TW201917148A - Curable siloxane adhesives - Google Patents

Abstract

The invention is siloxane polymer comprising a backbone of the following siloxane repeat units and end groups clusters formed from siloxane units. The clusters are functionalized by the presence of at least two functional reactive groups per cluster and at least one functional reactive group is a free radical polymerizable group and at least one functional reactive group is an alkenylalkoxysilane groups and the amount of free radically polymerizable group is at least 2 mole percent of the total moles of functional reactive groups in the polymer. The invention is also an adhesive made using such polymers.

Description

Curable siloxane adhesive

The present invention is generally directed to curable siloxane polymers.

A fluorinated alkane having a clustered ring end group is known (see, for example, U.S. Patent No. 9593209, US Pat. No. 6,096,865, WO 2014/124364, WO 2014/124388, WO 2014/124367, WO 2014/124382). At least some of these siloxanes have been taught to be curable.

Certain curable siloxane polymers are useful as adhesives. One method of curing these polymers is by free radical polymerization using acrylate or methacrylate groups. However, since the radicals exposed to the surface of the air are subjected to oxygen quenching, the radically curable composition sometimes suffers from insufficient curing of the surface region and surface wetting.

It is desirable to have an improved curable siloxane polymer that has faster cure and drying times while maintaining other important adhesive properties such as lap shear strength, tensile strength, elongation, and modulus.

The inventors have discovered an improved curable siloxane polymer that can be used as an adhesive component with improved cure and drying times while maintaining other important adhesive properties such as lap shear strength, tensile strength, Elongation, and modulus.

Thus, according to one aspect, the invention is a curable siloxane polymer comprising a backbone of the following oxane repeating units: Wherein j is an integer of at least 50, and j is preferably not more than 10,000, and R ¹ is independently H or an alkyl group of 1 to 4 carbon atoms or an aryl group of 6 to 12 carbon atoms at each occurrence. . R ^{1 is} preferably an alkyl group and is most preferably a methyl group. If R ¹ is an aryl group, it is preferably a phenyl group. The siloxane polymer can be branched, with the proviso that each branch has at least j repeating units. Linear polymers are preferred.

The siloxane polymers are characterized by the formation of end groups of the cluster. The clusters may be cyclic groups, cage structures, or the like. Preferably, the clusters are formed from a decane unit. Each cluster has at least 3 and preferably no more than 12 oxirane groups, more preferably no more than 10. The clusters are functionalized by the presence of at least two functionally reactive groups, preferably at least 3 reactive groups per cluster. Preferably, the number of functionally reactive groups is no more than five. At least one functionally reactive group is a radical polymerizable group (such as an acrylate or alkyl acrylate group), and at least one functionally reactive group is an alkenyl alkoxyalkyl group. The amount of alkenyl alkoxyalkyl group is the total number of moles of functionally reactive groups in the polymer (ie, the number of acrylate or alkyl acrylate groups and the number of alkenyl alkoxyalkyl groups) Sum of at least 2 moles. Preferably, the amount of alkenyl alkoxyalkylene group is less than 30 moles based on the total moles of functionally reactive groups. Alternatively, the molar ratio of acrylate or alkyl acrylate to alkenyl alkoxy decane is not less than 1:1, preferably at least 2:1, more preferably at least 8:1, and preferably Not more than 20:1.

It is important if the ratio of acrylate or alkyl acrylate groups to alkenyl alkoxy fluorenyl groups. If the ratio is too high (i.e., there are too few alkenyl alkoxyalkyl groups), the drying properties of the polymer are insufficient for the actual use as an adhesive (drying time is too long). If the ratio is too low (ie, there are too many alkenyl alkoxyalkyl groups), the adhesive may have one or more of the lap shear strength, tensile strength, elongation, and modulus down or Not good.

The adhesive according to the second embodiment of the present invention comprises A) a curable siloxane polymer as described above, B) optionally a polyalkoxy-terminated polyoxyl resin-polymer blend, C) optionally, a condensation reaction catalyst, and D) a free radical initiator.

Curable silicone polymer-adhesive component A

According to one embodiment, the invention is a curable siloxane polymer comprising a backbone of the following oxane repeating units: Wherein j is an integer of at least 50, more preferably at least 100, still more preferably at least 150, still more preferably greater than 500, and n is preferably no greater than 10,000, more preferably no greater than 1500; and R ¹ is as As defined above.

