United States Patent
`
`[19]
`
`Igarashi et al.
`
`[11] Patent Number:
`
`4,503,189
`
`[45] Date of Patent:
`
`Mar. 5, 1985
`
`[54] ADHESIVE COMPOSITIONS
`
`[75]
`
`Inventors: Sachio Igarashi, Suita; Kyuya
`Yamazaki, lbaraki, both of Japan
`
`[73] Assignee:
`
`Takeda Chemical Industries, Ltd.,
`Osaka, Japan
`
`[21] Appl. No.: 564,080
`
`[22] Filed:
`
`Dec. 20, 1983
`
`Foreign Application Priority Data
`[30]
`Dec. 21, 1982 [JP]
`Japan .............................. .. 57-225330
`
`[51]
`
`Int. Cl.3 ...................... .. C08L 9/02; COSL 27/06;
`C08L 67/00; COSL 83/00
`[52] U.S. Cl. .................................... 525/104; 525/105;
`525/125
`[58] Field of Search ............. .. 525/104, 105, 445, 440,
`525/125
`
`[56]
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`4,206,299
`
`6/1980 Yamazaki et al.
`
`................ .. 528/288
`
`FOREIGN PATENT DOCUMENTS
`
`29948 6/ 1981 European Pat. Off.
`
`.......... .. 525/445
`
`Primary Examiner—Allan M. Lieberman
`Attorney, Agent, or Firm-—Wenderoth, Lind & Ponack
`
`ABSTRACI‘
`[57]
`Adhesive compositions, which comprise (A) a polyester
`polyol, polyester polyurethane polyol or their mixture,
`(B) a silane coupling agent, (C) a vinyl-chloride copoly-
`merization resin, (D) a diene synthetic rubber and (E)
`an organic polyisocyanate.
`‘
`The adhesive compositions can be used as adhesives for
`plastic films, such as nylon, tetron and polyolefins, alu-
`minum foil, etc., and offers particularly excellent adhe-
`sion toward metallized films, whereby the resultant
`bonded films, even when boiled in an alkali or acid
`atmosphere, remain free from discoloration or disap-
`pearance in the metallized layers.
`
`3,969,306 7/1976 Borman et al.
`
`..................... 525/445
`
`5 Claims, No Drawings
`
`Wavelock
`Exhibit1013
`Page1
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:20)
`
`

`
`1
`
`ADHESIVE COMPOSITIONS
`
`4,503,189
`
`2
`water resistance, which has culminated into the present
`invention.
`Thus, the present invention relates to adhesive com-
`positions which comprise (A) a polyester polyol, poly-
`ester polyurethane polyol or their mixture, (B) a silane
`coupling agent, (C) a vinyl-chloride copolymerization
`resin, (D) a diene synthetic rubber and (E) an organic
`polyisocyanate.
`Examples of the polyester polyol, the component (A),
`which is useful in the present invention include polyes-
`ter polyols having hydroxyl groups at both of their
`terminals and a molecular weight of 3,000 to 100,000,
`preferably 10,000 to 50,000, as obtained by reacting
`dibasic acids, such as terephthalic acid, phthalic acid,
`isophthalic acid, adipic acid and sebacic acid, their dial-
`kyl esters or their mixtures with glycols, such as ethyl-
`ene glycol, propylene glycol, butylene glycol, diethyl-
`ene glycol and neopentyl glycol, triols, such as trimeth-
`ylolethane, trimethylolpropane, hexanetriol, glycerol,
`pentaerythritol,
`tris(hydroxyethyl)isocyanurate
`and
`quadrol, tetraols or their mixtures. Among the above
`polyester polyols, polyester glycols are particularly
`preferred. In producing the polyester polyols, use can
`be made of esterification or ester exchange reaction
`catalyst or polymerization catalysts normally employed
`to promote the reaction, such as antimony dioxide, zinc
`acetate, lead acetate and manganese acetate.
`Also, epoxy resins can be added to the polyester
`polyols. When an epoxy resin is added, its amount to be
`added is suitably in an amount 0 to 30 weight % relative
`the component (A). Examples of the epoxy resin in-
`clude reaction products of polyhydric phenols, such as
`bisphenol A and tetrahydroxydiphenylethane, and
`polyfunctional halohydrins, such" as epichlorohydrin
`and glycidol.
