CA1039440A - Adhesive compositions based on 2-cyanoacrylate monomers - Google Patents
Adhesive compositions based on 2-cyanoacrylate monomersInfo
- Publication number
- CA1039440A CA1039440A CA202,421A CA202421A CA1039440A CA 1039440 A CA1039440 A CA 1039440A CA 202421 A CA202421 A CA 202421A CA 1039440 A CA1039440 A CA 1039440A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- cyanoacrylate
- adhesive
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 title abstract description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims abstract description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 18
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 13
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 10
- ITCZEZQMUWEPQP-UHFFFAOYSA-N prop-2-enyl 2-cyanoprop-2-enoate Chemical compound C=CCOC(=O)C(=C)C#N ITCZEZQMUWEPQP-UHFFFAOYSA-N 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 5
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims 3
- 238000010526 radical polymerization reaction Methods 0.000 claims 3
- 229960004337 hydroquinone Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004830 Super Glue Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- -1 2-cyanoacrylate ester Chemical class 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Abstract
ABSTRACT
Adhesive compositions based on 2-cyanoacrylate monomers in which storage stability, cure speed and other properties are improved by inclusion of itaconic acid anhydride.
Adhesive compositions based on 2-cyanoacrylate monomers in which storage stability, cure speed and other properties are improved by inclusion of itaconic acid anhydride.
Description
~39~
This invention is concerned with improvements in or relating to adhesive compositions and is especially concerned with adhesive compositions based on 2-cyanoacrylates.
Adhesive compositions based on 2-cyanoacrylates may be used as single-part liquid adhesives for bonding a variety of materials. Examples of materials to which adhesive bonds can be formed by use of 2-cyanoacrylate adhesives include metals, plastics, glass and rubbers, and such materials are met with as parts of precision instruments and household articles. It 10 has also been proposed to use cyanoacrylate based adhesives for bonding blood vessels, living tissue in surgical operations, and vegetable tissue in gra$ting.
Although adhesive compositions based on 2-cyanoacrylates are potentially suitable for use in a wide variety of applications, they tend to have various attendant problems including ones relating to storage stability, cure speed and bond performance.
When 2-cyanoacrylates are stored even ill tightly closed vessels they exhibit a tendency to polymerise within a relatively short period of time at normal room temperatures. At higher temperatureOE this tendency to polymerise is enhanced. It has been proposed therefore to include in adhesive compositions based on 2-cyanoacrylates anionic polymerisation inhibitors, e . g. P205 or S02, in combination with a free radical polymerisation inhibitor e . g . hydroquinone or monomethyl ether of hydroquinone .
Compositions based on 2-cyanoacrylates containing anionic polymerisation inhibitors and free radical polymerisation inhibitors have not generally fully overcome difficulties associated with cure speed and bond performance.
Cure speed difficulties in general appear to result from a lack of tackiness of the composition necessitating holding of parts to be bonded in appropriate correlation with the adhesive between them until the 2-cyanoacrylate polymerises, ~L~3~
and builds up sufficient bonding strength. Bonds formed with
This invention is concerned with improvements in or relating to adhesive compositions and is especially concerned with adhesive compositions based on 2-cyanoacrylates.
Adhesive compositions based on 2-cyanoacrylates may be used as single-part liquid adhesives for bonding a variety of materials. Examples of materials to which adhesive bonds can be formed by use of 2-cyanoacrylate adhesives include metals, plastics, glass and rubbers, and such materials are met with as parts of precision instruments and household articles. It 10 has also been proposed to use cyanoacrylate based adhesives for bonding blood vessels, living tissue in surgical operations, and vegetable tissue in gra$ting.
Although adhesive compositions based on 2-cyanoacrylates are potentially suitable for use in a wide variety of applications, they tend to have various attendant problems including ones relating to storage stability, cure speed and bond performance.
When 2-cyanoacrylates are stored even ill tightly closed vessels they exhibit a tendency to polymerise within a relatively short period of time at normal room temperatures. At higher temperatureOE this tendency to polymerise is enhanced. It has been proposed therefore to include in adhesive compositions based on 2-cyanoacrylates anionic polymerisation inhibitors, e . g. P205 or S02, in combination with a free radical polymerisation inhibitor e . g . hydroquinone or monomethyl ether of hydroquinone .
