Curable composition, foam produced therefrom, and process for producing the foam

Provided is a curable composition comprising (A) a phenolic compound having a carbon-carbon double bond, (B) a compound having an SiH group, and (C) a foaming agent. The composition can be foamed and cured at room temperature or under heat at relatively low temperatures, and is poorly corrodable and poorly toxic.

DESCRIPTION 
1. Technical Field 
The present invention relates to a novel curable composition which foams 
and cures at room temperature or under heat at relatively low temperatures 
to give foams which are poorly corrodable and poorly toxic, to the foams 
made from the composition, and to a method for producing the foams. 
2. Background Art 
As having good mechanical characteristics and flame retardancy, phenolic 
foams are widely used for soundproofing, heat insulation, water sealing, 
vapor sealing, damping, protection, cushioning, decoration, etc. 
Phenolic foams include novolak foams to be produced by the use of acid 
catalysts and resolic foams to be produced by the use of alkali catalysts. 
To cure novolak foams, they must be heated, and their use is limited. 
Resolic foams can be cured at room temperature in the presence of acid 
catalysts, which, however, corrode metals. To solve this problem, 
neutralizing agents may be added to the curing system, but could not 
produce good results. Accordingly, desired are foams which can be produced 
and cured under heat at relatively low temperatures and which are poorly 
corrodable. 
The present invention has been made in consideration of the current 
situation noted above, and its object is to provide a curable composition 
which is poorly corrodable and poorly toxic and which can be foamed and 
cured at room temperature or under heat at relatively low temperatures in 
a curing method quite different from the conventional method using acids, 
to provide foams made from the composition, and to provide a method for 
producing the foams. 
Disclosure of the Invention 
Having assiduously studied, we, the present inventors have found that the 
object can be attained by a curable composition comprising (A) a phenolic 
compound having a carbon-carbon doublebond, (B) a compound having an SiH 
group, and (C) a foaming agent. 
The component (A) and the component (B) cure at room temperature or at 
relatively low temperatures through hydrosilylation for addition 
crosslinking. The component (C) acts as a foaming agent owing to the heat 
of the reaction, and produces a foam. Specifically, in the invention, the 
component (C) (foaming agent) absorbs the heat of vaporization or 
decomposition and prevents any rapid temperature increase during the 
reaction, and, as a result, foams having a fine cellular structure and a 
high expansion ratio are obtained. Preferably, the composition of the 
invention contains a hydrosilylation catalyst as an additional component 
(D). 
The phenolic compound of the component (A) preferably has a molecular 
backbone comprising at least one structure selected from the following 
formulae (1) to (3): 
##STR1## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.2 and R.sup.3 each 
represent a divalent substituent having from 1 to 6 carbon atoms; R.sup.4 
and R.sup.5 each represent a hydroxyl group and/or a monovalent 
substituent having from 0 to 6 carbon atoms; X and Y each represent a 
divalent substituent having from 0 to 10 carbon atoms; n and m each 
represent an integer of from 0 to 300; l represents an integer of from 1 
to 300 and p and q each represent an integer of from 0 to 3. 
##STR2## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.6, R.sup.7 and R.sup.8 
each represent a divalent substituent having from 1 to 6 carbon atoms; 
R.sup.9, R.sup.10 and R.sup.11 each represent a hydroxyl group and/or a 
monovalent substituent having from 0 to 6 carbon atoms; X and Y each 
represent a divalent substituent having from 0 to 10 carbon atoms; n and m 
each represent an integer of from 0 to 300 l and s each represent an 
integer of from 1 to 300; and p, q and r each represent an integer of from 
0 to 3. 
##STR3## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.12 represents a divalent 
substituent having from 0 to 6 carbon atoms; R.sup.13 and R.sup.14 each 
represent a hydroxyl group and/or a monovalent substituent having from 0 
to 10 carbon atoms; X and Y each represent a divalent substituent having 
from 0 to 10 carbon atoms; and n and m each represent an integer of from 0 
to 4. 
The SiH-having compound of the component (B) is preferably a compound to be 
represented by the following structural formula (4): 
##STR4## 
wherein m.gtoreq.2; n, l, p.gtoreq.0; 10.ltoreq.(m+n+l).times.p.ltoreq.80; 
R.sup.16, R.sup.17, R.sup.18 and R.sup.19 each represent a hydrogen atom 
or a hydrocarbon group having from 1 to 20 carbon atoms, which may have at 
least one phenyl group; R.sup.15 represents a substantially 
polyoxyalkylene group, and/or an organic group derived from the reaction 
of a hydrosilyl group with an alkenyl-aromatic compound. 
As the foaming agent of the component (C), preferred are volatile compounds 
having a boiling point of not higher than 100.degree. C. The volatile 
compounds are preferably selected from hydrocarbons, flons, carbon 
dioxide, air and nitrogen. 
To obtain foams from the curable composition, at least two compositions 
each comprising, as the main component, any of the component (A) and the 
component (B) are prepared, and mixed to be foamed and cured. 
Alternatively, at least two compositions each comprising, as the main 
component, any of the component (A) and the component (B) are prepared and 
mixed just before use, and the resulting mixture is directly sprayed over 
the surface of a substrate or cast into a mold, and foamed and cured. 
Best Modes of Carrying out the Invention 
The component (A) for use in the invention is not specifically defined, 
provided that it has a carbon-carbon double bond at which it reacts with 
the component (B) through hydrosilylation for addition crosslinking. 
Preferably, however, the component (A) has a backbone of a phenolic resin 
that is necessary to the moldings of the composition for their mechanical 
characteristics. As the component (A), preferred are compounds of the 
following structural formulae (1) to (3), since the raw materials for 
those are easily available. 
##STR5## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.2 and R.sup.3 each 
represent a divalent substituent having from 1 to 6 carbon atoms; R.sup.4 
and R.sup.5 each represent a hydroxyl group and/or a monovalent 
substituent having from 0 to 6 carbon atoms; X and Y each represent a 
divalent substituent having from 0 to 10 carbon atoms; n and m each 
represent an integer of from 0 to 300 l each represent an integer of from 
1 to 300; and p and q each represent an integer of from 0 to 3. 
