USOO6838499B2

(12) United States Patent (10) Patent No.: US 6,838,499 B2

Kimura (45) Date of Patent: Jan. 4, 2005

(54) CURABLE COMPOSITIONS (56) References Cited

U.S. PATENT DOCUMENTS
(75) Inventor: Tsuneo Kimura, Gunma-ken (JP)
4,985,277 A * 1/1991 Shimizu et al. ............. 427/18O
(73) Assignee: Shin-Etsu Chemical Co., Ltd., Tokyo 5,066,714. A * 11/1991 Inoue et al. ...... ... 524/731
(JP) 5,693,689 A * 12/1997 Gibbon ....................... 523/137
FOREIGN PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 JP 62025 180 A * 2/1987 ............ CO9D/5/00
U.S.C. 154(b) by 128 days. JP 63-10662 A 1/1988
JP O1165652 A 6/1989 ........... CO8L/63/OO
JP 10-511730 A 11/1998
(21) Appl. No.: 10/367,799 JP 11-61.100 A 3/1999
JP 11-106738 A 4/1999
(22) Filed: Feb. 19, 2003 WO WO 96/20980 A1 7/1996
(65) Prior Publication Data * cited by examiner
US 2003/0166739 A1 Sep. 4, 2003 Primary Examiner Margaret G. Moore
ASSistant Examiner Marc S. Zimmer
(30) Foreign Application Priority Data
(74) Attorney, Agent, or Firm-Birch, Stewart, Kolasch &
Feb. 19, 2002 (JP) ....................................... 2002-04O988 Birch, LLP
(51) Int. Cl." .............................................. C08K 5/5419 (57) ABSTRACT
(52) U.S. Cl. ........................... 524/268; 528/31; 528/32; A curable composition comprising a liquid base polymer, a
528/34; 524/588; 524/858; 524/860; 524/861; Silicone elastomer powder, and a crosslinking agent is in
524/862; 524/863; 525/477 putty form prior to curing, tack-free to the hand, easy to
(58) Field of Search ................................. 524/268, 588, work, and adherent.
524/858, 860, 861, 862, 863; 525/477;
528/31, 32, 34 8 Claims, No Drawings
 US 6,838,499 B2
1 2
CURABLE COMPOSITIONS an elastomer having a durometer hardness of 10 to 80 as
measured by the JIS Type A durometer hardness test, the
inclusion of the powder, even in a large amount, does not
TECHNICAL FIELD detract from rubber elasticity. The composition remains fully
This invention relates to curable compositions in putty
5 adherent, and the composition as cured is Satisfactorily
flexible.
form, and more particularly, to putty like curable composi
tions which are tack-free during manual operation and Therefore, the present invention provides a curable com
remain Stable with the passage of time. position comprising a liquid base polymer, a Silicone elas
tomer powder, and a crosslinking agent, the composition
BACKGROUND OF THE INVENTION being in putty form prior to curing.