Compositions based on 2-cyanoacrylates containing anionic polymerisation inhibitors and free radical polymerisation inhibitors have not generally fully overcome difficulties associated with cure speed and bond performance.
Cure speed difficulties in general appear to result from a lack of tackiness of the composition necessitating holding of parts to be bonded in appropriate correlation with the adhesive between them until the 2-cyanoacrylate polymerises, ~L~3~
and builds up sufficient bonding strength. Bonds formed with
2-cyanoacrylates tend to be rather brittle, become unreliable when aged and tend not ro resist strongly deterioration caused by heat.
It is an object of the present inve-llt:ion -to provide a 2-cyanoacrylate adhesive composition including a novel agent effective to improve storage stability, cure speed and other properties of the composition.
This and other advantages are obtained according to the present invention by the inclusion in adhesive compositions based on 2-cyanoacrylate ester monomer of small amounts of itaconic acid anhydride.
The adhesive composition of the present invention is based c,n one or more polymerizable esters of 2-cyanoacrylic acid according to the general formula.
CN O
H2C=C C OR
where R is an alkyl or alkenyl group having 1 to 16 carbon atom~"
a cyclohexyl group or a phenyl group, together with an anionic polymerisation inhibitor and a free radical p~lymerisation inhibitor, characterised in that the adhesive includes from abou-t 0.1 to about 10% by weight based on the weight of the composition of a compound according to the formula.
H H ~ CH2 C
04 O,,' ~0 In an adhesive composition according to the invention, the ester of 2-cyanoacrylic acid is preferably methyl-2-cyano-acrylate, ethyl-2-cyanoacrylate, allyl-2-cyanoacrylate or mixtures of these with each other. A proportion of allyl-2-~ -2-; ~3~
cyanoacrylate may be found particularly appropriate where good resistance to deterioration of bonds by heat is desirable, for example a mixture comprising methyl-2-cyanoacrylate ~nd about 2% by weight of the mixture of allyl-2-cyanoacrylate. Other examples of mixtures are those comprising methyl-2-cyar.oacrylate and up to 50% by weight of the mixture of ethyl-2-cyanoacrylate or up to 50% by weight of the mixture of allyl-2-cyanoacrylate.
In an adhesive composition according to the invention, we believe ~3~40 that itaconic acid anhydride contributes towards storage stability of the 2-cyanoacrylates by virture of its anhydride grouping, and to performance of adhesive bonds formed by use of 2-cyanoacrylate based adhesive compositions as a result of copolymerisation with the 2-cyanoacrylate by virtue of its exocyclic ethylenic double bond. Suitably, from 0.1% to 10% by weight itaconic acid anhydride may be used by weight of the composition. The quantity of itaconic acid anhydride used is chosen in light of properties required of the adhesive including stability and cure time requirements, and it i6 noted that the most lO appropriate amount to be used is dependent to some extent on the type of 2-cyanoacrylate used at least so far as bond strength is concerned. With the preferred 2-cyanoacrylates excellent results appear to be obtainable by use of from about 0.5% to about 3% (by weight of the composition) of itaconic acid anhydride. It appears that the setting time of the composition (i.e.
the time which elapses between pressing together brass sheets with a drop of the composition and the onset of immovability of the sheets with respect to each other) is not significantly adversely effected by the presence of such quantities of itaconic acid anhydride.
In an adhesive composition according to the invention stabili~ing quantities of an anionic or acidic polymerisation inhibitor and a free radical inhibitor are used. The anionic polymerisation inhibitor employed may be for example any one of those materials commonly known as acidic polymerisation inhibitors for 2-cyanoacrylates, for example P2O5 or 52 Similarly the free radical polymerisation inhibitor may be for example one of those materials commonly known as free radical polymerisation inhibitors for 2-cyanoacrylates for example hydroquinone or monomethyl ether of hydroquinone. These materials may be used in appropriate quantities; for example in the preferred compositions3() quantities of the order of 0 . 01% to 0 . 02% (by weight of the composition) monomethyl ether of hydroquinone and 0.001% (by weight of the composition) P2O5 are used.
