CA1315440C - Silicone adhesives and methods for making and using - Google Patents
Silicone adhesives and methods for making and usingInfo
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- CA1315440C CA1315440C CA000504138A CA504138A CA1315440C CA 1315440 C CA1315440 C CA 1315440C CA 000504138 A CA000504138 A CA 000504138A CA 504138 A CA504138 A CA 504138A CA 1315440 C CA1315440 C CA 1315440C
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Abstract
NOVEL SILICONE ADHESIVES AND METHODS FOR
MAKING AND USING
ABSTRACT OF THE DISCLOSURE
There is provided an adhesive composition comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing monomer, and (ii) an effective amount of acrylic-containing poly-diorganosiloxane; said acrylic-containing monomer and said acrylic-containing polydi-organosiloxane being present in an amount suffi-cient to produce upon polymerization thereof an adhesive solid, and (b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymeri-zation of said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane.
Methods for making and using the novel adhesive composition of the present invention are also provided.
MAKING AND USING
ABSTRACT OF THE DISCLOSURE
There is provided an adhesive composition comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing monomer, and (ii) an effective amount of acrylic-containing poly-diorganosiloxane; said acrylic-containing monomer and said acrylic-containing polydi-organosiloxane being present in an amount suffi-cient to produce upon polymerization thereof an adhesive solid, and (b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymeri-zation of said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane.
Methods for making and using the novel adhesive composition of the present invention are also provided.
Description
~ 3 ~ 5 4 ~ ~ 60SI 963 NOVEL SILICONE ADHESIVES AND METHQDS
FOR MAKING AND USING
Background of the Invent~on The present invention relates to silicone adhesive composi-tions and methods for making and using such compositions. Moreparticularly, the present invention relates to silicone adhe-sives comprising an acrylic-functional organopolysiloxàne, a reactive diluent and a polymerization initiator.
Over the past few years a new class of adhesive or bonding agent has been developed which offers as its main advantage a simple no mix application method and rapid bond formation at ambient temperature. These materials are modi~ied acrylic systems and are based on new modifying reactive polymers and a sur~ace-applied activator which catalyzes the polymerization of the reactive polymers. Application methods are similar to those used for contact adhesives; the adhesive base (e.g. reactive polymer and reactive diluent or monomer) is applied to one substrate surface and the activator is applied to the other substrate~sur~ace. The two surfaces are then brought together and held until handling strength is reached.
Generally an elastomeric polymer is colloidally dispersed in a monomer or a monomer/oligomer/polymer solution. The system is then polymerized using a ~ree radical mechanism, What occurs is a rapid, in situ polymerization of a (typically) methyl methacrylate system, toughened by elastomeric domains that have been incorporated into the structure by grafting.
:
~ 3 3 ~
An example of such a reactive adhesive is described in Bachman, U.S. Patent No. 4,34~,503. Brielly, this composition comprises 40 to 90 parts per hundred of an acrylic ester monomer capable of free radical polymerization and 60 to lO
parts per hundred of a monomeric polyacrylate ester prepolymer having terminal acrylate radicals linked by at least two divalent polyurethane or polyureide groups, which is catalyzed with an activator comprising l to lO parts per hundred of an aromatic perester free radical precursor, 0 5 to lO parts per hundred of an organic acid capable of cyclic tautomerism and up to 500 parts per million of a soluble compound of a transition metal cure accelerator. Bachman also states that it is conven-tional to include small percentages of silane monomers to increase moistfure resistance as wel) as to enhance bonding of the adhesive to glass and similar surfaces.
One shortcoming of prior art reactive adhesives is that they become brittle at low temperatures and, hence, are not useful in many applications, such as aernspace, where the adhesive must remain effective at temperatures as low as -50C
2C or more.
Another disadvantage of prior art reactive adhesives is that they tend to discolor after extended exposure to ultra-violet radiation, for example, from the sun.
Summary of the I_vention It is one object of the present invention to provide adhesive formulations that are useful over a broader tempera-ture range than prior art adhesive compositions.
13~
It is another object of the present invention to provide adhesive compositions which are substantially unaffected by ultraviolet radiation.
Another object of the present invention is to provide adhesive compositions capable oP producing high levels of bond strength in very brief cure times under either aerobic or non-aerobic conditions.
Still another object of the pre~ent invention is to provide method~ for effecting adhesive bonding of two or more substrates.
These and other objects will be obvious to the artisan in view of the following description and appended claims.
In accordance with the pr~sent invention there is provided as an adhesivP composition, the combination of an adhesive base and a catalyst, said adhesive base comprising:
(a) an ePfective amount of acryliccontaining sllane mono=er, (b) an e*fective amount of acrylic-containing polydiorganosiloxane; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane producing upon polymerization thereof an adhesive solid:
and said catalyst system comprising:
~3~4~
~3a- 60SI-963 (c) an amount of free radical precursor ef~ective for cataly~ing the polymerization reaction of said acrylic containing monomer and said acrylic-containing polydiorganosiloxane.
In accordance with a praferred aspect of the present invention there is provided s an adhesive composition, the combination of an adhesive base and a catalyst, said adhesiv~ base comprising:
~a) about lO to about 90 part~ per hundred of ` 10 acrylic-containing monomer, and (b) about 90 to about 10 parts per hundred of acrylic-containing polydiorganosiloxane, said acrylic-containing monomer and said acrylic-containing ; polydiorganosiloxane producing upon polymerization thereof an adhesive solid; and : ~ said catalyst comprising:
: ~ /
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/
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/:
/
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: :
B
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60SI-963, (c) an amount of free radical precursor effective for catalyzing the polymerization reaction of said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane.
Preferably, the acrylic-containing monomer is a silane such as methàcryloxypropyl bis (trimetbylsiloxy) methylsilane, the acrylic-containing polydiorganosiloxane has from about 0.1 to about 20 mole percent acrylir groups, and the catalyst is an amine/aldehyde adduct.
There is also provided a method for the adhesive bonding of at least two surfaces wherein the adhesive base is applied to at least one of the surfaces to be bonded and the free radical precursor is applied to at least one of the surfaces other than `
~ the surface(s) covered with the adhesive base. Contact of the ;~ adhesive base coated surface and the free radical precursor coated surface generates free radicals so as to cause - crosslinking of the acrylic-containing components of the adhesive base.
