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Description  |
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FIELD OF THE INVENTION
The present invention relates to a curable resinous composition comprising
an epoxy resin and an organic elastomeric polymer having at least one
silicon-containing reactive group in a molecule. More particularly, it
relates to a curable resinous composition comprising an epoxy resin, an
organic elastomeric polymer having at least one silicon-containing
reactive group in a molecule, a silicone compound having a
silicon-containing reactive group and a functional group reactive with an
epoxy group, and a curing agent for the epoxy resin, which affords a cured
product having improved mechanical properties such as flexibility, impact
resistance, toughness and strength.
BACKGROUND OF THE INVENTION
An epoxy resin finds various applications such as a molding material, an
adhesive, a coating, a plywood, a laminate and the like. However, in these
applications, it generally has a drawback such that it affords a cured
product having brittleness and poor peeling strength.
An organic elastomeric polymer having at least one silicon-containing
reactive group in a molecule has such an interesting characteristic that
it can be cured even at a room temperature to give an elastomer. However,
the cured elastomer has poor strength, which prevents its wide
application.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a curable resinous
composition comprising an epoxy resin and an organic elastomeric polymer
having a silicon-containing reactive group by which the brittleness and
peeling strength of the epoxy resin and strength of the organic polymer
are improved.
Accordingly, the present invention provides a curable resinous composition
comprising:
(A) an organic elastomeric polymer having at least one silicon-containing
reactive group in a molecule,
(B) an epoxy resin,
(C) a silicone compound having a silicon-containing reactive group and a
functional group reactive with an epoxy group, and
(D) a curing agent for the epoxy resin, wherein said silicon-containing
reactive group is a group of the formula:
##STR2##
wherein X is a hydroxyl group or a hydrolyzable group, R.sup.1 is a
monovalent hydrocarbon group having 1 to 20 carbon atoms or an
organosiloxy group, "a" is 0, 1, 2 or 3, "b" is 0, 1 or 2 provided that
the total of "a" and "b" is at least 1, and "m" is 0 or an integer of 1 to
18, a weight ratio of (A) to (B) being from 1:100 to 100:1 and a weight
ratio of (A)+(B) to (C) being from 100:0.1 to 100:20.
The present invention is based on the finding that the addition of the
silicone compound (C) to a composition of the organic elastomeric polymer
(A) and the epoxy resin (B) is very important to improve brittleness of
the epoxy resin and strength of the polymer (A).
DETAILED DESCRIPTION OF THE INVENTION
Specific examples of the organic elastomeric polymer having at least one
silicon-containing reactive group in a molecule (A) are polyethers
prepared by ring opening polymerization of cyclic ethers (e.g.
propyleneoxide, ethyleneoxide, tetrahydrofuran and the like); polyesters
prepared by polycondensation of a dibasic acid (e.g. adipic acid) and
glycol or ring opening polymerization of lactons; ethylene/propylene
copolymers; polyisobutylene and copolymers of isobutylene with isoprene
and the like; polychloroprene; polyisoprene and copolymers of isoprene
with butadiene, styrene, acrylonitrile and the like; polybutadiene and
copolymers of butadiene with styrene, acrylonitrile and the like;
polyolefins prepared by hydrogenating polyisoprene, polybutadiene or
isoprene/butadiene copolymers; polyacrylates prepared by radical
polymerization of acrylate (e.g. ethyl acrylate, butyl acrylate and the
like) and copolymers of acrylate with vinyl acetate, acrylonitrile,
styrene, ethylene and the like; graft polymers prepared by polymerizing a
vinyl monomer in the organic elastomeric polymer (A); polysulfides; and
the like. Among them, preferable are polyethers comprising repeating units
of the formula: --R--O-- wherein R is a C.sub.1 -C.sub.4 alkylene group
(e.g. polypropyleneoxide and the like); graft polymers prepared by
polymerizing a vinyl monomer (e.g. acrylate, styrene, acrylonitrile, vinyl
acetate and the like) in the presence of polyether (e.g.
polypropyleneoxide and the like); polyalkyl acrylate or copolymers of at
least 50% by weight of alkyl acrylate with vinyl acetate, acrylonitrile,
styrene, ethylene and the like, since they can introduce the
silicon-containing reactive group at a chain end of the molecule and are
suitable for the preparation of a liquid polymer in the absence of a
solvent. Particularly, polypropyleneoxide is preferable since it imparts
water resistance to the cured product and is cheap and easily handled as a
liquid material.
The silicon-containing reactive group is represented by the formula:
##STR3##
wherein X is a hydroxyl group or a hydrolyzable group, R.sup.1 is a
monovalent hydrocarbon group having 1 to 20 carbon atoms or an
organosiloxy group, "a" is 0, 1, 2 or 3, "b" is 0, 1 or 2 provided that
the total of "a" and "b" is at least 1, preferably from 1 to 4, and "m" is
0 or an integer of 1 to 18.
