AU688092B2 - Adhesive compositions - Google Patents

Adhesive compositions Download PDF

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Publication number
AU688092B2
AU688092B2 AU31750/95A AU3175095A AU688092B2 AU 688092 B2 AU688092 B2 AU 688092B2 AU 31750/95 A AU31750/95 A AU 31750/95A AU 3175095 A AU3175095 A AU 3175095A AU 688092 B2 AU688092 B2 AU 688092B2
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AU
Australia
Prior art keywords
acid
ester
salt
composition according
copolymer
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.)
Ceased
Application number
AU31750/95A
Other versions
AU3175095A (en
Inventor
Adrian Charles Archer
Alan Craig Smith
Michael John Williams
Mohsen Zakikhani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson UK Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Albright and Wilson UK Ltd filed Critical Albright and Wilson UK Ltd
Publication of AU3175095A publication Critical patent/AU3175095A/en
Application granted granted Critical
Publication of AU688092B2 publication Critical patent/AU688092B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

IUUIU11 28W511 Regulation 3.2(2)
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT ;r
I
o Application Number: Lodged: Invention Title: ADHESIVE COMPOSITIONS r o The following statement is a full description of this invention, including the best method of performing it known to us ADHESIVE COMPOSITIONS This invention relates to adhesive compositions and in particular to adhesive compositions including a copolymer or salt thereof of a vinylphosphonic acid (and/or ester or salt thereof) and an unsaturated carboxylic acid and/or ester thereof, and/or an unsaturated phosphonic acid ester.
Our co-pending GB Application No. 9513352.6 describes a dental cement composition containing a copolymer of the type hereinabove described.
The dental cement, when implanted in, for example, the cavity of a tocth, acts essentially as a "structural" component.
We have now found that the aforementioned copolymers will also function effectively as adhesion-promoters in "bond-forming" components.
Accordingly, the present invention provides a bond-forming adhesive composition comprising: An effective amount of up to 10% by weight of a copolymer or salt Sthereof of a monomeric vinylphosphonic acid and/or an ester or a salt thereof, and (ii) an unsaturated carboxylic acid or an ester thereof, or an unsaturated phosphonic acid ester, and a corresponding amount of 90% or more by weight of an adhesive carrier for the copolymer said carrier being based on polyvinyl acetate, epoxy-compounds, resins, gelatin or thermoplastics materials.
Optionally, the adhesive composition may also include one or more solvents for the copolymer The monomeric vinylphosphonic acid or salt may be unsubstituted.
Alternatively, the vinylphosphonic acid or salt may be provided with one or more substituent groups selected from t' tt grf: m; clb-. tedf... methyl and phenyl groups i.e.
ct-methyl vinylphosphonic acid or styrene vinylphosphonic acid.
The vinylphosphonic acid salt may be for example an alkali metal or alkaline earth metal salt or an amine based salt of the acid.
The unsaturated carboxylic acid may be, for example, selected from acrylic acid, methacrylic acid, itaconic acid, and inaleic acid. The ester may, for example, be selected from hydroxyethyl and hydroxypropyl esters of acrylic acid, methacrylic acid, itaconic acid or maleic acid. Alternatively, the ester may be a methyl or ethyl cyanoacrylate.
The adhesive carrier may, for example, be based on polyvinyl acetate, epoxy-compounds, gelatine, resins or thermoplastics.
The solvent, if required, will depend upon the constitution of the adhesive carrier as well as upon the nature of the surfaces to be bonded.
The ratio of the' .'Iphosphonic acid and/or ester or salt to the unsaturated carboxylic acid and/or ester thereof, a.J' unsaturated phosphonic ester in the copolymer may be in the range 10:90 to 99:1 by weight, for example about 50:50 by weight.
The copolymer may be present in an effective amount of up to 10%, for example up to preferably about 1% (all such percentages being by weight of the total adhesive composition).
Adhesive compositions according to the present invention have a wide variety of blnding applications. These include the bonding of metals to other metals, to plastics, to glass, wood, leather or rubber, and the bonding of each of the aforementioned components to each other.