`The polyester polyurethane polyol, the component
`(A), is obtained for example by formulating a polyester
`polyol, particularly a polyester glycol, an organic diiso-
`cyanate and further a low-molecular-weight glycol if
`necessary in such a proportion that the NCO/OH ratio
`may be 0.7 to 1.0 and allowing then to react. The reac-
`tion may be conducted by mixing 1 mole of a polyester
`glycol with 0.7 to 1.0 mole of an organic diisocyanate,
`by mixing a polyester glycol with a low-molecular-
`weight glycol at a given molar ratio and adding an
`organic diisocyanate in such an amount that the NCO-
`/OH ratio may be 0.7 to 1.0, and further by reacting a
`polyester glycol or a mixture of a polyester glycol and
`a low-molecular-weight glycol with an organic diisocy-
`anate at a molar ratio of NCO/OHEI to produce a
`prepolymer having isocyanate groups at its terminals,
`which is then reacted with a low-molecular-weight
`glycol, low-molecular-weight polyol or epoxy resin at
`an OH/excessive NCO of 2 to 20, preferably 4 to 10.
`The polyester glycol to be used in the above reaction
`is a linear polyester having hydroxyl groups at both of
`its terminals obtained by the reaction of the dibasic
`acids and glycols as mentioned above, and preferred use
`is made of such linear polyesters having a molecular
`weight of 500 to 10,000, particularly 500 to 3,000.
`As examples of the organic diisocyanate, there may
`be mentioned aliphatic diisocyanates being exemplified
`by trimethylene diisocyanate, tetramethylene diisocya-
`nate, hexamethylene diisocyanate, pentamethylene di-
`isocyanate, 1,2-propylene diisocyanate, 1,2-butylene
`diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene
`diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene
`diisocyanate, 2,6-diisocyanatomethyl caproate, etc.,
`
`Wavelock
`Exhibit1013
`Page2
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:21)
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`45
`
`50
`
`The present invention relates to adhesive composi-
`tions, and particularly to adhesive compositions which
`are useful for bonding metallized films to themselves.
`Metallized films are produced by the vacuum metal-
`lizing process. The principle of the vacuum metallizing
`process lies in heating an arbitrary metal (e.g., alumi-
`num, nickel, chromium or alloys thereof, etc.) in a high
`vacuum equipment in the neighborhood of lO—4Torr at
`temperatures higher than its melting point to cause the
`metal to vaporize, radiating and condensing the metal in
`the state of atoms or molecules on a cooled substrate
`plate to be metallized such as into plastic films, thereby
`forming polycrystal thin layers.
`The metallized films thus produced find widened
`application in decorative materials, electrical industry,
`agriculture, packaging systems, etc.
`As the characteristic features that the metallized film
`can offer, there may be mentioned, for example, (1)
`imparted beautiful metal gloss, (2) an improved barrier
`property against gases, steam, etc., (3) a reduced pin-
`hole formation as compared with aluminum foil, (4) a
`decreased thickness of 1/100 to 1/200 of that of alumi-
`num foil, thus making possible reduction in weight and
`saving of natural resources, and (5) an increased flexural
`strength owing to the metal supported onto plastic film.
`Principal uses of the metallized film include the areas
`of gold thread and silver thread. Such kinds of thread
`are manufactured by bonding by an adhesive two metal-
`lized films to each other with their film surfaces ex-
`posed, subjecting to the coloring step and the after-
`treatment step, and slitting into filaments, which are
`then wound up to a reel while twisting rayon, silk, etc.
`Such gold thread and silver thread are widely used in
`kimono dress, obi belting, suits, blouses, neckties, edges
`of tatami mat, etc.