When X is the hydrolyzable group, the group (I) is cross linked through
hydrolysis by water and a silanol condensation reaction in the presence or
absence of a catalyst for the silanol condensation. When X is a hydroxyl
group, the group (I) is cross linked through the silanol condensation
reaction in the presence or absence of a catalyst for silanol
condensation.
Specific examples of the hydrolyzable group are a hydrogen atom, a halogen
atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino
group, an amide group, an aminoxy group, a mercapto group, an alkenyloxy
group and the like. Among them, the alkoxy group is preferable since it is
mildly hydrolyzed and easily handled.
The silicon-containing reactive group has at least one silicon atom. When
the silicon atoms are bonded through siloxane linkages, the
silicon-containing reactive group preferably not more than 20 silicon
atoms.
In the formula (I), when R.sup.1 is the organosiloxy group, it may be an
triorganosiloxy group of the formula:
(R').sub.3 SiO-- (II)
wherein R' is, the same or different, a C.sub.1 -C.sub.20 monovalent
hydrocarbon group.
Among the silicon-containing reactive group (I), a group of the formula:
##STR4##
wherein R.sup.1 and X are the same as defined above, and "a" is 1, 2 or 3
is preferable.
The silicon-containing reactive group (I) chemically bonds to the backbone
chain of the organic elastomeric polymer. It is not preferable for the
silicon-containing reactive group to be bonded to the backbone chain
through an bond structure of the formula: .tbd.Si--O--C.tbd., since such
structure tends to be cleavaged by water. A preferable bonding structure
between the silicon atom of the reactive group and the backbone chain is,
for example, a structure of the formula: .tbd.Si--C.tbd.. Most preferably,
the reactive group is bonded to the backbone chain in the following
chemical structure:
##STR5##
wherein R.sup.1, X, a, b and m are the same as defined above. R.sup.2 is a
hydrogen atom or a C.sub.1 -C.sub.20 monovalent organic group; R.sup.3 is
a C.sub.1 -C.sub.20 divalent organic group; and "c" is 0 or 1.
The silicon-containing reactive group may be introduced in the organic
elastomeric polymer by following manners;
(1) Copolymerizing a monomer having a copolymerizable unsaturated bond and
the silicon-containing reactive group (e.g. vinyltrialkoxysilane,
methacryloyloxypropylmethyldialkoxysilane,
methacryloyloxypropyltrialkoxysilane and the like) with a polymerizable
monomer (e.g. ethylene, propylene, isobutylene, chloroprene, isoprene,
butadiene, acrylate and the like); or copolymerizing a monomer having a
copolymerizable epoxy group and the silicon-containing reactive group
(e.g. .gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane and the like) with
propyleneoxide or ethyleneoxide. By this manner, the silicon-containing
reactive group is introduced in the side chain of the organic polymer.
(2) Polymerizing a radically polymerizable monomer in the presence of a
mercapto or disulfide type chain transfer agent having the
silicon-containing reactive group (e.g. mercaptopropyltrialkoxysilane,
mercaptopropylmethyldialkoxysilane and the like).
(3) Polymerizing a radically polymerizable monomer by the use of an azo or
peroxide type polymerization initiator having the silicon-containing
reactive group (e.g. azobis-2-(6-methyldiethoxysilyl-2-cyanohexane) and
the like).
By the manners (2) and (3), the silicon-containing reactive group is
introduced at the chain end of the polymer molecule.
(4) Reacting a compound having a functional group Y' and the
silicon-containing reactive group with a polymer having a functional group
Y reactive with the functional group Y' (e.g. a hydroxyl group, a carboxyl
group, a mercapto group, an epoxy group, an isocyanate group and the like)
on the side chain and/or at the chain end of the molecule.
Specific examples of the reaction (4) are shown in following Table.
TABLE 1
______________________________________
Functional Functional
group Y group Y' Resulting bond
______________________________________
COOH HO COO
.uparw.
