WO1991008240A1 - Resine modifiee par silane - Google Patents

Resine modifiee par silane Download PDF

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Publication number
WO1991008240A1
WO1991008240A1 PCT/GB1990/001865 GB9001865W WO9108240A1 WO 1991008240 A1 WO1991008240 A1 WO 1991008240A1 GB 9001865 W GB9001865 W GB 9001865W WO 9108240 A1 WO9108240 A1 WO 9108240A1
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WO
WIPO (PCT)
Prior art keywords
silane
resin
modified
wax
waxes
Prior art date
Application number
PCT/GB1990/001865
Other languages
English (en)
Inventor
Leslie Phillip Martin
Michael Edward Slevin
Colin Beveridge
Original Assignee
Swift Adhesives Limited
Aei Cables Limited
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 Swift Adhesives Limited, Aei Cables Limited filed Critical Swift Adhesives Limited
Publication of WO1991008240A1 publication Critical patent/WO1991008240A1/fr
Priority to GB9209552A priority Critical patent/GB2256432B/en

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    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to silane- modified, cross-linkable resins and waxes, to processes for their production, to their use for example in adhesive compositions and to materials comprising such resins cross-linked to each other or to other compatible substances.
  • Silane modified medium to high molecular weight homo- and copolymers are widely used for the preparation of cable jacketing, wire insulation and piping and have been suggested for use as spacers in laminate materials and more recently as the basis for sealants and for adhesive compositions, in particular hot melt and pressure sensitive adhesives.
  • the cross-linked polymers provide the overall structural matrix for the cured compositions.
  • cross-linked matrices can of course hold other components of the uncured compositions, such as fillers colorants, plasticizers, etc and indeed the use in coating or adhesive compositions based on silane modified homo- or copolymers of fillers, colorants and plasticizers which contain groups which condense with silanols has also been suggested in International Patent Application No PCT/GB89/00534 where it is explained that such materials may thereby be bound more intimately into the cross-linked matrix of the cured compositions.
  • the properties of an adhesive or sealant composition depend upon the contributions made by its various components.
  • a pressure sensitive adhesive composition for example will comprise a relatively high molecular weight elastomer or rubbery polymer together with a low molecular weight tackifier resin - the elastomer providing an elastic matrix for the viscous, adhesion-effecting resin.
  • Tack modifying waxes by contrast serve to reduce the tack of adhesive or sealant compositions.
  • the desired performance profiles of an adhesive composition in form in which it is applied and the form which it adopts after application e.g. after drying, cooling or curing, may be selected, e.g. in terms of wetting, strength, adhesion, flexibility, temperature resistance etc.
  • cross-linkable silane modified polymers as the matrix forming polymers in adhesive and sealant compositions is known, e.g. from GB-A-2197326.
  • silane modification of the low molecular weight tack controlling components i.e. the use of silane-modified, cross-linkable tackifier resins or tack modifier waxes, in particular the use of silane modified tackifier resins, offers a particularly useful option in the design of cross-linkable adhesive compositions, sealant compositions, and the like.
  • the invention provides a silane- modified tackifier resin containing at least two silanol or protected silanol groups in the resin molecule.
  • the invention also provides a silane- modified tack modifying wax containing at least two silanol or protected silanol groups in the wax molecule.
  • silane-modified it is meant that the resin or wax has a molecular structure incorporating silane groups, e.g. as a result of silane grafting of a silane- free resin or wax.
  • silane-modified tackifier resins of the invention may conveniently be silane group carrying analogues of conventional tackifier resins, such as those described in for example Chapter 16 of the "Handbook of Pressure-sensitive adhesive technology", “Tackifier resins” by J.A. Schlademan, (Van Nostrand Reinhoid, 1982) .
  • Tackifier resins generally fall into two categories, those based on rosins and rosin derivatives and those based on hydrocarbon resins.
  • the second category itself includes aliphatic, aromatic and diene resins as well as mixed hydrocarbon resins and, for the purposes of sealant and hot melt and pressure sensitive adhesive formulation, the polyterpene, aliphatic and styrenic resins are of particular interest due to their lack of acidic or hydroxyl groups which might give rise to premature reactions.
  • Rosin derivative and terpene- phenolic resins are also of particular interest in this regard and other tackifier resins, such as the coumarone-indene resins, are of interest in connection with the manufacture of solvent based adhesives or for use in moulding compositions for example for tyre manufacture.
  • the rosin and rosin derivatives which may be silane modified according to the invention are materials which are generally derived from pine trees. Chemically they are abietic or pimaric type acids (e.g. abietic, neoabietic, palustric, dihydroabietic, dehydroabietic, pimaric and isopimaric acids) or derivatives thereof, e.g.