The siloxane polymers are characterized by the formation of end groups of the cluster. The clusters may be cyclic groups, cage structures, or the like. Preferably, the clusters are formed from a decane unit. Each cluster has at least 3, more preferably at least 4, and preferably no more than 10, more preferably no more than 8, and even more preferably no more than 6 alkoxyalkyl groups. The clusters are functionalized by the presence of at least two functionally reactive groups, preferably at least 3 reactive groups per cluster. Preferably, the number of functionally reactive groups is no more than five. At least one functionally reactive group is an acrylate or alkyl acrylate group, and at least one functionally reactive group is an alkenyl alkoxyalkyl group. The amount of alkenyl alkoxyalkyl group is the total number of moles of functionally reactive groups in the polymer (ie, the number of acrylate or alkyl acrylate groups and the number of alkenyl alkoxyalkyl groups) Sum of at least 2 moles. Preferably, the amount of alkenyl alkoxyalkylene group is at least 5 moles based on the total moles of functionally reactive groups. Preferably, the alkenyl alkoxyalkylene group is less than 30 mole%, more preferably less than 25 mole%, and even more preferably less than 20 moles, based on the total moles of the functionally reactive group. More preferably, less than 15% by mole, and most preferably less than 13% by mole. In other words, wherein the molar ratio of the acrylate or alkyl acrylate to the alkenyl alkoxy decane is not less than 1:1, preferably at least 2:1, more preferably at least 8:1, and preferably Not more than 20:1. The terminal groups are preferably at least 3, preferably at least 4 but not more than 25, preferably less than 10, preferably less than 8, more preferably less than 6 cyclic alkoxylated units. Group (for example, Wherein R ² is selected from the group consisting of H, an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms, an R ³ -acrylate or R ³ -alkyl acrylate, and an alkenyl alkoxy decane, Wherein R ³ is a direct bond or an alkyl group of 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms.

According to a preferred embodiment, the curable polymer has a cyclic end group and is represented by the following formula: Wherein j and R ¹ are as defined above. D ¹ is a single bond or a divalent hydrocarbon group of 1 to 20 carbon atoms. Each subscript k is independently 0, preferably at least 1, and not greater than 12 (i.e., such that each ring has 3, preferably 4 to 15 germanium atoms), more preferably k. More than 8, more preferably no more than 6, more preferably no more than 4, and most preferably no more than 2. R, at each occurrence, is independently (a) a monovalent hydrocarbon group or a monovalent hydrocarbon group substituted with a halogen or a hetero atom such as oxygen or nitrogen, and (b) a radical polymerizable group such as an acrylate or alkyl acrylate-containing group. a group) or (c) an alkenyl alkoxyalkyl group, the limitation being at least two R groups (b) or (c) on each ring, and in the presence of an acrylate, an alkyl acrylate, and The total number of moles of alkenyl alkoxydecane, the amount of alkenyl alkoxydecane being at least 2 mole percent, preferably at least 5 mole percent and not more than 30, preferably not more than 25, more preferably The ground is no greater than 20, optimally no greater than 15 mole percent.

The monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group may have 1 to 18 carbon atoms. Monovalent hydrocarbon groups suitable for R include, but are not limited to, alkyl and aryl groups. Examples of suitable alkyl groups are methyl, ethyl, propyl, butyl, and hexyl. Examples of suitable aryl groups are phenyl, tolyl, xylyl, and phenylmethyl. As described above, these may be substituted by a halogen atom such as fluorine or chlorine, for example, 1H, 1H, 2H, 2H-trifluoropropyl, 1H, 1H, 2H, 2H-perfluorobutyl, 1H, 1H, 2H, 2H-perfluoropentyl, 1H, 1H, 2H, 2H-perfluorohexyl, 1H, 1H, 2H, 2H-perfluoroheptyl, 1H, 1H, 2H, 2H-perfluorooctyl. Further, as described above, a hydrocarbon group having a hetero atom can be used. Examples of such hetero atom-containing groups include alkylsulfanyl groups (such as alkylthiomethyl, alkylthioethyl, alkylthiopropyl, alkylthiobutyl) and alkylphosphinoalkyl groups (such as alkanes) Phosphomethyl, alkylphosphoryl, alkylphosphoryl, alkylphosphonium butyl).