Description of the Invention There is provided by a preferred embodiment of the present invention an adhesive composîtion comprising an adhesive base ~ component and a catalyst system, said adhesive base comprising:
:~ :
~ a) from about 10 to about 90 parts per hundred of acrylic-containing monomer, .
~ 3 ~
60SI-963, (b) from about 90 to about 10 parts per hundred of acrylic containing polydiorganosiloxane, said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane producing upon polymerization thereof an adhesive solid; and said catalyst system comprising:
(c) an amount of free radical precursor effective for catalyzing the polymerization reaction of said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane.
Acrylic-containing monomer ~a),also referred to as reactive diluent, can ~e present in amounts ranging from about 10 to about 90 parts per hundred o' the adhesive base. Preferably, the reactive diluent i5 present in an amount, by weight, ranging from about 25 to about 90 parts per hundred, and most preferably is present in an amount of from about 40 to about 90 parts per hundred parts of adhesive base; e.g. components (a) ` and (b).
Suitable acrylate monomers are described in United -States Patent Number 4j348,503 to Bachman which patent issued September 7, ~9~82.: Briefly, the acrylate monomers disclosed by Bachman are the reaction products of acrylic and/or methacrylic acids with one or more mono- or polybasic9 substituted or unsubstituted alkyl, aryl or aralkyl alcohots. Typical of the acrylate monomers disclosed by Bachman are hydroxyethyl methacrylate, tetraethyleneglycol dimethacrylate~ hydroxyethyl acrylate and tetraethyleneglycol diacrylate.
~ 3 ~
Although organic acrylic-containing monomers can be employed in the practice of the present invention, it has been found that especially preferable acrylate monomers are silanes - such as, for ex~mple, methacryloxypropyl bis (trimethylsiloxy) methylsilane. As in the case of organic monomers, the silane monomers are also often utilized as a mixture of monomers, oligimers and cyclics. Other suitable acrylic-containing silane monomers can, of course, be easily ascertained by the artisan without undue experimentation. Further9 it should be understood that mixtures of organic acrylate monomers, mixtures of silane acrylate monomers, and mixtures of organic and silane acrylate monomers are within the intended scope of the present invention.
It is essential that component (b) of the adhesive base be a polydiorganosiloxane having acrylic-functional groups.
Preferably, there is present from about lO to about 90 parts acrylic-functional polydiorganosiloxane per lOO parts by weight of adhesive base; e.s. components (a) and (b). More preferably, acrylic-functional polydiorganosiloxane is present in an amount ranging from about lO to about 75 parts by weight and, most preferably, is present in an amount ranging from about lO to about 60 parts by weight per lOO parts by weight of adhesive base.
Acrylic-functional polydiorganosiloxanes are known in the art and are readily available from many commercial sources.
Suitable acrylic-functional polydiorganosiloxanes are described in U.S. Pat. Nos. 2,793,223 to Merker; 2,922,8D6 to Merker;
3,782,940 to Ohto et al.; 3,878,263 to Martin; -.
~ 3 ~
and 4,035,355 to Baney et al. The prPferred poly-siloxanes for practicing the present invention have acrylate~
functional siloxy units of the formula (I) ~ CH~ - C - C - D - (CH ~ (Rl)n SiO3 n R ~ 2 where R is hydrogen or methyl, Rl is a monovalent hydrocarbon radical, x is an integer equal to 1 to ~ inclusive, and n has a value of 1 or 2.
Acrylic-functional siloxy units of formula I are typically copolymerized with siloxy units having the formula Rl (II) -- SiO
, where R' is as previously defined.
Preferably there is from about 0.1 to a~out 20 mole percent of acrylic^functional siloxy units. More preferably there is from about 0.5 to about lO mole percent of acrylic-functional siloxy units and, most preferably there is from about 1 to about S mole percent acrylic-functional siloxy units.
60SI 963. - -The viscosity of acryllc-functional polydiorganosiloxane (b) is not crît~cal bu~ preferably is ~rorn about 10 centipoise at 25C to about 100,000 eentipoise at 25C. In more preferable embodiments of the present invention the viscosity ranges from about 100 cen~ipoise to abou~ 50,000 centipoise at 25C. Most preferably the viscosity of polydiorganbsil~xane - (b) is from about lO00 centipoise to about 15,000 centipoise at 2~C.
: It is also intended for purposes of the present invention that the term polydiorganosiloxane includes an amount of organic units or blocks effective for imparting the advantageous properties of organic polymers to the compositions of the present invention. Such organic units can also have acrylic functionality~ although this is not essential.
Furthermore, such polydiorganosiloxane-organic copolymers ean be either random copDlymers or block copol~ners. Examples of suitable organic units can be found in U.S. Pat. No. 4,34B,503 to Bachman and includes vinyl polymers, acrylic polymers, polyester polymers and glycGl polymers. specially preferable organic units are polyurethane units. It is also contemplated that mixtures of polydiorganosiloxanes, mixtures of polydioryanosilo%ane-organic copolymers, or mixtures of polydiorganosiloxanes and polydiorganosiloxane-organic copolymers can be utilized in the practice of the present invention.
The catalyst system is based essentially upon an aromatic perester free radical prec~rsor that will generally be capable of activation by neating or, for example~ an amine/aldehyde adduct. The aromatic perester catalyst is typified by t-butyl ; perbenzoate, although other aromatic peresters having catalytic ~L 3 ~
properties and suitabl~ for use herein are known and will be evident to those skilled in the art. For example, other benzoic acid perester derivatives9 as well as peresters derived from phthalic acid, chlorobenzoic acid and the like may be suitable for practiFing the present invention.
In general the amount of catalyst used will be from about 1 to about 10 parts by weight and, preferably, from about 2 to about 6 parts by weight, per hundred `parts by weight of adhesive base.
If curing i5 to be effected at room temperature rather than by heating it will be necessary to further include an activator ; in the catalyst system. The preferred activator is any co~mercially available amine/aldehyde adduct which reacts with the catalyst to produce the free radicals necessary to initiate polymerization. Typical of such adducts are the rubber vulcanization accelerators sold by R.T. ~anderbilt Company under the trademarks VANAX 808 and VANAX 833. The artisan will, of course, be able to determine other suitable activators without undue experimentation.