##STR6## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.6, R.sup.7 and R.sup.8 
each represent a divalent substituent having from 1 to 6 carbon atoms; 
R.sup.9, R.sup.10 and R.sup.11 each represent a hydroxyl group and/or a 
monovalent substituent having from 0 to 6 carbon atoms; X and Y each 
represent a divalent substituent having from 0 to 10 carbon atoms; n and m 
each represent an integer of from 0 to 300 l and s each represent an 
integer of from 1 to 300; and p, q and r each represent an integer of from 
0 to 3. 
##STR7## 
wherein R.sup.1 represents H or CH.sub.3 ; R.sup.12 represents a divalent 
substituent having from 0 to 6 carbon atoms; R.sup.13 and R.sup.14 each 
represent a hydroxyl group and/or a monovalent substituent having from 0 
to 10 carbon atoms; X and Y each represent a divalent substituent having 
from 0 to 10 carbon atoms; and n and m each represent an integer of from 0 
to 4. 
The phenol compound to form the phenolic resin backbone is not specifically 
defined, and any and every ordinary one is employable herein. For example, 
it includes novolak and/or resolic phenols from phenol, cresol, xylenol, 
resorcinol catechol, pyrogallol, etc.; and bisphenolic compounds such as 
bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. 
In vies of its availability, allylated bisphenol A is preferable. As 
examples of the allylated bisphenol A, mentioned are 2,2'-diallylbisphenol 
A, O,O'-diallyl bisphenol A and so on. 
To introduce an alkenyl group into the phenolic resin backbone, employed 
are two methods, one comprising first producing a phenolic resin backbone 
with no alkenyl group and thereafter introducing an alkenyl group 
thereinto, and the other comprising producing a phenolic resin backbone 
with an alkenyl group partly or entirely from an alkenyl-having compound. 
In the former method where an alkenyl group is introduced into a phenolic 
resin backbone already produced, for example, a main chain backbone having 
a functional group such as a hydroxyl group, an alkoxide group, a carboxyl 
group, an epoxy group or the like, at the terminal or in the main chain or 
side chain is first produced, and then this is reacted with an organic 
compound having both an active group that is active to the functional 
group and an alkenyl group, to thereby introduce the alkenyl group 
thereinto. 
Examples of the organic group having both an active group that is active to 
the functional group and an alkenyl group include C.sub.3-20 unsaturated 
fatty acids, acid halides and acid anhydrides, such as acrylic acid, 
methacrylic acid, vinylacetic acid, acrylic acid chloride, acrylic acid 
bromide, etc.; unsaturated aliphatic alcohols such as vinyl alcohol, allyl 
alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 
7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 2-(allyloxy) ethanol, neopentyl 
glycol monoallyl ether, glycerin diallyl ether, trimethylolpropane diallyl 
ether, trimethylolethane diallyl ether, pentaerythritol triallyl ether, 
1,2,6-hexanetriol diallyl ether, sorbitan diallyl ether, vinylbenzyl 
alcohol, etc.; C.sub.3-20 unsaturated aliphatic alcohol-substituted 
carbonic acid halides such as allyl chloroformate (CH.sub.2 =CHCH.sub.2 
OCOCl), allyl bromoformate (CH.sub.2 =CHCH.sub.2 OCOBr), etc.; and allyl 
chloride, allyl bromide, vinyl(chloromethyl)benzene, 
allyl(chloromethyl)benzene, allyl(bromomethyl)benzene, allyl 
(chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl 
(chloromethyl) ether, 1-hexenyl(chloromethoxy)benzene, 
allyloxy(chloromethyl)benzene, allyl isocyanate, allyl glycidyl ether, 
etc. Examples of the concrete reaction include a method of reacting a 
phenol group with a halogenoallyl compound in the presence of a basic 
catalyst; a method of reacting a phenol group with allyl glycidyl ether in 
the presence of an epoxidation catalyst; and a method of reacting an 
isocyanate with allyl alcohol in the presence of an urethanation catalyst. 
For the alkenyl group introduction, also employable is interesterification. 
This is to interesterify the alcohol residue in the ester moiety of a 
polyester or acrylic resin with an alkenyl-having alcohol or phenol 
derivative in the presence of an interesterification catalyst. The 
alkenyl-having alcohol and phenol derivatives to be used for the 
interesterification with the alcohol residue may be any alcohol or phenyl 
derivatives having at least one alkenyl group and at least one hydroxyl 
group. The catalyst may be or may not be used. If used, the catalyst is 
preferably any of acids or titanium or tin catalysts. 
In the method of producing a phenolic resin backbone partly or entirely 
from an alkenyl-having compound, an aromatic compound having a double bond 
is reacted with a phenol, for example, along with formaldehyde or 
diisocyanate. Concretely, allylphenol is polycondensed with any other 
phenol in the presence of an acid or base, along with formaldehyde. 
The number of carbon-carbon double bonds in the component (A) is preferably 
larger than 1.0/molecule on average, more preferably not smaller than 
2/molecule. If the number of carbon-carbon double bonds in the component 
(A) is not larger than 1/molecule, the reaction of the component (A) with 
the component (B) does not produce a crosslinked structure. 
The structure of the component (A) may be linear or branched, and the 
molecular weight thereof is not specifically defined. However, in order to 
uniformly mix the component (A) with the component (B) and to foam the 
resulting mixture, it is desirable that the component (A) has a mean 
molecular weight of from 100 to 100,000, more preferably from 100 to 
10,000. 
The SiH-having compound of the component (B) is not specifically defined, 
and may be any of linear or cyclic organohydrogenpolysiloxanes or 
hydrosilyl-having organic compounds having a molecular weight of not 
larger than 30,000. 