`Since acids, alkalis, high-pressure hot water, etc. are
`employed in the coloring and after-treatment steps fol-
`lowing the bonding of two metallized films to each
`other, the adhesive used must protect the metal depos-
`ited layers under such severe conditions. Aluminum,
`which is used almost exclusively as the deposited metal
`in the present uses, is an amphoteric metal per se and
`shows inferior acid and alkali resistances. The plastic
`films provided with aluminum metallized layer being
`bonded to each other by use of a conventionally known
`adhesive, when exposed to the above severe conditions,
`for example by boiling in an aqueous alkali solution with
`a pH in the neighborhood of 11, demonstrate decreased
`metal gloss because the metallized layers are corroded
`for a short period of time, and in an extreme case, come
`to lose the metallized layers. Therefore, the metallized
`films are currently produced through the two steps of 55
`forming a special coating film layer on the metallized
`layer and then bonding together with an adhesive.
`The present inventors, after extensive investigation
`into such an adhesive as may provide adequate protec-
`tion to the aluminum metallized layer by one step of 60
`merely bonding together without applying a special
`coating layer on the metallized layer, found that a com-
`position consisting of a mixture of a polyester polyol,
`polyester polyurethane polyol or their mixture, a silane
`coupling agent and an organic polyisocyanate being
`admixed with a vinyl-chloride’copolymerization resin
`and a diene synthetic rubber exhibits improved acid
`resistance, alkali resistance and high-temperature hot
`
`65
`
`

`
`4,503,189
`
`3
`alicyclic diisocyanates being exemplified by 1,3-
`cyclopentanediisocyanate,
`l,4-cyclohexanediisocya-
`nate, 1,3-cyclohexanediisocyanate, 3-isocyanatomethyl-
`3,5,5-trimethylcyclohexyl isocyanate (isophorone diiso-
`cyanate),
`4,4’-methylenebis(cyclohexylisocyanate),
`methyl-2,4-cyclohexanediisocyanate,
`methyl-2,6-
`cyclohexanediisocyanate, 1,4-bis(isocyanatomethyl)cy-
`clohexane, I,3-bis(isocyanatomethyl)cyclohexane, etc.,
`aromatic dfisocyanates being exemplified by m-pheny-
`lene diisocyanate, p-phenylene diisocyanate, 4,4’-diphe-
`nyl diisocyanate,
`1,5-naphthalenediisocyanate,
`4,4’-
`diphenylmethanediisocyanate, 2,4~ or 2,6-tolylene diiso-
`cyanate or mixture thereof, 4,4’-toluidinediisocyanate,
`dianisidinediisocyanate, 4,4’-diphenyl ether diisocya-
`nate, etc., aralkyl diisocyanates being exemplified by
`l,3- or 1,4-xylylene diisocyanate or mixture thereof,
`ai,m’-diisocyanate-I,4-diethylbenzene and the like.
`As the low-molecular-weight polyol, polyols having
`not less than 2, preferably 2 to 8 hydroxyl groups, in the
`molecule and a molecular weight of normally not more
`than 400, particularly 60 to 400, are preferred, and there
`may be mentioned, by way of example, diols such as
`ethylene glycol, diethylene glycol, 1,4-butanediol and
`1,6-hexaneglycol, triols such as glycerol, trimethylol-
`propane and 1,2,6-hexanetriol, and polyols not less than
`tetraols such as pentaerythritol, methylglycoside, xyli-
`tol, sorbitol and sucrose.
`Each of the above reactions for producing the polyes-
`ter polyurethane polyols is conducted normally at a
`reaction temperature of 50° to 100° C., and may be
`carried out in the presence of, or in the absence of, an
`organic solvent inert to isocyanate group as described
`later. If desired, conventional urethane reaction cata-
`lysts, organic tin compounds, tertiary amines, etc. may
`be used. In cases in which the production steps are
`conducted in practice in the presence of an organic
`solvent, when the organic solvent is employed in such
`an amount as the concentration of the final reaction
`mixture may be about 10 to 90 weight %, preferably 20
`to 80 weight %, the above mentioned polyester polyol
`and polyester polyurethane polyol can be mixed at any
`ratio and used.