The amount of amine/aldehyde activator employed is not critical and generally will be that which is provided by coating therewith one of the surfaces to be bonded. Of course, the concentration should be sufficient to react with substantially all of the catalyst present in the adhesive Z5 composition and to insure migration throughout the adhesive composition in a relatively short period of time. Typically, the activator will be employed in a volumetric ratio of about 1:4 to the adhesive formulation.
~ 3 ~
6ûS I -953 When a dramatically increased rate of cure is required there may be further added to the adhesive compos~tion of the present ln~ention certain dibasic acids as a cure accelerator.
Further, an increased cure rate is provided by both acrylic S acid and methacrylic acid~
Another optional component is a transition metal cure accelerator. These transition metal cure accelerators are compounds of iron, copper, cobalt, manganese, tin, ti~anium, chromium and antimony Preferably the compound will pro~ide the metal in an oxidized valence state. Examples of suitable transition metal cure accelerators are cobalt naphthalate, cupric octoate, ferric sulfate, manganic sulfate and the like.
Other suitable compounds will be obvious to those skilled in the art~
When used, the transition metal cure accelerator is normally incorporated in small quantities, for example~ about 2 parts per hundred or less. Even amounts as low as 50 to 500 parts per million will have a significant effect on the rate of cure. Of course, if the monomers employed in a particular formulation are especially slow to polymerize, even larger quant-ties of ~ransition metal cure acceterator can be used.
Because the metal accelerator can be included in the adhesiYe base without causing premature curing, it can be dispersed homogeneously throughout and, upon initiation of`the reaction (by chemical or th~rmal means) the metal will be immediately accessible to all reacti~e portions of the co~position, thereby promoting uniform and complete curing.
This feature is especially valuable in applications in which ~ 3 ~
the surfaces to be bonded are spaced more than a minimum distance from one another, for example, more than l5 or 20 mils apart.
In addition to the foregoing principal components, other materials may also be incorporated int~ the present compositions. For example, it is conventional to include inert fillers to improve impact resistance or to modify viscosity.
Other substances, such as dyes9 fire retardants, stabilizers, plasticizers, antioxidants, and the like may also be included.
The adhesive compositions of the present invention are used to bond two or more surfaces together by applying to at least one of the surfaces the adhesive base as previously described.
Contact of the coated surface with a second surface to be bonded thereto is effected; the perester catalyst is activated to generate free radicals, and contact between the ~surfaces is maintained for a period of time and under such conditions as to effect curing of the adhesive composition. The method preferably is one in which an amine/aldehyde adduct activator is entployed; in which case the adduct is applied to the second surface to be bonded.
In order to better enable those skilled in the art to practice the present invention, the following examples are provided by way of illustration and not by way of limitation.
All parts are by w~ight unless otherwise noted.
~ 3 ~
EXAMPL ES
- Example 1 In these examples an adhesive base was prepared with varying amounts of methacryloxypropyl bis (trimethylsiloxy) methylsilane reactive diluent (monomer/oligimer/cyclics) and polydimethylsiloxane polymer having 2X methacrylic groups on the polymer chain. To 100 parts by weight of the adhesive base was added 4 parts by weight t-butylperbenzoate initiator, 0 or 3 parts by weight methacrylic acid accelerator and 0 or 1 part by weight cobalt naphthalate. To this mixture was then added ; ~ - 25 parts by weight Vanox ~08 activator. The time required for : gelation to occur was measured in order to determine preferred ratios of the various ingredients. The results are set forth in Table I.
;
~ \ ' '' \ ' \
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60S I -963, --l3-Table I
- Expmt. ~1) ReactiYe (2) Methacrylic Naphth- Cure(3 No. Polymer Diluent Acid alate Time la lO0 pts ~ ---- l week lb " ---- 3 pts ~ l4 hrs lc " ~ 3 pts . l pt 3 hrs 2a 75 pts 25 pts. ---- ---- l wk 2b " " 3 pts ---- 4.5 hrs 2c " " 3 pts l pt ~ 3.5 hrs 3a 50 pts 50 pts -~~~ ~~~~ l wk 3b " " 3 pts ---- :3.5 ~rs 3c " " 3 pts l pt 4.5 hrs 4a 25 pts 75 pts ~ l wk ; ~ 4b " " ~ 3 pts ---- : 2.5 h~rs : 15 4c " ~ 3 pts l pt 9 hrs : 5a ---- lO0 pts ---- ---- l wk :
., .
5b ~ " 3 pts ---- 1.3 hrs , .
: 5c ---- " ; 3 pts; l pt 20 hrs~
~l) polydimethylsiloxane having 2X methacrylic groups (2) methacryloxypropyl bis(trimethylsiloxy)methylsilane : ~ (monomer/oligimer/cyclics) (3) ~ime from iddition of activitor to gelation " .
FOR MAKING AND USING
Background of the Invent~on The present invention relates to silicone adhesive composi-tions and methods for making and using such compositions. Moreparticularly, the present invention relates to silicone adhe-sives comprising an acrylic-functional organopolysiloxàne, a reactive diluent and a polymerization initiator.
Over the past few years a new class of adhesive or bonding agent has been developed which offers as its main advantage a simple no mix application method and rapid bond formation at ambient temperature. These materials are modi~ied acrylic systems and are based on new modifying reactive polymers and a sur~ace-applied activator which catalyzes the polymerization of the reactive polymers. Application methods are similar to those used for contact adhesives; the adhesive base (e.g. reactive polymer and reactive diluent or monomer) is applied to one substrate surface and the activator is applied to the other substrate~sur~ace. The two surfaces are then brought together and held until handling strength is reached.
Generally an elastomeric polymer is colloidally dispersed in a monomer or a monomer/oligomer/polymer solution. The system is then polymerized using a ~ree radical mechanism, What occurs is a rapid, in situ polymerization of a (typically) methyl methacrylate system, toughened by elastomeric domains that have been incorporated into the structure by grafting.