In the prior art, room temperature-curable organopolysi The inventive compositions are puttylike in the uncured
loxane compositions are widely used as Sealing agents or the State, but acquire high pressure resistance immediately after
like. Prior to curing, they are liquid or pasty and thus tacky application, and develop adherence after curing. Therefore,
to the worker hands So that manual operation is Substantially 15
the inventive compositions are highly compliant with those
prohibited. applications where liquid and pasty curable compositions
have been traditionally used, Such as, for example, gasket
Adhesives and Sealing agents in putty form are also materials including automobile oil seal materials (FIPG
known in the art. Among others, Silicone putties using materials), adhesive Seals between electric conductors and
organopolysiloxanes as base polymers are well known. AS resin covers, adhesive Seals between resin casings or con
compared with other organic rubbers, Silicone putties have nectors and electric conductors, and adhesive Seals for
good heat resistance and freeze resistance and maintain Vacuum or pressurized chambers. Also, the inventive com
Stable rubber physical properties and electrical properties positions are highly compliant with the uses where adhesive
even at elevated temperatures or in a hot humid Seal materials to be applied in-situ or in factory must cease
environment, and thus used in a variety of applications flowing immediately after application, Such as, for example,
including electric, electronic, automotive and building 25
adhesive Seals between rubber gaskets and glass Surface,
industries. In particular, Silicone putties endowed with a multilayer glass joint Seals, adhesive Seals at water-proof
curing ability are used as shape-forming, dental impression sheet joints and end faces, adhesive Seals between Solar
and building Sealing materials and find many other applica collectors and rooftop waterproof sheets, adhesive Seals
tions. between Solar photovoltaic panels and roofing, Surface
These putty like curable Silicone compositions are gener bonds of Siding panels to building wall members, adhesive
ally formulated by compounding a poly organosiloxane as a Seals between glass or transparent resin plates and window
base polymer with a filler for imparting a putty form prior to frames in microwave Ovens, meters or other instruments. In
curing Such as fumed Silica, finely divided quartz, calcium addition to the foregoing applications, the inventive com
carbonate, diatomaceous earth and aluminum Silicate, and 35
positions can be advantageously used as repairing materials
optionally adding a curing or curing agent for imparting for toys, figurative models, Structures, Shaped articles and
curing ability. In order that these compositions be endowed electric or electronic parts, and as clay of the curing type,
with a putty form, made tack-free to the hands or fingers and because they are curable at room temperature and eliminate
effectively worked, the viscosity of the base polymer and the a need for heating Ovens.
type and quantity of the filler must be carefully Selected. 40
Otherwise, the properties of the cured product are Substan DETAILED DESCRIPTION OF THE
tially limited. INVENTION
JP-A 63-10662 discloses a puttylike silicone composition The curable compositions of the present invention are
comprising a polyorganosiloxane and a polymethylsilses defined as comprising a liquid base polymer, a Silicone
quioxane. However, the polymethylsilsesquioxane is a non elastomer powder, and a crosslinking agent and are Suitable
elastic resin and has a durometer hardness of at least 90 as
especially as various adhesive Seal materials.
measured by the JIS Type Adurometer hardness test. When The inventive curable compositions include, but are not
the polymethylsilsesquioxane is compounded in a curable
Silicone composition, the rubber as cured lackS flexibility limited to, Silicone, modified Silicone, acrylic, polysulfide,
due to an increased hardneSS and has poor adhesion and polyurethane and polyisobutylene base compositions. Of
sealing tightness. JP-A 10-511730 discloses a sealing com
50 these, Silicone rubber compositions are preferred.
position comprising a high Viscosity oil as a base polymer, The Silicone rubber compositions in one preferred
which composition is Self-Supporting prior to curing. JP-A embodiment of the present invention are those compositions
11-61100 and JP-A 11-106738 disclose sealing composi comprising a diorganopolysiloxane as a base polymer. Their
tions comprising a high molecular weight gum-like base 55
curing type is preferably condensation curing, addition
polymer and fumed Silica. All these compositions are unsat curing or radiation curing type, but is not limited thereto.
isfactory in ease of working and rubber elasticity. Condensation curing type compositions are most preferred.