  • esters condensation or polymerization products, disproportionation products, and hydrogenation products thereof, such as glycerol, ethylene glycol, diethylene glycol, methanol or pentaerythritol esters or phenol or maleic anhydride condensation products, etc.
  • the hydrocarbon resin tackifying resins which may be silane modified according to the invention include in particular the C-5, C-9 and (C-5) 2 resins, i.e. those based on monomer units containing on average 5,9 or (5x2) carbons; these are generally produced by polymerization of crude monomers obtained from wood, coal or petroleum. Indene, styrene, methylindenes, ethylstyrenes, piperylenes, isoprene, 2-methylbut-2- ene, dicyclopentadiene, methyldicyclopentadienes, pinenes and dipentene are particularly commonly used monomers.
  • the hydrocarbon resins may also be modified, e.g. hydrogenated, alkylated, phenol-modified, acid modified, etc, as is conventional in the field of tackifier resins.
  • the tackifier resins suitable for silane modification according to the invention and the silane modified resins according to the invention preferably are liquid at ambient temperature or have relatively low softening points, for example of 5-190°F (-15 to 88"C), especially 10-150°F (-12 to 66"C) particularly 40-135°F (4 to 57°C).
  • the resins conveniently have relatively low molecular weights, thus for example the resins which are silane modifiable according to the invention conveniently have number average molecular weights of about 250-2500, especially 300-2000, particularly 400 to 1500, more particularly 500 to 1100.
  • Many tackifier resins are available commercially and can be silane modified according to the invention.
  • Escorez 5380 (a hydrocarbon resin available from Exxon) , Unitack R100 (a rosin ester available from Union Camp Corp.), Dertophene T (a terpene phenolic resin available from DRT) , Krystalex F100 and FR75 ( ⁇ -methyl styrene polymers available from Hercules, Inc.), Piccotex 120 (a vinyl-toluene/ ⁇ -methyl styrene modified hydrocarbon resin available from Hercules, Inc.), Staybelite (a hydrogenated rosin available from Hercules, Inc.), and Nirez 1085 (a terpene resin available from Reichhold Chemicals) .
  • Escorez 5380 a hydrocarbon resin available from Exxon
  • Unitack R100 a rosin ester available from Union Camp Corp.
  • Dertophene T a terpene phenolic resin available from DRT
  • Krystalex F100 and FR75 ⁇ -methyl styrene polymers available from Hercule
  • tack modifying waxes which can be silane modified according to the invention are generally long chain aliphatic hydrocarbons with no side chains or with relatively short side chains. They are crystalline, low molecular weight materials although the degree of crystalinity can vary.
  • the waxes suitable for silane modification according to the present invention are particularly preferably low molecular weight waxes such as paraffin waxes, microcrystalline waxes and Fischer- Tropsch waxes and, less preferably, higher molecular weight waxes such as polywaxes and A-C polythenes.
  • the waxes silane modified according to the invention will have number average molecular weights of 300-2000, preferably 300-1000, especially 350-800.
  • the waxes suitable for silane modification will generally have melting points above ambient temperature, e.g. above 90°F (32 ⁇ C), preferably of 110-230°F (43 to 110°C), particularly of 120-190 ⁇ F (49 to 88"C) .
  • waxes are available commercially and may be silane modified according to the invention.
  • paraffin wax 150/155"F (66/68 ⁇ C) and microcrystalline wax 175"F (79°C) both available from Astor Chemicals
  • Fischer Tropsch waxes available from Sasol
  • AC6 polythenes available from Allied Colloids
  • Polywax 2000 available from Baseco
  • the silane groups may be present in a monomer which is (co)polymerized to produce the silane modified resins or waxes of the invention or alternatively the silane modification of the tackifier resins or tack modifying waxes to produce the silane modified resins and waxes according to the invention may be performed analogously to the conventional silane grafting of higher molecular weight, matrix-forming polymers, e.g. as described in US-A-3646155, GB-A-1286460, GB-A-1347426, GB-A-1406680, GB-A-1450934 and GB-A-1542543.
  • silane grafting may be effected by reaction of the unmodified resin or wax with an unsaturated silane, e.g. vinyl triethoxysilane, in the presence of a catalyst, e.g. a peroxide initiator, to produce a silane modified resin or wax respectively.
  • a catalyst e.g. a peroxide initiator
  • the silane group introduced in this way will be a protected silanol group which can be deprotected by hydrolysis enabling it to engage in a catalysed silanol condensation (cross-linking) reaction with other silanol groups or with other groups reactive with silanols, e.g. alcohol, thiol or amine groups.
  • silane modified resins and waxes according to the invention may be represented by formula I
  • R is the residue of the unmodified resin or wax; n is an integer of at least 2, preferably 2-10, especially 2-8; A is a bond or a divalent linking group, e.g. an optionally substituted divalent organic radical such as an alkylene, alkyleneoxy, alkylenephenylene or alkyleneoxyalkylene group; Y is a blocking group not displaceable by hydrolysis, e.g. a G,. 4 alkyl group; m is 1,2 or 3, preferably 2 or 3; and X is a leaving group displaceable by hydrolysis, conveniently a halogen atom (e.g. chlorine) or a group ZO or ZCOO where Z is a C_,_ 10 , preferably C_,_ 4 , alkyl or alkoxyalkyl group.
  • A is a bond or a divalent linking group, e.g. an optionally substituted divalent organic radical such as an alkylene, alkyleneoxy, alkylenephenylene or alkylene