As examples of the linear or cyclic organohydrogenpolysiloxanes, mentioned 
are compounds of the following general formula (4) or (5): 
##STR8## 
wherein m.gtoreq.2; n, l, p.gtoreq.0; 10.ltoreq.(m+n+l).times.p.ltoreq.80; 
R.sup.16, R.sup.17, R.sup.18 and R.sup.19 each represent a hydrogen atom 
or a hydrocarbon group having from 1 to 20 carbon atoms, which may have at 
least one phenyl group; R.sup.15 represents a substantially 
polyoxyalkylene group, and/or an organic group derived from the reaction 
of a hydrosilyl group with an alkenyl-aromatic compound. 
##STR9## 
wherein m.gtoreq.2; n, l, p.gtoreq.0; 3.ltoreq.(m+n+l).times.p.ltoreq.20; 
R.sup.15 represents a substantially polyoxyalkylene group, and/or an 
organic group derived from the reaction of a hydrosilyl group with an 
alkenyl-aromatic compound; R.sup.16 and R.sup.17 each represent a hydrogen 
atom or a hydrocarbon group having from 1 to 20 carbon atoms, which may 
have at least one phenyl group. 
To obtain the polyorganohydrogensiloxanes of formulae (4) and (5), 
employable is a method of reacting a polyoxyalkylene compound having a 
functional group capable of reacting with SiH, such as a double bond 
(e.g., allyl group), a hydroxyl group or the like at the terminal with a 
polyorganohydrogensiloxane; a method of producing them from 
polyoxyalkylene chain-having silicon compounds; or a method of reacting a 
polyoxyalkylene chain-having silicon compound with a polyorganosiloxane 
for rearrangement therebetween. 
Concretely, for example, a linear or cyclic polyorganohydrogensiloxane of a 
formula (6) or (7): 
##STR10## 
wherein m.gtoreq.2; l, p.gtoreq.0; 10.ltoreq.(m+l).times.p.ltoreq.80; 
R.sup.16, R.sup.17, R.sup.18 and R.sup.19 each represent a hydrogen atom 
or a hydrocarbon group having from 1 to 20 carbon atoms, which may have at 
least one phenyl group, 
##STR11## 
wherein m.gtoreq.2; l, p.gtoreq.0; 3.ltoreq.(m+l).times.p.ltoreq.20; 
R.sup.16 and R.sup.17 each represent a hydrogen atom or a hydrocarbon 
group having from 1 to 20 carbon atoms, which may have at least one phenyl 
group, is reacted with any of the following: 
##STR12## 
or the linear or cyclic polyorganohydrogensiloxane of formula (6) or (7) 
is reacted with any of the following: 
##STR13## 
wherein 5.ltoreq.m.ltoreq.80; and R.sup.15 represents a polyoxyalkylene 
chain having a molecular weight of from 100 to 10,000, or a hydrocarbon 
group having from 2 to 20 carbon atoms, which may have at least one phenyl 
group, 
##STR14## 
wherein 3.ltoreq.m.ltoreq.20; and R.sup.15 represents a polyoxyalkylene 
chain having a molecular weight of from 100 to 10,000, or a hydrocarbon 
group having from 2 to 20 carbon atoms, which may have at least one phenyl 
group, for rearrangement or equilibration therebetween. 
The other hydrosilyl-having organic compounds having a molecular weight of 
not larger than 30,000 are not specifically defined for their structure. 
Examples of the compounds may be represented by the following general 
formula (8): 
EQU R.sup.20 Xa (8) 
wherein X represents a group having at least one hydrosilyl group; R.sup.20 
represents a mono- to tetra-valent organic group having from 2 to 150 
carbon atoms; and a represents an integer of from 1 to 4. 
In formula (8), X represents a group having at least one hydrosilyl group. 
Specific examples of the group of X include hydrosilyl groups as derived 
from various polyhydrogensiloxanes, which are represented by the following 
formulae (9) to (11): 
##STR15## 
wherein 1.ltoreq.(m+n).times.1.ltoreq.10; n.gtoreq.1; R.sup.21 represents 
any of a methyl, ethyl or phenyl group; Z represents a divalent 
substituent having from 0 to 10 carbon atoms and composed of constituent 
elements of C, H, N, O, S, Si and halogen only, 
##STR16## 
wherein l.ltoreq.(m+p).times.1+(n+q).times.r.ltoreq.10; m+n.gtoreq.1; l, 
p, q, r.gtoreq.0; R.sup.21 represents any of a methyl, ethyl or phenyl 
group; Z represents a divalent substituent having from 0 to 10 carbon 
atoms and composed of constituent elements of C, H, N, O, S, Si and 
halogen only, and the following hydrosilyl groups: 
##STR17## 
As examples of the divalent substituent Z in formulae (9) to (11), 
mentioned are the following: 
##STR18## 
Two or more of those divalent substituents may be bonded to each other via 
a covalent bond therebetween to give one divalent substituent Z. 
More specific examples of the hydrosilyl groups of formulae (9) to (11) 
include the following: 
##STR19## 
Of various hydrosilyl groups mentioned above, especially preferred are 
those mentioned below, in view of the miscibility of the component (B) 
comprising them with the other components and of the reactivity of those 
hydrosilyl groups themselves. 
##STR20## 
R.sup.20 in formula (8) is not specifically defined, provided that it is a 
mono- to tetra-valent organic group directly bonding to the group X via a 
covalent bond therebetween. It includes, for example, the following: 
##STR21## 
In the formulae mentioned above, the waved line in the bicyclic compounds 
indicates any of endo- or exo-configuration. 
Of those, preferred are the following groups, in view of the miscibility of 
the component (B) comprising them with the component (A). 