The diorganopolysiloxane used herein as the base poly
SUMMARY OF THE INVENTION mer preferably has the average compositional formula:
An object of the invention is to provide a curable com 60
position which is fully adherent and in putty form prior to
curing and cures into a product exhibiting high flexibility. wherein R is independently Selected from among Substituted
We have found that when a silicone elastomer powder is or unsubstituted monovalent hydrocarbon groups, prefer
included in a curable composition comprising a liquid base ably having 1 to 12 carbon atoms, more preferably 1 to 10
polymer and a crosslinking agent, the composition becomes 65 carbon atoms, and “a” is a number of 1.90 to 2.05. Suitable
putty like and tack-free to the worker hands So that it can be monovalent hydrocarbon groups represented by R include
effectively worked. Since the silicone elastomer powder is alkyl groups Such as methyl, ethyl, propyl, butyl,
 US 6,838,499 B2
3 4
2-ethylbutyl and octyl, cycloalkyl groupS. Such as cyclohexyl penyloxy and isobute nyloxy, amino groups Such as
and cyclopentyl, alkenyl groupS. Such as Vinyl, hexenyl and N-butylamino and N,N-diethylamino, and amide groups
allyl, aryl groups Such as phenyl, tolyl, Xylyl, naphthyl and Such as N-methylacetamide, with the alkoxy, ketoxime,
diphenyl, aralkyl groups Such as benzyl and phenylethyl, alkenyloxy and acyloxy groups being preferred. The
and Substituted groups of the foregoing in which Some or all crosslinking agent is blended in amounts of 1 to 50 parts by
of the hydrogen atoms attached to carbon atoms are Substi weight, more preferably 2 to 20 parts by weight per 100 parts
tuted with halogen atoms or cyano groups, for example, by weight of the hydroxyl or organoxy end-capped organ
chloromethyl, trifluoropropyl, 2-cyanoethyl and opolysiloxane.
3-cyanopropyl, and Such groups which contain or have Curing catalysts are often used in the condensation curing
Substituted thereon an amino, ether (-O-), carbonyl type Silicone rubber compositions. Illustrative of the curing
(-CO-), carboxyl (-COOH) or sulfonyl (-SO-) catalysts are alkyl tin esterS Such as dibutyltin diacetate,
grOup. dibutyltin dilaurate and dibutyltin dioctoate, titanates and
In the first preferred embodiment wherein the silicone titanium che late compoundS Such as
rubber composition is of the condensation curing type, the tetraiSopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-
base polymer is preferably a diorganopolysiloxane of the 15 ethylhexoxy)titanium, dipropoxy bis(acetylacetonato)
following general formula (1) or (2) whose molecular chain titanium, and titanium isopropoxyoctylene glycol, organo
is end-capped with a hydrolyzable group Such as a hydroxyl metallic compounds Such as Zinc naphthenate, Zinc Stearate,
or OrganOXy group. Zinc 2-ethyloctoate, iron 2-ethylhexoate, cobalt
2-ethylhexoate, manganese 2-ethylhexoate, cobalt
(1) naphthe nate, and alkoxy aluminum compounds;
R R R R a mino alkyl-substituted alkoxysilane S Such as
HO-Si-X-(SiO)-Si-X-Si-OH 3-aminopropyltriethoxysilane and N-f-(aminoethyl)-y-
aminopropyltrimethoxysilane; amines and Salts thereof Such
R R R R as hexylamine and dodecylamine phosphate, quaternary
(2) 25 ammonium Salts Such as benzyltriethylammonium acetate;
R3-a R R R3-a
alkali metal Salts of lower fatty acids Such as potassium
Y-Si-X-(SiO)-Si-X-Si-Y, acetate, Sodium acetate and Sodium oxalate; dialkylhydroxy
lamines Such as dimethylhydroxylamine and diethylhy
R R
droxylamine; and guanidyl-containing Silanes or Siloxanes
Such as tetramethylguanidylpropyltrimethoxysilane,
Herein R is a substituted or unsubstituted monovalent hydro tetramethylguanidylpropylmethyldimethoxysilane, and
carbon group, X is an oxygen atom or a divalent hydrocar tetramethylguanidylpropyltris(trimethylsiloxy)silane. These
bon group having 1 to 8 carbon atoms, Y is a hydrolyzable catalysts may be used alone or in admixture of two or more.
group, n is Such a number that the diorganopolysiloxane has The curing catalyst is used in amounts of 0 to 10 parts by
a viscosity of at least 25 centistokes (cs) at 25 C., more 35 weight, preferably 0.01 to 5 parts by weight per 100 parts by
preferably 100 to 1,000,000 cs at 25°C., and “a” is 2 or 3. weight of the diorganopolysiloxane.