`The silane coupling agent (B) which is useful in the
`present invention may be any of the compounds being
`represented by the structural formulae R—SiE(X)3 or
`R—-Siz(R’)(X)2 (wherein R is an organic group having
`a vinyl, epoxy, amino, substituted amino or mercapto
`group; R’ is a lower alkyl group; X is methoxy, ethoxy
`or chlorine), and examples of such compounds include
`chlorosilanes such as vinyltrichlorosilane, aminosilanes
`such as N-(dimethoxymethylsi1ylpropyl)ethylenedia-
`mine, aminopropyltziethoxysilane, N-(trimethoxysilyl-
`propyl)ethylenediamine and N-(triethoxysilylpropyl)e-
`thylenediamine, epoxysilanes
`such as
`'y-glycidoxy-
`propyltrimethoxysilane and [3-(3,4-epoxycyclohexyl)e-
`thyltrimethoxysilane, vinylsilanes such as vinyltriethox-
`ysilane and vinyltris(/3-methoxyethoxy)silane, and mer-
`captosilanes such as 7-mercaptopropyltrimethoxysi-
`lane. The silane coupling agent serves the particular
`purpose of enhancing the bonding strength with the
`metallized layer and also improving hot water resis-
`tance.
`With reference to the addition method for the silane
`coupling agent,
`it may be mixed with the polyester
`polyol at the beginning of the urethane reaction to con-
`duct the reaction, or it may be added during the ure-
`thane reaction or after the completion of the reaction.
`The amount of the silane coupling agent based upon
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`.
`
`4
`component (A) is in the range of about 0.05 to 30 weight
`%, preferably about 0.1 to 10 weight %, provided,
`however, that when a silane coupling agent having a
`hydroxyl group active to the isocyanate group is added
`at the beginning of, or in the course of the reaction, the
`urethane reaction in the production step for the compo-
`nent (A), the reaction must be carried out by taking into
`account the active hydroxyl group of the silane cou-
`pling agent so that NCO/(OH+active hydrogen) may
`be 0.7 to 1.0.
`copolymerization resin (C),
`The vinyl-chloride
`which is useful in the present invention, denotes copoly-
`merization resins composed mainly of vinyl chloride
`and vinyl acetate. It may be copolymers from vinyl
`alcohol, maleic anhydride, etc. as well as vinyl chloride
`and vinyl acetate; it may be any of copolymers, only if
`their composition falls under the ranges of about 70 to
`92 mole % of vinyl chloride, about 1 to 30 mole % of
`vinyl acetate, about 0 to 10 mole % of vinyl alcohol and
`about 0 to 10 mole % of maleic acid. Especially, those
`containing maleic acid are preferred. Their molecular
`weights are in the range of about 10,000 to 50,000, pref-
`erably about 15,000 to 40,000. The addition ratio of the
`vinyl-chloride copolymerization resin (C) to the com-
`ponent (A) is in the range of about 5 to 40 weight %,
`preferably about 10 to 30 weight %. When the addition
`ratio is less than 5 weight %, it occurs in some instances
`that the bonding strength decreases or the acid, alkali
`and heat resistance deteriorates. When it is beyond 40
`weight %, it occurs in some instances that the bonding
`strength decreases or the heat resistance deteriorates.
`As the diene synthetic rubber (D) which is useful in
`the present invention, there may be mentioned, for ex-
`ample, chlorinated rubber, homopolymers of butadiene,
`isoprene, isobutylene, chloroprene etc., or copolymers
`from butadiene, isoprene, etc. with acrylonitrile, sty-
`rene, etc. Also, such component (D) may be, for exam-
`ple, polybutadiene and polyisoprene having their termi-
`nals converted into hydroxyl, carboxyl, epoxy and
`other groups. Their appearance may be either liquid or
`solid but the aqueous emulsion form is not preferred,
`because the water contained therein reacts with the
`organic polyisocyanate (E).
`The amount of the diene synthetic rubber (D) relative
`to component (A) is in the range of about 5 to 40 weight
`%, preferably about 10 to 30 weight %, When the addi-
`tion ratio is less than 5 weight %, the acid, alkali and
`heat resistance deteriorates, and in the case of the addi-
`tion ratio of beyond 40 weight %, it takes place in some
`instances that the bonding strength decreases or the
`alkali and heat resistance deteriorates.