:
~ 3 3 ~
An example of such a reactive adhesive is described in Bachman, U.S. Patent No. 4,34~,503. Brielly, this composition comprises 40 to 90 parts per hundred of an acrylic ester monomer capable of free radical polymerization and 60 to lO
parts per hundred of a monomeric polyacrylate ester prepolymer having terminal acrylate radicals linked by at least two divalent polyurethane or polyureide groups, which is catalyzed with an activator comprising l to lO parts per hundred of an aromatic perester free radical precursor, 0 5 to lO parts per hundred of an organic acid capable of cyclic tautomerism and up to 500 parts per million of a soluble compound of a transition metal cure accelerator. Bachman also states that it is conven-tional to include small percentages of silane monomers to increase moistfure resistance as wel) as to enhance bonding of the adhesive to glass and similar surfaces.
One shortcoming of prior art reactive adhesives is that they become brittle at low temperatures and, hence, are not useful in many applications, such as aernspace, where the adhesive must remain effective at temperatures as low as -50C
2C or more.
Another disadvantage of prior art reactive adhesives is that they tend to discolor after extended exposure to ultra-violet radiation, for example, from the sun.
Summary of the I_vention It is one object of the present invention to provide adhesive formulations that are useful over a broader tempera-ture range than prior art adhesive compositions.
13~
It is another object of the present invention to provide adhesive compositions which are substantially unaffected by ultraviolet radiation.
Another object of the present invention is to provide adhesive compositions capable oP producing high levels of bond strength in very brief cure times under either aerobic or non-aerobic conditions.
Still another object of the pre~ent invention is to provide method~ for effecting adhesive bonding of two or more substrates.
These and other objects will be obvious to the artisan in view of the following description and appended claims.
In accordance with the pr~sent invention there is provided as an adhesivP composition, the combination of an adhesive base and a catalyst, said adhesive base comprising:
(a) an ePfective amount of acryliccontaining sllane mono=er, (b) an e*fective amount of acrylic-containing polydiorganosiloxane; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane producing upon polymerization thereof an adhesive solid:
and said catalyst system comprising:
~3~4~
~3a- 60SI-963 (c) an amount of free radical precursor ef~ective for cataly~ing the polymerization reaction of said acrylic containing monomer and said acrylic-containing polydiorganosiloxane.
In accordance with a praferred aspect of the present invention there is provided s an adhesive composition, the combination of an adhesive base and a catalyst, said adhesiv~ base comprising:
~a) about lO to about 90 part~ per hundred of ` 10 acrylic-containing monomer, and (b) about 90 to about 10 parts per hundred of acrylic-containing polydiorganosiloxane, said acrylic-containing monomer and said acrylic-containing ; polydiorganosiloxane producing upon polymerization thereof an adhesive solid; and : ~ said catalyst comprising:
: ~ /
~: /
: : /
/
`~ : /
/:
/
: :~ ~ : :
: :
B
~ 3 ~
60SI-963, (c) an amount of free radical precursor effective for catalyzing the polymerization reaction of said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane.
Preferably, the acrylic-containing monomer is a silane such as methàcryloxypropyl bis (trimetbylsiloxy) methylsilane, the acrylic-containing polydiorganosiloxane has from about 0.1 to about 20 mole percent acrylir groups, and the catalyst is an amine/aldehyde adduct.
There is also provided a method for the adhesive bonding of at least two surfaces wherein the adhesive base is applied to at least one of the surfaces to be bonded and the free radical precursor is applied to at least one of the surfaces other than `
~ the surface(s) covered with the adhesive base. Contact of the ;~ adhesive base coated surface and the free radical precursor coated surface generates free radicals so as to cause - crosslinking of the acrylic-containing components of the adhesive base.
Description of the Invention There is provided by a preferred embodiment of the present invention an adhesive composîtion comprising an adhesive base ~ component and a catalyst system, said adhesive base comprising:
:~ :
~ a) from about 10 to about 90 parts per hundred of acrylic-containing monomer, .
~ 3 ~
60SI-963, (b) from about 90 to about 10 parts per hundred of acrylic containing polydiorganosiloxane, said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane producing upon polymerization thereof an adhesive solid; and said catalyst system comprising:
(c) an amount of free radical precursor effective for catalyzing the polymerization reaction of said acrylic-contain-ing monomer and said acrylic-containing polydiorganosiloxane.
Acrylic-containing monomer ~a),also referred to as reactive diluent, can ~e present in amounts ranging from about 10 to about 90 parts per hundred o' the adhesive base. Preferably, the reactive diluent i5 present in an amount, by weight, ranging from about 25 to about 90 parts per hundred, and most preferably is present in an amount of from about 40 to about 90 parts per hundred parts of adhesive base; e.g. components (a) ` and (b).
Suitable acrylate monomers are described in United -States Patent Number 4j348,503 to Bachman which patent issued September 7, ~9~82.: Briefly, the acrylate monomers disclosed by Bachman are the reaction products of acrylic and/or methacrylic acids with one or more mono- or polybasic9 substituted or unsubstituted alkyl, aryl or aralkyl alcohots. Typical of the acrylate monomers disclosed by Bachman are hydroxyethyl methacrylate, tetraethyleneglycol dimethacrylate~ hydroxyethyl acrylate and tetraethyleneglycol diacrylate.
~ 3 ~
Although organic acrylic-containing monomers can be employed in the practice of the present invention, it has been found that especially preferable acrylate monomers are silanes - such as, for ex~mple, methacryloxypropyl bis (trimethylsiloxy) methylsilane. As in the case of organic monomers, the silane monomers are also often utilized as a mixture of monomers, oligimers and cyclics. Other suitable acrylic-containing silane monomers can, of course, be easily ascertained by the artisan without undue experimentation. Further9 it should be understood that mixtures of organic acrylate monomers, mixtures of silane acrylate monomers, and mixtures of organic and silane acrylate monomers are within the intended scope of the present invention.
It is essential that component (b) of the adhesive base be a polydiorganosiloxane having acrylic-functional groups.
Preferably, there is present from about lO to about 90 parts acrylic-functional polydiorganosiloxane per lOO parts by weight of adhesive base; e.s. components (a) and (b). More preferably, acrylic-functional polydiorganosiloxane is present in an amount ranging from about lO to about 75 parts by weight and, most preferably, is present in an amount ranging from about lO to about 60 parts by weight per lOO parts by weight of adhesive base.
Acrylic-functional polydiorganosiloxanes are known in the art and are readily available from many commercial sources.