1~3~
In an adhesive composition according to the invention there may be included materials intended to increase the visco-sity of the fluid composition so that it is somewhat thickened and thereby may be more easily applied. A polymeric material may be used for this purpose, for example polymethyl metha-crylate or a copolymer compound formed from 2-cyanoacrylate and styrene or methyl styrene as more fully described in the U.S. Patent ~o. 3,968,186 issued July 6, 1976, inventors Heinz Tomaschek and Victor Winkovic entitled "Improvements in or relating to Adhesive Compositions".
In order that the above and others of the various aspects of the invention may become more clear there are hereinafter described various examples o-f 2-cyanoacrylate based adhesive compositions of which ten adhesive compositions are illustrative of aspects of the invention. It is of course to be clearly understood that the illustrative examples have been selected for description to illustrate the invention by way of example only and not by way of limitation thereof.
EXAMPLE ]
. . .
This example illustrates the extended storage stability of 2-cyanoacrylate adhesive compositions containing itaconic acid anhydride.
Control Composition 1 This comprised methyl-2-cyanoacrylate stabillzed with 0.01% by weight monomethyl ether of hydroquinone and 0.001%
by weight phosphorus pentoxide. Control composition 1 polyme-rized after a storage period of 60 days at 45C.
First Illustrative Composition This was forrned by adding to a sample of Control Composition 1, an additional amount of itaconic acid anhydride to provide 1% by weight of the illustrative composition. It was ~3~4~
observed that the composition remained fluid for 80 days at 45 C and increased in viscosity after this period, and remained fluid for 90 days at room ternperature.
..
-4a-~3~
Control Composition 2 This comprised ethyl-2-cyanoacrylate stabilized with 0.01% by weight monomethyl ether of hydroa~uinone and 0.001% by weight P205. This composition polymerised after a storage period of 60 days at room temperature.
Second Illustrative ~omposition This was formed by adding to a sample of Control Composition 2 an additional amount of itaconic acid anhydride to provide 1% by weight of the adhesive composition. This composition remained fluid for 90 days at room 10 temperature.
Control Composition 3 This comprised a mixture of 9~% by weight methyl-2-cyanoacrylate and 2% by weight allyl 2-cyanoacrylate stabilizecl with 0.01% by weight monomethyl ether of hydroquinone and 0 . 001% P2O5 . This composition polymerised after 40 days storage at room temperature.
Third Illustrative Composition This was formed by adding to a sarnple of Control Composition 3 sufficient itaconic acid anhydride to provide 1% by weight of the adhesive composition.
This composition remained fluid for 90 days at room temperature.
Example 2 This Example and Example 3 illustrate improved tensile shear strength of 2-cyanoacrylate adhesive compositions containing itaconic acid anhydride.
~)ne drop of control composition 1 was placed between overlapping portions of two brass sheets (dimensions 150 x 10 x 5 mm) which had been thoroughly cleaned with acetone before application of the composition. The bonds were formed by holding the sheets together, and were aged for one hour at room temperature and then were broken in tension on an Instron 1113/4 testing machine at a cross-head separation speed of 10 mm/min. A tensile shear ~trength of 160 Kp/cm2 was obtained .
~39~
Using the first illustrative composition to form bonds as just above set out, and testing them in the same way after ageing them for one hour at room temperature, a tensile shear strength test result of 192 Kp/cm2 was obtained .
Example 3 Control Composition 4 This comprised allyl-2-cyanoacrylate stabilized with 0.01% (by weight of the composition) monomethyl ether of hydroquinone and 0.001% (by weight 10 of the composition) P2O5.
One drop of this con~position was placed between two bra~s sheets (dimensions 150 x 10 x 5 mm) and a bond formed as described in Example 2. The tensile shear strength of the bonds, evaluated (after ageing for one hour at room temperature) as described in Example 2 was 55 Kp/cm2.
Fourth Illustrative Composition This was formed by adding amount (to provide 1~6 by weight of the fourth illustrative composition) of itaconic acid anhydride to a sample of - Control Composition 4. The tensile sheer strength of bonds formed by use 20 of this fourth illustrative composition as set out in Example 2 and evaluated (after ageing for one hour at room temperature) as in Example 2, was observed to be 105 Kp/cm2.