`As the organic polyisocyanate (E), by way of exam-
`ple, there may be mentioned polyisocyanate monomers
`such as organic diisocyanates employed as raw material
`for the component (A); organic triisocyanates being
`exemplified by triphenylmethane-4,4’-4"-triisocyanate,
`l,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene,
`etc., and organic tetraisocyanates being exemplified by
`4,4’-diphenyldimethylmethane-2,255,5’-tetraisocyanate;
`dimers and trimers derived from the above polyisocya-
`nate monomers and polyurethane polyisocyanates ob-
`tained by the reaction of such polyisocyanate mono-
`mers with low-molecular-weight polyols utilized like-
`wise as raw material for the component (A), and the
`like.
`
`The NCO/OH in the reaction between the polyisocy-
`anate monomer and the low-molecular-weight polyol
`may be not less than 1.5 equivalents, and normally
`
`Exhibit 1013
`Wavelock
`Page 3
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:22)
`
`

`
`4,503,189
`
`5
`6
`sebacic acid: 1/ 1 (molar ratio); ethylene glycol/ 1,4-
`ranges from 1.5 to 10, preferably from 1.7 to 5. This
`reaction can be conducted normally at about 30° to 100°
`butylene glycol = 1/ 1 (molar ratio) was synthesized, and
`100 g of the resultant polyester glycol was dissolved in
`C., in the presence of, or in the absence of, a solvent
`100 g of a 1/ 1 (weight ratio) solvent mixture of tolue-
`inert to isocyanate group as described later, but it in
`some instances is convenient to carry out the reaction in 5 ne/methyl ethyl ketone (composition I).
`the presence of such solvent. In conducting the reac-
`(2) A mixture of 215 g of a polyester glycol (molecu-
`tion, if desired, organic metal or tertiary amine catalysts
`lar weight of 2150: dimethyl
`terephthalate/sebacic
`may be added, the reaction temperature may be raised
`acid: 1/ 1 molar ratio, ethylene glycol/1,4-butylene
`to form the allophanate bonds, or a small amount of
`glycol=1/1 molar ratio), l7.4goftolylene diisocyanate
`water or amines (e.g., ethylenediamine, hexamethylene- 10 (2,4-/2,6-isomers=80/20), 240.6 g of a 1/ 1 mixture of
`diamine, etc) may be added to form the biuret bonds.
`methyl ethyl ketone/toluene and 0.05 g of dibutyltin
`When a solvent inert to isocyanate group is used, it is
`dilaurate as a catalyst was allowed to react at 60° C. for
`convenient to adjust the solid content of the resulting
`4 hours, to which was added 3.5 g of trimethylolpro-
`polyurethane polyisocyanate solution to a range of
`pane, followed by allowing the whole mixture to react
`about 50 to 90 weight %.
`15 for 2 hours. By this procedure, there was obtained a
`The adhesive composition according to the present
`polyurethane polyol with a solid content of 50 weight
`invention is produced by mixing the above-mentioned
`% (composition II).
`(A) polyester polyol, polyester polyurethane polyol or
`(3) A mixture of 950 g of a polyester glycol (molecu-
`their mixture, (B) silane coupling agent, (C) vinyl-chlo-
`lar weight of 1900: dimethyl
`terephthalate/sebacic
`ride copolymerization resin, (D) diene synthetic rubber 20 acid: 1/ 1 molar ratio, ethylene glycol/1,4-butylene
`and (E) organic polyisocyanate in such proportions that
`glyco1= 1/ 1 molar ratio, 111.2 g of isophorone diisocya-
`the molar equivalent ratio of NCO equivalents from
`nate, 1079 g of a 1/ 1 (weight ratio) solvent mixture of
`polyisocyanate (E0 to the active hydrogen equivalents
`methyl ethyl ketone/toluene and 0.2 g of dibutyltin
`from the sum of (A), (B), (C) and (D) may be in the
`dilaurate as a catalyst was allowed to react at 70° C. for
`range of about 1 to 10, preferably about 2 to 6.