##STR6##
##STR7##
.uparw. H.sub.2 N COO.sup.- H.sub.3.sup.+Nor
CONH
.uparw. OCN COOCONH
.uparw. CH.sub.2CHCOO
COOCH.sub.2 CH.sub.2 COO
OH OCN OCONH
SH
##STR8##
##STR9##
.uparw. OCN SCONH
.uparw. CH.sub.2CHCOO
SCH.sub.2 CH.sub.2 COO
.uparw. CH.sub.2CH SCH.sub.2 CH.sub.2
.uparw. ClCH.sub.2 SCH.sub.2
##STR10## HOOC
##STR11##
.uparw. HS
##STR12##
.uparw. H.sub.2 N
##STR13##
.uparw. HO
##STR14##
NH.sub.2
##STR15##
##STR16##
.uparw. OCN NHCONH
.uparw. HOOC .sup.+NH.sub.3 O.sup.- COor
NHCO
.uparw. ClCH.sub.2
##STR17##
.uparw. CH.sub.2CHCOO
NHCH.sub.2 CH.sub.2 COO
CONH.sub.2 OCN CONHCONH
CHCH.sub.2 HS CH.sub.2 CH.sub.2 S
.uparw. HSi CH.sub.2 CH.sub.2 Si
NCO HOOC NHCOOCO
.uparw. HO NHCOO
.uparw. HS NHCOS
.uparw. H.sub.2 N NHCONH
##STR18## HO
##STR19##
.uparw. H.sub.2 N
##STR20##
______________________________________
Specific examples of the polymer having the functional group Y are
polyetherpolyols comprising repeating units of the formula: --R--O--
wherein R is a C.sub.2 -C.sub.4 alkylene group (e.g. polypropylenepolyol,
polyethylenepolyol, polytetramethylenediol and the like); polyesterpolyols
prepared by polycondensation of a dibasic acid (e.g. adipic acid) and
glycol or ring opening polymerization of lactons; polyols or
polycarboxylic acids of polyisobutylene; polyols or polycarboxylic acids
of polybutadiene or copolymers of butadiene with styrene, acrylonitrile
and the like; polyols of polyolefins prepared by hydrogenating
polyisoprene or polybutadiene; polymer having an isocyanate functional
group prepared by reacting the above polyols or polycarboxylic acids with
polyisocyanate; polymers having an ethylenically unsaturated bond prepared
by reacting the above polyols with a halogen-containing ethylenically
unsaturated compound, and the like. Among them, preferable are those
having the functional group Y at the chain end of the molecule.
Specific examples of the silicon-containing compound having the functional
group Y' are amino group-containing silanes (e.g.
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-aminopropyltriethoxysilane and the like); mercapto
group-containing silanes (e.g. .gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane and the like); epoxysilanes
(e.g. .gamma.-glycidoxypropyltrimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like);
ethylenically unsaturated silanes (e.g. vinyltriethoxysilane,
.gamma.-methacryloyloxypropyltrimethoxysilane,
.gamma.-acryloyloxypropylmethyldimethoxysilane and the like);
chlorine-containing silanes (e.g. .gamma.-chloropropyltrimethoxysilane and
the like); isocyanate-containing silanes (e.g.
.gamma.-isocyanatepropyltriethoxysilane,
.gamma.-isocyanatepropylmethyldimethoxysilane and the like); and
hydrosilanes (e.g. methyldimethoxysilane, trimethoxysilane,
methyldiethoxysilane and the like.
Among the combinations of the polymer having the functional group Y and the
compound having the functional group Y', (i) a combination of the polymer
having an isocyanate group and the amino group- or mercapto
group-containing silane and (ii) a combination of the polymer having an
ethylenically unsaturated group and the hydrosilane are preferable. Among
the combination (ii), a combination of polypropyleneoxide having an
allylether group at the chain end and the hydrosilane is particularly
preferable. In the combination (ii), a silyl group can be introduced in
the polymer by a hydrosilylation reaction in the presence of a platinum
catalyst.
The organic polymer (A) has at least one, preferably 1.2 to 6
silicon-containing reactive groups in a molecule on the average. When the
number of the silicon-containing group in a molecule is less than one on
the average, the composition of the invention is not effectively cured and
the improvement of the properties is not satisfactorily achieved.
Preferably, the silicon-containing reactive group is attached to the chain
end of the organic polymer molecule, because the terminal
silicon-containing reactive group elongates the chain length between the
adjacent cross linking sites in the cured product so that, on one hand,
the brittleness of the epoxy resin is more effectively improved, and on
the other hand, the elastomeric cured product comprising predominantly the
polymer (A) has better strength.
The molecular weight of the organic polymer (A) is usually from 500 to
50,000, preferably from 1,000 to 20,000 since in this molecular weight
range, the polymer is in a liquid state.
The silicon-containing reactive group having a silicon atom to which a
hydroxyl group is attached may be prepared by hydrolyzing the
silicon-containing reactive group having a silicon atom to which a
hydrolyzable group is attached.
Preferable examples of the organic polymer (A) are disclosed in U.S. Pat.
Nos. 3,408,321, 3,453,230 and 3,592,795, Japanese Patent Publication No.
32673/1974, Japanese Patent Kokai Publication (unexamined) Nos.
156599/1975, 73561/1976, 6096/1979, 13767/1980, 13768/1980, 82123/1980,
123620/1980, 125121/1980, 131021/1980, 131022/1980, 135135/1980,
137129/1980, 179210/1982, 191703/1983, 78220/1984, 78221/1984, 78222/1984,
78223/1984 and 168014/1984.
The epoxy resin (B) may be any one of conventionally used ones. Specific
examples of the epoxy resin (B) are flame-retardant epoxy resins (e.g.
epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F
type epoxy resin, glycidyl ether of tetrabromobisphenol A and the like),
novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins,
epoxy resins of the type of glycidyl ether of bisphenol A-propyleneoxide
adduct, glycidyl p-oxybenzoate type epoxy resin, m-aminophnol type epoxy
resins, diaminodiphenylmethane type epoxy resins, urethane modified epoxy
resins, alicyclic epoxy resins, glycidyl ether of polyhydric alcohol (e.g.