Example 4 The tensile shear strength of bonds formed as described in Example 2 but using control Composition 3 or various illustrative compositions prepared from it by addition of various amounts of itaconic anhydride was measured (after ageing for one hour at room temperature) as in Example 2. The results are as shown:
It is an object of the present inve-llt:ion -to provide a 2-cyanoacrylate adhesive composition including a novel agent effective to improve storage stability, cure speed and other properties of the composition.
This and other advantages are obtained according to the present invention by the inclusion in adhesive compositions based on 2-cyanoacrylate ester monomer of small amounts of itaconic acid anhydride.
The adhesive composition of the present invention is based c,n one or more polymerizable esters of 2-cyanoacrylic acid according to the general formula.
CN O
H2C=C C OR
where R is an alkyl or alkenyl group having 1 to 16 carbon atom~"
a cyclohexyl group or a phenyl group, together with an anionic polymerisation inhibitor and a free radical p~lymerisation inhibitor, characterised in that the adhesive includes from abou-t 0.1 to about 10% by weight based on the weight of the composition of a compound according to the formula.
H H ~ CH2 C
04 O,,' ~0 In an adhesive composition according to the invention, the ester of 2-cyanoacrylic acid is preferably methyl-2-cyano-acrylate, ethyl-2-cyanoacrylate, allyl-2-cyanoacrylate or mixtures of these with each other. A proportion of allyl-2-~ -2-; ~3~
cyanoacrylate may be found particularly appropriate where good resistance to deterioration of bonds by heat is desirable, for example a mixture comprising methyl-2-cyanoacrylate ~nd about 2% by weight of the mixture of allyl-2-cyanoacrylate. Other examples of mixtures are those comprising methyl-2-cyar.oacrylate and up to 50% by weight of the mixture of ethyl-2-cyanoacrylate or up to 50% by weight of the mixture of allyl-2-cyanoacrylate.
In an adhesive composition according to the invention, we believe ~3~40 that itaconic acid anhydride contributes towards storage stability of the 2-cyanoacrylates by virture of its anhydride grouping, and to performance of adhesive bonds formed by use of 2-cyanoacrylate based adhesive compositions as a result of copolymerisation with the 2-cyanoacrylate by virtue of its exocyclic ethylenic double bond. Suitably, from 0.1% to 10% by weight itaconic acid anhydride may be used by weight of the composition. The quantity of itaconic acid anhydride used is chosen in light of properties required of the adhesive including stability and cure time requirements, and it i6 noted that the most lO appropriate amount to be used is dependent to some extent on the type of 2-cyanoacrylate used at least so far as bond strength is concerned. With the preferred 2-cyanoacrylates excellent results appear to be obtainable by use of from about 0.5% to about 3% (by weight of the composition) of itaconic acid anhydride. It appears that the setting time of the composition (i.e.
the time which elapses between pressing together brass sheets with a drop of the composition and the onset of immovability of the sheets with respect to each other) is not significantly adversely effected by the presence of such quantities of itaconic acid anhydride.
In an adhesive composition according to the invention stabili~ing quantities of an anionic or acidic polymerisation inhibitor and a free radical inhibitor are used. The anionic polymerisation inhibitor employed may be for example any one of those materials commonly known as acidic polymerisation inhibitors for 2-cyanoacrylates, for example P2O5 or 52 Similarly the free radical polymerisation inhibitor may be for example one of those materials commonly known as free radical polymerisation inhibitors for 2-cyanoacrylates for example hydroquinone or monomethyl ether of hydroquinone. These materials may be used in appropriate quantities; for example in the preferred compositions3() quantities of the order of 0 . 01% to 0 . 02% (by weight of the composition) monomethyl ether of hydroquinone and 0.001% (by weight of the composition) P2O5 are used.
1~3~
In an adhesive composition according to the invention there may be included materials intended to increase the visco-sity of the fluid composition so that it is somewhat thickened and thereby may be more easily applied. A polymeric material may be used for this purpose, for example polymethyl metha-crylate or a copolymer compound formed from 2-cyanoacrylate and styrene or methyl styrene as more fully described in the U.S. Patent ~o. 3,968,186 issued July 6, 1976, inventors Heinz Tomaschek and Victor Winkovic entitled "Improvements in or relating to Adhesive Compositions".
