardancy at all. EXAMPLES 10 TO 13
[0201] Flame retardancy tests were carried out following the
procedure of Example 1 and using the compounds represented by
--[--N.dbd.P(--O-crossli- nking
group-O--).sub.x(--O-Ph).sub.y-].sub.n--, which was synthesized
following the procedure of Synthesis Example 2. The results are
shown in Table 1.
1TABLE 1 Crosslinking Tm T5 Td Flame retardancy Example group x y
Mw (.degree. C.) (.degree. C.) (.degree. C.) UL-94 10 m-phenylene
0.002 1.996 670 103 343 366 V-0 11 p-phenylene 0.002 1.996 730 102
338 350 V-0 12 p-phenylene 0.007 1.986 710 103 353 360 V-0 13
p-phenylene 0.021 1.958 710 101 352 365 V-0
[0202] In Table 1, Tm (.degree. C.) is the melting temperature as
determined by thermogravimetric analysis (TG/DTA analysis), T5
(.degree. C.) is the temperature at which 5% weight loss occurred
as determined by thermogravimetric analysis, Td (.degree. C.) is
the decomposition temperature as determined by thermogravimetric
analysis.
[0203] As shown in Table 1, the moldability each of the resin
compositions containing the flame retardant comprising the
compounds represented by the above general formula was good, and
juicing was not observed.
SYNTHESIS EXAMPLE 4
Synthesis of Compound D; Phenoxy-Phosphazene Having
4,4'-Sulfonyldiphenylene-(Bisphenol-S Residue) Crosslinked
Structure
[0204] In a 4-necked, 1-liter flask, 1.28 moles (121.14 g) of
phenol and 0.017 mole (4.26 g) of bisphenol-S were dissolved in 500
ml of tetrahydrofuran (THF), and 7.6 g of sodium metal in the form
of cut pieces was added thereto at 25.degree. C. or lower. After
the completion of the addition, the temperature was elevated to
61.degree. C. over 1 hour, and the stirring was continued for 6
hours at 61.sup.0.C to 68.degree. C. to prepare a sodium phenolate
mixed solution.
[0205] In parallel with the above reaction, 290 g of a 20%
chlorobenzene solution containing 0.5 unit mole (58 g) of
dichlorophosphazene oligomers (a mixture of 58.57% of trimer,
12.26% of tetramer, 11.11% of pentamer and hexamer, 2.82% of
heptamer, 12.04% of octamer and higher oligomers) was placed in a
4-necked, 2-liter flask, and the above-mentioned sodium phenolate
mixed solution, previously prepared, was added dropwise thereto
with stirring and with cooling at 25.degree. C. or lower. After the
dropwise addition, the mixture was subjected to a reaction with
stirring at 71 to 73.degree. C. for 15 hours.
[0206] After the completion of the reaction, the reaction mixture
was concentrated, and the concentrate was re-dissolved in 500 ml of
chlorobenzene. Then, the solution was washed sequentially with
water, with a 5% aqueous NaOH solution three times, with a 5%
sulfuric acid, with a 5% aqueous sodium hydrogencarbonate solution
and with water three times, and concentrated to dryness to give 108
g of a pale yellow waxy product.
[0207] Yield: 93.5%.
[0208] This product had a weight average molecular weight (Mw) of
810 as determined by GPC analysis based on polystyrene standards,
and a melting temperature (Tm) of 103.degree. C. as determined by
TG/DTA analysis, and the 5% weight loss temperature (T5) and the
decomposition starting temperature (Td) of the product were 330 and
347.degree. C., respectively.
[0209] The product had a residual chlorine content of 0.09%. It was
determined from the phosphorus content and CHN elemental analysis
data that the approximate composition of this product was
[N.dbd.P(--O-Ph-SO.sub.2-Ph-O--).sub.0.025(--O-Ph).sub.1.95].
SYNTHESIS EXAMPLES 5 TO 6
Preparation of Compound E and Compound F: Phenoxyphosphazene Having
4,4'-sulfonyldiphenylene-(bisphenol-S residue) crosslinked
Structure
[0210] Pale yellow waxy products were prepared following the
reaction and work-up procedures of Synthesis Example 4 and using
1.254 moles (118.03 g) of phenol and 0.033 mole (8.26 g) of
bisphenol-S [or 1.122 moles (105.60 g) of phenol and 0.099 mole
(24.77 g) of bisphenol-S]. It was confirmed from the analysis
results that the following compounds were obtained.
[0211] Compound E:
[N.dbd.P(--O-Ph-SO.sub.2-Ph-O--).sub.0.05(--O-Ph).sub.1- .90]
[0212] Yield: 91.5%, residual chlorine 0.01% or less, Mw=820,
Tm=103.degree. C., T5=332.degree. C., Td=347.degree. C.
[0213] Compound F:
[N.dbd.P(--O-Ph-SO.sub.2-Ph-O--).sub.0.15(--O-Ph).sub.1- .70]
[0214] Yield: 90.0%, residual chlorine=0.11%, Mw=850,
Tm=102.degree. C., T5=333.degree. C., Td=355.degree. C.
SYNTHESIS EXAMPLES 7 TO 8
Preparation of Compound G and Compound H: Phenoxyphosphazene Having
4,4'-oxydiphenylene Group-Crosslinked Structure
[0215] The following highly viscous compounds were prepared
following the reaction and work-up procedures of Synthesis Example
4 on the same scale and using 13.4 g (0.066 mole) of
bis(4-hydroxyphenyl)ether and 111.7 g (1.188 moles) of phenol [or
26.8 g (0.132 mole) of bis(4-hydroxyphenyl)ether and 99.3 g (1.056
moles) of phenol)] and 27.6 g (1.2 moles) of Na metal.
[0216] Compound G:
[N.dbd.P(--O-Ph-O-Ph-O--).sub.0.1(--O-Ph).sub.1.8]
[0217] Yield: 99.8%, residual chlorine=0.01% or less, Mw=1510,
Tm=not detected, T5=346.degree. C., Td=353.degree. C.
[0218] Compound H:
[N.dbd.P(--O-Ph-O-Ph-O--).sub.0.2(--O-Ph).sub.1.6]
[0219] Yield: 97.9%, residual chlorine=0.11%, Mw=1950, Tm=not
detected, T5=318.degree. C., Td=375.degree. C.