`25 8 hours, to which was added 17.9 g of trimethylolpro-
`When the composition obtained by mixing the above
`pane, followed by allowing the whole mixture to react
`components (A) through (E) is highly viscous, dilution
`for 2 hours. By this procedure, there was obtained a
`may be effected with organic solvents, such as ketones
`polyurethane polyol with a solid content of 50 weight
`exemplified by acetone, methyl ethyl ketone and methyl
`% (composition III).
`isobutyl ketone, esters typified by ethyl acetate, butyl 30
`(4) A mixture of 174.2 g of tolylene diisocyanate and
`acetate and 2-ethoxyethyl acetate, aromatics exemp1i-
`73.0 g of ethyl acetate was heated at 65° C., and 44.7 g
`fied by toluene and xylene and ethers typified by diox-
`of trimethylolpropane was gradually added, followed
`ane and tetrahydrofuran. The composition normally
`by allowing the reaction to proceed for 3 hours to give
`exhibits a solid content in the range\of about 20 to 80
`a polyurethane polyisocyanate with a solid content of
`weight %.
`35 75 weight % and an NCO content of 14.4 weight %
`In conducting a bonding treatment with the use of the
`(composition IV).
`adhesive composition according to the present inven-
`(5) A mixture of 222.3 g of isophorone diisocyanate
`tion, the conventionally employed methods, such as the
`and 89.0 g of ethyl acetate was heated to 65° C., and
`method which comprises allowing the composition to
`44.7 g of trimethylolpropane was gradually added, fol-
`adhere to the surface of a film by a dry laminator, etc., 40 lowed by allowing the reaction to proceed for 5 hours
`evaporating a solvent if used, mating the surfaces to be
`to give a polyurethane polyisocyanate with a solid con-
`bonded and curing the composition at ordinary temper-
`tent of 75 weight % and an NCO content of 11.8 weight
`ature or under heating, are adopted.
`% (composition V).
`The coating amount is normally in the range of about
`The polyester glycol (composition I) and polyester
`2 to 6 g/m2.
`45 polyurethane polyols (compositions II and III) thus
`The adhesive composition according to the present
`prepared were combined with the silane coupling
`invention can be used as an adhesive for films of plas-
`agents, vinyl-chloride compolymerizaticn resins and
`ties, such as nylon, tetron and polyolefins, aluminum
`synthetic rubbers to be described in the Table 1 below
`foil, etc., and offers particularly excellent adhesion
`as well as the polyisocyanates (compositions IV and V)
`toward metallized films, whereby the resultant bonded 50 to prepare compositions for adhesive 1 through 12 as
`films, even when boiled in an alkali or acid atmosphere,
`shown in Table 1. For the purpose of comparison with
`remain free from discoloration or disappearance in the
`the compositions 1 through 12, adhesives 13 through 17
`metallized layers.
`were also prepared without addition of the silane cou-
`The examples are described below to illustrate the
`pling agent, vinyl-chloride copolymerization resin and
`present invention more specifically.
`55 synthetic rubber. With these compositions, tests on the
`bonding strength with the metallized film, acid resis-
`tance, alkali resistance, hot water resistance and oil
`EXAMPLE
`resistance were carried out. The results are illustrated in
`(1) A polyester glycol of about 20,000 in molecular
`Table 2.
`weight being composed of dimethyl terephthalate/-
`TABLE 1
`
`Adhesive
`composition
`No.
`
`Polyester
`glycol
`(A)
`I
`
`Polyester
`polyurethane
`polyol (A)
`II
`III
`
`The present invention
`1
`100
`
`Mixing ratios of the components {parts by weight)
`Organic
`Silane
`Vinyl-chloride
`polyisocyanate
`coupling
`copolymerization
`(E)
`-
`agent QB)
`resin (C)
`V
`a
`a
`
`IV
`
`Diene
`synthetic Methyl
`rubber (D)
`ethyl
`a
`b
`ketone Toluene
`
`b
`
`NCO/OI-I
`ratio
`
`10
`
`1
`
`20
`
`10
`
`50
`
`15
`
`3.7
`
`Wavelock
`Exhibit 1013
`Page 4
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:23)
`
`

`
`7
`8
`
`TABLE l-continued
`
`4,503,189
`
`I00
`100
`100
`
`50
`50
`100
`
`50
`50
`
`30
`30
`30
`
`I00
`100
`100
`
`10
`20
`20
`
`l
`
`1
`
`1
`
`1
`1
`
`1
`1
`
`0.5
`2
`1
`
`Mixing ratios of the components {parts by weight)
`Diene
`Organic
`Silane
`Vinyl—chloride
`Polyester
`Polyester
`synthetic Methyl
`polyisocyanate
`coupling
`copolymerization
`polyurethane
`glycol
`Adhesive
`composition
`(A)
`polyol 1A!
