GB2293605A - Adhesive compositions - Google Patents

Adhesive compositions Download PDF

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Publication number
GB2293605A
GB2293605A GB9518630A GB9518630A GB2293605A GB 2293605 A GB2293605 A GB 2293605A GB 9518630 A GB9518630 A GB 9518630A GB 9518630 A GB9518630 A GB 9518630A GB 2293605 A GB2293605 A GB 2293605A
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GB
United Kingdom
Prior art keywords
acid
composition according
copolymer
ester
salt
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.)
Granted
Application number
GB9518630A
Other versions
GB2293605B (en
GB9518630D0 (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 GB9518630D0 publication Critical patent/GB9518630D0/en
Publication of GB2293605A publication Critical patent/GB2293605A/en
Application granted granted Critical
Publication of GB2293605B publication Critical patent/GB2293605B/en
Anticipated expiration legal-status Critical
Expired - Fee Related 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)

Abstract

An adhesive composition, wherein said adhesive comprises:- (a) a copolymer, or salt thereof, of (i) a monomeric vinylphosphonic acid and/or ester or salt thereof, and/or an (ii) an unsaturated carborylic acid and/or an ester thereof and/or an unsaturated phosphonic acid ester, and (b) an adhesive carrier in which the copolymer (a) is, or can be, soluble, and optionally one or more solvents whereby the copolymer (a) is rendered soluble in the carrier (b). (b) may be polyvinyl acetate, gelatin or epoxy compound.

Description

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 tooth, 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 an adhesive composition comprising: (a) a copolymer or salt thereof of (i) 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 (b) an adhesive carrier in which the copolymer (a) is, or can be, soluble.
Optionally, the adhesive composition may also include one or more solvents whereby the copolymer (a) is rendered soluble in the carrier (b).
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 alkyl, aryl, aralkyl and alkaryl groups.
For example, the substituent group or groups may be selected from methyl and phenyl groups i.e.
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 maleic 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 (b) 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 (b), as well as upon the nature of the surfaces to be bonded.
The ratio of the vinylphosphonic acid and/or ester or salt to the unsaturated carboxylic acid and/or ester thereof, and/or unsaturated phosphonic ester in the copolymer (a) may be in the range 10:90 to 99:1 by weight, for example about 50:50 by weight.
The copolymer (a) may be present in an effective amount of up to 10%, for example up to 5%, 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 bonding 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 (a) may be mixed with the carrier (b) before use.
Alternatively, the copolymer (a) may be applied to one of two surfaces to be bonded and the carrier (b) 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 of vinylphosphonic 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 1 2mm), and a constant amount of glue (0.02g) spread evenly onto it prior to placing on top ofthe wood.
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.
TABLE 1 Average Coupon % copolymer Amount of Tensile Tensile No w/w adhesive (g) Strength Strength (mPa) (mPa) 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 5 1% 0.021 10.0 7.22 6 1% 0.020 4.92 7 1% 0.020 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 15 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 25 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 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 50 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 Sample No % Copolymer Tensile Strength Average w/w (mPa) 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 4.39 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.
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 ofthe 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 Sample Ratio Tensile Average No VPA: AA Strength Tensile in copolymer (mPa) 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 3.5 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 (16)

1. An adhesive composition comprising: (a) a copolymer or salt thereof of (i) 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 (b) an adhesive carrier in which the copolymer (a) is, or can be, soluble.
2. A composition according to Claim 1, including one or more solvents whereby the copolymer (a) is rendered soluble in the carrier (b).
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 alkyl, aryl, aralkyl and alkaryl groups.
5. A composition according to Claim 4, in which the substituent group or groups are selected from methyl and phenyl groups.
6. A composition according to any one of Claims 1 to 5, in which the vinylphosphonic acid salt is an alkali metal or alkaline earth metal salt or an amine based salt of the acid.
7. A composition according to any one of Claims 1 to 6, in which the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
8. A composition according to any one of Claims 1 to 6, in which the ester is selected from hydroxyethyl and hydroxypropyl esters of acrylic acid, methacrylic acid, itaconic acid or maleic acid.
9. A composition according to any of Claims 1 to 6, in which the ester is methyl cyanoacrylate or ethyl cyanoacrylate
10. A composition according to any one of Claims 1 to 9, in which the adhesive carrier (b) is based on polyvinyl acetate, epoxy-compounds, gelatine, resins or thermoplastics.
11. A composition according to any one of Claims 1 to 10, in which the ratio of the vinylphosphonic acid and/or ester or salt to the unsaturated carboxylic acid and or ester thereof and/or unsaturated phosphonic acid ester in the copolymer (a) is in the range 10:90 to 99:1 by weight.
12. A composition according to Claim 11, in which the ratio is about 50:50 by weight.
13. A composition according to any one of Claims 1 to 12, in which the copolymer (a) is present in the adhesive composition in an effective amount of up to 10% by weight of the total composition.,
14. A composition according to Claim 13, in which the copolymer (a) is present in an effective amount of up to 5% by weight of the total composition.
15. A composition according to Claim 13 or 14, in which the copolymer (a) is present in an amount of about 1% by weight of the total composition.
16. An adhesive composition, substantially as hereinbefore described with reference to any one of the Examples.
GB9518630A 1994-09-20 1995-09-12 Adhesive compositions Expired - Fee Related GB2293605B (en)

Applications Claiming Priority (1)

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

Publications (3)

Publication Number Publication Date
GB9518630D0 GB9518630D0 (en) 1995-11-15
GB2293605A true GB2293605A (en) 1996-04-03
GB2293605B GB2293605B (en) 1998-05-06

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GB9418947A Pending GB9418947D0 (en) 1994-09-20 1994-09-20 Adhesive compositions
GB9518630A Expired - Fee Related GB2293605B (en) 1994-09-20 1995-09-12 Adhesive compositions

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GB (2) GB9418947D0 (en)

Cited By (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
WO2006062713A2 (en) * 2004-12-08 2006-06-15 3M Innovative Properties Company Aqueous adhesive composition
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
WO2010029057A1 (en) * 2008-09-10 2010-03-18 Basf Se Vinyl phosponic acid or copolymers thereof as adhesive additives
US8173722B2 (en) 2008-07-10 2012-05-08 Aesculap Ag Adhesive compositions for use in surgical therapy

Citations (5)

* 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
GB1468188A (en) * 1974-11-26 1977-03-23 Stauffer Chemical Co Flame retardant binder for flammable materials
US4014837A (en) * 1973-09-17 1977-03-29 Stauffer Chemical Company Fire retardant polymeric additives
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement
WO1993003106A1 (en) * 1991-08-08 1993-02-18 Lohmann Gmbh & Co. Kg Pressure-sensitive adhesive strip

Patent Citations (5)

* 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
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
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement
WO1993003106A1 (en) * 1991-08-08 1993-02-18 Lohmann Gmbh & Co. Kg Pressure-sensitive adhesive strip

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI Abstact Accession No85-144069/24 & JP 60 078 906 A *

Cited By (7)

* 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
WO2006062713A2 (en) * 2004-12-08 2006-06-15 3M Innovative Properties Company Aqueous adhesive composition
WO2006062713A3 (en) * 2004-12-08 2007-03-01 3M Innovative Properties Co Aqueous adhesive composition
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

Also Published As

Publication number Publication date
GB2293605B (en) 1998-05-06
AU688092B2 (en) 1998-03-05
AU3175095A (en) 1996-04-04
GB9518630D0 (en) 1995-11-15
GB9418947D0 (en) 1994-11-09

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 20010912