SYNTHESIS EXAMPLES 9 TO 10
Preparation of Compound I and Compound J: Phenoxyphosphazene Having
4,4'-thiodiphenylene Group-Crosslinked Structure
[0220] The following highly viscous compounds were prepared
following the reaction and work-up procedures of Synthesis Examples
7 and 8 and using 14.4 g (0.066 mole) [or 28.8 g (0.132 mole)] of
thiodiphenol.
[0221] Compound I:
[N.dbd.P(--O-Ph-S-Ph-O--).sub.0.1(--O-Ph).sub.1.8]
[0222] Yield: 98.8%, residual chlorine=0.09%, Mw=1690, Tm=not
detected, T5=340.degree. C., Td=344.degree. C.
[0223] Compound J:
[N.dbd.P(--O-Ph-S-Ph-O--).sub.0.2(--O-Ph).sub.1.6]
[0224] Yield: 95.1%, residual chlorine=0.01%, Mw=3050, Tm=not
detected, T5=344.degree. C., Td=348.degree. C.
SYNTHESIS EXAMPLES 11 TO 12
Preparation of Compound K and Compound L: Phenoxyphosphazene Having
4,4'-diphenylene Group-Crosslinked Structure
[0225] The following highly viscous compounds were prepared
following the reaction and work-up procedures of Synthesis Examples
7 and 8 and using 12.3 g (0.066 mole) [or 24.6 g (0.132 mole)] of
4,4'-diphenol.
[0226] Compound K:
[N.dbd.P(--O-Ph-Ph-O--).sub.0.1(--O-Ph).sub.1.8]
[0227] Yield: 99.9%, residual chlorine=0.01%, Mw=1590, Tm=not
detected, T5=348.degree. C., Td=349.degree. C.
[0228] Compound L:
[N.dbd.P(--O-Ph-Ph-O--).sub.0.2(--O-Ph).sub.1.6]
[0229] Yield: 97.0%, residual chlorine=0.11%, Mw=1900, Tm=not
detected, T5=345.degree. C., Td=347.degree. C.
EXAMPLE 14
[0230] A flame-retardant resin composition was prepared by adding
15 parts of phenoxyphosphazene having
4,4'-sulfonyldiphenylene(bisphenol-S residue)-crosslinked structure
(Compound D) and 0.5 part of PTFE to a resin comprising 75 parts of
an aromatic polycarbonate resin and 25 parts of ABS resin, mixing
the components in a mixer, and melting and kneading the mixture by
means of a laboplasto mill.
[0231] This composition was made into test pieces having a
thickness of 1/8 inch by a heat-press. The test pieces were
evaluated for flame retardancy according to the test method of
UL-94 and the heat distortion temperature thereof was measured
according to ASTM D-648.
[0232] As a result, the specimens did not permit dripping of molten
resin so that the flame retardancy was V-0, and the heat distortion
temperature was 111.degree. C. Juicing was not observed during the
molding of this resin composition.
EXAMPLE 15
[0233] A flame-retardant resin composition was prepared in the same
manner as in Example 14 except that 18 parts of Compound E were
used without using PTFE. Furthermore, following the procedure of
Example 14, test pieces were prepared therefrom, and the evaluation
of the flame retardancy thereof and measurement of the heat
distortion temperature thereof were carried out.
[0234] As a result, the test pieces did not give flaming drips
capable of igniting cotton so that the flame retardancy was V-0,
and the heat distortion temperature was 112.degree. C. Juicing was
not observed during the molding of this resin composition. The
results confirm that said compound is capable of exhibiting the
desired flame-retardancy without using PTFE, and demonstrate that
said compound is a true non-halogen-based flame
retardancy-imparting agent.
EXAMPLES 16 TO 22
[0235] Flame-retardant resin compositions were prepared following
the procedure of Example 14 and using Compounds F-L. Furthermore,
following the procedure of Example 14, test pieces were prepared
therefrom, and the evaluation of the flame retardancy thereof and
measurement of the heat distortion temperature thereof were carried
out.
[0236] The results are shown in Table 2.
2TABLE 2 Heat distortion Ex. Flame retardant Flame retardancy
Juicing temperature 16 Compound F V-0 none 115.degree. C. 17
Compound G V-0 none 112.degree. C. 18 Compound H V-0 none
113.degree. C. 19 Compound I V-0 none 110.degree. C. 20 Compound J
V-0 none 111.degree. C. 21 Compound K V-0 none 114.degree. C. 22
Compound L V-0 none 115.degree. C.
EXAMPLE 23
[0237] To a resin comprising 70 parts of
poly(2,6-dimethyl-1,4-phenylene)o- xide and 30 parts of
rubber-modified impact resistant polystyrene was added 15 parts of
Compound E, i.e., phenoxyphosphazene having crosslinked structure,
and the components were mixed in a mixer. The mixture was melted
and kneaded by means of a laboplasto mill to thereby give a
flame-retardant resin composition.
[0238] This resin composition was made into test piece having a
thickness of 1/8 inch by a heat-press. The test pieces were
evaluated for flame retardancy according to the test method of
UL-94 and the heat distortion temperature thereof was measured
according to ASTM D-648.
[0239] As a result, flame retardancy was V-0, and the heat
distortion temperature was 131.degree. C. Juicing was not observed
during the molding of this resin composition.
EXAMPLE 24
[0240] A flame-retardant resin composition was prepared following
the procedure of Example 23 and using compound H in place of
Compound E. Furthermore, following the procedure of Example 23,
test pieces were prepared therefrom, and the evaluation of the
flame retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0241] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 133.degree. C. Juicing was not observed
during the molding of this resin composition.
EXAMPLE 25
[0242] A flame-retardant resin composition was prepared following
the procedure of Example 23 and using compound J in place of
Compound E. Furthermore, following the procedure of Example 23,
test pieces were prepared therefrom, and the evaluation of the
flame retardancy thereof and measurement of the heat distortion
temperature thereof were carried out.
[0243] As a result, the flame retardancy was V-0, and the heat
distortion temperature was 130.degree. C. Juicing was not observed
during the molding of this resin composition.