##STR22## 
The method for producing the hydrosilyl-having organic compounds of formula 
(8) is not specifically defined, and any desirable method is employable 
for the production. For example, employable are (i) a method of treating a 
curing agent precursor having an SiCl group in the molecule with a 
reducing agent such as LiAlH.sub.4, NaBH.sub.4 or the like to thereby 
reduce the SiCl group in the precursor into an SiH group; (ii) a method of 
reacting an organic compound having a functional group X in the molecule 
with a compound having both a functional group Y capable of reacting with 
the functional group X and a hydrosilyl group in the molecule; and (iii) a 
method of selectively hydrosilylating an alkenyl-having organic compound 
with a polyhydrosilane compound having at least two hydrosilyl groups to 
thereby make the thus-reacted organic compound still have a hydrosilyl 
group in the molecule. 
Of those methods, generally preferred is the method (iii), as the reaction 
steps constituting it are simple. In this case, two or more hydrosilyl 
groups in some polyhydrosilane compounds will react with the alkenyl group 
in the organic compound to increase the molecular weight of the resulting 
products. The products of organic compounds having such an increased 
molecular weight can also be used as the component (B) with no problem. 
More specific examples of the component (B) are mentioned below. 
##STR23## 
The number of the hydrosilyl groups to be in the component (B) for use in 
the invention shall be at least one on average in one molecule, but is 
preferably larger without interfering with the miscibility of the 
component (B) with the other components. In the invention, the component 
(A) and the component (B) are cured through hydrosilylation. For this, if 
the number of hydrosilyl groups in the component (B) is smaller than 2, 
the curing will be retarded and will often produce curing failures. 
The compositional ratio of the component (A) and the component (B) is not 
specifically defined, but shall be suitably determined depending on the 
structures of those components and on the intended physical properties of 
cured products. Preferably, however, the ratio of the molar number x of 
the carbon-carbon double bond in the component (A) to the molar number y 
of the SiH group in the component (B), x/y, falls between 1/30 and 30/1, 
more preferably between 1/10 and 10/1. If the component (A) is excess over 
the defined range, the crosslinking density of the cured product will be 
low and the product could not have good mechanical strength. On the 
contrary, if the component (B) is excess over the defined range, 
sufficient crosslinking could not be attained. 
The foaming agent of the component (C) for use in the invention is not 
specifically defined, and may be selected from any ordinary foaming agents 
applicable to organic foams of polyurethanes, phenols, polystyrenes, 
polyolefins, etc. In order to produce stable foams, however, a volatile 
compound is previously added to the composition as the foaming agent, and 
the composition is foamed under heat or under reduced pressure. 
Where a volatile compound is used as the foaming agent, it is desirable 
that the compound has a boiling point of not higher than 100.degree. C., 
more preferably not higher than 80.degree. C., even more preferably not 
higher than 50.degree. C. In consideration of the equipment for foaming 
and of the easiness in handling the compound, it is desirable that the 
compound has a boiling point of from -30.degree. C. to 35.degree. C. or 
so. 
The type of the volatile compound is not specifically defined. In view of 
their handleability and safety, however, preferably used are one or more 
selected from organic compounds such as hydrocarbons, flons, ethers, etc., 
and carbon dioxide, nitrogen, air, etc., either singly or as combined. 
The hydrocarbons include methane, ethane, propane, n-butane, isobutane, 
n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 
3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclobutane, 
cyclopentane, cyclohexane, etc. 
The flons include trichlorofluoromethane (R11), dichlorodifluoromethane 
(R12), chlorotrifluoromethane (R13), bromotrifluoromethane (R13B1), 
tetrafluoromethane (R14), dichlorofluoromethane (R21), 
chlorodifluoromethane (R22), trifluoromethane (R23), difluoromethane 
(R32), fluoromethane (R41), tetrachlorodifluoroethane (R112), 
trichlorotrifluoroethane (R113), dichlorotetrafluoroethane (R114), 
dibromotetrafluoroethane (R114B2), chloropentafluoroethane (R115), 
hexafluoroethane (R116), chlorotrifluoroethane (R123), tetrafluoroethane 
(R134a), dichlorofluoroethane (R141b), chlorodifluoroethane (R142b), 
difluoroethane (R152a), octafluoropropane (R218), 
dichloropentafluoropropane (R225), hexafluoropropane (R236ea), 
pentafluoropropane (R245fa), octafluorocyclobutane (RC318), 
hexafluorobutane (R356mffm), pentafluorobutane (R365mfc), decafluorohexane 
(R4310mee), etc. In view of the environmental problems with those flons, 
hydrochlorofluorocarbons (HCFC) of so-called substituent flons are 
preferred to chlorofluorocarbons (CFC), and more preferred are 
hydrofluorocarbons (HFC). Especially preferred are tetrafluoroethane, 
difluoroethane, octafluoropropane, hexafluoropropane, pentafluoropropane, 
octafluorocyclobutane, hexafluorobutane and pentafluorobutane. 
The ethers include dimethyl ether, diethyl ether, ethylmethyl ether, 
dipropyl ether, diisopropyl ether, butylmethyl ether, butylethyl ether, 
tert-butylmethyl ether tert-butylethyl ether, 1,1-dimethylpropylmethyl 
ether, methylpentafluoroethyl ether, 2,2,2-trifluoroethyl ether, 
methyl(trifluoromethyl)tetrafluoroethyl ether, etc. 
As other means of foaming the composition, also employable are inorganic 
foaming agents such as NaHCO3, (NH.sub.4).sub.2 CO.sub.3, NH.sub.4 
HCO.sub.3, NH.sub.2 NO.sub.2, Ca(N.sub.3).sub.2, NaBH.sub.4, etc.; organic 
foaming agents such as azodicarbonamide, azobisisobutyronitrile, barium 
azodicarboxylate, dinitrosopentamethylenetetramine, 
paratoluenesulfonylhydrazide, etc.; carbon dioxide to be generated by the 
reaction of isocyanates with active hydrogen-containing compounds; 
mechanical stirring, etc. Any of those foaming means may be combined with 
the foaming agent (C). 
In the invention, usable is a catalyst for hydrosilylation as the component 
(D). 