The substituted or unsubstituted monovalent hydrocarbon In the second preferred embodiment wherein the inven
groups represented by R are as exemplified above for the tive Silicone rubber composition is of the addition curing
foregoing R. Among others, methyl, phenyl and vinyl are type, the diorganopolysiloxane used as the base polymer
preferred, with methyl being most preferred. The divalent 40 should have at least two alkenyl groups at ends of the
hydrocarbon groups represented by X are those having 1 to molecular chain and/or within the molecular chain. This
8 carbon atoms, preferably 2 to 6 carbon atoms, for example, diorganopolysiloxane should preferably have a Viscosity of
alkylene groupS Such as methylene, ethylene and propylene, at least 25 cs at 25°C., more preferably 100 to 10,000,000
cycloalkylene groupS Such as cyclohexylene, arylene groups cs at 25 C.
Such as phenylene, and Substituted groups of the foregoing 45 AS a crosslinking agent for the diorganopolysiloxane, an
in which Some or all of the hydrogen atoms are Substituted organohydrogenpolysiloxane having at least two, preferably
with halogen atoms. Preferably, X is an oxygen atom or at least three SiH groups in a molecule is used. The orga
ethylene group. The hydrolyzable groups represented by Y nohydrogenpolysiloxane used herein may be Selected from
include alkoxy groupS. Such as methoxy, ethoxy and butoxy, well-known ones and preferably from those having a vis
ketoxime group S Such as dimethylketoxime and 50 cosity of up to 300 cs at 25 C. The organohydrogenpolysi
methylethylketoxime, acyloxy groupS. Such as acetoxy, alk loxane is preferably used in Such amounts as to give 0.3 to
enyloxy groups Such as isopropenyloxy and isobutenyloxy, 10 mol, more preferably 0.5 to 5 mol of SiH groups per mol
amino groupS. Such as N-butylamino and N,N-diethylamino, of alkenyl groups in the organopolysiloxane as the base
amide groupS. Such as N-methylacetamide, and chlorine polymer.
atoms. Of these, alkoxy groups are preferred. 55 To the composition of the Second preferred embodiment,
In order that the composition afford a cured product a curing catalyst is preferably added in a catalytic amount.
having Satisfactory rubber physical properties and mechani It may be selected from well-know addition reaction
cal Strength, the diorganopolysiloxane used herein should catalysts, for example, Group VIII metals and compounds
preferably have a viscosity of at least 25 cs at 25 C., more thereof, especially platinum compounds. Illustrative of the
preferably 100 to 1,000,000 cs at 25° C. 60 platinum compounds are chloroplatinic acid and platinum
AS a crosslinking agent for the diorganopolysiloxane, a olefin complexes. The addition reaction catalyst is prefer
Silane or Siloxane compound having at least two hydrolyZ ably added in amounts of 0.1 to 2,000 ppm, more preferably
able groups in a molecule is used. Examples of Suitable 1 to 1,000 ppm based on the diorganopolysiloxane as the
hydrolyzable groups include alkoxy groups Such as base polymer.
methoxy, ethoxy and butoxy, ketoxime groupS. Such as 65 In the third preferred embodiment wherein the inventive
dimethylketoxime and methylethylketoxime, acyloxy Silicone rubber composition is of the radiation curing type,
groupS Such as acetoxy, alkenyloxy groupS Such as isopro the diorganopolysiloxane used as the base polymer should
 US 6,838,499 B2
S 6
have aliphatic unsaturated groups (e.g., vinyl, allyl, tim. With an average particle size of less than 0.1 um, the
alkenyloxy, acrylic or methacrylic groups), mercapto powder may become too cohesive. With an average particle
groups, epoxy groups, hydrosilyl groups or other groups at size of more than 1,000 um, the powder may become
ends of the molecular chain and/or within the molecular non-uniform.
chain. This diorganopolysiloxane should preferably have a The silicone elastomer powder is preferably blended in
viscosity of at least 25 cs at 25 C., more preferably 100 to amounts of 25 to 500 parts by weight, more preferably 50 to
10,000,000 cs at 25° C. 400 parts by weight per 100 parts by weight of the base
The composition further contains a reaction initiator or polymer. With too small an amount of the powder, the
crosslinking agent. AS is well known in the art, the initiators composition may become tacky to the hand. With too large
include acetophenone, propiophenone, benzophenone, an amount of the powder, difficulties may arise in working.