EXAMPLE 26
[0244] A varnish was prepared by adding 10 parts of Compound D to
100 parts of bisphenol-A type epoxy resin. A glass cloth was
impregnated with the varnish and then the impregnated glass cloth
was dried to thereby produce a prepreg. Subsequently, a prescribed
number of pieces of the prepregs were laminated on one another and
the laminate was subjected to a heat-press processing at a
temperature of 160.degree. C. or higher to prepare a glass epoxy
board having a thickness of {fraction (1/16)} inch, and the board
was then cut into pieces of a predetermined size for use as a test
piece. The test piece was evaluated for flame retardancy according
to the test method of UL-94.
[0245] As a result, the flame retardancy was V-0, and Juicing was
not observed during the heat-press processing of this resin
composition.
EXAMPLE 27
[0246] Following the procedure of Example 26 and using compound H
in place of Compound E, test piece was prepared to evaluate the
flame retardancy.
[0247] As a result, the flame retardancy was V-0, and juicing was
not observed during the heat-press processing of this resin
composition.
EXAMPLE 28
[0248] Following the procedure of Example 26 and using compound J
in place of Compound E, test piece was prepared to evaluate the
flame retardancy.
[0249] As a result, the flame retardancy was V-0, and juicing was
not observed during the heat-press processing of this resin
composition.
SYNTHESIS EXAMPLE 13
Synthesis of Chlorophosphazene
[0250] 99.5% phosphorus pentachloride (PCl.sub.5) (12 moles, 2512
g), 99.5% ammonium chloride (NH.sub.4Cl) (12.8 moles, 688 g), 97.0%
zinc chloride (ZnCl.sub.2) (0.16 mole, 20 g) and monochlorobenzene
(MCB) (5 liters) were placed in a reaction vessel equipped with a
temperature controller, a stirrer and a refluxing device. Reaction
was commenced at 24.degree. C., and the temperature was gradually
raised, to finally reach 130.degree. C. over a period of 3 hours
from the start of the reaction. Reflux was continued with stirring
at 130.degree. C.-134.degree. C. for two hours, and the reaction
mixture was filtered to remove 76 g of a white residue, thereby
giving 6883 g of chlorophosphazene as an almost colorless
transparent solution in MCB (1343 g, calculated as 100%
chlorophosphazene; chlorophosphazene concentration in the solution:
19.51%). Yield: 96.56% (relative to phosphorus pentachloride)
[0251] Analysis by .sup.31P-NMR revealed that trimer m=3 (wherein m
represents m as defined in the foregoing general formula): 54%,
tetramer m=4: 19%, pentamer m>5: 27%.
[0252] Said solution was concentrated to give a 39.5% solution of
chlorophosphazene for use as the starting material in Synthesis
Example 14.
SYNTHESIS EXAMPLE 14
Synthesis of Phenoxyphosphazene
[0253] Phenol (PhOH) (31.14 moles, 2931 g), Na metal (25.95 moles,
596.67 g) and tetrahydrofuran (THF) (7 liters) were fed into a
reaction vessel equipped with a temperature controller, a stirrer
and a refluxing device, and the mixture was refluxed with stirring
for 8 hours. The reaction mixture solution turned slightly colored.
To this, solution was added dropwise, at a temperature of
42.degree. C. to 79.degree. C., a solution prepared by dissolving
said 39.5% solution containing chlorophosphazene prepared in
Synthesis Example 13 (3172.41 g) in 5.5 liters of THF. After the
dropwise addition was completed, reflux was continued with stirring
at 78.degree. C. for 10 hours.
[0254] Subsequently, the reaction mixture was concentrated and then
dissolved in 8 liters of monochlorobenzene, 5 liters of water and 3
liters of a 5% aqueous NaOH solution. The resultant mixture was
successively washed in the following order: twice with 7 liters of
a 5% aqueous NaOH solution, once with 7 liters of a 5% hydrochloric
acid, once with 7 liters of a 7% aqueous NaHCO.sub.3 solution and
twice with 7 liters of water. After the washing, the resulting
mixture was dried by adding MgSO.sub.4 and then concentrated.
Finally, the concentrate was dried at 80.degree. C. in a vacuum at
a pressure of 3 torr or lower for 12 hours, to give 2437 g of
phenoxyphosphazene in the form of a yellow sherbet.
[0255] Yield: 97.5%
[0256] Analytical results are as follows. Analysis by .sup.31P-NMR
revealed the following: trimer m=3: 55%, tetramer m=4: 18%,
pentamer m>=5: 27%, weight average molecular weight Mw=720 by
GPC, mp=109.degree. C., 5% weight loss temperature Td
(5%)=343.degree. C., decomposition temperature Td=366.degree. C.,
percentage of residue after heat decomposition (600.degree.
C.)=19%, residual PhOH=0.038 wt %, residual MCB=0.042 wt %,
residual chlorine=0.102%.
EXAMPLE 29
[0257] A flame-retardant resin composition was prepared by adding
15 parts of phenoxyphosphazene prepared in Synthesis Example 14, as
a flame retardant, and 7.5 parts of potassium titanate fibers
(produced by Otsuka Chemical Co., Ltd., trade name: TISMO N-102,
the same applies hereinafter) to a resin comprising 75 parts of an
aromatic polycarbonate resin and 25 parts of ABS resin, mixing the
components in a mixer, and melting and kneading the mixture by
means of a laboplasto mill.
[0258] This composition was made into test pieces having a
thickness of {fraction (1/16)} inch by a heat-press. The test
pieces were evaluated for flame retardancy according to the test
method of UL-94 and the heat distortion temperature thereof was
measured according to ASTM D-648. Furthermore, the test pieces were
evaluated for the presence or absence of flaming particles (drips)
which ignite cotton during the test for flame retardancy, the
presence or absence of generation of volatile gases during kneading
by a laboplasto mill and any change in the appearance after forming
the test pieces. The results are shown in Table 3.
EXAMPLES 30 TO 31
[0259] A flame-retardant resin composition was prepared in the same
manner as in Example 29 except that kaolin (a reagent produced by
Wako Pure Chemical Industrie, Ltd.) or Mica (tradename: Clarite
Mica 400W, produced by Kuraray Co., Ltd.) was used in place of the
potassium titanate fibers. The obtained compositions were evaluated
for their perfomances in the same manner as in Example 29. The
results are shown in Table 3.