The hydrosilylation catalyst includes a simple substance of platinum; solid 
platinum as carried by a carrier such as alumina, silica, carbon black or 
the like; chloroplatinic acid; complexes of chloroplatinic acid with 
alcohols, aldehydes, ketones, etc.; platinum-olefin complexes (e.g., 
Pt(CH.sub.2 .dbd.CH.sub.2).sub.2 (PPh.sub.3).sub.2, Pt(CH.sub.2 
.dbd.CH.sub.2).sub.2 Cl.sub.2), platinum-vinylsiloxane complexes (e.g., 
Pt.sub.n (ViMe.sub.2 SiOSiMe.sub.2 Vi).sub.n, Pt[(MeViSiO).sub.4 ].sub.m), 
platinum-phosphine complexes (e.g., Pt(PPh.sub.3).sub.4, 
Pt(PBu.sub.3).sub.4), platinum-phosphite complexes (e.g., Pt[P(OPh).sub.3 
].sub.4, Pt[P(OBu).sub.3 ].sub.4) (in those formulae, Me is amethyl group, 
Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and 
m are integers); dicarbonyldichloro-platinum, Karstedt catalysts; 
platinum-hydrocarbon composites described in Ashby's U.S. Pat. Nos. 
3,159,601 and 3,159,662; and platinum alcoholate catalysts described in 
Lamoreaux's U.S. Pat. No. 3,220,972. In addition, platinum chloride-olefin 
composites described in Modic's U.S. Pat. No. 3,516,946 are also usable in 
the invention. As other examples of the catalysts except platinum 
compounds, mentioned are RhCl (PPh.sub.3).sub.3, RhCl.sub.3, Rh/Al.sub.2 
O.sub.3, RuCl.sub.3, IrCl.sub.3, FeCl.sub.3, AlCl.sub.3, 
PdCl.sub.2.2H.sub.2 O, NiCl.sub.2, TiCl.sub.4, etc. Of those, preferred 
are chloroplatinic acid, platinum-olefin complexes and 
platinum-vinylsiloxane complexes, as having high catalytic activity. One 
or more of these catalysts are usable herein either singly or as combined. 
The amount of the catalyst to be added is not specifically defined, but is 
preferably between 10.sup.-1 and 10.sup.-8 mols, more preferably between 
10.sup.-2 and 10.sup.-6 mols, per mol of SiH. 
Along with the catalyst noted above, employable is a promoter of phosphine 
compounds and phosphine complexes. The phosphine compounds include 
triphenylphosphine, PMe.sub.3, PEt.sub.3, PPr.sub.3 (where Pr is a propyl 
group, and the same shall apply hereinunder), P(n-Bu).sub.3, 
P(cyclo-C.sub.6 H.sub.11).sub.3, P(P-C.sub.6 H.sub.4 Me).sub.3, 
P(o-C.sub.6 H.sub.4 Me).sub.3, etc., which, however, are not limitative. 
The phosphine complexes include, for example, Cr(CO).sub.5 PPh.sub.3, 
Cr(CO).sub.4 (PPh.sub.3).sub.2 (cis- and trans-isomers), Cr(CO).sub.3 
(PPh.sub.3).sub.3 (fac- and mer-isomers), and Mo and V analogues of those 
Cr compounds; Fe(CO).sub.4 PPh.sub.3, Fe(CO).sub.3 (PPh.sub.3).sub.2, and 
Ru and Os analogues of those Fe compounds; COCl.sub.2 (PPh.sub.3), 
RhCl(PPh.sub.3).sub.3, RhCl(CO)(PPh.sub.3).sub.3, IrCl(CO) (PPh).sub.2, 
NiCl.sub.2 (PPh).sub.2, PdCl.sub.2 (PPh).sub.2, PtCl.sub.2 (PPh).sub.2, 
and ClAu(PPh.sub.3). Other metal complexes such as those with metals noted 
above but having phosphines except triphenylphosphine may also be 
effective promoters. In addition, complexes having phosphites such as P 
(OPh).sub.3, arsines such as AsPh.sub.3, and stibines such as SbPh.sub.3 
may also be promoters. 
The amount of the promoter to be added is not specifically defined, but is 
preferably between 10.sup.-2 and 10.sup.2 mols, more preferably between 
10.sup.-1 and 10.sup.1 mols, per mol of the catalyst. 
The curable composition of the invention may further contain any of 
fillers, aging retardants, radical inhibitors, UV absorbents, adhesion 
improvers, flame retardants, cell controlling agents such as 
polydimethylsiloxane-polyalkylene oxide surfactants or other organic 
surfactants (polyethylene glycol alkylphenyl ethers, etc.), acid or basic 
compounds, storage stability improvers, antiozonants, photo-stabilizers, 
thickeners, plasticizers, coupling agents, antioxidants, thermal 
stabilizers, conductivity-imparting agents, antistatic agents, 
radiation-blocking agents, nucleating agents, phosphorus-containing 
peroxide-degrading agents, lubricants, pigments, metal inactivators, 
physical properties-regulating agents, etc., without interfering with the 
object and the effect of the invention. 
As specific examples of the fillers, mentioned are glass fiber, carbon 
fiber, mica, graphite, diatomaceous earth, white clay, fume silica, 
precipitated silica, silicic anhydride, alumina, carbonblack, calcium 
carbonate, clay, talc, titanium oxide, magnesium carbonate, barium 
sulfate, quartz, aluminium powder, flint powder, zinc powder, inorganic 
balloons, rubber granules, wood powder, phenolic resins, melamine resins, 
polyvinyl chloride resins, etc. 
Herein usable are any ordinary antioxidants, such as citric acid, 
phosphoric acid, and sulfur-containing antioxidants. 
The sulfur-containing antioxidants include mercaptans, salts of mercaptans, 
sulfides including sulfide-carboxylates and hindered phenol sulfides, 
polysulfides, salts of dithiocarboxylic acids, thioureas, thiophosphates, 
sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, 
monothioacids, polythioacids, thioamides, sulfoxides, etc. 