Xanthol, fluorein, ben Zaldehyde, anthraquinone, An adhesion promoter may be added to the putty like
triphenylamine, carbazole, 3-methylacetophenone, curable composition of the invention for improving the
4-methylace top he none, 3-penty lace top he none, adhesion. Suitable adhesion promoters include Silane cou
pling agents. Such as amino group-containing alkoxysilanes
4-methoxyacetophe none, 3-bromo acetophe none, and titanium coupling agents, with the Silane coupling
4- ally lace top he none, p-diac etylben Zene, 15 agents being preferred. An appropriate amount of the adhe
3-methoxyben Zophe none, 4-methylben Zophenone, sion promoter is 0.1 to 30 parts by weight, more preferably
4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 0.2 to 20 parts by weight per 100 parts by weight of the
4-chloro-4'-benzylbenzophenone, 3-chloroxanthol, 3,9- diorganopolysiloxane as the base polymer.
dichloroxanthol, 3-chloro-8-nonylxanthol, benzoin, benzoin In addition to the Silicone elastomer powder, one or more
methyl ether, benzo in butyl ether, bis(4- filler may be added to the puttylike curable composition of
dimethylaminophenyl)ketone, benzyl methoxy ketal, and the invention for reinforcement or other purposes, if desired.
2-chlorothioxanthol. The initiator is preferably blended in Examples of the filler which is generally used in the Silicone
amounts of 0.1 to 20 parts by weight, more preferably 0.5 to rubber composition of this type include reinforcing fillers
10 parts by weight per 100 parts by weight of the organop Such as fumed Silica, precipitated Silica, quartz flour, carbon
olysiloxane. 25 powder, talc, Zeolite and bentonite, fibrous fillerS Such as
In the curable composition of the invention is included a asbestos, glass fibers, carbon fibers and organic fibers, and
Silicone elastomer powder. The use of the Silicone elastomer basic fillerS Such as calcium carbonate, Zinc carbonate,
powder makes the curable composition puttylike and tack magnesium oxide and celite, which may be Surface treated
free to the worker hands. The composition also becomes with Silanes, siloxanes, resin acids or the like. The amount
Stable with the passage of time. In addition, the composition of the filler other than the silicone elastomer powder is
when cured exhibits good elasticity and Seal tightness. preferably 1 to 500 parts by weight, more preferably 5 to 200
The silicone elastomer powder used herein is a finely parts by weight per 100 parts by weight of the base polymer,
divided silicone rubber. Though not critical, the silicone though not critical.
elastomer is preferably prepared by reacting an organopol Various compounds are optionally added to the Silicone
ySiloxane having, on the average, at least two olefinic 35 rubber composition of the invention as long as they do not
unsaturated groups in a molecule with another organopol compromise the putty form and ease of working of the
ySiloxane having, on the average, at least two Silicon-bonded composition and the flexibility and adhesion of the cured
hydrogen atoms in a molecule in the presence of an addition composition. For example, thixotropic agents Such as poly
reaction catalyst. ethylene glycol and derivatives thereof, heat resistance
In one exemplary process, a mixture of an organopolysi 40 improverS Such as red iron oxide and cerium oxide, freeze
loxane having, on the average, at least two olefinic unsat resistance improvers, dehydrating agents, anti-rusting
urated groups in a molecule, another organopolysiloxane agents, liquid reinforcements Such as network polysiloxane
having, on the average, at least two Silicon-bonded hydrogen comprising triorganosiloxy units and SiO2 units and/or
atoms in a molecule and an addition reaction catalyst is monoorganosiloxy units, and the like are added in conven
agitated and mixed while heating at a temperature of 25 to 45 tional amounts, if desired.