Suitable acrylic-functional polydiorganosiloxanes are described in U.S. Pat. Nos. 2,793,223 to Merker; 2,922,8D6 to Merker;
3,782,940 to Ohto et al.; 3,878,263 to Martin; -.
~ 3 ~
and 4,035,355 to Baney et al. The prPferred poly-siloxanes for practicing the present invention have acrylate~
functional siloxy units of the formula (I) ~ CH~ - C - C - D - (CH ~ (Rl)n SiO3 n R ~ 2 where R is hydrogen or methyl, Rl is a monovalent hydrocarbon radical, x is an integer equal to 1 to ~ inclusive, and n has a value of 1 or 2.
Acrylic-functional siloxy units of formula I are typically copolymerized with siloxy units having the formula Rl (II) -- SiO
, where R' is as previously defined.
Preferably there is from about 0.1 to a~out 20 mole percent of acrylic^functional siloxy units. More preferably there is from about 0.5 to about lO mole percent of acrylic-functional siloxy units and, most preferably there is from about 1 to about S mole percent acrylic-functional siloxy units.
60SI 963. - -The viscosity of acryllc-functional polydiorganosiloxane (b) is not crît~cal bu~ preferably is ~rorn about 10 centipoise at 25C to about 100,000 eentipoise at 25C. In more preferable embodiments of the present invention the viscosity ranges from about 100 cen~ipoise to abou~ 50,000 centipoise at 25C. Most preferably the viscosity of polydiorganbsil~xane - (b) is from about lO00 centipoise to about 15,000 centipoise at 2~C.
: It is also intended for purposes of the present invention that the term polydiorganosiloxane includes an amount of organic units or blocks effective for imparting the advantageous properties of organic polymers to the compositions of the present invention. Such organic units can also have acrylic functionality~ although this is not essential.
Furthermore, such polydiorganosiloxane-organic copolymers ean be either random copDlymers or block copol~ners. Examples of suitable organic units can be found in U.S. Pat. No. 4,34B,503 to Bachman and includes vinyl polymers, acrylic polymers, polyester polymers and glycGl polymers. specially preferable organic units are polyurethane units. It is also contemplated that mixtures of polydiorganosiloxanes, mixtures of polydioryanosilo%ane-organic copolymers, or mixtures of polydiorganosiloxanes and polydiorganosiloxane-organic copolymers can be utilized in the practice of the present invention.
The catalyst system is based essentially upon an aromatic perester free radical prec~rsor that will generally be capable of activation by neating or, for example~ an amine/aldehyde adduct. The aromatic perester catalyst is typified by t-butyl ; perbenzoate, although other aromatic peresters having catalytic ~L 3 ~
properties and suitabl~ for use herein are known and will be evident to those skilled in the art. For example, other benzoic acid perester derivatives9 as well as peresters derived from phthalic acid, chlorobenzoic acid and the like may be suitable for practiFing the present invention.
In general the amount of catalyst used will be from about 1 to about 10 parts by weight and, preferably, from about 2 to about 6 parts by weight, per hundred `parts by weight of adhesive base.
If curing i5 to be effected at room temperature rather than by heating it will be necessary to further include an activator ; in the catalyst system. The preferred activator is any co~mercially available amine/aldehyde adduct which reacts with the catalyst to produce the free radicals necessary to initiate polymerization. Typical of such adducts are the rubber vulcanization accelerators sold by R.T. ~anderbilt Company under the trademarks VANAX 808 and VANAX 833. The artisan will, of course, be able to determine other suitable activators without undue experimentation.
The amount of amine/aldehyde activator employed is not critical and generally will be that which is provided by coating therewith one of the surfaces to be bonded. Of course, the concentration should be sufficient to react with substantially all of the catalyst present in the adhesive Z5 composition and to insure migration throughout the adhesive composition in a relatively short period of time. Typically, the activator will be employed in a volumetric ratio of about 1:4 to the adhesive formulation.
~ 3 ~
6ûS I -953 When a dramatically increased rate of cure is required there may be further added to the adhesive compos~tion of the present ln~ention certain dibasic acids as a cure accelerator.
Further, an increased cure rate is provided by both acrylic S acid and methacrylic acid~
Another optional component is a transition metal cure accelerator. These transition metal cure accelerators are compounds of iron, copper, cobalt, manganese, tin, ti~anium, chromium and antimony Preferably the compound will pro~ide the metal in an oxidized valence state. Examples of suitable transition metal cure accelerators are cobalt naphthalate, cupric octoate, ferric sulfate, manganic sulfate and the like.
Other suitable compounds will be obvious to those skilled in the art~
When used, the transition metal cure accelerator is normally incorporated in small quantities, for example~ about 2 parts per hundred or less. Even amounts as low as 50 to 500 parts per million will have a significant effect on the rate of cure. Of course, if the monomers employed in a particular formulation are especially slow to polymerize, even larger quant-ties of ~ransition metal cure acceterator can be used.
Because the metal accelerator can be included in the adhesiYe base without causing premature curing, it can be dispersed homogeneously throughout and, upon initiation of`the reaction (by chemical or th~rmal means) the metal will be immediately accessible to all reacti~e portions of the co~position, thereby promoting uniform and complete curing.
This feature is especially valuable in applications in which ~ 3 ~
the surfaces to be bonded are spaced more than a minimum distance from one another, for example, more than l5 or 20 mils apart.
In addition to the foregoing principal components, other materials may also be incorporated int~ the present compositions. For example, it is conventional to include inert fillers to improve impact resistance or to modify viscosity.
Other substances, such as dyes9 fire retardants, stabilizers, plasticizers, antioxidants, and the like may also be included.
The adhesive compositions of the present invention are used to bond two or more surfaces together by applying to at least one of the surfaces the adhesive base as previously described.
Contact of the coated surface with a second surface to be bonded thereto is effected; the perester catalyst is activated to generate free radicals, and contact between the ~surfaces is maintained for a period of time and under such conditions as to effect curing of the adhesive composition. The method preferably is one in which an amine/aldehyde adduct activator is entployed; in which case the adduct is applied to the second surface to be bonded.
In order to better enable those skilled in the art to practice the present invention, the following examples are provided by way of illustration and not by way of limitation.