In order that the above and others of the various aspects of the invention may become more clear there are hereinafter described various examples o-f 2-cyanoacrylate based adhesive compositions of which ten adhesive compositions are illustrative of aspects of the invention. It is of course to be clearly understood that the illustrative examples have been selected for description to illustrate the invention by way of example only and not by way of limitation thereof.
EXAMPLE ]
. . .
This example illustrates the extended storage stability of 2-cyanoacrylate adhesive compositions containing itaconic acid anhydride.
Control Composition 1 This comprised methyl-2-cyanoacrylate stabillzed with 0.01% by weight monomethyl ether of hydroquinone and 0.001%
by weight phosphorus pentoxide. Control composition 1 polyme-rized after a storage period of 60 days at 45C.
First Illustrative Composition This was forrned by adding to a sample of Control Composition 1, an additional amount of itaconic acid anhydride to provide 1% by weight of the illustrative composition. It was ~3~4~
observed that the composition remained fluid for 80 days at 45 C and increased in viscosity after this period, and remained fluid for 90 days at room ternperature.
..
-4a-~3~
Control Composition 2 This comprised ethyl-2-cyanoacrylate stabilized with 0.01% by weight monomethyl ether of hydroa~uinone and 0.001% by weight P205. This composition polymerised after a storage period of 60 days at room temperature.
Second Illustrative ~omposition This was formed by adding to a sample of Control Composition 2 an additional amount of itaconic acid anhydride to provide 1% by weight of the adhesive composition. This composition remained fluid for 90 days at room 10 temperature.
Control Composition 3 This comprised a mixture of 9~% by weight methyl-2-cyanoacrylate and 2% by weight allyl 2-cyanoacrylate stabilizecl with 0.01% by weight monomethyl ether of hydroquinone and 0 . 001% P2O5 . This composition polymerised after 40 days storage at room temperature.
Third Illustrative Composition This was formed by adding to a sarnple of Control Composition 3 sufficient itaconic acid anhydride to provide 1% by weight of the adhesive composition.
This composition remained fluid for 90 days at room temperature.
Example 2 This Example and Example 3 illustrate improved tensile shear strength of 2-cyanoacrylate adhesive compositions containing itaconic acid anhydride.
~)ne drop of control composition 1 was placed between overlapping portions of two brass sheets (dimensions 150 x 10 x 5 mm) which had been thoroughly cleaned with acetone before application of the composition. The bonds were formed by holding the sheets together, and were aged for one hour at room temperature and then were broken in tension on an Instron 1113/4 testing machine at a cross-head separation speed of 10 mm/min. A tensile shear ~trength of 160 Kp/cm2 was obtained .
~39~
Using the first illustrative composition to form bonds as just above set out, and testing them in the same way after ageing them for one hour at room temperature, a tensile shear strength test result of 192 Kp/cm2 was obtained .
Example 3 Control Composition 4 This comprised allyl-2-cyanoacrylate stabilized with 0.01% (by weight of the composition) monomethyl ether of hydroquinone and 0.001% (by weight 10 of the composition) P2O5.
One drop of this con~position was placed between two bra~s sheets (dimensions 150 x 10 x 5 mm) and a bond formed as described in Example 2. The tensile shear strength of the bonds, evaluated (after ageing for one hour at room temperature) as described in Example 2 was 55 Kp/cm2.
Fourth Illustrative Composition This was formed by adding amount (to provide 1~6 by weight of the fourth illustrative composition) of itaconic acid anhydride to a sample of - Control Composition 4. The tensile sheer strength of bonds formed by use 20 of this fourth illustrative composition as set out in Example 2 and evaluated (after ageing for one hour at room temperature) as in Example 2, was observed to be 105 Kp/cm2.
Example 4 The tensile shear strength of bonds formed as described in Example 2 but using control Composition 3 or various illustrative compositions prepared from it by addition of various amounts of itaconic anhydride was measured (after ageing for one hour at room temperature) as in Example 2. The results are as shown:
3~
Composition Control Illustrative 3 5th 3rd 6th 7th Amount of itaconic anhydride (% by weight of composition) 0 0.5 1 1.5 2 Tensile shear strength (Kp/cm~) 135 184 200 191 158 Example 6 10 This Example illustrates the strength of bond to be achieved after a relatively short time by use, in Control composition 5, of itaconic acid anhydride .