  • the invention provides a process for the preparation of silane modified resins or waxes according to the invention, said process comprising reacting a tackifier resin or tack modifier wax with an unsaturated silane of formula II
  • A' conveniently represents a group of formula
  • Y 2 represents hydrogen or C ⁇ _ 4 alkyl
  • Y 3 represents a C ⁇ straight, branched or cyclic alkylene group, a phenylene group, a carbonyloxy group, a carbonyloxy (C x . 10 alkylene) group, a alkylene) carbonyloxy group or a (C x _ 10 alkylene) carbonyloxy (C J . K , alkylene) group, optionally carrying pendant glycidoxy groups.
  • a 1 represents a C 2 _ 5 monoalkenyl group, such as vinyl or allyl, or a (C 2 _ 3 alkenyl)carbonyloxy(C 2 _ 3 alkylene) group, such as a gamma-methacryloxypropyl group
  • unsaturated silanes of formula II include vinyl trimethoxy silane, vinyl triethoxy silane and gamma-methacryloxypropyltrimethoxy silane.
  • Unsaturated silanes of formula II are known or may be prepared by conventional methods.
  • the silane side chains may constitute a relatively high proportion by weight of the silane modified resin or wax, e.g. 5 to 90%, generally 10 to 60%, preferably 20 to 50% and especially preferably 30 to 40%, and the ratio of unsaturated silane to resin or wax used in the grafting reaction, or alternatively the weight ratio of monomers where copolymerisation is used, should be chosen accordingly.
  • the ratio of silane to wax or resin will be selected to ensure that an average at least 2, preferably 2-8, especially 3-5, silane groups are introduced per resin or wax molecule.
  • the catalyst used in the preparation of the silane grafted resins or waxes is preferably a free-radical generating compound such as for example benzoyl peroxide, dicumyl peroxide or other catalysts referred to in the literature, e.g. in US-A-3646155.
  • the free radical generator may conveniently be used in a concentration of about 0.01 to 3% relative to the weight of resin or wax used.
  • the silane grafting reaction is conveniently effected at a temperature of at least 140°C, preferably between 150"C and 250°C, and may be performed in conventional apparatus such as a Ko-Kneader.
  • a third method of producing the silane modified resins and waxes may be appropriate when the resin or wax contains groups or atoms which will prevent the conventional grafting reaction from working effectively, for example the acid groups in terpene phenolic or rosin derivative resins. This method will involve the use of an aminosilane of general formula III
  • a 2 is an optionally substituted divalent organic radical as defined above for A, and Y,X and m are as defined above. Reaction with amines of formula III will introduce silane side chains of formula
  • silane-amine grafted products can subsequently be further grafted using the conventional peroxide catalysed reaction scheme.
  • novel silane modified cross-linkable resins and waxes according to the invention may be used in moulding, adhesive, coating and sealant compositions and the like compositions where tackifier resins and/or tack modifying waxes are conventionally used.
  • the silane modified resins and waxes may wholly or particially replace unmodified resins or waxes.
  • compositions, where they contain tackifier resins and tack modifying waxes should contain silane modified resins and waxes according to the invention.
  • the silane modified waxes and, more particularly the silane modified resins may function as cross-linking agents for other materials, e.g. for the matrix forming polymer of such compositions. All that is required is that the matrix forming polymer should carry groups reactive with silanols, e.g. hydroxy, isocyanate, a ine, thiol and silanol (or more generally protected silanol) groups.
  • silanols e.g. hydroxy, isocyanate, a ine, thiol and silanol (or more generally protected silanol) groups.
  • Cross-linking of the compositions occurs when the silane groups are hydrolysed, e.g. as follows:
  • silane modified resins and waxes of the invention can serve to cross-link can be any of a wide range of natural or synthetic polymers or macromolecules which contain or have been modified to introduce groups (hereinafter "reactive groups") which condense with silanols.
  • silane modified polymers such as for example those referred to in GB-A-2197326, PCT/GB89/00533, PCT/GB89/00536, PCT/GB89/00535, EP-A-240044, JP-A-59102931, JP-A- 58132032 and British Patent Application No. 8924619.3, and the documents mentioned therein
  • materials containing reactive groups other than silanes may advantageously be cross-linked using the silane modified resins and waxes of the invention.
  • hydroxyl reactive groups occur on a variety of polymers , and macromolecules such as polyvinyl alcohol, polyvinyl acetate, polysaccharides, starch, cellulose and derivatives thereof and hydroxyl groups may conveniently be introduced onto hydroxyl group free polymers or macromolecules by conventional grafting or copolymerization techniques.
  • Other materials which may be cross-linked by the silane modified cross-linking agents of the invention include isocyanate, amine, carboxylic acid, halogen and thiol group containing materials, e.g. polyisocyanates, acid modified polymers or rubbers (such as the aleic anhydride modified SEBS available from Shell Chemical Co.
  • Polymers having a wide range of molecular weights may be silane grafted to produce matrix forming polymers for the preparation of the compositions of the present invention; in general polymers having melt flow indices (MFIs) of forming 1 to 2800 may be used and MFIs of 2- 1000, especially 5-800 and particularly 150-800, are preferred.