100° C., whereby the organopolysiloxane is cured. The The puttylike curable composition of the invention can be
resulting elastomer is finely divided by means of a high prepared by mixing predetermined amounts of the above
Shear grinding machine. Exemplary of the high shear grind mentioned components in a planetary mixer, Shinagawa
ing machine are a roll mill, Sand grinder, ball mill and the mixer or the like according to a conventional process.
like. This process yields a powder of particles of different 50 With respect to the curing method and conditions of the
shapes. putty like curable composition of the invention, any well
In another process, a mixture of an organopolysiloxane known method and conditions may be employed depending
having, on the average, at least two olefinic unsaturated on the type of composition.
groups in a molecule and another organopolysiloxane In the case of condensation curing type, the composition
having, on the average, at least two Silicon-bonded hydrogen 55 must be Stored in a moisture-free atmosphere because the
atoms in a molecule is dispersed in water using a nonionic composition can cure with moisture in the air.
Surfactant or ionic Surfactant, to which an addition reaction As used herein, the term “putty form” or “puttylike'
catalyst is added whereupon curing reaction takes place. The means that unlike the paste which is tacky to the hand, the
resulting elastomer is then Separated and dried. This proceSS composition is clay-like and tack-free to the hand, and can
yields a powder of Spherical particles. 60 be manually shaped to a rope or any other shape.
In order that the composition be endowed with putty form, From the handling and processing aspect, the curable
tack-free properties to the worker hands, and ease of work composition of the invention preferably has a Williams
ing prior to curing, and in order that the cured composition plasticity at 25°C. of 50 to 500, more preferably 70 to 400,
be endowed with flexibility and adherence, a silicone elas and most preferably 80 to 350. The composition with too
tomer powder of Spherical particles is preferred. 65 low a plasticity may be too Soft and tacky to the hand
The Silicone elastomer powder preferably has an average whereas the composition with too high a plasticity may be
particle size of 0.1 to 1,000 um, more preferably 1 to 100 too hard and interfere with manual operation.
 US 6,838,499 B2
7 8
Prior to curing, the curable composition of the invention viscosity of 100 mPats, 75 parts by weight of a spherical
is puttylike, tack-free to the hand and effective to manual Silicone elastomer powder having an average particle size of
operation and yet remains fully adherent. The composition, 4 um, 15 parts by weight of fumed Silica Surface treated with
when cured, exhibits high flexibility. dimethyldichlorosilane and having a specific Surface area of
110 m /g, 6 parts by weight of vinyltributanoximesilane, 0.1
EXAMPLE part by weight of dioctyltin dilaurate, and 1 part by weight
Examples of the invention are given below by way of of Y-aminopropyltriethoxysilane were milled under a
illustration and not by way of limitation. Note that the reduced pressure, obtaining a putty like Sample 5.
viscosity is a measurement at 25 C. 1O Example 6
Example 1 100 parts by weight of a dimethylpolysiloxane capped
100 parts by weight of a dimethylpolysiloxane capped with a trimethoxysilyl group at either end of the molecular
with a hydroxyl group at either end of the molecular chain chain and having a viscosity of 20,000 mPats, 100 parts by
and having a viscosity of 20,000 mPats, 200 parts by weight 15 weight of a spherical Silicone elastomer powder having an
of a spherical Silicone elastomer powder having an average average particle size of 12 um, 20 parts by weight of fumed
particle Size of 12 um, 6 parts by weight of Silica Surface treated with hexamethyldisilaZane and having
methyltributanoximesilane, 0.1 part by weight of dibutyltin a specific Surface area of 200 m/g, 8 parts by weight of
dioc to ate, and 1 part by weight of Vinyltrimethoxysilane, 2 parts by weight of dipropoxybis
y-aminopropyltriethoxysilane were milled under a reduced (acetylacetonato) titanium, and 1 part by weight of
preSSure, obtaining a puttylike Sample 1. Y-glycidoxypropyltrimethoxysilane were milled under a
reduced pressure, obtaining a putty like Sample 6.