EXAMPLES 32 TO 35
[0260] Flame-retardant resin compositions were prepared following
the procedure of Example 29 and using each of Compounds E-H in
place of the phenoxyphosphazene of Synthesis Example 2. The
obtained compositions were evaluated for their performances in the
same manner as in Example 29. The results are shown in Table 3.
EXAMPLE 36
[0261] A flame-retardant resin composition was prepared following
the procedure of Example 29 and using a resin comprising 60 parts
of poly (2,6-dimethyl-1,4-phenylene)oxide and 40 parts of rubber
modified impact resistant polystyrene in place of the resin
comprising polycarbonate resin and ABS resin. The obtained
composition was evaluated for their performances in the same manner
as in Example 29. The results are shown in Table 3.
EXAMPLE 37
[0262] A varnish was prepared by adding 15 parts of the
phenoxyphosphazene prepared in Synthesis Example 14 and 7.5 parts
of potassium titanate fibers to 100 parts of bisphenol-A type epoxy
resin. A glass cloth was impregnated with the varnish and the
impregnated glass cloth was dried to prepare a prepreg.
Subsequently, a prescribed number of pieces of the prepregs were
laminated on one another, and the laminate was pressed with heating
to give a glass-epoxy board having a thickness of {fraction (1/16)}
inch, and the board was cut into test pieces of predetermined size.
These test pieces were subjected to the flame test according to the
test method of UL-94, and the heat distortion temperature was
measured according to the above-mentioned method. The results are
shown in Table 3.
COMPARATIVE EXAMPLE 9
[0263] A resin composition was prepared in the same manner as in
Example 29 except that potassium titanate fibers were not added.
The performances of the composition were evaluated as described in
Example 29. The results are shown in Table 3.
COMPARATIVE EXAMPLE 10
[0264] A resin composition was prepared in the same manner as in
Example 36 except that potassium titanate fibers were not added.
The performances of the composition were evaluated as described in
Example 29. The results are shown in Table 3.
COMPARATIVE EXAMPLE 11
[0265] A resin composition was prepared in the same manner as in
Example 37 except that potassium titanate fibers were not added.
The performances of the composition were evaluated as described in
Example 29. The results are shown in Table 3.
3TABLE 3 Flame Heat distortion Volatization Discoloration
retardancy Degree of temperature of gas during during (UL-94)
dripping (.degree. C.) molding molding Juicing Ex. 29 V-0 Not
dripped 121 Not volatilized Not discolored none 30 V-0 Not dripped
128 Not volatilized Not discolored none 31 V-0 Not dripped 124 Not
volatilized Not discolored none 32 V-0 Not dripped 119 Not
volatilized Not discolored none 33 V-0 Not dripped 120 Not
volatilized Not discolored none 34 V-0 Not dripped 118 Not
volatilized Not discolored none 35 V-0 Not dripped 124 Not
volatilized Not discolored none 36 V-0 Not dripped 140 Not
volatilized Not discolored none 37 V-0 Not dripped -- Not
volatilized Not discolored none Comp. Ex. 9 V-2 Dripped 117
Volatilized Discolored none 10 V-2 Dripped 139 Volatilized Not
discolored none 11 V-2 Not dripped -- Not volatilized Not
discolored none
SYNTHESIS EXAMPLE 15
Synthesis of 4-cyanophenoxy Group-Containing Phenoxyphosphazene
[0266] A 4-necked, 2-liter flask equipped with a stirrer, a heater,
a thermometer and a dehydrator was charged with 0.44 mole (52.4 g)
of 4-cyanophenol, 2.20 moles (207.0 g) of phenol, 2.64 moles (105.6
g) of sodium hydroxide and 1000 ml of toluene. The mixture was
refluxed with heating so as to remove water from the system to
thereby prepare a solution of sodium salts of cyanophenol and
phenol in toluene.
[0267] To the solution of sodium salts of cyanophenol and phenol in
toluene was added dropwise 580 g of a 20% solution containing 1
unit mole (115.9 g) of dichlorophosphazene oligomers (a mixture of
59% of trimer, 12% of tetramer, 11% of pentamer and hexamer, 3% of
heptamer and 15% of octamer and higher cyclic and straight-chain
compounds) in chlorobenzene with stirring while maintaining the
internal temperature at 30.degree. C. or lower. This mixed solution
was refluxed for 12 hours, and then the reaction mixture was washed
twice by adding a 5% aqueous solution of sodium hydroxide.
Subsequently, the organic layer was neutralized with dilute
sulfuric acid, washed twice with water, filtered, concentrated and
dried in a vacuum (the condition of the vacuum drying: 80.degree.
C., 5 mmHg, 12 hours) to give 220 g of a pale yellow viscous
liquid. The yield calculated based on the dichlorophosphazene
oligomers used was 92%.
[0268] The product had a residual hydrolyzable chlorine content of
0.09%, showed .sup.1H-NMR spectral peaks in the range of 7.6 to 6.6
ppm and .sup.31P-NMR spectral peaks in the range of 10 to 6, -11 to
-14 and -16 to -21 ppm, and had a weight average molecular weight
of 1500 as determined by GPC based on polystyrene standards.
[0269] It was confirmed from the results of carbon, hydrogen,
nitrogen and phosphorus elemental analysis that the composition of
the product was
[N.dbd.P(OC.sub.6H.sub.4CN).sub.0.33(OPh).sub.1.67]. This
composition was in agreement with the ratio of 4-cyanophenol and
phenol fed, so that the desired compound was synthesized. The
product did not show a definite melting point, and showed a
decomposition temperature of 327.degree. C. as determined by TG/DTA
analysis.
SYNTHESIS EXAMPLES 16 TO 19
[0270] 4-Cyanophenoxy group-containing phenoxyphosphazene compounds
were synthesized following the procedure of Synthesis Example 15
and varying the ratio of 4-cyanophenol and phenol used. The results
are shown in Table 4.
[0271] From the results of carbon, hydrogen, nitrogen, chlorine and
phosphorus elemental analysis and of the measurement of .sup.1H-NMR
and .sup.31P-NMR spectra, it was confirmed that the compositions of
these products were in agreement with the ratio of 4-cyanophenol
and phenol fed and that the desired compounds were synthesized,
respectively.