  • MFIs melt flow indices
  • the matrix forming polymer is formed by silane grafting a polar copolymer, e.g. ethylene vinyl acetate, ethylene methyl acrylate, ethylene butyl acrylate or ethylene acrylic acid
  • the polar comonomer content is preferably 14-40%, especially 18-33%.
  • the matrix forming polymer component preferably forms up to 90%, conveniently 10-40%, and especially preferably about 30%, of the composition.
  • silane modified resin or wax cross-linking agents according to the invention may be formulated in preprepared cross-linkable compositions, e.g. moulding, sealant, adhesive or coating compositions, or they may be added to materials which are to be crosslinked.
  • the present invention provides a cross-linkable composition
  • a cross-linkable composition comprising: a reactive group-containing polymer or macromolecule; a silane modified resin according to the invention and/or a silane modified wax according to the invention; and, optionally packaged separately from said resin or wax, a silanol condensation catalyst.
  • the composition of the invention is a one-part composition containing both the silane modified component(s) and the silanol condensation catalyst mixed in together.
  • the composition of the invention is preferably packaged in a water-tight container, preferably together with a desiccant, e.g silica gel.
  • the composition of the invention is in the form of a multipart (e.g. 2 part) system with the condensation catalyst packaged separately from the silane modified component(s) , the different parts of the composition being brought together when cross-linking of the overall composition is desired.
  • the hydrolysis of the silane groups and the subsequent cross-linking by reaction with other reactive groups is catalysed by the condensation catalyst.
  • suitable catalysts include, for example, metal carboxylates, e.g. dibutyl tin dilaurate, organometallics, e.g. tetrabutyl titanate, organic bases, e.g. ethylamine, and mineral and fatty acids.
  • metal carboxylates e.g. dibutyl tin dilaurate
  • organometallics e.g. tetrabutyl titanate
  • organic bases e.g. ethylamine
  • mineral and fatty acids Several such compounds are identified in for example US-A-3646155.
  • condensation catalysts organotin compounds, such as dibutyl tin dilaurate are preferred.
  • the catalyst conveniently makes up from 0.005-0.2%, preferably about 0.02%, of the composition as a whole (excluding volatile solvents)
  • compositions of the invention may contain conventional hot melt adhesive components (such an antioxidants, diluents, fillers, colorants, and conventional tack and viscosity modifiers) in conventional or near conventional concentrations.
  • conventional hot melt adhesive components such an antioxidants, diluents, fillers, colorants, and conventional tack and viscosity modifiers
  • sealant and adhesive compositions it is however to be understood that the compositions of the invention may take other forms, e.g. coating or moulding compositions, and in these forms may contain components conventional to such forms in concentrations conventional or near conventional to such forms.
  • compositions of the invention are to be bonded to substrates, e.g. as is the case with sealants, adhesives and coating compositions
  • silane groups in the composition components e.g. waxes, resins or matrix forming polymers, will enhance binding of the cured compositions to many surfaces, especially metal or glass surfaces.
  • an adhesive composition according to the invention is to be solvent based it will have the advantage of cross linking at room temperature while nonetheless being a one part formulation.
  • Conventional solvent based adhesives are either cured by heating or must be two part formulations using a chemical curing process.
  • the solvent based adhesive compositions according to the present invention have significant advantages in terms of convenience of application and curing.
  • solvents particular mention may be made of aromatic and aliphatic hydrocarbons, chlorinated hydrocarbons, nitroparaffins, and oxygenated solvents such as ketones and esters, e.g. hexane, toluene, methyl ethyl ketone, acetone or (for flammable adhesives) methylene chloride or mixtures thereof.
  • Solvent based adhesives may conveniently contain tackifier resins as up to 90% of the total solids content, plasticisers (up to 80% of solids) , fillers (up to 80% of solids) and colourants and stabilisers (generally not more than 10% of solids) .
  • the total level of solids in the solvent can conveniently range from about 10% for a sprayable adhesive to about 95% in sealants.
  • composition of the invention is a hot melt adhesive composition it will preferably contain a silane modified tackifier resin but it may also contain an unmodified tackifer resin, for example a resin or resin mixture conventional for hot melt adhesives.
  • the unmodified resin or resin mixture should however be selected to achieve the desired balance between compatibility with the silane modified component(s) and the other components of the adhesive, the melt flow properties of the adhesive as a whole and the specific adhesion to the substrates intended to be bonded with the adhesive.
  • suitable non silane modified tackifying resins may include: aromatic modified resins such as ⁇ -methyl styrene homopolymers or copolymers, e.g.
  • Krystalex F100 ( ⁇ -methyl styrene polymer)
  • Krystalex FR75 (a modified ⁇ -methyl styrene copolymer) or Piccotex ( a vinyl toluene- ⁇ -methyl styrene copolymer)
  • Hercules Chemical Co. aliphatic petroleum hydrocarbon resins