The radical inhibitors include phenol-based radical inhibitors such as 
2,2'-methylene-bis(4-methyl-6-t-butylphenol), 
tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate)methane, 
etc.; and amine-based radical inhibitors such as 
phenyl-.beta.-naphthylamine, .alpha.-naphthylamine, 
N,N-sec-butyl-p-phenylenediamine, phenothiazine, 
N,N'-diphenyl-p-phenylenediamine, etc. 
The UV absorbents include, for example, 
2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 
bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, etc. 
As the adhesion improvers, usable are any ordinary adhesives; silane 
coupling agents such as aminosilane compounds, epoxysilane compounds, 
etc.; and other compounds. As specific examples of those adhesion 
improvers, mentioned are phenolic resins, epoxy resins, 
.gamma.-aminopropyltrimethoxysilane, 
N-(.beta.-aminoethyl)aminopropylmethyldimethoxysilane, coumarone-indene 
resins, rosin ester resins, terpene-phenolic resins, 
a-methylstyrene-vinyltoluene copolymers, polyethylmethylstyrenes, alkyl 
titanates, aromatic polyisocyanates, etc. 
The flame retardants include halogen-containing flame retardants such as 
tetrabromobisphenol A, tetrabromobisphenol A-epoxy, decabromodiphenyl 
oxide, etc.; phosphorus-containing flame retardants such as triethyl 
phosphate, tricresyl phosphate, tris(chloroethyl) phosphate, 
tris(chloropropyl) phosphate, tris(dichlorpropyl) phosphate, ammonium 
polyphosphate, red phosphorus, etc.; and inorganic flame retardants such 
as aluminium hydroxide, magnesium hydroxide, antimony trioxide, antimony 
pentoxide, etc. These flame retardants may be used either singly or as 
combined. 
Now, the production method of the invention is described below. 
The curable composition of the invention is mixed with a reaction catalyst 
and optional additives, and foamed and cured togivefoams. The foaming and 
curing temperature is preferably not higher than 200.degree. C., more 
preferably not higher than 100.degree. C. At too high temperatures higher 
than 200.degree. C., the component (A) and the component (B) will cure too 
rapidly, and the foaming agent (C) will evaporate. 
No specific limitation is made on the formulation of the composition. In 
view of the handlability of the curable composition, however, it is 
desirable that two or more compositions each consisting essentially of any 
of the components (A) and (B) are prepared and mixed, and the resulting 
mixture is cured. The foaming agent (C) may be added to either one of the 
components (A) and (B), or to both of them in portions. It may be added 
thereto while the components (A) and (B) are mixed together, or after they 
are mixed. The method of adding the reaction catalyst (D) is not 
specifically defined, and any method favorable to the adding operation may 
be employed. It may be added to either one of the components (A) and (B), 
or may be added to the system of these components being mixed, or may even 
be added to the mixture of these components having been mixed. 
To produce the foams of the invention, it is desirable that two or more 
mixtures each comprising the curable composition of the invention, the 
catalyst and optional additives in any desired combination are separately 
prepared, mixed just before use, and molded by extrusion or injection. The 
mixing method is not specifically defined, and any ordinary method of hand 
mixing, electric mixing, static mixing, collisional mixing or the like is 
employable. 
The foaming method for producing the foams is not also specifically 
defined, and any ordinary foaming method generally used for producing 
polyurethane foams, phenolic foams, silicone foams and others is 
employable herein, which includes, for example, extrusion foaming, 
continuous foaming, casting foaming, discontinuous foaming, in-field 
foaming, etc. 
The continuous foaming method may be any of a slab foaming method where the 
composition is freely foamed on paper or plastic film being continuously 
fed onto a belt conveyer, or a double-conveyer method where the 
composition is foamed along with a sheet substrate such as paper, plywood, 
sheet metal or the like, and laminated therewith. In the casting foaming 
method, the composition is cast into a mold having a desired shape, and 
foamed and cured therein to give a foam of which the shape corresponds to 
the inner profile of the mold. The discontinuous foaming method is used 
for producing sandwich panels, etc. The in-field foaming method includes a 
simple spraying method for one liquid, a two-liquid spraying method, a 
two-liquid casting method, and a two-liquid coating method. These are 
employed essentially for heat insulation of buildings.

Examples of the invention and Comparative Examples are mentioned below, 
which, however, are not intended to restrict the scope of the invention. 
Production Example 1 
114 g of bisphenol A, 145 g of potassium carbonate, 140 g of allyl bromide, 
and 250 ml of acetone were put into a four-neck flask equipped with a 
thermometer, a reflux condenser, a dropping funnel and a stirring motor, 
and stirred therein at 60.degree. C. for 12 hours. The supernatant was 
collected, washed with an aqueous solution of sodium hydroxide in a 
separatory funnel, and then washed with water. The oil layer was dried 
with magnesium sulfate, and the solvent was evaporated away. Thus was 
obtained a pale yellow liquid. Through its .sup.1 H-NMR, this liquid was 
identified as allylated bisphenol (allyl ether type) in which the OH group 
of the bisphenol A moiety was allyletherified. 
Production Example 2 
The allylated bisphenol that had been obtained in Production Example 1 was 
heated at 180.degree. C. for 3 hours while being stirred in a nitrogen 
atmosphere, and it gave a yellow-brown viscous liquid. Through its .sup.1 
H-NMR, this liquid was identified as C-allylated bisphenol in which the 
allyl group was Claisen-rearranged (A-1). 
Production Example 3 
36.9 g of novolak-phenol resin (PSM4261, manufactured by Gun-ei Chemical 
Co.; having an OH content of 9.71 mmols/g) and 160 ml of acetone were put 
into a four-neck flask equipped with a thermometer, a reflux condenser, a 
dropping funnel and a stirring motor, to which was added 50 g of potassium 
carbonate with stirring. Then, 52 g of allyl bromide was dropwise added 
thereto little by little, and reacted at 55.degree. C. for 6 hours. The 
reaction mixture was filtered, concentrated, and washed with alkali and 
acid in that order, and thereafter the solvent was evaporated away. Thus 
was obtained a pale yellow liquid. Through its .sup.1 H-NMR, this liquid 
was identified as O-allylated novolak-phenol resin (allyl ether type) in 
which the OH group was allylated (A-2). 