N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine,
triglycidylisocyanurate, polyalkyleneglycol diglycidyl ether, glycerin and
the like), hydantoin type epoxy resins, epoxidized unsaturated polymer
such as petroleum resin, and the like. Among them, those having two epoxy
groups of the formula:
##STR21##
in a molecule are preferable since they are highly reactive during curing
and the cured product easily forms a three dimensional network. Most
preferable are the bisphenol A type epoxy resins and the novolak type
epoxy resins.
The curing agent (D) for the epoxy resin used according to the present
invention may be any one of the conventionally used ones. Specific
examples of the curing agent are amines (e.g. triethylenetetramine,
tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine,
m-xylenediamine, m-phenylenediamine, diaminodiphenylmethane,
diaminodiphenylsulfone, isophoronediamine,
2,4,6-tris-(dimethylaminomethyl)phenol and the like); tert-amine salts;
polyamide resins; imidazoles; dicyanediamides; complex compounds of boron
trifluoride, carboxylic acid anhydrides (e.g. phthalic anhydride,
hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
endomethylenetetrahydrophthalic anhydride, dodecinyl succinic anhydride,
pyromellitic anhydride, chlorendic anhydride and the like); alcohols;
phenols; and carboxylic acids.
The amount of the curing agent (D) varies with the kinds of the epoxy resin
and/or the curing agent. Usually, 0.1 to 300 parts by weight of the curing
agent (D) is used based on 100 parts by weight of the epoxy resin (B).
The resinous composition according to the present invention contains the
silicone compound having a silicon-containing reactive group and a
functional group reactive with an epoxy group (C) as one of the essential
components.
Examples of the functional group reactive with the epoxy group are a
primary, secondary or tertiary amino group, a mercapto group, an epoxy
group and a carboxyl group. The silicon-containing reactive group is the
same as that of the organic polymer (A). Particularly, the alkoxysilyl
group is preferable due to its good handling properties.
Specific examples of the silicone compound (C) are amino group-containing
silanes (e.g. .gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltriethoxysilane,
.gamma.-ureidopropyltriethoxysilane,
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane,
.gamma.-anilinopropyltrimethoxysilane and the like); mercapto
group-containing silanes (e.g. .gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldiethoxysilane and the like); epoxy
group-containing silanes (e.g. .gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like);
carboxysilanes (e.g. .beta.-carboxyethyltriethoxysilane,
.beta.-carboxyethylphenylbis(2-methoxyethoxy)silane,
N-.beta.-(N-carboxymethylaminoethyl)-.gamma.-aminopropyltrimethoxysilane
and the like). The silane compound may be used along or as a mixture with
at least one other silane compound.
A weight ratio of the epoxy resin (B) to the organic polymer (A) is from
100:1 to 1:100. When the amount of the organic polymer (A) is less than
the lower limit, impact strength or toughness of the cured product is not
desirably improved. When the amount of the organic polymer (A) exceeds the
upper limit, the strength of the cured product is insufficient. A
preferable weight ratio of the epoxy resin (B) to the organic polymer (A)
varies with the final use of the cured product. In order to improve impact
resistance, flexibility, toughness and peel strength of the cured epoxy
resin, 1 to 100 parts by weight, preferably 5 to 100 parts by weight of
the organic polymer (A) is used based on 100 parts by weight of the epoxy
resin (B). In order to improve strength of the cured organic elastomeric
polymer, 1 to 200 parts by weight, preferably 5 to 100 parts by weight of
the epoxy resin is used based on 100 parts by weight of the organic
polymer (A).
The amount of the silicone compound (C) is so selected that a weight ratio
of the total weight of the organic polymer (A) and the epoxy resin (B) to
the weight of the silicone compound (C), i.e. (A+B)/C, is from 100:0.1 to
100:20, preferably from 100:0.2 to 100:10.
The curable resinous composition of the invention may be prepared by mixing
the four components (A), (B), (C) and (D) according to a conventional
method. For example, the components are mixed with a mixer, rolls or a
kneader at a room or elevated temperature. Alternatively, the components
are dissolved in a suitable solvent and mixed. By a suitable combination
of the components, a one pack type or two pack type composition can be
prepared.
In addition to the four essential components (A), (B), (C) and (D), the
composition of the invention may optionally contains other conventionally
used additives such as a filler, a plasticizer, a silanol condensation
catalyst for curing the organic polymer (A), an anti-aging agent, a
ultraviolet absorbing agent, a lubricant, a pigment, a foaming agent and
the like.
Specific examples of the filler are wood meal, pulp, cotton chip, asbestos,
glass fiber, carbon fiber, mica, walnut shell flour, rice hull flour,
graphite, diatomaceous earth, china clay, fumed silica, precipitated
silica, silicic anhydride, carbon black, calcium carbonate, clay, talc,
titanium oxide, magnesium carbonate, quartz powder, aluminum powder, flint
powder, zinc powder, and mixtures thereof.