All parts are by w~ight unless otherwise noted.
~ 3 ~
EXAMPL ES
- Example 1 In these examples an adhesive base was prepared with varying amounts of methacryloxypropyl bis (trimethylsiloxy) methylsilane reactive diluent (monomer/oligimer/cyclics) and polydimethylsiloxane polymer having 2X methacrylic groups on the polymer chain. To 100 parts by weight of the adhesive base was added 4 parts by weight t-butylperbenzoate initiator, 0 or 3 parts by weight methacrylic acid accelerator and 0 or 1 part by weight cobalt naphthalate. To this mixture was then added ; ~ - 25 parts by weight Vanox ~08 activator. The time required for : gelation to occur was measured in order to determine preferred ratios of the various ingredients. The results are set forth in Table I.
;
~ \ ' '' \ ' \
\
: \
~ 3 ~
60S I -963, --l3-Table I
- Expmt. ~1) ReactiYe (2) Methacrylic Naphth- Cure(3 No. Polymer Diluent Acid alate Time la lO0 pts ~ ---- l week lb " ---- 3 pts ~ l4 hrs lc " ~ 3 pts . l pt 3 hrs 2a 75 pts 25 pts. ---- ---- l wk 2b " " 3 pts ---- 4.5 hrs 2c " " 3 pts l pt ~ 3.5 hrs 3a 50 pts 50 pts -~~~ ~~~~ l wk 3b " " 3 pts ---- :3.5 ~rs 3c " " 3 pts l pt 4.5 hrs 4a 25 pts 75 pts ~ l wk ; ~ 4b " " ~ 3 pts ---- : 2.5 h~rs : 15 4c " ~ 3 pts l pt 9 hrs : 5a ---- lO0 pts ---- ---- l wk :
., .
5b ~ " 3 pts ---- 1.3 hrs , .
: 5c ---- " ; 3 pts; l pt 20 hrs~
~l) polydimethylsiloxane having 2X methacrylic groups (2) methacryloxypropyl bis(trimethylsiloxy)methylsilane : ~ (monomer/oligimer/cyclics) (3) ~ime from iddition of activitor to gelation " .
4 ~ ~
The properties of each of the foregoing adhesive materials were studied and a polymer to reactive diluent ratio of 1:1 was found to provide the most acceptable formulation for further , study.-Example 2 In this example there was employed 50 parts by weight of the polymer of example 1, 50 parts by weight of the reactive diluent of example 1, 4 parts by weight t-butylperbenzoate, 25 parts by weight Vanox 808 accelerator, and the amount of : ~ 10 methacrylic acid was varied to determine the effect on cure : time. The results are set forth-in Table II.
\
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- ~
;; '\~
~ '`".
~.
~ 3 ~
~15-Table 11 Metyhacrylic Acld Cure Time 1 part 3.5 hours 3 parts 3.3 hours . 6 parts 3.0 hours 9 parts 2 8 hours ~ .
12 parts ; 2.5 hours : ~ 15 parts . 2.4 hours 18 parts : 2.2 hours : 21 parts ~- 2.2 hours 24 parts 2.0 hours :: :
~, ,.
~ 3 ~
60SI-963 .
Although the gelation time continued to decrease, the physical properties of the adhesive material began to Jeteriorate when more than about 15 parts methacrylic acid were included in the composition. Thus, 9 parts by weight methacrylic acid were utilized-in the following examples, :
Example 3 In this example there was employed 50 parts by weight of the polymer of example 1, 50 parts by weight of the reactive diluent of example 1, 4 parts by weight t-butylperbenzoate, 9 parts by weight methacrylic acid, and the amount of activator (Vanox 808) was varied to determine the effect on cure time.
The results are set forth in Table III.
`\ j ~
:: "
~ 3 ~
Table III
, Activator Cure Time . 25 parts : 1.5 hours ' ,, '' :
20 parts 1.3 hours , 15 parts 1.1 hours ~: ~ lO parts : 0.8 hour 5 parts ~ 0.6 hour 4 parts : ~ : ~ 0.4 hour ~ :
.: :
:`~ : :3 parts: ~: 0.4 hour , ~, . .
i : . 1:0 ~ 2 parts 0.17 hour ; ~ ~ l part ~ 0.17 hour O.S part~ 0.25 hour ;~ : 0.25 part 0.25 hour ~ :
` These results illustrate that optimum cure time for this formulation was obtained ~when 1 to 2 parts of activator are :
; employed.
' ~L3~ 5~
Example 4 In this example there was employed 50 parts by weight of the polymer of~ example 1, 50 parts by weight of the reactive diluent of example 1, 9 parts by weight methacrylic acid, 2 parts by weight activator (Yanox 808) and the amount of t-butylperbenzoate catalyst was varied to determine the eFfect on cure time. The results are set forth in Table I~.
.
Table IV
t-bu_~lperbenzoateCure Time - . _ l part lZ min~
2 parts 10.5 min.
3 parts , 10.5 min.
4 parts 10.5 min.
~ 5 parts 10.5 min.
10 parts 10 min.
15 parts 10 min.
These results show that it is merely necessary to provide an effective amount of t-butylperbenzoate initiator as the cure time is not significantly affected by including an excess of 2G catalyst.
The properties of each of the foregoing adhesive materials were studied and a polymer to reactive diluent ratio of 1:1 was found to provide the most acceptable formulation for further , study.-Example 2 In this example there was employed 50 parts by weight of the polymer of example 1, 50 parts by weight of the reactive diluent of example 1, 4 parts by weight t-butylperbenzoate, 25 parts by weight Vanox 808 accelerator, and the amount of : ~ 10 methacrylic acid was varied to determine the effect on cure : time. The results are set forth-in Table II.
\
\
- \
- ~
;; '\~
~ '`".
~.
~ 3 ~
~15-Table 11 Metyhacrylic Acld Cure Time 1 part 3.5 hours 3 parts 3.3 hours . 6 parts 3.0 hours 9 parts 2 8 hours ~ .
12 parts ; 2.5 hours : ~ 15 parts . 2.4 hours 18 parts : 2.2 hours : 21 parts ~- 2.2 hours 24 parts 2.0 hours :: :
~, ,.
~ 3 ~
60SI-963 .