Control composition 5 comprised 50% by weight allyl-2-cyanoacrylate and 49.9% methyl-2-cyanoacrylate stabilized as in Control Composition 1 Eighth and ninth illustrative compositions were formed by addition of various amounts of itaconic acid anhydride to Control composition 5.
The tensile shear strength of bonds formed as described in Example 2 but using Control composition 5 or the eighth or ninth illustrative 20 composition was measured. These bonds were allowed to cure for 2 minutes only at room temperature before being subject to breaking tension in the Instron tester as referred to in Example 2. Results were as follows:
Composition Control ~llustrative 8th 9th Amount of itaconic anhydride ~% by weight of composition) 0 0.5 1.5 Tensile shear strength (Kptcm2) 40 59 91 3LU3S~4~3 These results show that when bonds are formed, a greater tensile shear strength is achieved after two minutes cure with compositions including quantities of itaconic acid anhydride, and that greater tensile shear strengths are obtainable with the larger amount of itaconic acid anhydride.
Example 6 This example shows improved heat resistance of adhesive bonds formed by use of allyl-2-cyanoacrylate adhesive including itaconic acid , anhydride.
One drop of Control composihon 6, which comprised allyl-2-cyano-acrylate stabilized as in Control Composition 1, was placed between two brass sheets (dimensions 150 x 10 x 5 mm) which had been thoroughly cleaned with acetone. The bonded sheets were warmed to 100C. for 24 hours.
~fter cooling to room temperature a tenslle shear strength of 34 Kp/cm2 was obtained using an Instron tester as referred to in Example 2.
A tenth illustrative composition was made from a sample of Control composition 6 by addition of an amount of itaconic acid anhydride to provide ~; 1% by weight of the tenth illustrative composition. The tensile shear strength of a brass-brass bond formed (in the same way as with Control composition 6 using this tenth illustrative composition and aged at 100C. for 24 hours was measured as just above referred to and found to be 135 Kp/cm2.
' Example 7 The tensile shear strength of adhesive bonds made u~ing the first and third illustrative compositions (see Examples 1 and 4) was measured in relation to the cure time. The bonds were made, aged at room temperature, and tested as in Example 2 except that the time (cure time) between making the bonds and testing them on the Instron machine was varied.
3û
1039~
1 Cure Time 2 Min. 15 Min. 1 Hr. 24 ~Irs.
First illustrative composition Tensile shear strength (Kp/cm2) 95 153 182 223 Third illustrative composition Tensile shear strength (Kp/cm2~ 103 161 200 242 The results indicate a progressive increase in bond strength, and it is noted that after 15 minutes, the tensile shear strength result for the third illustrative composition is in excess of the value for Control composition 3 after ageing for one hour, and the tensile shear strength results for both the first and second illustrative compositions after one hour cure time is well in excess of results obtained with control compositions 1 and 3 as shown by Examples 2 and 4.
_9_
Composition Control Illustrative 3 5th 3rd 6th 7th Amount of itaconic anhydride (% by weight of composition) 0 0.5 1 1.5 2 Tensile shear strength (Kp/cm~) 135 184 200 191 158 Example 6 10 This Example illustrates the strength of bond to be achieved after a relatively short time by use, in Control composition 5, of itaconic acid anhydride .
Control composition 5 comprised 50% by weight allyl-2-cyanoacrylate and 49.9% methyl-2-cyanoacrylate stabilized as in Control Composition 1 Eighth and ninth illustrative compositions were formed by addition of various amounts of itaconic acid anhydride to Control composition 5.
The tensile shear strength of bonds formed as described in Example 2 but using Control composition 5 or the eighth or ninth illustrative 20 composition was measured. These bonds were allowed to cure for 2 minutes only at room temperature before being subject to breaking tension in the Instron tester as referred to in Example 2. Results were as follows:
Composition Control ~llustrative 8th 9th Amount of itaconic anhydride ~% by weight of composition) 0 0.5 1.5 Tensile shear strength (Kptcm2) 40 59 91 3LU3S~4~3 These results show that when bonds are formed, a greater tensile shear strength is achieved after two minutes cure with compositions including quantities of itaconic acid anhydride, and that greater tensile shear strengths are obtainable with the larger amount of itaconic acid anhydride.