The curable composition of the invention can be cured at a room temperature
although the curing rate is increase at an elevated temperature of
100.degree. to 150.degree. C. When the composition is cured at a room
temperature, the epoxy resin (B) and the curing agent (C) are so selected.
In addition, when the liquid epoxy resin is used, a non-solvent type
curable composition of the invention is prepared.
The composition of the present invention may be formed by a conventional
molding method.
When the composition contains the epoxy resin (B) in an amount larger than
that of the organic polymer (A), it is preferably molded by the same
method as used for molding the epoxy resin, for example, compression
molding, transfer molding and injection molding. Thereby, a molded article
and a laminated article (e.g. copper-clad laminate and compressed
laminated wood) having improved impact resistance, flexibility and
toughness are produced. The composition having the above ratio of the
epoxy resin (A) and the organic polymer (B) may be used as an adhesive
with improved peel strength, a foam plastic with improved flexibility, a
binding agent for a fiber board or a particle board, a coating, a binding
agent for shell molding, a binder of a brake lining, a binder of a
grindstone and a matrix resin of a composite material containing glass
fiber or carbon fiber.
When the composition contains the organic polymer (A) in an amount larger
than that of the epoxy resin (B), it is preferably molded by the same
method as used for molding a solid rubber such as a natural rubber or a
liquid elastomer such as polyurethane. Thereby, a molded elastomeric
article and an expanded elastomeric article having improved strength are
produced. The composition having the above ratio of the epoxy resin (A)
and the organic polymer (B) may be used as an adhesive with improved peel
strength, a sealing agent and a pressure sensitive adhesive.
The present invention will be hereinafter explained further in detail by
following examples, wherein parts are by weight unless otherwise
indicated.
PREPARATION EXAMPLE 1
To a flask equipped with a stirrer, polypropyleneoxide (Average molecular
weight, 3,000) (300 g) was charged followed by the addition of
tolylenediisocyanate (26 g) and dibutyltin dilaurate (0.2 g). The mixture
was stirred at 100.degree. C. for 5 hours in a stream of nitrogen gas.
Then, .gamma.-aminopropyltriethoxysilane (22.1 g) was added to the mixture
and stirred at 100.degree. C. for 3 hours to obtain polyether having a
triethoxysilyl group at a chain end and about two silicon-containing
reactive groups in a molecule. Average molecular weight, about 6,600.
PREPARATION EXAMPLE 2
To an autoclave equipped with a stirrer, polypropyleneoxide 97% of the
terminal groups of which being allylether groups (Average molecular
weight, 8,000) (800 g) was charged followed by the addition of
methyldimethoxysilane (19 g). Then, a solution of chloroplatinic acid (8.9
g of H.sub.2 PtCl.sub.6.6H.sub.2 O dissolved in a mixture of 18 ml of
isopropyl alcohol and 160 ml of tetrahydrofuran) (0.34 ml) was added, and
the reaction was carried out at 80.degree. C. for 6 hours.
An amount of the unreacted hydrogenated silicon-containing group in the
reaction mixture was monitored by IR spectrum analysis to find that
substantially no said group remained. According to determination of the
silicon-containing group by NMR, it was confirmed that polypropyleneoxide
having, at the chain end, about 1.7 groups of the formula:
(CH.sub.3 O).sub.2 Si(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 O--
in a molecule on the average.
PREPARATION EXAMPLE 3
To a flask equipped with a stirrer, polypropyleneoxide-triol (Average
molecular weight, 3,000) (300 g) was charged followed by the addition of
metal sodium (9.2 g) and xylene (600 ml) and reacted at 120.degree. C. for
5 hours in a stream of nitrogen gas. Then, the reaction mixture was cooled
to 80.degree. C. After adding dibromomethane (17.4 g), the mixture was
reacted for 5 hours. Thereafter, acrylic chloride (36.2 g) was added and
reacted at 80.degree. C. for 6 hours. The reaction mixture was cooled to a
room temperature and filtered to remove the salt. From the reaction
mixture, xylene was evaporated off to obtain a polymer having about 4
groups of CH.sub.2 .dbd.CHCO-- at the chain ends per molecule. Average
molecular weight, about 6,100.
To a flask equipped with a stirrer, 61 g of the obtained polymer and
.gamma.-aminopropyltrimethoxysilane (5.4 g) were charged and reacted at
110.degree. C. for 10 hours to obtain polyether having about 3
trimethoxysilyl groups per molecule. Average molecular weight, about
6,600.
PREPARATION EXAMPLE 4
To a reactor, polypropyleneoxide 90% of the terminal groups of which being
CH.sub.2 .dbd.CHCH.sub.2 CO-- (Average molecular weight, 8,000) (100 g)
was charged followed by the addition of methyldimethoxysilane (1.77 g) and
a 10% solution of chloroplatinic acid (H.sub.2 PtCl.sub.6.6H.sub.2 O) in
isopropyl alcohol (0.013 g). The mixture was reacted at 80.degree. C. for
4 hours. After confirming disappearance of absorption by Si--H near 2,100
cm.sup.-1 in IR spectrum, the reaction was terminated.