  • styrene-modified hydrocarbon resins e.g. Escorez 5300 (available from Exxon) .
  • the tackifier resin will conveniently make up from 5 to 40% by weight, prefrably 10-40%, and especially preferably about 30-35%, of the adhesive, preferably with 10 to 100%, especially 50 to 100% being silane modified tackifier resin.
  • Hot melt adhesive compositions according to the invention preferably contain at least one antioxidant.
  • conventional adhesives antioxidants such as butylated hydroxytoluene (BHT) may be used.
  • BHT butylated hydroxytoluene
  • a preferred antioxidant is pentaerythritol-tetrakis-3- (3,5-di-tert.butyl-4-hydroxyphenyl)-propionate, which is available under the trade name Irganox 1010 from Ciba- Geigy UK Ltd. of Manchester.
  • the antioxidant will generally be present in the adhesive at about 0.1-2.5% by weight, preferably 0.5-1%.
  • Adhesive compositions according to the invention preferably also comprise a further polymer or polymer mixture besides the matrix forming polymer which contains the reactive groups.
  • the further polymer or polymer mixture will be selected to achieve, inter alia, a balance between compatibility with the catalyst and the other components of the adhesive and the viscosity and tack characteristics of the adhesive.
  • the matrix forming polymer is based on a (co)polymer deriving from polar (co)monomers
  • the further polymers are preferably selected from compatible (co) olymers also deriving from polar (co)monomers, e.g.
  • ethylene copolymers such as EVA, ethylene-methy1 acrylate (EMA) , ethylene-ethyl acrylate (EEA) and ethylene butyl acrylate (EBA) , conveniently copolymers having polar comonomer residue contents of 12-40%, preferably 18-35% and especially preferably about 28% and MFIs of 1 to 2800, conveniently 5-800, preferably 20-500 and most preferably 150-400.
  • the further polymers are preferably selected from homo- and copolymers of apolar monomers, such as for example polyethylene, polypropylene, polybutylene, and SEBS (for example low crystallinity range molecular weight homo-or copolymers, such as that available under the trade name Vestoplast 608 from H ⁇ ls (UK) Limited of Manchester, or low molecular weight polyethylene, such as polyethylene AC6 or AC8 available from Allied Cheical Corporation International NV SA of Birmingham) .
  • apolar monomers such as for example polyethylene, polypropylene, polybutylene, and SEBS (for example low crystallinity range molecular weight homo-or copolymers, such as that available under the trade name Vestoplast 608 from H ⁇ ls (UK) Limited of Manchester, or low molecular weight polyethylene, such as polyethylene AC6 or AC8 available from Allied Cheical Corporation International NV SA of Birmingham) .
  • Adhesive compositions according to the invention may contain components such as diluents or modifiers, conveniently as about 5-40%, preferably about 30%, of the total adhesive. These components may serve to regulate the viscosity and setting speed of the adhesive and may be included to enhance the wieking of the adhesive into the substrates to be bonded.
  • diluents of silane modified waxes according to the invention is preferred although conventional unmodified waxes (e.g. petroleum waxes such as paraffin waxes or microcrystalline waxes such as Okerin 8981 from Astor Chemicals of West Drayton, Middlesex, low molecular weight polyethylene, and synthetic waxes, such as Fischer-Tropsch waxes) may be used.
  • waxes are used as diluents, they should conveniently have softening temperatures in the range of 50-120°C.
  • unmodified waxes microcrystalline waxes, Fischer-Tropsch waxes and paraffin waxes having softening temperatures in the ranges of 65 to 94°C (e.g. 79°C), 110 to 120°C and 54 to 72°C respectively, and mixtures of low molecular weight polyethylene (such as polyethylene AC6 or AC8) and a microcrystalline wax having a softening temperature of about 90°C (such as Micro 549 available from Holmes Chemical Company of Uxbridge) are particularly suitable.
  • the adhesive is formulated as a two part system, the silane modified component(s) and the catalyst being separately packaged, the other components can appear in one or both of the separate componsitions; the silane modified component containing compositions will however preferably contain the matrix forming polymer and any unmodified or modified tackifier resin and an antioxidant and the catalyst-containing composition will preferably contain a further polymer; the plasticizers and other unmodified diluents etc. may be in either or both compositions.
  • the catalyst containing composition particularly conveniently comprises about 99% of a polymer compatible with the matrix forming polymer (e.g. EVA, EMA, EEA, EBA, polyethylene, polypropylene or SEBS) and 1% of acatalyst (e.g. dibutyl tin dilaurate) .
  • the adhesive of the invention is formulated as a single composition it will advantageously be packaged in water-tight containers, for example aluminium cartridges, which containers advantageously will also include a desiccant, for example a sachet of silica gel at the end of a cartridge for a hot melt adhesive applicator.
  • a desiccant for example a sachet of silica gel at the end of a cartridge for a hot melt adhesive applicator.
  • a colouring agent for example a whitener such as titanium dioxide.
  • a whitener such as titanium dioxide.
  • colouring agents are particularly readily dispersed within the adhesive if introduced as solid dispersions in an polymer compatible with the matrix forming polymer.