`ggy
`agent (B)
`resin (C1
`rubber {D}
`ethyl
`NCO/OH
`No.
`I
`II
`III
`IV
`V
`:1
`b
`a
`b
`a
`b
`ketone Toluene
`ratio
`
`2
`100
`20
`l
`20
`10.
`50
`15
`3.6
`3
`100
`20
`50
`15
`2.4
`4
`20
`50
`15
`3.3
`5
`20
`50
`15
`2.2
`6
`30
`50
`15
`2.5
`7
`50
`15
`3.7
`8
`50
`15
`2.6
`9
`50
`15
`2.0
`10
`50
`15
`2.7
`1 I
`50
`15
`3,6
`12
`50
`1 5
`3.3
`Comparative example
`3.7
`10
`13
`100
`3.7
`10
`14
`100
`3.7
`10
`10
`15
`100
`16
`100
`10
`20
`10
`50
`15
`3.7
`17
`100
`10
`20
`50
`15
`2.1
`
`Note:
`Silane coupling agent;
`a y-G1ycidoxypropyltrirnethoxysilane
`b N—(trimethoxysilylpropyhethylenediamine
`Vinyl-chloride copolymerization resin;
`at A resin composed of vinyl chloride/vinyl acetate/maleic anhydride = 86/lJ/1 (molar ratio)
`1) A resin composed of vinyl chloride/vinyl acetate/vinyl alcohol = 91/3/6 (molar ratio)
`Diene synthetic rubber;
`a A liquid rubber of acrylonitrile/butadiene eopolyrner
`b Polybutadienediol (molecular weight of 2000).
`
`20
`
`20
`
`20
`
`10
`
`10
`
`10
`10
`
`10
`10
`
`10
`10
`10
`8
`
`20
`20
`
`20
`20
`
`15
`15
`20
`
`20
`
`50
`
`15
`
`d
`
`Hi3h'P’°55“’€
`hot water
`test“,
`
`t.
`C
`' °“ “me
`Acid
`P°e15"°“8‘h(“)
`Alkali
`resistance resistance
`(average
`Adhesive
`Value)
`test(,,)
`test“)
`composition
`_
`35 Comparative example
`Corroded
`Corroded Corroded
`13
`100
`”
`"
`Good
`14
`120
`"
`"
`"
`1 5
`1 10
`Good
`"
`"
`16
`120
`C°"°ded
`"
`17
`13°
`40 Note:
`(“A test specimen was cut into a size of 200 mm X 15 mm. and a T peel test was
`effected with a tensile testing machine at a tensile rate of 300 mm/min in accordance
`with the testing method of ASTM Dl876~6l. The peel strength (g/15 mm) was
`expressed in terms of the average value for 10 test specimens.
`(“Alkali resistance test.
`A test specimen was cut into 1 mm wide pieces by a knife, and such pieces were
`boiled in a 0.16% aqueous NazCO3 solution at 100' C. for 60 minutes.
`(“Acid resistance test
`A test specimen was cut into 1 mm wide pieces with a knife, and such pieces were
`boiled in a 0.2% aqueous CH3COOl-l solution at 100° C. for 120 minutes.
`ml-Iigh-pressure hot water test.
`A test specimen was cut into pieces of 1 mm X 100 mm, which were immersed in
`high-pressure hot water at 130' C. for 60 minutes.