The compositions can also be used for thread-locking or thread-sealing applications, as well as in the construction of gaskets.
In formulating adhesive compositions according to the present invention, the copolymer may be mixed with the carrier before use.
Alternatively, the copolymer may be applied to one of two surfaces to be bonded and the carrier applied to the other surface.
After bonding, the adhesive composition may be cured by any suitable curing means, for example by air-drying, by the application of a vacuum, or by ultra-violet radiation.
Adhesive compositions according to the present invention have been found to reduce water-penetration at the bond interface, In addition, there will be a potential reduction in corrosion if one or both of the surfaces to be bonded are made of metal.
The present invention will be illustrated by way of the following examples A water based polyvinyl acetate wood glue (available from Evode Ltd as EVOSTICK* W) was used as a base to dissolve a copolymer ofvinylphosphonic acid and acrylic acid. The polymer dissolved readily in the base and the resulting adhesive composition was used to bond metal to wood. The metal surface consists of mild steel corrosion-coupons.
In order to let the glue dry and to provide the other surface a wooden oral spatula was used.
After degreasing with acetone, an area on the end of each coupon was measured (10 x 12mm), and a constant amount of glue (0.02g) spread evenly onto it prior to placing on top of the wood.
I I- I, After leaving overnight, the sample of wood glued to metal was tensile tested on a Hounsfield 500L tensile tester to determine the strength of the adhesive bond.
EXAMPLE 1 In this Example, the copolymer consisted of 50 parts by weight vinylphosphonic acid and 50 parts by weight acrylic acid. The amount of copolymer in the glue base was varied from 1% to 8% by weight of the total adhesive composition and four samples were tested at each level of copolymer.
The results are give in TABLE 1 (below): *EVOSTICK is a Registered Trade Mark.
a TABLE 1 Coupon No copolymer WiW Amount of adhesive (g) Tensile Strength (m.Pa) Average Tensile Strength (mPa) *0e* 9~ 0 *0000* 1 Blank 0,021 5,67 4.44 2 Blank 0,020 6.83 3 Blank 0.020 1,00 4 Blank 0.021 4.25 1% 0.021 10.0 7.22 6 1% 0.020 4.92 7 1% 0.20 7.17 8 1% 0.020 6.79 9 2% 0.030 6.96 6.40 10 2% 0.020 4.83 11 2% 0,021 6,67 12 2% 0.020 7.13 13 3% 0,020 6.17 5.73 14 3% 0.020 3.42 3% 0.021 6.67 16 3% 0,020 6.67 17 4% 0.021 4.5 6.02 18 4% 0,020 7.79 19 4% 0.020 6.21 20 4% 0.020 5.58 21 6% 0,021 1.83 4.30 22 6% 0.021 7.21 23 6% 0.021 4.71 24 6% 0.020 3.46 8% 0.020 5.54 3.84 26 8% 0.030 3.83 27 8% 0.021 2.75 28 8% 0.020 3.25 6 The results clearly demonstrate that the addition of the copolymer enhances the adhesion of wood to metal. This is confirmed by visual observation, as the BLANK sample after failure has the glue deposits on the wood and not on the metal, whilst all the other samples have wood-to-glue failure with most of the glue deposits being present on the metal.
EXAMPLE 2 In this Example, the copolymer again consisted of 50 parts by weight vinylphosphonic acid and parts by weight acrylic acid. The amount of copolymer in the glue base was varied from 0.02% to 1% by weight of the total adhesive composition. The results are given in TABLE 2 (below) TABLE 2 r r r r c rrr
D
r 4 r r r r r r o r a r r rr r Sample No Copolymer w/w Tensile Strength (mPa) Average Tensile Strength (mPa) 2.1 Blank 4.19 2.2 Blank 4.4375 4.31 2.3 0.02% 3.93 3.93 2.4 0.10% 4.39 439 2.5 0.20% 5.39 5.39 2.6 0.50% 5.11 5.11 2.7 1.0% 6.97 7.095 2.8 1.0 7.22 From the results above, it would appear that 1% copolymer is the optimum level.
7 EXAMPLE 3 In this Example, the constitution of the copolymer was varied from 4:96 to 50:50 parts by weight vinylphosphonic acid to acrylic acid. A level of 1% by weight of the copolymer was added to the adhesive carrier and the tensile strength measured as described hereinabove. The results are given in TABLE 3 (below) TABLE 3 0 *s
S.
Sample No Ratio VPA: AA in copolymer Tensile Strength (mPa) Average Tensile Strength (mPa) 3.1 Blank 4.8 4.48 3.2 Blank 4.19 3.3 Blank 4.44 3.4 50:50 6.32 50:50 6.97 6.87 3.6 50:50 7.22 3.7 30:70 5.51 5.51 3.8 20:80 5.36 5.36 3.9 10:90 4.9 4.9 3.10 4:96 5.03 5.03 From the results above, it would appear that a 50:50 ratio of vinylphosphonic acid to acrylic acid provides the most effective improvement in the metal-to-wood adhesion properties of the adhesive compound.