  • the hot melt adhesive compositions according to the present invention will be heated to melting, generally to 100-200°C preferably about 110- 170 ⁇ C, mixed (e.g. in a cartridge loaded applicator or by the mixing in a mixer head of the two compositions of a two composition system) and applied to the substrates to be bonded, generally in a film thickness up to about 3mm, preferably up to about 1mm, although this can be achieved by applying a larger amount and scraping off the excess.
  • the adhesive characteristics of the system should be sufficient to maintain a bond between the substrates while cross-lkinking occurs.
  • the silane modified component(s) in the compositions of the invention water is required.
  • the necessary water can be supplied by ambient moisture.
  • the composition may contain further components which gradually release moisture into the system, for example fillers with surface-bound moisture or moisture filled polymer microspheres such as those sold as paint opacifiers by Rohm and Haas Company under the trade name ROPAQUE OP-62 (see EP-A-119054 of Rohm and Haas) .
  • Hot melt adhesive compositions according to the invention may be used in most applications where hot melt adhesives have been used and where full bonding strength is not required immediately after the application of the adhesive.
  • the adhesive compositions of the invention are thus particularly suited to use in product assembly (for example in the furniture and automobile industries) , packaging and labelling.
  • compositions of the invention are capable of chemically bonding to the surfaces of many substrates.
  • compositions of the present invention are particularly suitable for bonding to or coating of cellulosic and silicaceous substrates, for example paper and glass.
  • silane modified tackifier resins and/or tack modifying waxes capable of reacting with reactive groups on the matrix forming polymer it may also be possible to produce compositions, especially moulding, jacketting or insulating compositions, which may be processed at lower temperatures than would be possible using unmodified resins or waxes. This is of particular interest for compositions which also contain moisture releasing components as by the use of lower processing temperatures premature moisture release can be reduced.
  • silane modified and catalyst components in the compositions of the present invention may be selected to achieve particular desired characteristics, for example rate or controlability of curing, and by varying the monomer make-up and the MFI of the matrix forming polymer, and by utilizing blends of polymers the formulation characteristics (such as viscosity, softening point, wetting ability, etc.), for the compositions may be controlled to give a readily processable material.
  • silane modified waxes and resins according to the invention may be used in moulding compositions and thus in a yet still further aspect the invention also provides cross-linked, e.g. cured, silane modified resins and waxes or compositions thereof and articles made therefrom.
  • Silane grafting of the tackifier resins listed in Table I below is performed by reacting 100 parts by weight of the resin with up to 100 parts by weight of vinyl trimethoxy silane (to achieve a resin: silane molar ratio of 1:2) and using 7 parts by weight of dicumyl peroxide as the free radical generator.
  • 0.5 parts by weight of Flectol H available from Monsanto may be added in as an antioxidant and the reaction may be effected in heated vessel provided with a stirrer.
  • Hot melt packaging adhesives are prepared having the following formulations (the tabulated figures are parts by weight) :
  • silane grafted matrix forming polymers are reaction products of vinyl trimethoxy silane and unmodified polymer prepared with a silane content of about 2-3% using the procedure described in British Patent Application No. 8924619.3 or that of US-A- 3646155.
  • Two part hot melt adhesives are prepared having the following formulations:
  • silane grafted matrix forming polymer EVA, EMA or EBA as used in Example 3 or 24-400 ethylene acrylic acid (EAA) silane grafted in an analogous fashion
  • Parts one and two are mixed at a temperature of 110 to 160°, preferably 140-160°C.
  • hot melt adhesive compositions of Examples 3 and 4 may conveniently contain other additives such as polywaxes, AC polythenes, plasticizers, antioxidants, colorants and fillers, e.g in the following percentages by weight relative to the total of the components already specified:
  • Antioxidant (Irganox 1010) 1%
  • Pressure sensitive adhesive compositions are prepared having the following formulations:
  • Wingtack 10 (from Goodyear)
  • These adhesive compositions may be mixed and applied in melt form.
  • silane grafted rubbers are prepared as the reaction product of 100 parts of the basic rubber with 2-3 parts of vinyl trimethoxy silane using the procedures set forth in British Patent Application No. 8924619.3 and PCT/GB89/00533.
  • Contact adhesive compositions are formulated as follows:
  • the polymer, polyterpene and catalyst are disposed in the solvent in a Silverson mixer.
  • Sealant compositions are formulated as follows:
  • Catalyst 13 0.02 0.02 0.020.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
  • the silane grafted rubber may be prepared by reacting 100 parts of rubber with 2-3 parts of vinyl trimethoxysilane using the procedure of British Patent Application 8924619.3 and PCT/GB89/00533.
  • the fillers are mixed with the rubber in a Brabender internal mixer, chopped and then aded to the resin, plasticizer, solvents and catalyst in a Silverson mixer.
  • Formulation 1 is prefered for where weather resistance is required.