4 TABLE 4 Synthesis Example 16 17 18 19 4-Cyanophenol (mole) 0.88
1.32 1.76 2.20 Phenol (mole) 1.76 1.32 0.88 0.44 Yield (%) 95 96 95
95 Hydrolyzable chlorine (%) 0.08 0.11 0.15 0.06 Property Resinoid
Solid Solid Solid Weight-average 1000 1050 1130 1210 molecule
weight Melting point (.degree. C.) Not Not Not 248 detected
detected detected Decomposition temp. (.degree. C.) 358 373 367
411
SYNTHESIS EXAMPLE 20
[0272] 4-Cyanophenoxy group-containing isopropylphenoxyphosphazene
compound was synthesized following the procedure of Synthesis
Example 15 and using 4-isopropylphenol in place of phenol used in
Synthesis Example 15. The result is shown in Table 5. From the
results of carbon, hydrogen, nitrogen, chlorine and phosphorus
elemental analysis and of the measurement of .sup.1H-NMR and
.sup.31P-NMR spectra, it was confirmed that the composition of this
product was in agreement with the ratio of 4-cyanophenol and
4-isopropylphenol fed and that the desired compound was
synthesized.
SYNTHESIS EXAMPLE 21
[0273] 4-Cyanophenoxy group-containing naphthoxyphosphazene
compound was synthesized following the procedure of Synthesis
Example 15 and using 2-naphthol in place of phenol used in
Synthesis Example 15. The result is shown in Table 5.
[0274] From the results of carbon, hydrogen, nitrogen, chlorine and
phosphorus elemental analysis and of the measurement of .sup.1H-NMR
and .sup.31P-NMR spectra, it was confirmed that the composition of
this product was in agreement with the ratio of 4-cyanophenol and
2-naphthol fed and that the desired compound was synthesized.
SYNTHESIS EXAMPLE 22
[0275] 4-Cyanophenoxy group-containing propoxyphosphazene compound
was synthesized in the same manner as in Synthesis Example 15 with
the exception of using n-propanol in place of phenol used in
Synthesis Example 15 and using 2-cyanophenol in place of
4-cyanophenol and also with the exception of preparing the sodium
salts of these with use of sodium metal. The result is shown in
Table 5.
[0276] From the results of carbon, hydrogen, nitrogen and
phosphorus elemental analysis and of the measurement of .sup.1H-NMR
and .sup.31P-NMR spectra, it was confirmed that the composition of
this product was in agreement with the ratio of 2-cyanophenol and
n-propanol fed and that the desired compound was synthesized.
SYNTHESIS EXAMPLE 23
[0277] 4-Cyanophenoxy group-containing ethylhexyloxy-phosphazene
compound was synthesized in the same manner as in Synthesis Example
15 with the exception of using 2-ethylhexanol in place of phenol
used in Synthesis Example 15 and also with the exception of
preparing the sodium salts of 2-ethylhexanol and 4-cyanophenol with
use of metallic sodium. The result was shown in Table 5.
[0278] From the results of carbon, hydrogen, nitrogen, chlorine and
phosphorus elemental analysis and of the measurement of .sup.1H-NMR
and .sup.31P-NMR spectra, it was confirmed that the composition of
this product was in agreement with the ratio of 4-cyanophenol and
2-ethylhexanol fed and that the desired compound was
synthesized.
SYNTHESIS EXAMPLE 24
[0279] 4-Cyanophenoxy group-containing phosphazene compound was
synthesized in the same manner as in Synthesis Example 15 with the
exception of using 2.00 moles of 2-allylphenol and 0.20 mole of
n-propanol in place of 2.20 moles of phenol used in Synthesis
Example 15 and also with the exception of preparing the sodium
salts of 2-allylphenol, n-propanol and 4-cyanophenol with use of
sodium metal. The results was shown in Table 5.
[0280] From the results of carbon, hydrogen, nitrogen, chlorine and
phosphorus elemental analysis and the measurement of .sup.1H-NMR
and .sup.31P-NMR spectra, it was confirmed that the composition of
this product was in agreement with the ratio of 4-cyanophenol,
2-allylphenol and n-propanol fed and that the desired compound was
synthesized.
SYNTHESIS EXAMPLE 25
[0281] Dichlorophosphazene polymer was prepared by heating 1.5
moles (521.6 g) of hexachlorocyclotriphosphazene at 250.degree. C.
for 12 hours in an atmosphere of nitrogen to conduct ring-opening
polymerization. Unreacted hexachlorocyclotriphosphazene was removed
by sublimation at 70.degree. C. for 7 hours under reduced pressure.
To 224.3 g (yield: 43%) of the dichlorophosphazene polymer thus
obtained was added chlorobenzene to give a 20% solution. A solution
of sodium salts of cyanophenol and phenol in toluene was prepared
following the procedure of Synthesis Example 15.
[0282] To this solution of sodium salts of the phenols in toluene,
580 g of the previously prepared 20% chlorobenzene solution
containing 1 unit mole (115.9 g) of dichlorophosphazene polymer as
dissolved therein was added dropwise at an internal temperature of
30.degree. C. or below with stirring, and the mixed solution thus
obtained was refluxed for 12 hours. The reaction mixture was
concentrated and precipitated again in a 5% aqueous solution of
sodium hydroxide. Subsequently, the precipitated polymer was
dissolved in tetrahydrofuran and precipitated again in water. This
procedure was repeated three times. The obtained polymer was dried
in a vacuum (vacuum drying conditions: 80.degree. C., 5 mmHg, 12
hours) to give 213 g of a pale yellow viscous liquid. The results
were shown below in Table 5.
[0283] It was confirmed from elemental analysis data of carbon,
hydrogen, nitrogen, chlorine and phosphorus and spectral data of
.sup.1H-NMR and .sup.31P-NMR that the composition of the final
product was in agreement with the ratio of 4-cyanophenol and phenol
fed so that the desired product was synthesized.
5 TABLE 5 Synthesis Example 20 21 22 23 24 25 Yield (%) 92 95 90 91
90 89 Hydro- 0.06 0.15 0.11 0.08 0.09 0.12 lyzable chlorine (%)
Property Liquid Solid Liquid Liquid Solid Solid Weight- 990 1110
950 1080 1220 386000 average molecule weight Melting Not 140 Not
Not Not Unclear point (.degree. C.) detected detected detected
detected De- 342 402 310 314 326 340 composition temp. (.degree.