Claims (13)

1. A bond-forming adhesive composition comprising: An effective amount of up to 10% by weight of a copo!ymer or salt thereof of a monomeric vinylphosphonic acid and/or an ester or a salt thereof, and (ii) an unsaturated carboxylic acid or an ester thereof, or an unsaturated phosphonic acid ester, and a corresponding amount of 90% or more by weight of an adhesive carrier for the copolyrrer said carrier being based on polyvinyl acetate, epoxy-compounds, resins, gelatin or thermoplastics materials.
2. A composition according to Claim 1, further including one or more solvents for the copolymer
3. A composition according to Claim 1 or 2, in which the vinylphosphonic acid or salt is unsubstituted.
4. A composition according to Claim 1 or 2, in which the vinylphosphonic acid or salt is provided with one or more substituent groups selected from methyl and phenyl groups.
A composition according to any one of Claims 1 to 4, in which the vinylphosphonic acid salt is an alkali metal salt, an alkaline earth metal salt or an amine-based salt of the acid.
6. A composition according to any one of Claims 1 to 5, in which the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, itaconic acid, and maleic acid. t\ 3 9
7. A composition according to any one of Claims 1 to 5, in which the ester is selected from hydroxyethyl and hydroxypropyl esters of acrylic acid, methacrylic acid, itaconic acid or maleic acid.
8. A composition according to any one of Claims 1 to 5, in which the ester is methyl cyanoacrylate or ethyl cyanoacrylate.
9. A composition according to any one of Claims 1 to 8, in which the ratio of the vinylphosphonic acid or ester or salt to the unsaturated carboxylic acid or ester thereof, or the unsaturated phosphonic acid ester in the copolymer is in the range 10:90 to 99:1 by weight.
10. A composition according to Claim 9, in which the ratio is about 50:50 by Sjight. *e
11. A composition according to any one of the preceding claims, in which the copolymer is present in an effective amount of up to 5% by weight of the total composition.
12. A composition according to Claim 11, in which the copolymer is present in an amount of about 1% by weight of the total composition.
13. A bond-forming adhesive composition, substantially as hereinbefore described with reference to any one of the Examples. DATED this 18th day of November, 1997. ALBRIGHT WILSON UK LIMITED WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA CJH:JZ (DOC.18) AU3175095.WPC ABSTRACT ADHESIVE COMPOSITIONS An adhesive composition, wherein said adhesive comprises a copolymer or salt thereof of a monomeric vinylphosphonic acid and/or ester or salt thereof, and (ii) an unsaturated carboxylic acid and/or an ester thereof and/or an unsaturated phosphonic acid ester, and an adhesive carrier in which the copolymer is, or can be, soluble, and optionally one or more solvents whereby the copolymer is rendered soluble in the carrier *4 ft
AU31750/95A 1994-09-20 1995-09-19 Adhesive compositions Ceased AU688092B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9418947 1994-09-20
GB9418947A GB9418947D0 (en) 1994-09-20 1994-09-20 Adhesive compositions

Publications (2)

Publication Number Publication Date
AU3175095A AU3175095A (en) 1996-04-04
AU688092B2 true AU688092B2 (en) 1998-03-05

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ID=10761626

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AU31750/95A Ceased AU688092B2 (en) 1994-09-20 1995-09-19 Adhesive compositions

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6030710A (en) * 1997-06-30 2000-02-29 Alcoa Inc. Copolymer primer for aluminum alloy food and beverage containers
US7851522B2 (en) 2004-12-08 2010-12-14 3M Innovative Properties Company Adhesive
DE102008033378A1 (en) * 2008-07-10 2010-01-14 Aesculap Ag Adhesive composition, useful in surgical medicine for closure of wounds and to glue animal or human tissues, comprises liquid mixture of cyanoacrylate monomers and plasticizer and an aqueous liquid component comprising e.g. amino acid
US8173722B2 (en) 2008-07-10 2012-05-08 Aesculap Ag Adhesive compositions for use in surgical therapy
WO2010029057A1 (en) * 2008-09-10 2010-03-18 Basf Se Vinyl phosponic acid or copolymers thereof as adhesive additives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965216A (en) * 1972-09-21 1976-06-22 Stauffer Chemical Company Fire retardant crosslinked copolymers
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014837A (en) * 1973-09-17 1977-03-29 Stauffer Chemical Company Fire retardant polymeric additives
GB1468188A (en) * 1974-11-26 1977-03-23 Stauffer Chemical Co Flame retardant binder for flammable materials
DE4126230C2 (en) * 1991-08-08 1994-02-17 Lohmann Gmbh & Co Kg PSA tape and its use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965216A (en) * 1972-09-21 1976-06-22 Stauffer Chemical Company Fire retardant crosslinked copolymers
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement

Also Published As

Publication number Publication date
GB9418947D0 (en) 1994-11-09
GB9518630D0 (en) 1995-11-15
GB2293605A (en) 1996-04-03
GB2293605B (en) 1998-05-06
AU3175095A (en) 1996-04-04

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