Abstract

L'invention se rapporte à des résines à pouvoir collant modifiées par silane et à des cires de modification de l'adhésivité. Ces composés sont particulièrement utiles dans la composition de préparations adhésives, telles que notamment des préparations adhésives thermofusibles.
PCT/GB1990/001865 1989-11-29 1990-11-29 Resine modifiee par silane WO1991008240A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9209552A GB2256432B (en) 1989-11-29 1992-05-01 Crosslinkable multicomponent systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8927003.7 1989-11-29
GB898927003A GB8927003D0 (en) 1989-11-29 1989-11-29 Chemical compounds

Publications (1)

Publication Number Publication Date
WO1991008240A1 true WO1991008240A1 (fr) 1991-06-13

Family

ID=10667133

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1990/001865 WO1991008240A1 (fr) 1989-11-29 1990-11-29 Resine modifiee par silane

Country Status (2)

Country Link
GB (2) GB8927003D0 (fr)
WO (1) WO1991008240A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389170A (en) * 1993-06-11 1995-02-14 Dow Corning Corporation Method for bonding substrates using molten moisture reactive organosiloxane compositions
WO1996023845A1 (fr) * 1995-02-01 1996-08-08 Exxon Chemical Patents Inc. Resines de petrole modifiees par du silane
EP0741151A1 (fr) * 1995-05-03 1996-11-06 Total Raffinage Distribution S.A. Procédé de préparation d'une composition paraffine/polymère greffé
WO2000043427A1 (fr) * 1999-01-25 2000-07-27 The Dow Chemical Company Polymeres contenant des silanols partiellement neutralises
US8101276B2 (en) 2008-09-16 2012-01-24 Henkel Corporation Pressure sensitive adhesive compositions and articles prepared using such compositions
US8440304B2 (en) 2008-09-16 2013-05-14 Henkel Corporation Acrylic pressure sensitive adhesive formulation and articles comprising same
US9023946B2 (en) 2009-12-22 2015-05-05 Henkel IP & Holding GmbH Moisture cure hot melt adhesives
WO2015153058A1 (fr) * 2014-03-31 2015-10-08 Exxonmobil Chemical Patents Inc. Greffe radicalaire sur des résines fonctionnalisées pour pneus
WO2015153059A3 (fr) * 2014-03-31 2015-11-26 Exxonmobil Chemical Patents Inc. Groupes fonctionnels réactifs doubles pour résines dans des pneus
WO2015153055A3 (fr) * 2014-03-31 2015-12-03 Exxonmobil Chemical Patents Inc. Groupements espaceurs pour des résines fonctionnalisées dans des pneus
US9212300B2 (en) 2007-08-10 2015-12-15 Henkel Ag & Co. Kgaa Reactive hot melt adhesive
US9365751B2 (en) 2012-07-24 2016-06-14 Henkel IP & Holding GmbH Reactive hot melt adhesive
US9428677B2 (en) 2013-01-24 2016-08-30 Henkel IP & Holding GmbH Reactive hot melt adhesive
US20170066898A1 (en) * 2014-03-31 2017-03-09 Exxonmobil Chemical Patents Inc. Silica Treating of Functionalized Resins in Tires
CN106589322A (zh) * 2016-11-18 2017-04-26 江苏麒祥高新材料有限公司 一种改性萜烯酚树脂及其制备方法及其在轮胎胎面胶中的应用
US10221346B2 (en) 2014-01-14 2019-03-05 Henkel IP & Holding GmbH Reactive hot melt adhesives with improved adhesion

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JPS5573716A (en) * 1978-11-28 1980-06-03 Mitsui Petrochem Ind Ltd Silane-modified tackifier resin
JPS55160074A (en) * 1979-05-31 1980-12-12 Sekisui Chem Co Ltd Hot-melt adhesive composition
EP0042481A1 (fr) * 1980-06-19 1981-12-30 Hüls Aktiengesellschaft Homo et copolymères de diènes 1,3 portant des groupes silylés réactifs, procédé pour leur préparation ainsi que leur utilisation
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JPS5573716A (en) * 1978-11-28 1980-06-03 Mitsui Petrochem Ind Ltd Silane-modified tackifier resin
JPS55160074A (en) * 1979-05-31 1980-12-12 Sekisui Chem Co Ltd Hot-melt adhesive composition
EP0042481A1 (fr) * 1980-06-19 1981-12-30 Hüls Aktiengesellschaft Homo et copolymères de diènes 1,3 portant des groupes silylés réactifs, procédé pour leur préparation ainsi que leur utilisation
JPS6121174A (ja) * 1984-07-09 1986-01-29 Sekisui Chem Co Ltd 表面保護用粘着テ−プもしくはシ−ト