C.)
EXAMPLES 38 TO 48
[0284] Flame-retardant resin compositions were prepared by adding
15 parts of each of the cyanophenoxy group-containing phosphazene
compounds prepared in Synthesis Examples 15 to 25 to a resin
comprising 75 parts of an aromatic polycarbonate resin and 25 parts
of ABS resin, mixing the components with a mixer, and melting and
kneading the mixture with a laboplasto mill.
[0285] Each of these compositions was made into test pieces having
the predetermined shape with a heat-press. These test pieces were
subjected to the flame test according to the test method of UL-94,
and Izod impact strength and the heat distortion temperature
thereof were measured according to the following methods. These
results are shown below in Table 6.
[0286] Flame Test
[0287] Carried out by the vertical flame test according to the
UL-94 standard, and the result was used as an index of flame
retardancy. (Test piece: {fraction (1/16)} inch in thickness, 5
inches in length, 0.5 inch in width)
[0288] Izod Impact Strength
[0289] Measured at 23.degree. C. according to JIS K-7110 and the
result was used as an index of impact resistance. (Test piece
thickness 1/8 inch, with V notch)
[0290] Heat Distortion Temperature
[0291] Measured under the load of 18.6 kg/cm.sup.2 according to
ASTM D-648, and the result was used as an index of heat
resistance.
COMPARATIVE EXAMPLE 12
[0292] Test pieces were prepared and the properties thereof were
evaluated in the same manner as in Example 38 with the exception of
using triphenyl phosphate in place of the phosphazene compound used
in Example 38. The results are shown below in Table 6.
COMPARATIVE EXAMPLE 13
[0293] Test pieces were prepared and the properties thereof were
evaluated in the same manner as in Example 38 with the exception of
using a condensed phosphoric acid diphenyl ester crosslinked with
resorcinol (a compound similar to CR733S produced by DAIHACHI
CHEMICAL INDUSTRY CO., LTD.) in place of phosphazene compound used
in Example 38. The results were shown below in Table 6.
COMPARATIVE EXAMPLE 14
[0294] Test pieces were prepared and the properties thereof were
evaluated in the same manner as in Example 38 with the exception of
not using the flame retardant. The results are shown below in Table
6.
EXAMPLE 49
[0295] A flame-retardant resin composition was prepared following
the procedure of Example 38 and using 0.5 part of zinc chloride in
addition to the components used in Example 38. Furthermore,
following the procedure of Example 38, test pieces were prepared
therefrom, and then the flame retardancy thereof was evaluated and
Izod impact resistance and the heat distortion temperature thereof
were measured. The results are shown below in Table 6.
EXAMPLE 50
[0296] A flame-retardant resin composition was prepared following
the procedure of Example 38 and using 0.6 part of
polytetrafluoroethylene (Prodoct of DAIKIN INDUSTRIES LTD.,
Tradename: F-201) in addition to the components used in Example 38.
Furthermore, following the procedure of Example 38, test pieces
were prepared therefrom, and then the flame retardancy thereof was
evaluated and Izod impact resistance and the heat distortion
temperature thereof were measured. The results are shown below in
Table 6.
EXAMPLES 51 TO 55
[0297] Flame-retardant resin compositions were prepared by adding
15 parts of each of the cyanophenoxy group-containing phosphazene
compounds prepared in Synthesis Examples 15 to 19 to a resin
comprising 70 parts of poly(2,6-dimethyl-1,4-phenylene)oxide and 30
parts of a rubber-modified impact resistant polystyrene, mixing the
components with a mixer, and melting and kneading the mixture with
a laboplasto mill. The flame test according to UL-94 was carried
out, and Izod impact resistance and the heat distortion temperature
were measured according to the above-mentioned methods. These
results are shown below in Table 6.
COMPARATIVE EXAMPLE 15
[0298] A resin composition was prepared following the procedure of
Example 51 and using triphenyl phosphate in place of the
phosphazene compound used in Example 51. Furthermore, following the
procedure of Example 51, test pieces were prepared therefrom, and
then the flame retardancy thereof was evaluated and Izod impact
resistance and the heat distortion temperature thereof were
measured. The results are shown below in Table 6.
COMPARATIVE EXAMPLE 16
[0299] A resin composition was prepared following the procedure of
Example 51 and using the condensed phosphoric acid diphenyl ester
crosslinked with resorcinol (a compound similar to CR733S produced
by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) in place of the
phosphazene compound used in Example 51. Furthermore, following the
procedure of Example 51, test pieces were prepared therefrom, and
then the flame retardancy thereof was evaluated and Izod impact
resistance and the heat distortion temperature thereof were
measured. The results are shown below in Table 6.
COMPARATIVE EXAMPLE 17
[0300] A resin composition was prepared following the procedure of
Example 51 and using no flame retardant. Furthermore, following the
procedure of Example 38, test pieces were prepared therefrom, and
then the flame retardancy thereof was evaluated and Izod impact
resistance and the heat distortion temperature thereof were
measured. The results are shown below in Table 6
EXAMPLE 56
[0301] A flame-retardant resin composition was prepared by adding
10 parts of the cyanophenoxy group-containing phosphazene compound
prepared in Synthesis Example 15 to 100 parts of nylon-6 having a
number average molecular weight of 25,000, mixing the components
with a mixer, and melting and kneading the mixture with a
laboplasto mill.
[0302] Following the procedure of Example 38, test piece was
prepared therefrom, and the flame test was carried out according to
the test method of UL-94. The result is shown below in Table 6.
COMPARATIVE EXAMPLE 18
[0303] A resin composition was prepared following the procedure of
Example 56 and using the condensed phosphoric acid diphenyl ester
crosslinked with resorcinol (a compound similar to CR733S produced
by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) in place of the
phosphazene compound used in Example 56. Furthermore, following the
procedure of Example 56, test piece was prepared therefrom, and the
flame retardancy thereof was evaluated. The result is shown below
in Table 6.
EXAMPLE 57
[0304] A flame-retardant resin composition was prepared by mixing
70 parts of a polycarbonate resin, 30 parts of a polybutylene
terephtalate resin and 20 parts of the cyanophenoxy
group-containing phosphazene compound prepared in Synthesis Example
15 with a mixer, and melting and kneading the mixture with a
laboplasto mill.