The iodine number of the product was 2.0. Form this number, it was found
that the product had, on the average, 1.2 silicon-containing reactive
group and 0.6 polymerizable unsaturated group per molecule.
100 g of the product was charged in a reactor, degassed under reduced
pressure, replaced with nitrogen gas and heated to 90.degree. C. with
stirring. Then, a mixture of n-butyl acrylate (95.4 g),
tris(2-hydroxyethyl)isocyanuric acid triacrylate (1.8 g),
.gamma.-methacryloyloxypropyldimethoxymethylsilane (1.5 g),
.gamma.-mercaptopropyldimethoxymethylsilane (2.3 g) and
2,2'-azobisispbutyronitrile (hereinafter referred to as "AIBN") (0.5 g)
was dropwise added over 2 hours in an atmosphere of nitrogen. After 15 and
30 minutes from the completion of addition of the mixture, AIBN (each 0.25
g dissolved in 4 time weight of acetone) was further added. Thereafter,
the reaction mixture was stirred for 30 minutes to obtain a slightly
yellowish viscous liquid polymer. Viscosity, 460 P (23.degree. C.)
PREPARATION EXAMPLE 5
Butyl acrylate (80 g), vinyl acetate (20 g),
.gamma.-methacryloyloxypropylmethyldimethoxysilane (2.3 g),
.gamma.-mercaptopropylmethyldimethoxysilane (1.8 g) and
azobis-2-(6-methyldiethoxysilyl-2-cyanohexane) (1.0 g) were homogeneously
mixed. 25 g of the mixture was then charged in a four-necked 200 ml flask
equipped with a stirrer and a condenser and heated at 80.degree. C. on an
oil bath with introducing nitrogen gas. Within several minutes, the
polymerization was initiated to generate heat. After the heat generation
calmed, the rest of the mixture was dropwise added over 3 hours to proceed
polymerization. After the heat generation ceased, the polymerization was
terminated. The produced polymer had an average molecular weight of about
11,000 according to GPC analysis.
EXAMPLE 1 AND COMPARATIVE EXAMPLES 1-2
Bisphenol A type epoxy resin (Epikote 828 (trade name) manufactured by Yuka
Shell Epoxy Co., Ltd.) (50 parts), the polymer prepared in Preparation
Example 2 (100 parts), 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) (1
part), 2,4,6-tris-(dimethylaminomethyl)phenol (2.5 parts),
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane (2.5 parts) and
dibutyltin laurate (1 part) were thoroughly mixed and carefully poured in
a polyethylene made frame so as to avoid the formation of bubbles. Then,
the mixture was cured at 23.degree. C. for 7 days and post-cured at
50.degree. C. for 7 days to produce a sheet of the cured product having a
thickness of 2 mm.
From the sheet, a No. 3 dumbbell was punched according to JIS (Japanese
Industrial Standard) K 6301. Tensile strength at break (T.sub.B) and
elongation at break (E.sub.B) were measured at a pulling rate of 500
mm/min. to find that T.sub.B was 75 kg/cm.sup.2 and E.sub.B was 460%.
For comparison, in the same manner as in Example 1 but not using
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane, a sheet of a
cured product was produced. T.sub.B was 7 kg/cm.sup.2.
Further, in the same manner as in Example 1 but not using Epikote 828, a
sheet of a cured product was produced. T.sub.B was 5 kg/cm.sup.2.
EXAMPLES 2-5
In the same manner as in Example 1 but using the polymer prepared in
Preparation Example 1, 3, 4 or 5 in place of the polymer prepared in
Preparation Example 2, a sheet of a cured product was produced. T.sub.B
and E.sub.B of each sheet are shown in Table 2.
TABLE 2
______________________________________
Example No. 2 3 4 5
______________________________________
Polymer Prep. Prep. Prep. Prep
Ex. 1 Ex. 3 Ex. 4 Ex. 5
T.sub.B (kg/cm.sup.2)
152 114 42 28
E.sub.B (%) 260 340 440 240
______________________________________
EXAMPLES 6-8
In the same manner as in Example 1 but using a silicone compound in an
amount as shown in Table 3 in place of
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane, a sheet of a
cured product was produced. T.sub.B and E.sub.B of each sheet are shown in
Table 3.
TABLE 3
______________________________________
Example
No. 6 7 8
______________________________________
Silicone .gamma.-Aminopropyl-
.gamma.-glycidoxy-
.gamma.-mercapto-
compound triethoxysilane
propylmethoxy-
propylmethoxy-
(parts) (4) silane silane
(6) (4)
T.sub.B 82 31 72
(kg/cm.sup.2)
E.sub.B (%)
420 410 430
______________________________________
EXAMPLES 9-11
In the same manner as in Example 1 but using an epoxy resin and a curing
agent in amounts as shown in Table 4, a sheet of a cured product was
produced. T.sub.B and E.sub.B of each sheet are shown in Table 4.