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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389170A (en) * 1993-06-11 1995-02-14 Dow Corning Corporation Method for bonding substrates using molten moisture reactive organosiloxane compositions
WO1996023845A1 (fr) * 1995-02-01 1996-08-08 Exxon Chemical Patents Inc. Resines de petrole modifiees par du silane
EP0741151A1 (fr) * 1995-05-03 1996-11-06 Total Raffinage Distribution S.A. Procédé de préparation d'une composition paraffine/polymère greffé
FR2733759A1 (fr) * 1995-05-03 1996-11-08 Total Raffinage Distribution Procede de preparation d'une compostion paraffine / polymere greffe
WO2000043427A1 (fr) * 1999-01-25 2000-07-27 The Dow Chemical Company Polymeres contenant des silanols partiellement neutralises
US9212300B2 (en) 2007-08-10 2015-12-15 Henkel Ag & Co. Kgaa Reactive hot melt adhesive
US8101276B2 (en) 2008-09-16 2012-01-24 Henkel Corporation Pressure sensitive adhesive compositions and articles prepared using such compositions
US8440304B2 (en) 2008-09-16 2013-05-14 Henkel Corporation Acrylic pressure sensitive adhesive formulation and articles comprising same
US9023946B2 (en) 2009-12-22 2015-05-05 Henkel IP & Holding GmbH Moisture cure hot melt adhesives
US9365751B2 (en) 2012-07-24 2016-06-14 Henkel IP & Holding GmbH Reactive hot melt adhesive
US9428677B2 (en) 2013-01-24 2016-08-30 Henkel IP & Holding GmbH Reactive hot melt adhesive
US10221346B2 (en) 2014-01-14 2019-03-05 Henkel IP & Holding GmbH Reactive hot melt adhesives with improved adhesion
CN106133014A (zh) * 2014-03-31 2016-11-16 埃克森美孚化学专利公司 轮胎用官能化树脂的自由基接枝
US20170058058A1 (en) * 2014-03-31 2017-03-02 Exxonmobil Chemical Patents Inc. Free Radical Grafting of Functionalized Resins for Tires
KR20160122830A (ko) * 2014-03-31 2016-10-24 엑손모빌 케미칼 패턴츠 인코포레이티드 타이어의 작용화 수지에 대한 스페이서 기
KR20160124822A (ko) * 2014-03-31 2016-10-28 엑손모빌 케미칼 패턴츠 인코포레이티드 타이어용 작용화 수지의 자유 라디칼 그라프팅
WO2015153059A3 (fr) * 2014-03-31 2015-11-26 Exxonmobil Chemical Patents Inc. Groupes fonctionnels réactifs doubles pour résines dans des pneus
CN106133002A (zh) * 2014-03-31 2016-11-16 埃克森美孚化学专利公司 轮胎中的官能化树脂的间隔基团
CN106414108A (zh) * 2014-03-31 2017-02-15 埃克森美孚化学专利公司 用于轮胎中树脂的双反应性官能团
US20170051085A1 (en) * 2014-03-31 2017-02-23 Exxonmobil Chemical Patents Inc. Spacer Groups for Functionalized Resins in Tires
US20170058057A1 (en) * 2014-03-31 2017-03-02 Exxonmobil Chemical Patents Inc. Dual Reactive Functional Groups for Resins in Tires
WO2015153055A3 (fr) * 2014-03-31 2015-12-03 Exxonmobil Chemical Patents Inc. Groupements espaceurs pour des résines fonctionnalisées dans des pneus
US20170066898A1 (en) * 2014-03-31 2017-03-09 Exxonmobil Chemical Patents Inc. Silica Treating of Functionalized Resins in Tires
JP2017511409A (ja) * 2014-03-31 2017-04-20 エクソンモービル ケミカル パテンツ インコーポレイテッド タイヤ用官能化樹脂のフリーラジカルグラフト化
WO2015153058A1 (fr) * 2014-03-31 2015-10-08 Exxonmobil Chemical Patents Inc. Greffe radicalaire sur des résines fonctionnalisées pour pneus
US9840569B2 (en) 2014-03-31 2017-12-12 Exxonmobil Chemical Patents Inc. Spacer groups for functionalized resins in tires
US9884924B2 (en) 2014-03-31 2018-02-06 Exxonmobil Chemical Patents Inc. Dual reactive functional groups for resins in tires
KR101869180B1 (ko) * 2014-03-31 2018-06-19 엑손모빌 케미칼 패턴츠 인코포레이티드 타이어의 작용화 수지에 대한 스페이서 기
US10059825B2 (en) 2014-03-31 2018-08-28 Exxonmobil Chemical Patents Inc. Silica treating of functionalized resins in tires
US10059782B2 (en) 2014-03-31 2018-08-28 Exxonmobil Chemical Patents Inc. Free radical grafting of functionalized resins for tires
CN106589322B (zh) * 2016-11-18 2018-09-25 江苏麒祥高新材料有限公司 一种改性萜烯酚树脂及其制备方法及其在轮胎胎面胶中的应用
CN106589322A (zh) * 2016-11-18 2017-04-26 江苏麒祥高新材料有限公司 一种改性萜烯酚树脂及其制备方法及其在轮胎胎面胶中的应用

Also Published As

Publication number Publication date
GB9209552D0 (en) 1992-07-08
GB2256432B (en) 1994-07-27
GB2256432A (en) 1992-12-09
GB8927003D0 (en) 1990-01-17

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