Although the gelation time continued to decrease, the physical properties of the adhesive material began to Jeteriorate when more than about 15 parts methacrylic acid were included in the composition. Thus, 9 parts by weight methacrylic acid were utilized-in the following examples, :
Example 3 In this example there was employed 50 parts by weight of the polymer of example 1, 50 parts by weight of the reactive diluent of example 1, 4 parts by weight t-butylperbenzoate, 9 parts by weight methacrylic acid, and the amount of activator (Vanox 808) was varied to determine the effect on cure time.
The results are set forth in Table III.
`\ j ~
:: "
~ 3 ~
Table III
, Activator Cure Time . 25 parts : 1.5 hours ' ,, '' :
20 parts 1.3 hours , 15 parts 1.1 hours ~: ~ lO parts : 0.8 hour 5 parts ~ 0.6 hour 4 parts : ~ : ~ 0.4 hour ~ :
.: :
:`~ : :3 parts: ~: 0.4 hour , ~, . .
i : . 1:0 ~ 2 parts 0.17 hour ; ~ ~ l part ~ 0.17 hour O.S part~ 0.25 hour ;~ : 0.25 part 0.25 hour ~ :
` These results illustrate that optimum cure time for this formulation was obtained ~when 1 to 2 parts of activator are :
; employed.
' ~L3~ 5~
Example 4 In this example there was employed 50 parts by weight of the polymer of~ example 1, 50 parts by weight of the reactive diluent of example 1, 9 parts by weight methacrylic acid, 2 parts by weight activator (Yanox 808) and the amount of t-butylperbenzoate catalyst was varied to determine the eFfect on cure time. The results are set forth in Table I~.
.
Table IV
t-bu_~lperbenzoateCure Time - . _ l part lZ min~
2 parts 10.5 min.
3 parts , 10.5 min.
4 parts 10.5 min.
~ 5 parts 10.5 min.
10 parts 10 min.
15 parts 10 min.
These results show that it is merely necessary to provide an effective amount of t-butylperbenzoate initiator as the cure time is not significantly affected by including an excess of 2G catalyst.
Claims (48)
1. An adhesive composition, comprising (a) an adhesive base comprising (i) an effective amount: of acrylic-containing silane monomer, (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid, and (b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof.
2. A composition as in claim 1, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 10 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
3. A composition as in claim 1, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 25 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
4. A composition as in claim 1, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 40 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
5. A composition as in claim 1, wherein said silane is methacryloxypropyl bis(trimethylsiloxy) methylsilane.
6. A composition as in claim 2, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
7. A composition as in claim 3, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 75 parts per hundred parts of said adhesive base, on a weight basis.
8. A composition as in claim 4, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 60 parts per hundred parts of said adhesive base, on a weight basis.
9. A composition as in claim 1, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 0.1 mole percent to about 20 mole percent:
of acrylic-functional siloxy units.
of acrylic-functional siloxy units.
10. A composition as in claim 1, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 0.5 mole percent to about 10 mole percent of acrylic-functional siloxy units.
11. A composition as in claim 1, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 1 mole percent to about 5 mole percent of acrylic-functional siloxy units.
12. A composition as in claim 1, wherein catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of said adhesive base.
13. A composition as in claim 1, wherein catalyst (b) is present in an amount of from about 2 to about 6 parts by weight per 100 parts by weight of said adhesive base.
14. A composition as in claim 12, wherein catalyst (b) is t-butylperbenzoate.
15. A composition as in claim 1, further comprising an amount of activator effective for reacting with catalyst (b) to generate free radicals in an amount effective for catalyzing the polymerization of acrylic containing monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii).
16. A composition as in claim 15, wherein said activator is an amine/aldehyde adduct.
17. A composition as in claim 1, further comprising an effective amount of transition metal cure accelerator.
18. A composition as in claim 17, wherein said transition metal cure accelerator is selected from the group consisting of cobalt naphthalate, cupric octoate, ferric sulfate and manganic sulfate.
19. A composition as in claim 17, wherein said transition metal cure accelerator is present in an amount up to about 2 parts by weight per 100 parts by weight of adhesive composition.
20. An adhesive composition, comprising:
(a) an adhesive base, comprising on a weight basis:
(i) from about 25 to about 90 parts of acrylic-containing silane monomer per hundred parts of said adhesive base, and (ii) from about 10 to about 75 parts of acrylic-containing polydiorganosiloxane per hundred parts of said adhesive base, said acrylic-containing polydiorganosiloxane having from about 0.1 to about 20 mole percent acrylic-functional siloxy units and a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C;
(b) about 1 to about 10 parts by weight per hundred parts by weight of said adhesive base of free radical precursor catalyst;
(c) an amount of amine/aldehyde activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic containing silane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor 9b); and (d) an effective amount of acrylic acid, methacrylic acid, or mixture thereof.
(a) an adhesive base, comprising on a weight basis:
(i) from about 25 to about 90 parts of acrylic-containing silane monomer per hundred parts of said adhesive base, and (ii) from about 10 to about 75 parts of acrylic-containing polydiorganosiloxane per hundred parts of said adhesive base, said acrylic-containing polydiorganosiloxane having from about 0.1 to about 20 mole percent acrylic-functional siloxy units and a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C;
(b) about 1 to about 10 parts by weight per hundred parts by weight of said adhesive base of free radical precursor catalyst;
(c) an amount of amine/aldehyde activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic containing silane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor 9b); and (d) an effective amount of acrylic acid, methacrylic acid, or mixture thereof.
21. A method for making an adhesive composition, comprising:
I. mixing:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid;
(b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof.
I. mixing:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid;
(b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof.
22. A method as in claim 21, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base;
acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base;
and catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of adhesive base.
acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base;
and catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of adhesive base.
23. A method as in claim 22, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 0.1 to 10 mole percent acrylicfunctional siloxy units.
24. A method as in claim 21, further comprising mixing an amount of activator effective for reacting with catalyst (b) to generate free radicals in an amount effective for catalyzing the polymerization of acrylic-containing monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii).