[0305] Following the procedure of Example 38, test piece was
prepared therefrom, and the flame test was carried out according to
the test method of UL-94. The result is shown below in Table 6.
COMPARATIVE EXAMPLE 19
[0306] A resin composition was prepared following the procedure of
Example 57 and using the condensed phosphoric acid diphenyl ester
crosslinked with resorcinol (a compound similar to CR733S produced
by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) in place of the
phosphazene compound used in Example 57. Furthermore, following the
procedure of Example 57, test piece was prepared therefrom, and the
flame retardancy thereof was evaluated. The result is shown below
in Table 6.
EXAMPLE 58
[0307] A varnish was prepared by adding 10 parts of the
cyanophenoxy group-containing phosphazene compound prepared in
Synthesis Example 15 to 100 parts of bisphenol-A type epoxy resin.
A glass cloth was impregnated with the varnish and the impregnated
glass cloth was dried to give a prepreg. Subsequently, the
predetermined number of pieces of prepregs were laminated, and the
laminate was subjected to a heat-press processing at 160.degree. C.
or above to give two types of glass-epoxy board, one having a
thickness of 1/8 inch and the other having a thickness of {fraction
(1/16)} inch. The obtained board was cut into the predetermined
size to give test pieces.
[0308] These test pieces were subjected to the flame test according
to the test method of UL-94. The results were shown below in Table
6. Juicing was not observed during the heat-press processing of the
resin composition.
EXAMPLE 59
[0309] A flame-retardant resin composition was prepared in the same
manner as in Example 58 with the exception of using the compound
prepared in Synthesis Example 23 in place of the cyanophenoxy
group-containing phosphazene compound used in Example 58 (the
compound prepared in Synthesis Examples 15). Following the
procedure of Example 58, test pieces were prepared and the flame
retardancy thereof was evaluated. The result is shown below in
Table 6. Juicing was not observed during the heat-press processing
of this resin composition.
COMPARATIVE EXAMPLE 20
[0310] A resin composition was prepared in the same manner as in
Example 58 with the exception of using a condensed phosphoric acid
diphenyl ester crosslinked with resorcinol (a compound similar to
CR733S produced by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) in place
of the phosphazene compound prepared in Synthesis Example 15.
Following the procedure of Example 58, test pieces were prepared
and the flame retardancy thereof was evaluated. The result is shown
below in Table 6. Juicing was observed during the heat-press
processing of this resin composition.
COMPARATIVE EXAMPLE 21
[0311] A resin composition was prepared in the same manner as in
Example 58 with the exception of using no flame retardant.
Following the procedure of Example 58, test pieces were prepared
and the flame retardancy thereof was evaluated. The result is shown
below in Table 6.
6 TABLE 6 Heat Burning Flame Izod impact distortion quality
retardancy strength temperature On ignition (UL-94) (kgf .multidot.
cm/cm) (.degree. C.) Ex. 38 none V-0 59 100 39 none V-0 59 103 40
none V-0 58 103 41 none V-0 59 105 42 none V-0 58 107 43 none V-0
58 103 44 none V-0 59 107 45 none V-0 55 92 46 none V-0 56 94 47
none V-0 58 101 48 none V-0 57 102 49 none V-0 60 110 50 none V-0
58 105 51 none V-0 9 128 52 none V-0 8 128 53 none V-0 9 130 54
none V-0 9 130 55 none V-0 9 131 56 none V-0 -- -- 57 none V-0 --
-- 58 none V-0 -- -- 59 none V-0 -- -- Conp. Ex. 12 FS V-2 49 80 13
FS V-2 50 89 14 FS .multidot. Burnt Not rated 61 111 out 15 FS V-2
5 110 16 FS V-2 6 115 17 FS .multidot. Burnt Not rated 9 133 out 18
none V-1 -- -- 19 FS V-2 -- -- 20 FS V-2 -- -- 21 FS .multidot.
Burnt Not rated -- -- out FS = Flame detardancy was not shown
[0312] Table 6 shows that the resin compositions of the present
invention comprising optimum amounts of resins and phosphazene
compounds are very well-balanced among excellent flame retardancy,
impact resistance and heat resistance (Examples 38 to 59). It is
also seen from Example 49 that when a small amount of zinc chloride
is added to a resin composition comprising a resin mixture of an
aromatic polycarbonate resin, ABS resin and a cyanophenoxy
group-containing phosphazene compound, the resulting has still
higher flame retardancy and impact resistance. On the other hand,
when a phosphoric acid ester compound is used as a flame retardant,
the resulting resin compositions are poor in flame retardancy and
heat resistance and are of low value for use (Comparative Examples
12, 13, 15, 16 and 18 to 20).
EXAMPLE 60
[0313] Pellets of a flame-retardant resin composition according to
the present invention were prepared by kneading with a biaxial
extruder a mixture of 100 parts of a resin composition comprising
75 parts of an aromatic polycarbonate resin (Trade name: Iupilon
S-2000N, Product of MITSUBISHI ENGINEERING PLASTICS Co., Ltd.) and
25 parts of ABS resin (Trade name: SANTAK UT-61, Product of MITSUI
CHEMICALS INC.), 5.0 parts of a triphenyl phosphate (Product of
WAKO Pure Chemical Industrie, Ltd.), 5.0 parts of the
phenoxyphosphazene prepared in Synthesis Example 14 and 0.6 part of
polytetrafluoroethylene (Trade name: G-307, Product of ASAHI GLASS
Co., Ltd.), followed by pelletization.
COMPARATIVE EXAMPLES 22 AND 23
[0314] Pellets of resin compositions were prepared in the same
manner as in Example 60 with the exception of using 10 parts of
triphenyl phosphate alone (Comparative Example 22) or 10 parts of
phenoxyphosphazene alone (Comparative Example 23), without using
triphenyl phosphate in combination with the phenoxyphosphazene.
EXAMPLES 61 TO 63
[0315] Pellets of flame-retardant resin compositions according to
the present invention were prepared in the same manner as in
Example 60 with the exception of using triphenyl phosphine oxide
(Product of KANTO CHEMICAL Co., Inc., Example 61), tricresyl
phosphate (Product of WAKO Pure Chemical Industrie, Ltd., Example
62) or resolsinol bis(2,6-dimethylphenyl phophate), Example 63) in
place of the triphenyl phosphate as the halogen-free organic
phosphorus compound.