Example 2
Example 7
100 parts by weight of a dimethylpolysiloxane capped 25
with a hydroxyl group at either end of the molecular chain 100 parts by weight of a polypropylene oxide capped with
and having a viscosity of 20,000 mPats, 200 parts by weight a methyldimethoxysilylpropyl group at either end of the
of a spherical Silicone elastomer powder having an average molecular chain and having a viscosity of 4,000 mPas, 300
particle Size of 12 um, 6 parts by weight of parts by weight of a spherical Silicone elastomer powder
Vinyltriisoprope noxysilane, 1 part by weight of having an average particle size of 12 um, 2 parts by weight
tetramethylguanidylpropyltrimethoxysilane, and 1 part by of dibutyltin dimethoxide, and 1 part by weight of
weight of Y-aminopropyltriethoxysilane were milled under a Y-ethylene diaminopropyltrimethoxysilane were milled
reduced pressure, obtaining a puttylike Sample 2. under a reduced preSSure, obtaining a putty like Sample 7.
Example 3 35
Comparative Examples 1-7
Aputtylike Sample 3 was prepared as in Example 1 except Compositions were prepared as in Examples 1 to 7
that a spherical Silicone elastomer powder having an average without adding the Silicone elastomer powder. They are
particle size of 4 um was used instead of the Spherical designated Samples 1' to 7.
Silicone elastomer powder having an average particle size of
12 um. 40 The form of the compositions of Examples and Compara
tive Examples was inspected by visual observation. A 50-g
Example 4 portion taken out of the composition was kneaded with
hands to examine the workability (ease of kneading or
100 parts by weight of a dimethylpolysiloxane capped tackiness). The composition was rated OK when easy to
with a hydroxyl group at either end of the molecular chain 45 knead and NG when difficult or impossible to knead. The
and having a viscosity of 50,000 mPas, 20 parts by weight results are shown in Tables 1 and 2.
of a dimethylpolysiloxane capped with a trimethylsiloxy For each of Examples 1 to 7, the puttylike composition
group at either end of the molecular chain and having a was shaped into a sheet of 2 mm thick and cured for 7 dayS
viscosity of 100 mPa is, 100 parts by weight of a spherical in an atmosphere of 23+2° C. and RH 50+5%. The physical
Silicone elastomer powder having an average particle size of 50 properties (hardness, elongation and tensile Strength) of the
12 um, 10 parts by weight of fumed Silica Surface treated rubber sheet were measured according to JIS K-6249.
with dimethyldichlorosilane and having a specific Surface Separately, aluminum plates of 25 mmx100 mmx0.3 mm
area of 110 m f/g, 6 parts by weight of (thick) were bonded with the composition to assemble a
vinyltributanoximesilane, 0.1 part by weight of dioctyltin
dilau rate, and 1 part by weight of Shear adhesion test piece having an bond thickness of 2 mm
y-aminopropyltriethoxysilane were milled under a reduced 55 and a bond area of 2.5 cm and the composition cured under
preSSure, obtaining a puttylike Sample 4. the same conditions as above. Using this test piece, the
longitudinal Shear Strength and percent cohesive failure were
Example 5 measured. Further, for each of Examples 1 to 7, a 200-g
portion of the putty like composition was wrapped with
100 parts by weight of a dimethylpolysiloxane capped 60 polyethylene film and placed in an aluminum laminate
with a hydroxyl group at either end of the molecular chain package whose opening was heat Sealed. The wrapped
and having a viscosity of 50,000 mPas, 20 parts by weight composition in the package was kept at 70° C. for 7 days.
of a dimethylpolysiloxane capped with a trimethylsiloxy The thus aged composition was examined for form, work
group at either end of the molecular chain and having a ability and plasticity. The results are also shown in Table 1.