TABLE 4
______________________________________
Example No.
9 10 11
______________________________________
Epoxy resin*.sup.1
Epikote 834 Epikote 1001
Epikote 152
(parts) (3) (20) (10)
Curing agent*.sup.2
G-624 TETA DMP-30
(parts) (15) (2) (1.5)
T.sub.B (kg/cm.sup.2)
56 43 23
E.sub.B (%)
480 400 560
______________________________________
Note:-
*.sup.1 Epikote 834 and 1001: Bisphenol A type epoxy resin (Yuka Shell
Epoxy Co. Ltd.)
Epikote 152: Phenol novolak type epoxy resin (Yuka Shell Epoxy Co. Ltd.).
*.sup.2 G624: Polyamide resin (Tokyo Kasei Co., Ltd.).
TETA: Triethylenetetraamine.
DMP30: 2,4,6Tris(dimethylaminomethyl)phenol.
EXAMPLE 12
The polymer prepared in Preparation Example 1 (25 parts),
2,2'-methylene-bis-(4-methyl-6-t-butylphenol) (0.5 part), Epikote 828 (100
parts), isophoronediamine (25 parts), water (0.05 part), dibutyltin
dilaurate (1 part) and
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane (4 parts) were
thoroughly mixed and degassed. Then, the mixture was poured in
polyethylene made frame and cured at 50.degree. C. for 1 day and then at
150.degree. C. for 2 hours. The Izod impact strength of the cured product
was 6.1 Kg.multidot.cm/cm.
EXAMPLES 13-30 AND COMPARATIVE EXAMPLES 3-5
The polymer prepared in Preparation Example 2 (100 parts), Epikote 828 (50
parts), a silane compound shown in Table 5, an epoxy resin curing agent
shown in Table 5, a bisphenol type antioxidant (Noklack NS-6 manufactured
by Ohuchi Shinko Kabushikikaisha) (1 part) and a silanol condensation
catalyst shown in Table 5 were thoroughly mixed. The adhesive
characteristics (tensile shear strength and T-shape peeling strength) of
the mixture were evaluated according to the methods defined by JIS
(Japanese Industrial Standard) K 6850 and K 6854.
TENSILE SHEAR STRENGTH
On an aluminum plate (according to JIS H 4000. A-1050P. 100 mm.times.25
mm.times.2.0 mm), the mixture was coated in a thickness of about 0.05 mm.
A pair of the same plates coated with the mixture were laminated with
facing the coated surfaces to each other and pressed by hand. The
laminated plates were kept at 23.degree. C. for one day and then at
50.degree. C. for three days and peeled off at a pulling rate of 50
mm/min. to measure the tensile shear strength.
T-SHAPE PEELING STRENGTH
On an aluminum plate (according to JIS H 4000. A-1050P. 200 mm.times.25
mm.times.0.1 mm), the mixture was coated in a thickness of about 0.5 mm. A
pair of the same plates coated with the mixture were laminated with facing
the coated surfaces to each other and pressed five times by moving a hand
roller with 5 kg of load along the length in one direction. The laminated
plates were kept at 23.degree. C. for one day and then at 50.degree. C.
for three days and peeled off at a pulling rate of 200 mm/min. to measure
the T-shape peeling strength.
The results are shown in Table 5.
In Table 5, the results of the compositions of Comparative Examples 3 to 5
are also shown.
The composition of Comparative Example 3 was the same as that of Example 13
except that the silane compound was not used. The composition of
Comparative Example 4 was the same as that of Example 19, 29 or 30 except
that the organic polymer having silicon-containing reactive group and the
silanol condensation catalyst were not used.
The composition of Comparative Example 5 is a conventional adhesive
composition of the epoxy resin.
The results shown in Table 5 clearly indicate that peeling strength is
improved by the use of the compositions of the present invention.
TABLE 5
__________________________________________________________________________
Tensile
T-shape peeling
Silanol condensation
Epoxy resin curing strength
strength
Example No.
catalyst (parts).sup.( *.sup.1)
agent (parts).sup.( *.sup.2)
Silane compound (parts)
(kg/cm.sup.2)
(kg/cm.sup.2)
__________________________________________________________________________
13 #918 (2) DMP-30 (5)
NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (2.5)
110 12.0
14 .uparw. (1)
TETA (5) NH.sub.2 C.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
(1.5) 65 4.0
15 .uparw. TD 982 (10)
NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (1.5)
75 6.5
16 Stann BL (2)
DMP-30 (5)
.uparw. (2.0) 90 9.0
17 .uparw. .uparw. HSC.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
70.5) 7.5
18 Stann SB65 (2)
TETA (5) NH.sub.2 C.sub.3 H.sub.6 Si(OCH.sub.2 CH.sub.3)
.sub.3 (1.5) 60 4.5
19 LF 101 (2)
DMP-30 (5)
NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (1.0)
130 12.0
20 .uparw. (0.5)
.uparw. NH.sub.2 C.sub.2 H.sub.4 NHC.sub.2 H.sub.4
NHC.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
120 ) 12.5
21 .uparw. TETA (5) NH.sub.2 C.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
(1.0) 70 4.8
22 .uparw. (1.0)
DMP-30 (5)
##STR22## 80 7.2
23 .uparw. .uparw.