COMPARATIVE EXAMPLES 24 TO 26
[0316] Pellets of resin compositions were prepared in the same
manner as in Examples 61 to 63 with the exception of using 10 parts
of triphenyl phosphine oxide alone (Comparative Example 24),
tricresyl phosphate alone (Comparative Example 25) or resolsinol
bis(2,6-dimethylphenyl phophate) (Comparative Example 26), without
using the halogen-free organic phosphorus compound in combination
with the phenoxyphosphazene.
EXAMPLE 64
[0317] Pellets of a flame-retardant resin composition according to
the present invention were prepared in the same manner as in
Example 60 with the exception of using the phosphazene compound
prepared in Synthesis Example 3 in place of the
phenoxyphosphazene.
EXAMPLE 65
[0318] Pellets of a flame-retardant resin composition according to
the present invention were prepared in the same manner as in
Example 60 with the exception of using the phosphazene compound
prepared in Synthesis Example 4 in place of the
phenoxyphosphazene.
EXAMPLE 66
[0319] Pellets of a flame-retardant resin composition according to
the present invention were prepared in the same manner as in
Example 60 with the exception of using a modified-PPE resin (Trade
name: Xyron X9108, Product of ASAHI CHEMICAL Co., Ltd.) in place of
the resin mixture of polycarbonate resin and ABS resin.
[0320] The resins, the halogen-free organic phosphorus compounds
and the phosphazene compounds used in Examples 60 to 66 and
Comparative Examples 22 to 26 are all shown in Table 7. Figures in
parentheses are the amounts used (parts).
7 TABLE 7 Hagogen- free phos- phorus Resin compound Phosphazene
compound Ex. 60 PC(75)/ABS(25) TPP(5) Synthesis Example 14(5) 61
PC(75)/ABS(25) TPPO(5) Synthesis Example 14(5) 62 PC(75)/ABS(25)
TCP(5) Synthesis Example 14(5) 63 PC(75)/ABS(25) LBDP(5) Synthesis
Example 14(5) 64 PC(75)/ABS(25) TPP(5) Synthesis Example 3(5) 65
PC(75)/ABS(25) TPP(5) Synthesis Example 4(5) 66 Modified-PPE TPP(5)
Synthesis Example 14(5) resin (100) Comp. Ex. 22 PC(75)/ABS(25) TPP
(10) -- 23 PC(75)/ABS(25) -- Synthesis Example 14(10) 24
PC(75)/ABS(25) TPPO(10) 25 PC(75)/ABS(25) TOP(10) 26 PC(75)/ABS(25)
LBDP -- (10)
[0321] PC: Aromatic polycarbonate resin (Trade name: Iupilon
S-2000N, Product of MITSUBISHI ENGINEERING PLASTICS Co., Ltd.)
[0322] ABS: ABS resin (Trade name: SANTAK UT-61, Product of MITSUI
CHEMICALS INC.)
[0323] TPP: Triphenyl phosphate (Product of WAKO Pure Chemical
Industrie, Ltd.)
[0324] TPPO: Triphenyl phosphine oxide (Product of KANTO CHEMICAL
Co., Ltd.)
[0325] TCP: Tricresyl phosphate (Product of WAKO Pure Chemical
Industrie, Ltd.)
[0326] LBDP: Resolsinol bis(2,6-dimethylphenyl phophate)
[0327] The pellets of the resin compositions prepared in Examples
60 to 66 and Comparative Examples 22 to 26 were injection-molded to
give test pieces having predetermined shape. These test pieces were
subjected to the flame test according to the test method of UL-94,
and measurement was made of the flexural modulus, heat distortion
temperature, Izod impact strength and melt flow rate. The flame
test, heat distortion temperature and Izod impact strength were
measured according to the method as described above. The flexural
modulus and melt flow rate were measured according to the following
methods.
[0328] Flexural Modulus
[0329] Measured according to JIS K-7203.
[0330] Melt Flow Rate
[0331] Measured at 240.degree. C. under a load of 10 kg/cm.sup.2
according to JIS K-7210.
[0332] These results are shown below in Table 8.
EXAMPLE 67
[0333] A varnish of a flame-retardant composition of the present
invention was prepared by mixing 100 parts of a bisphenol A type
epoxy resin (Trade name: EP5400, Product of ASAHI DENKA KOGYO
K.K.), 7.5 parts of triphenyl phosphate, 7.5 parts of the
phenoxyphosphazene prepared in Synthesis Example 14 and 0.6 part of
polytetrafluoroethylene (G-307).
[0334] A glass cloth was impregnated with this varnish and the
impregnated glass cloth was dried to give a prepreg. Subsequently,
5 pieces of the prepregs were laminated and pressed with heating at
160.degree. C. under a pressure of 50 kg/cm.sup.2 to give a
glass-epoxy board having a thickness of 1.6 mm. The obtained glass
epoxy board was cut into a length of 12.7 cm and a width of 1.3 cm
to give test pieces. These test pieces were subjected to each of
the tests as described above. The results are shown below in Table
8.
8TABLE 8 Flame Flexural Heat distortion Izod impact Melt flow
retardancy modulus temperature strength rate (UL-94) (Kg/cm.sup.2)
(.degree. C.) (Kgf .multidot. cm/cm) (g/10 min) Ex. 60 V-0 2.4
.times. 10.sup.4 94 88 35 61 V-0 2.4 .times. 10.sup.4 80 88 36 62
V-0 2.4 .times. 10.sup.4 99 87 40 63 V-0 2.4 .times. 10.sup.4 97 78
65 64 V-0 2.4 .times. 10.sup.4 101 85 45 65 V-0 2.4 .times.
10.sup.4 90 87 30 66 V-0 2.5 .times. 10.sup.4 133 20 71 67 V-0 0.1
.times. 10.sup.4 79 -- -- Comp. Ex. 22 V-2 2.4 .times. 10.sup.4 85
67 28 23 V-1 2.4 .times. 10.sup.4 69 68 15 24 HB 2.4 .times.
10.sup.4 57 59 45 25 V-1 2.4 .times. 10.sup.4 91 60 35 26 V-1 2.4
.times. 10.sup.4 97 58 30
* * * * *