Production Example 4 
A stirrer, a dropping funnel, a condenser equipped with a three-way stop 
cock at its top, and a thermometer were fitted to a 1-liter four-neck 
flask. 120 g of methylhydrogenpolysiloxane (KF-99, manufactured by 
Shin-etsu Chemical Co.) (2.0 mols in terms of SiH), 241 .mu.l of a xylene 
solution of platinum-vinylsiloxane complex (2.0.times.10.sup.-2 mmols in 
terms of platinum atom), and 120 ml of toluene were put into this flask. 
The resulting mixture was heated at 80.degree. C., and a solution of 70 g 
of ethylene oxide polymer (its one terminal was modified with a methyl 
group and the other terminal was with an allyl group, and this had a 
number-average molecular weight of 350) (0.20 mmols in terms of allyl) as 
dissolved in 70 ml of toluene was dropwise added to the mixture over a 
period of 0.5 hours. After the addition, the mixture was further stirred 
at 80.degree. C. for 2 hours. Then, this was filtered, and the resulting 
filtrate was concentrated to obtain a colorless transparent liquid. 
Through its .sup.1 H-NMR, this liquid was identified as polyalkylene 
oxide-modified methylhydrogenpolysiloxane (B-1). 
Production Example 5 
120 g of methylhydrogenpolysiloxane and 52 g (0.5 mols) of styrene were 
processed in the same manner as in Production Example 4 to obtain a 
colorless, transparent, viscous liquid of styrene-modified 
methylhydrogenpolysiloxane (B-2). 
Production Example 6 
A three-way stop cock-equipped condenser, an equalizing dropping funnel, a 
thermometer, a magnetic tip and a glass stopper were fitted to a 200-ml 
four-neck flask. 12.03 g of cyclic polyhydrogensiloxane (LS8600, 
manufactured by Shinetsu Chemical Co.) and 20 ml of toluene were put into 
this flask, which was then purged with nitrogen. The mixture in the flask 
was heated at 50.degree. C. with stirring, and a mixture comprised of 20 
.mu.l of a solution of chloroplatinic acid catalyst (solution of 1 g of 
H.sub.2 PtCl.sub.6.6H.sub.2 O as dissolved in 1 g of ethanol and 9 g of 
1,2-dimethoxyethane), 30 ml of toluene and 2.76 g of 1,9-decadiene was 
dropped into the flask over a period of 2 hours. After the addition, these 
were reacted at 50.degree. C. for further 1 hour. The reaction mixture was 
washed with an aqueous saturated solution of ammonium chloride (100 
ml.times.2) and ion-exchanged water (100 ml.times.1), and then dried with 
sodium sulfate. The volatiles were evaporated away, and a colorless 
transparent liquid was obtained. Through its NMR and others, this liquid 
was identified as decadiene of which the both terminals were modified with 
cyclic polysiloxane (B-3). 
EXAMPLE 1 
0.6 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) and 6.0 g of HCFC141b were added to 15.4 g of 
C-allylated bisphenol (A-1) that had been prepared in Production Example 
2, and stirred to prepare a composition. This was mixed with 11.0 g of 
polyalkylene oxide-modified methylhydrogenpolysiloxane (B-1) that had been 
prepared in Production Example 4, at room temperature, whereupon the 
resulting mixture was foamed, while generating heat, to give a foam having 
an expansion ratio of about 6 times. 
EXAMPLE 2 
0.1 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) was added to 15.4 g of C-allylated bisphenol (A-1) 
that had been prepared in Production Example 2, and stirred to prepare a 
composition. This was rapidly mixed with 20.4 g or styrene-modified 
methylhydrogenpolysiloxane (B-2) that had been prepared in Production 
Example5, and 4.0 g of HCFC141b, at room temperature, whereupon the 
resulting mixture was foamed, while generating heat, to give a foam having 
an expansion ratio of about 5 times. 
EXAMPLE 3 
0.6 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) and 10.0 g of pentafluoropropane (R245fa) were 
added to 15.4 g of C-allylated bisphenol (A-1) that had been prepared in 
Production Example 2, and stirred to prepare a composition. This was mixed 
with 11.0 g of polyalkylene oxide-modified methylhydrogenpolysiloxane 
(B-1) that had been prepared in Production Example 4, at room temperature, 
whereupon the resulting mixture was foamed, while generating heat, to give 
a foam having an expansion ratio of about 25 times. 
EXAMPLE 4 
0.15 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) and 3.2 g of pentafluoropropane (R245fa) were 
added to 10.8 g of C-allylated bisphenol (A-1) that had been prepared in 
Production Example 2, and stirred to prepare a composition. This was mixed 
with 10.6 g of polyalkylene oxide-modified methylhydrogenpolysiloxane 
(B-1) that had been prepared in Production Example 4, at room temperature, 
whereupon the resulting mixture was foamed, while generating heat, to give 
a foam having an expansion ratio of about 26 times. 
EXAMPLE 5 
0.15 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) and 2.0 g of tetrafluoroethane (R134a) were mixed 
with 10.8 g of C-allylated bisphenol (A-1) that had been prepared in 
Production Example 2, in an autoclave to prepare a composition. This was 
mixed with 10.6 g of polyalkylene oxide-modified 
methylhydrogenpolysiloxane (B-1) that had been prepared in Production 
Example 4, whereupon the resulting mixture was foamed, while generating 
heat, to give a foam having an expansion ratio of about 25 times. 