Example 6 This example shows improved heat resistance of adhesive bonds formed by use of allyl-2-cyanoacrylate adhesive including itaconic acid , anhydride.
One drop of Control composihon 6, which comprised allyl-2-cyano-acrylate stabilized as in Control Composition 1, was placed between two brass sheets (dimensions 150 x 10 x 5 mm) which had been thoroughly cleaned with acetone. The bonded sheets were warmed to 100C. for 24 hours.
~fter cooling to room temperature a tenslle shear strength of 34 Kp/cm2 was obtained using an Instron tester as referred to in Example 2.
A tenth illustrative composition was made from a sample of Control composition 6 by addition of an amount of itaconic acid anhydride to provide ~; 1% by weight of the tenth illustrative composition. The tensile shear strength of a brass-brass bond formed (in the same way as with Control composition 6 using this tenth illustrative composition and aged at 100C. for 24 hours was measured as just above referred to and found to be 135 Kp/cm2.
' Example 7 The tensile shear strength of adhesive bonds made u~ing the first and third illustrative compositions (see Examples 1 and 4) was measured in relation to the cure time. The bonds were made, aged at room temperature, and tested as in Example 2 except that the time (cure time) between making the bonds and testing them on the Instron machine was varied.
3û
1039~
1 Cure Time 2 Min. 15 Min. 1 Hr. 24 ~Irs.
First illustrative composition Tensile shear strength (Kp/cm2) 95 153 182 223 Third illustrative composition Tensile shear strength (Kp/cm2~ 103 161 200 242 The results indicate a progressive increase in bond strength, and it is noted that after 15 minutes, the tensile shear strength result for the third illustrative composition is in excess of the value for Control composition 3 after ageing for one hour, and the tensile shear strength results for both the first and second illustrative compositions after one hour cure time is well in excess of results obtained with control compositions 1 and 3 as shown by Examples 2 and 4.
_9_
Claims (5)
1. An adhesive composition comprising one or more polymerizable esters of 2-cyanoacrylic acid according to the general formula where R is an alkyl of alkenyl group having 1 to 16 carbon atoms, a cyclohexyl group or a phenyl group, together with an anionic polymerization inhibitor and a free radical poly-merization inhibitor, characterized in that the adhesive in-cludes from about 0.1 to about 10% by weight based on the weight of the composition of a compound according to the formula
2. An adhesive composition according to claim 1 wherein the ester of 2-cyanoacrylic acid includes at least one member of the group consisting of methyl-2-cyanoacrylate, ethyl-2-cyanoacrylated and allyl-2-cyanoacrylate said composition con-taining from about 0.5% to about 3.0% by weight based on the weight of the composition of itaconic acid anhydride, said free radical polymerization inhibitor being selected from the group consisting of hydroquinone and the monomethyl ether of hydro-quinone and said anionic polymerization inhibitor being selected from the group consisting of P205 and SO2.
3. An adhesive composition according to claim 2 wherein the ester of 2-cyanoacrylic acid is a mixture of methyl-2-cyanoacrylate and up to about 50% by weight of the mixture of ethyl-2-cyanoacrylate or allyl-2-cyanoacrylate.
4. An adhesive composition according to claim 3 com-prising a mixture of about 98% by weight methyl-2-cyanoacrylate and about 2% by weight allyl-2-cyanocrylate.