`
`45
`
`50
`
`What is claimed is:
`
`55
`
`60
`
`65
`
`1. An adhesive composition which comprises (A) a
`polyester polyol, a polyester polyurethane polyol, or a
`mixture of said polyols, said polyols each having a mo-
`lecular weight of 3,000 to 100,000, (B) a silane coupling
`agent in an amount of about 0.05 to 30 weight %, based
`on component (A), said silane coupling agent (B) being
`one represented by the structural
`formulae R-—-
`SiE(X)3 or R—-Si—E(R’)(X2) wherein R is an organic
`group having a vinyl, epoxy, amino, a substituted amino
`or a mercapto group; R’ is a lower alkyl group; and X is
`methoxy, ethoxy or chlorine, (C) a vinyl-chloride copo-
`lymerization resin in an amount of about 5-40 weight
`%, based on component (A), said vinyl chloride poly-
`merization resin being composed mainly of vinyl chlo-
`ride and vinyl acetate and having a molecular weight in
`the range of about 10,000 to 50,000, (D) a diene syn-
`thetic rubber in an amount of about 5-50 weight %,
`
`Exhibit 1013
`Wavelock
`Page 5
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:24)
`
`The vinyl chloride copolymerization resins, which do
`not dissolve merely be mixing, were heated and dis-
`solved in advance in a solvent mixture of methyl ethyl
`1<etone/toluene, and added to other components on the
`occasion of use.
`
`Test conditions 1
`
`Substrate;
`Aluminum metallized polyethylene terephthalate
`(thickness of l2p.).
`Coating amount of adhesives;
`3 to 4 g/m2
`Curing conditions;
`45° C., 3 days
`Test samples;
`Each of adhesives as illustrated in Table 1.
`A composition was applied on the aluminum metal-
`lized surface of aluminum metallized polyethylene tere-
`phthalate by a dry laminator, and after evaporation of
`the solvent, the face to be bonded was mated onto the
`aluminum metallized surface of another aluminum met-
`allized polyethylene terephthalate film. Subsequently,
`the composition was cured, and tests as shown in Table
`2 were conducted.
`
`
`
`Acid
`Alkali
`resistance resistance
`testa’)
`test“)
`
`High-pressure
`hot water
`test“)
`
`Peel strength“)
`(average
`Adhesive
`value)
`composition
`The present invention
`1
`210
`2
`I90
`3
`240
`4
`270
`5
`250
`6
`250
`7
`240
`s
`220
`9
`10
`11
`12
`
`210
`190
`220
`
`Good
`"
`"
`"
`,,
`.,
`"
`"
`I7
`"
`”
`"
`
`Good
`"
`"
`"
`7,
`7.
`"
`"
`I’
`"
`"
`"
`
`Good
`”
`”
`"
`,.
`..
`"
`"
`II
`"
`"
`"
`
`

`
`4,503,189
`
`9
`based on component (A), and (B) an organic polyisocy-
`anate wherein the quantity of polyisocyanate (E) is such
`that the molar equivalent ratio of NCO equivalents
`from polyisocyanate (E) to the active hydrogen equiva-
`lents from the sum of (A), (B), (C) and (D) is in the
`range of about 1 to 10.
`2. An adhesive composition claimed in claim 1,
`wherein the polyester polyol of the component (A) is a
`polyester glycol.
`3. An adhesive composition claimed in claim 1,
`wherein the polyester polyurethane polyol of the com-
`
`10
`ponent (A) is one obtained by the reaction of a polyester
`glycol, an organic, diisocyanate and a low-mo1ecular-
`weight polyol.
`-
`4. An adhesive composition claimed in claim 1,
`wherein the diene synthetic rubber (D) is a copolymer
`from butadiene with acrylonitrile.
`5. An adhesive composition claimed in claim 1,
`wherein the organic polyisocyanate (E) is a polyure-
`thane polyisocyanate obtained by the reaction of a poly-
`isocyanate with a low-molecular-weight polyol.
`*
`*
`*
`*
`*
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Wavelock
`Exhibit1013
`Page6
`(cid:58)(cid:68)(cid:89)(cid:72)(cid:79)(cid:82)(cid:70)(cid:78)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:20)(cid:22)(cid:3)(cid:3)(cid:3)(cid:3)(cid:3)(cid:51)(cid:68)(cid:74)(cid:72)(cid:3)(cid:25)