EXAMPLE 6 
0. 6 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) and 5. 0 g of cyclopentane were added to 17. 0 g 
of O-allylated novolak-phenol resin (allyl ether type) (A-2) that had been 
prepared in Production Example 3, and stirred to prepare a composition. 
This was mixed with 10.7 g of polyalkylene oxide-modified 
methylhydrogenpolysiloxane (B-1) that had been prepared in Production 
Example 4, at room temperature, whereupon the resulting mixture was 
foamed, while generating heat, to give a foam having an expansion ratio of 
about 6 times. 
EXAMPLE 7 
0.1 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight in 
terms of platinum atom) was added to 15.4 g of C-allylated bisphenol (A-1) 
that had been prepared in Production Example 2, and stirred to prepare a 
composition. This composition was put into a 100-ml stainless steel 
autoclave, into which was introduced carbon dioxide to be up to an 
increased pressure of 10 kgf/cm.sup.2, with stirring (liquid A). On the 
other hand, 11.0 g of polyalkylene oxide-modified 
methylhydrogenpolysiloxane (B-1) that had been prepared in Production 
Example 4 was put into a different autoclave, into which was introduced 
carbon dioxide to be up to an increased pressure of 10 kgf/cm.sup.2 in the 
same manner as above (liquid B). The liquid A and the liquid B were 
gradually jetted out, while their temperatures were controlled with 
heaters, to give a foam having an expansion ratio of about 5 times. 
EXAMPLE 8 
14.2 g of the composition described in Example 4, which was comprised of 
C-allylated bisphenol, platinum-vinylsiloxane solution and 
pentafluoropropane (R245fa), and 10.6 g of modified 
methylhydrogenpolysiloxane (B-1) were mixed in a static mixer, and cast 
into a capped aluminium container (length 15 cm, width 15 cm, depth 2.5 
cm). Then, the mixture foamed in the container to give a foam having the 
same volume as that of the container. 
EXAMPLE 9 
14.2 g of the composition described in Example 4, which was comprised of 
C-allylated bisphenol, platinum-vinylsiloxane solution and 
pentafluoropropane (R245fa), and 10.6 g of modified 
methylhydrogenpolysiloxane (B-1) were separately pressurized with 
nitrogen, mixed by collision, and jetted out through a spray gum onto the 
surface of a vertical concrete substrate. The thus-sprayed mixture foamed 
and cured, without falling in drops, to give a flat foam having a smooth 
surface and having a uniform thickness. 
EXAMPLE 10 
A piece of cold rolled steel plates sheet, of which the surface had been 
well cleaned, was pierced into the foam produced in Example 1, and left in 
an atmosphere at a temperature of 35.degree. C. and a relative humidity of 
60% for 1 week. Then, the sheet steel piece was drawn out and 
macroscopically observed. No rust was found around it. 
Comparative Example 1 
1.4 g of an aqueous solution of 70% paratoluenesulfonic acid was added to a 
mixture comprised of 20.0 g of a commercially-available resol-type 
phenolic resin, 0.4 g of a silicone surfactant and 1.0 g of HCFC141b, and 
mixed, whereupon the resulting mixture was foamed, while generating heat, 
to give a foam having an expansion ratio of about 6 times. This was left 
in an atmosphere at a temperature of 35.degree. C. and a relative humidity 
of 60% for 1 week, with a sheet steel piece being pierced thereinto in the 
same manner as in Example 10. After having been drawn out of the foam, the 
steel piece was covered with much rust on its entire surface. 
Industrial Applicability 
The curable composition of the invention is foamed and cured at room 
temperature or under heat at relatively low temperatures. In addition, as 
being poorly corrodable and poorly toxic, foams of the composition are 
widely used for soundproofing, heat insulation, water sealing, vapor 
sealing, damping, protection, cushioning, decoration, etc. 
For vehicles, for example, the present invention is applicable to cushions, 
ceilings, cores in door trims, damping and sound-absorbing materials in 
floor cushions, heat-insulating materials in car coolers, air sealants in 
dampers, water-sealing parts, gaskets, air filters, center pillar 
garnishes, head linings, quarter light trims, dust covers, safety foams in 
fuel tanks, oil filters, flexible containers, crush pads, sun visors, head 
rests, insulators, dashboards, door panels, pillars, consoles, 
energy-absorbing bumpers, heat-insulating materials in freezer vans, 
refrigerator vans, tank lorries, freezing and refrigerating container 
trucks, sound-absorbing materials in girder bridges, etc.; for ships, it 
is applicable to heat-insulating materials, buoyant materials, cores in 
FRP boards, buoys, etc.; for bedding, it is applicable to cushions, etc.; 
for furniture, it is applicable to cushions, packing materials, etc.; for 
electric and electronic instruments, it is applicable to filters, 
sound-absorbing and heat-insulating materials, sound-absorbing materials 
in printers, ear pads in headphones, etc.; for packages, it is applicable 
to shock absorbers; for building and construction, it is applicable to 
heat-insulating materials in roofs, ceilings, walls and floors, covers of 
water pipes, door panels, siding panels, cores in metal siding panels, 
cores in partitioning panels, cores in tatami (straw mats) and fusuma 
(papered sliding doors), heat-insulating cores in bath tubs, joints, 
sealants, cable sealants, adhesives, heat-insulating panels in system 
ceilings, heat-insulating and water-proofing materials in roofs, 
air-sealing and heat-insulating materials in refrigerator storehouses and 
airtight storehouses, heat-insulating materials in plant tanks and pipes, 
etc.; for household electric appliances, it is applicable to heat-sealing 
materials in refrigerators, freezers and electric jars, dew inhibitors in 
air conditioners, etc.; for daily necessaries, it is applicable to sports 
goods, medical appliances, powder puffs for cosmetics, shoulder pads, 
slippers, sandals, kenzans (pin holders), toys, etc. 
In addition, the curable composition, the foams of the composition and the 
method for producing them of the invention are applicable to patterning of 
articles through injection molding, to formation of model samples using 
patterns, and to formation of decorations and accessories.