##STR23## 110 9.5
24 DBTA (2) .uparw. NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (0.5)
120 12.5
25 DBTA (1) TETA (5) NH.sub.2 C.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
(1.0) 73 5.1
26 .uparw. TD 982 (10)
.uparw. 70 6.5
27 .uparw. DMP-30 (5)
HOOCC.sub.2 H.sub.4 Si(OCH.sub.2 CH.sub.3).sub.
3 (2.0) 70 7.3
28 Kerope S (2)
.uparw. NH.sub.2 C.sub.3 H.sub.6 Si(OCH.sub.3).sub.3
(1.0) 110 6.5
29 .uparw. (1)
.uparw. NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (1.0)
120 7.2
30 ALCH (2) .uparw. .uparw. 95 6.3
Com. 3 #918 (2) DMP-30 (5)
None 18 3.2
Com. 4.sup.( *.sup.3)
None .uparw. NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3 H.sub.6
Si(OCH.sub.3).sub.3 (1.0)
50 Note.sup.(
*.sup.5)
Com. 5.sup.( *.sup.4)
None None None 122 Note.sup.(
__________________________________________________________________________
*.sup.5)
Note
.sup.(*.sup.1) #918, Stann BL and SB65: Organic tin compounds (Sankyo
Organic Synthesis Co., Ltd., Japan).
LF 101: An organic tin compound (Tokyo Fine Chemical Co., Ltd., Japan).
DBTA: Dibutyltin deacetylacetonate.
Kerope S: An organic aluminum compound (Hope Pharmaceuticals Co., Ltd.,
Japan).
ALCH: An organic aluminum compound (Kawaken Fine Chemical Co., Ltd.,
Japan).
.sup.(*.sup.2) DMP-30 and TETA: See Note.sup.(*.sup.2) of Table 4.
TD 982: Polyamide resin (Dainippon Ink Kagaku Co. Ltd., Japan).
.sup.(*.sup.3) Epikote 828:DMP30:NH.sub.2 C.sub.2 H.sub.4 NHC.sub.3
H.sub.6 Si(OCH.sub. 3).sub.3 = 50:10:1 (parts by weight).
.sup.(*.sup.4) An epoxy type adhesive (E Set M by Konishi Co., Ltd.).
.sup.(*.sup.5) Very easily peeled off.
PREPARATION EXAMPLE 6
To a reactor, the polymer prepared in Preparation Example 2 (75 g) was
charged, evacuated under reduced pressure and flashed with a nitrogen gas.
After heated to 90.degree. C. and stirred, a mixture of n-butyl acrylate
(24.5 g), .gamma.-mercaptopropylmethyldimethoxysilane (0.4 g) and AIBN
(0.1 g) was dropwise added over 1 hour in an atmosphere of nitrogen. After
15 and 30 minutes from the completion of addition of the mixture, AIBN
(each 0.0025 g dissolved in 4 time weight of acetone) was further added.
Thereafter, the reaction mixture was stirred for 30 minutes to obtain a
slightly yellowish viscous liquid polymer having Brookfield viscosity of
260 poise (23.degree. C). According to the GC analysis, the amount of the
unreacted monomers was 0.9%.
PREPARATION EXAMPLE 7
In the same manner as in Preparation Example 6 but using a mixture of
n-butyl acrylate (19.6 g), acrylonitrile (4.9 g),
.gamma.-mercaptopropylmethyldimethoxysilane (0.4 g) and AIBN (0.1 g), a
polymer were prepared. Viscosity, 410 poise (23.degree. C.). Amount of the
unreacted monomers, 1.1%.
PREPARATION EXAMPLE 8
In the same manner as in Preparation Example 6 but using 50 g of the
polymer prepared in Preparation Example 2 and a mixture of n-butyl
acrylate (47.13 g), .gamma.-mercaptopropylmethyldimethoxysilane (1.62 g)
and AIBN (0.4 g), a polymer was prepared. Viscosity, 235 poise. Amount of
the unreacted monomers, 0.8%.
PREPARATION EXAMPLE 9
n-Butyl acrylate (95.84 g), .gamma.-mercaptopropylmethyldimethoxysilane
(2.02 g), .gamma.-methacryloxypropylmethyldimethoxysilane (1.57 g),
neopentylglycol diacrylate (0.30 g) and AIBN (0.25 g) were homogeneously
mixed. 30 g of the mixture was then charged in a four-necked 200 ml flask
equipped with a stirrer and a condenser and heated at 80.degree. C. on an
oil bath with introducing nitrogen gas. Within several | | |