 US 6,838,499 B2
10

Initial Form putty putty putty putty putty

Workability OK OK OK OK OK
Plasticity 81 85 89 175 312
Hardness (Durometer A) 24 26 2O 25 32
Elongation (%) 22O 21O 3OO 2SO 220 350 150
Tensile strength (MPa) 0.8 0.9 1.1 1.0 1.5
Al plate shear strength (MPa) 0.4 0.4 0.5 0.6 0.9 1.2 O.3
Cohesive failure (%) 1OO 100 100 1 OO 100 1OO
7 days Appearance putty putty putty putty putty putty putty
aged Workability OK OK OK OK OK OK OK
Plasticity 8O 88 87 172 310 290 88

TABLE 2 TABLE 3
Comparative Example Example Comparative Example
1. 2 3 4 5 6 7 8 9 8 9

Form liquid liquid liquid paste paste paste liquid Form putty putty liquid liquid
Workability NG NG NG NG NG NG NG 25 Workability OK OK NG NG

Example 8 Japanese Patent Application No. 2002-040988 is incor

porated herein by reference.
100 parts by weight of a dimethylpolysiloxane capped
with a vinyl group at either end of the molecular chain and Although some preferred embodiments have been
having a viscosity of 3,000 mPas, 3.0 parts by weight of a described, many modifications and variations may be made
SiH-containing dimethylpolysiloxane having a Viscosity of 35
thereto in light of the above teachings. It is therefore to be
20 mPa's, 300 parts by weight of a spherical silicone understood that the invention may be practiced otherwise
elastomer powder having an average particle size of 12 um, than as Specifically described without departing from the
and an amount of an isopropanol Solution of chloroplatinic Scope of the appended claims.
acid to give 50 ppm of platinum based on the entire
Siloxanes were milled, obtaining a putty like Sample 8. 40 What is claimed is:
1. A curable composition comprising a liquid base
Example 9 polymer, a Silicone elastomer powder, and a crosslinking
agent, the composition being in putty form prior to curing.
100 parts by weight of a dimethylpolysiloxane capped 45 2. The curable composition of claim 1 which is a curable
with a bis(acryloxymethyldimethylsiloxy)methylsilyl group Silicone rubber composition.
at either end of the molecular chain and having a Viscosity 3. The curable composition of claim 2 wherein the curable
of 3,000 mPats, 3 parts by weight of diethoxyacetophenone, Silicone rubber composition is of the condensation curing,
and 300 parts by weight of a spherical Silicone elastomer addition curing or radiation curing type.
powder having an average particle size of 12 um were 50 4. The curable composition of claim 2 wherein the curable
milled, obtaining a puttylike Sample 9. Silicone rubber composition is of the condensation curing
type and wherein the liquid base polymer is a diorganopol
ysiloxane having the following general formula (1) or (2):
Comparative Examples 8-9
55
(1)
R R R R
Compositions were prepared as in Examples 8 and 9
without adding the Silicone elastomer powder. They are HO-Si-X-(SiO)-Si-X-Si-OH
designated Samples 8' to 9'. R R R R
60
The form of the compositions of Examples and Compara
tive Examples was inspected by visual observation. A 50-g
portion taken out of the composition was kneaded with wherein R is a Substituted or unsubstituted monovalent
hands to examine the workability (ease of kneading or hydrocarbon group, X is an oxygen atom or a divalent
tackiness). The composition was rated OK when easy to 65 hydrocarbon group having 1 to 8 carbon atoms, and n is Such
knead and NG when difficult or impossible to knead. The a number that the diorganopolysiloxane has a Viscosity of at
results are shown in Table 3. least 25 cs at 25 C.,
 US 6,838,499 B2
11 12
and wherein the liquid base polymer is a diorganopolysi
R3-a R R R3-a
(2) loxane having at least two alkenyl groups in a molecule.
6. The curable composition of claim 1, further comprising
Y-Si-X-(SiO)-Si-X-Si-Y,
5
a silane coupling agent.
R R 7. The curable composition of claim 1 having a plasticity
of 50 to 500 prior to curing.
wherein Y is a hydrolyzable group, a is 2 or 3, and R, X, and 8. The curable composition of claim 1 which is used as an
in are as defined above. adhesive Seal material.
5. The curable composition of claim 2 wherein the curable 10
Silicone rubber composition is of the addition curing type