25. A method as in claim 24, wherein said activator is an amine/aldehyde adduct.
26. A method as in claim 21, further comprising mixing an effective amount of transition metal cure accelerator.
27. An article of manufacture, comprising:
I. a first component comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorgano-Claim 27 continued:
siloxane: said acrylic-containing silane monomer and said acrylic-containing polydiorgano- siloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof;
and II. a second component comprising:
(d) an amount of activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic-containing sislane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor (b);
said first and second components being separate from one another prior to use.
I. a first component comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorgano-Claim 27 continued:
siloxane: said acrylic-containing silane monomer and said acrylic-containing polydiorgano- siloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprising an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof;
and II. a second component comprising:
(d) an amount of activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic-containing sislane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor (b);
said first and second components being separate from one another prior to use.
28. An article as in claim 27, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 10 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
29. An article as in claim 27, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 25 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
30. An article as in claim 27, wherein acrylic-containing monomer (a)(i) is present in an amount of from about 40 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
31. An article as in claim 27, wherein said silane is methacryloxypropyl bis(trimethylsiloxy) methylsilane.
32. An article as in claim 28, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts per hundred parts of said adhesive base, on a weight basis.
33. An article as in claim 29, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 75 parts per hundred parts of said adhesive base, on a weight bais.
34. An article as in claim 30, wherein acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 60 parts per hundred parts of said adhesive base, on a weight basis.
35. An article as in claim 27, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 0.1 mole percent to about 20 mole percent of acrylic-functional siloxy units.
36. An article as in claim 27, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 0.5 mole percent to about 10 mole percent of acrylic-functional siloxy units.
37. An article as in claim 27, wherein acrylic-containing polydiorganosiloxane (a)(ii) has from about 1 mole percent to about 5 mole percent of acrylic-functional siloxy units.
38. An article as in claim 27, wherein catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of said adhesive base.
39. An article as in claim 27, wherein catalyst (b) is present in an amount of from about 2 to about 6 parts by weight per 100 parts by weight of said adhesive base.
40. An article as in claim 38, wherein catalyst (b) is t-butylperbenzoate.
41. An article as in claim 27, wherein said activatox is an amine/aldehyde adduct.
42. An article as in claim 27, said first component further comprising an effective amount of transition metal cure accelerator.
43. An article as in claim 42, wherein said transition metal cure accelerator is selected from the group consisting of cobalt naphthalate, cupric octoate, ferric sulfate and manganic sulfate.
44. An article as in claim 42, wherein said transition metal cure accelerator is present in an amount up to about 2 parts by weight per 100 parts by weight of adhesive composition.
45. A method for adhering a first substrate to a second substrate, comprising:
I. applying to said first substrate a composition comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprisiny an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane;
(c) an effective amount of acrylic acid, methacrylic acid, or mixtures thereof;
II. contacting said first and second substrates; and III. curing said composition to an adhesive solid.
I. applying to said first substrate a composition comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing monomer and said acrylic-containing polydiorganosiloxane being present in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprisiny an amount of free radical precursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane;
(c) an effective amount of acrylic acid, methacrylic acid, or mixtures thereof;
II. contacting said first and second substrates; and III. curing said composition to an adhesive solid.
46. A method as in claim 45,wherein curing is effected by heating.
47. A method for adhering a first substrate to a second substrate, comprising:
I. applying to said first substrate a first componant comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane being in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprising an amount of free radical preoursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof;
II. applying to said second substrate a second component comprising:
(d) an amount of activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic-containing silane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor (b);
III. contacting said first and second substrates; and IV. allowing said composition to cure to an adhesive solid.
I. applying to said first substrate a first componant comprising:
(a) an adhesive base comprising:
(i) an effective amount of acrylic-containing silane monomer, and (ii) an effective amount of acrylic-containing polydiorganosiloxane having a viscosity of from about 1000 centipoise to about 15,000 centipoise at 25°C; said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane being in an amount sufficient to produce upon polymerization thereof an adhesive solid, (b) a catalyst comprising an amount of free radical preoursor effective for catalyzing the polymerization of said acrylic-containing silane monomer and said acrylic-containing polydiorganosiloxane; and (c) an effective amount of acrylic acid, methacrylic acid, or mixture thereof;
II. applying to said second substrate a second component comprising:
(d) an amount of activator effective for generating free radicals in an amount effective for catalyzing the polymerization of acrylic-containing silane monomer (a)(i) and acrylic-containing polydiorganosiloxane (a)(ii) upon contact with free radical precursor (b);
III. contacting said first and second substrates; and IV. allowing said composition to cure to an adhesive solid.
48. A method as in claim 47, wherein acrylic-containing monomer (a)(l) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base;
acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base; and catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of adhesive base.
acrylic-containing polydiorganosiloxane (a)(ii) is present in an amount of from about 10 to about 90 parts by weight per hundred parts by weight of adhesive base; and catalyst (b) is present in an amount of from about 1 to about 10 parts by weight per hundred parts by weight of adhesive base.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71186585A | 1985-03-14 | 1985-03-14 | |
| US711,865 | 1985-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1315440C true CA1315440C (en) | 1993-03-30 |
Family
ID=24859858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000504138A Expired - Fee Related CA1315440C (en) | 1985-03-14 | 1986-03-14 | Silicone adhesives and methods for making and using |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS61246277A (en) |
| CA (1) | CA1315440C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3419314B2 (en) * | 1998-07-08 | 2003-06-23 | 信越化学工業株式会社 | Liquid radiation-curable resin composition and optical fiber |
| DE102010013196B4 (en) * | 2010-03-29 | 2015-10-29 | Hilti Aktiengesellschaft | Two-component chemical mortar composition with improved adhesion to the surface of semi-cleaned and / or damp boreholes in mineral subsoil and their use |
| JP5765303B2 (en) * | 2012-08-20 | 2015-08-19 | 信越化学工業株式会社 | Optical pressure-sensitive adhesive composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716083A (en) * | 1981-05-15 | 1982-01-27 | Hitachi Ltd | Adhesive polymerizable by action of both light and heat |
| JPS58173174A (en) * | 1982-04-06 | 1983-10-12 | Japan Synthetic Rubber Co Ltd | Radical adhesive composition |
-
1986
- 1986-03-11 JP JP5158886A patent/JPS61246277A/en active Pending
- 1986-03-14 CA CA000504138A patent/CA1315440C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246277A (en) | 1986-11-01 |
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