5. An adhesive composition according to claim 2 comprising from about 0.01 to about 0.02% by weight of the composition of said free radical polymerization inhibitor and about 0.001% by weight of the composition of said anionic polymerization inhibitor.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2871773A GB1467424A (en) | 1973-06-16 | 1973-06-16 | Adhesive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039440A true CA1039440A (en) | 1978-09-26 |
Family
ID=10279970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA202,421A Expired CA1039440A (en) | 1973-06-16 | 1974-06-12 | Adhesive compositions based on 2-cyanoacrylate monomers |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3948794A (en) |
| JP (1) | JPS582984B2 (en) |
| AT (1) | AT333397B (en) |
| CA (1) | CA1039440A (en) |
| DE (1) | DE2429070C2 (en) |
| FR (1) | FR2233376B1 (en) |
| GB (1) | GB1467424A (en) |
| SE (1) | SE411223B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5934296B2 (en) * | 1976-06-16 | 1984-08-21 | 松下電器産業株式会社 | Electron beam resist and its usage |
| US4139693A (en) * | 1978-03-29 | 1979-02-13 | National Starch And Chemical Corporation | 2-Cyanoacrylate adhesive compositions having enhanced bond strength |
| JPS5853676B2 (en) * | 1979-12-24 | 1983-11-30 | 東亞合成株式会社 | adhesive composition |
| DE3006017C2 (en) * | 1980-02-18 | 1982-06-03 | Teroson Gmbh, 6900 Heidelberg | Cyanoacrylate adhesive composition |
| US4933234A (en) * | 1987-08-13 | 1990-06-12 | Minnesota Mining And Manufacturing Company | Primed polymeric surfaces for cyanoacrylate adhesives |
| US5135598A (en) * | 1987-08-13 | 1992-08-04 | Minnesota Mining And Manufacturing Company | Priming polymeric surfaces for cyanoacrylate adhesives |
| US5383899A (en) * | 1993-09-28 | 1995-01-24 | Hammerslag; Julius G. | Method of using a surface opening adhesive sealer |
| US20060094833A1 (en) * | 2004-11-01 | 2006-05-04 | Loctite (R&D) Limited | Shock resistant cyanoacrylate compositions |
| US9783714B2 (en) * | 2013-03-15 | 2017-10-10 | Henkel IP & Holding GmbH | Cyanoacrylate compositions |
| IT201900010053A1 (en) * | 2019-06-25 | 2020-12-25 | Permabond Eng Adhesives Ltd | COMPOSITIONS OF CYANOACRYLIC ADHESIVES WITH IMPROVED RESISTANCE TO HIGH TEMPERATURES |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2765332A (en) * | 1954-02-11 | 1956-10-02 | Eastman Kodak Co | Stabilized alpha-cyanoacrylate adhesive compositions |
| US2873211A (en) * | 1955-10-26 | 1959-02-10 | American Marietta Company Ston | Carboxylic-nitrile-acrylate ester coating composition, process and coated product |
| US3223083A (en) * | 1960-09-09 | 1965-12-14 | President And Directors Of Geo | Method for adhesively securing together skin and other soft tissue and bone |
| US3697618A (en) * | 1967-03-16 | 1972-10-10 | Nat Starch Chem Corp | Pressure-sensitive adhesive |
| US3564078A (en) * | 1968-05-17 | 1971-02-16 | Eastman Kodak Co | Alpha-cyanoacrylate adhesive compositions |
| IE34874B1 (en) * | 1971-01-13 | 1975-09-03 | Intercontinental Chem Co Ltd | Cyanoacrylate adhesive compositions |
-
1973
- 1973-06-16 GB GB2871773A patent/GB1467424A/en not_active Expired
-
1974
- 1974-06-12 CA CA202,421A patent/CA1039440A/en not_active Expired
- 1974-06-12 JP JP49067578A patent/JPS582984B2/en not_active Expired
- 1974-06-12 US US05/478,514 patent/US3948794A/en not_active Expired - Lifetime
- 1974-06-13 SE SE7407824A patent/SE411223B/en unknown
- 1974-06-14 AT AT491474A patent/AT333397B/en not_active IP Right Cessation
- 1974-06-14 FR FR7420832A patent/FR2233376B1/fr not_active Expired
- 1974-06-18 DE DE2429070A patent/DE2429070C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA491474A (en) | 1976-03-15 |
| SE411223B (en) | 1979-12-10 |
| DE2429070A1 (en) | 1975-01-16 |
| DE2429070C2 (en) | 1985-02-14 |
| JPS5048039A (en) | 1975-04-28 |
| JPS582984B2 (en) | 1983-01-19 |
| FR2233376B1 (en) | 1978-01-13 |
| AT333397B (en) | 1976-11-25 |
| GB1467424A (en) | 1977-03-16 |
| US3948794A (en) | 1976-04-06 |
| SE7407824L (en) | 1974-12-17 |
| FR2233376A1 (en) | 1975-01-10 |
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