Examples of suitable acrylate and alkyl acrylate groups include methyl methacrylate, methyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.

Examples of suitable alkenyl alkoxyalkylene groups include vinyltrimethoxydecane, vinylmethyldimethoxydecane, allyltrimethoxydecane, allylmethyldimethoxydecane, 3- Butenyltrimethoxydecane, 3-butenylmethyldimethoxydecane, 4-pentenyltrimethoxydecane, 4-pentenylmethyldimethoxydecane, 5-hexenyltrimethyl Oxydecane, 5-hexenylmethyldimethoxydecane, 6-heptenyltrimethoxynonane, 6-heptenylmethyldimethoxydecane, 7-octenyltrimethoxydecane, 7-Octenylmethyldimethoxydecane, 8-decenyltrimethoxydecane, 8-decenylmethyldimethoxydecane, 9-nonenyltrimethoxydecane, 9-decene Methyldimethoxydecane, 10-undecenyltrimethoxynonane, and 10-undecylmethyldimethoxydecane.

The clustered mixed functionally capped polyorganosiloxane of the present invention can be prepared by having a vinyl terminal (e.g., vinyl, allyl, 1-butenyl, 1-pentenyl). , 1-hexenyl, etc.) linear siloxane polymer, cyclic or cage methyl hydrazine polymer, vinyl functional methacrylate monomer, and vinyl The functional trimethoxydecane or dimethoxydecane is reacted in the presence of a rhodium hydrogenation catalyst (generally containing Pt, Ru, Ni species). The reaction is generally carried out at 50 ° C and higher and in an inert atmosphere. The reaction can be carried out with or without a solvent. At the end of the reaction, the catalyst can be quenched by the addition of a ligand such as diallyl maleate. If no quenching is carried out, the catalyst can also be removed by passing the reaction mixture through a bed of carbon black.

When used as a component in the adhesive formulation of the present invention, the amount of curable polyorganosiloxane having a clustered end group and a dual cure functionality is preferably at least 10% by weight, preferably at least 20%. % by weight, more preferably at least 30% by weight, and more preferably at least 40% by weight, alternatively at least 50% by weight, alternatively at least 60% by weight, but preferably not more than 99.9, 99.8, or according to some embodiments 99.7 wt%, more preferably no more than 98, 97, or 95 wt%. When component B is present, component A is preferably present at no more than 90 weight percent, and more preferably no greater than 85 weight percent. Alternatively, it is present at no more than 65 weight percent, no greater than 60 weight percent, and no greater than 50 weight percent, with all percentages being based on the total amount of components A through D used in the adhesive formulation. Component B

An optional component B in the above adhesive composition is a polyalkoxy-terminated resin-polymer blend. The polyalkoxy-terminated resin-polymer blend preferably comprises the reaction product of: i) a decane comprising a unit of the formula (R ^{2 '} ₃ SiO _{1/2) and} (SiO _4/2 ) a resin wherein each R ^{2 ' is} independently a monovalent hydrocarbon group, with the proviso that at least one R ^{2 '} per molecule has a terminal aliphatic unsaturation, wherein the decane resin has a range of from 0.5:1 to 1.5:1 ( Mo ² (M:Q ratio) of R ^{2 '} ₃ SiO _1/2 ) unit ("M" unit) and (SiO _4/2 ) unit ("Q" unit), ii) inclusion formula (R ^2' ₃ a polydiorganosiloxane having SiO _{1/2) ii} and (R ² SiO _2/2 ) _hh units ("D" units), wherein the subscript hh is 20 to 1000 and the subscript ii has an average of 2, and Iii) alkoxy-functional organohydrogenoxane oligomers. Alkoxy-functional organohydroquinone oligo has a unitary formula (HR ₂ SiO _1/2 ) _n (R ₃ SiO _1/2 ) _f (HRSiO _2/2 ) _o (R ₂ SiO _2/2 ) _h (RSiO _3/2 ) _i (HSiO _3/2 ) _p (SiO _4/2 ) _kk , wherein R and D ¹ are as described above, each R ^{3 is} independently a monovalent hydrocarbon group as described above for R, subscript b is 0 or 1, subscript c is 0, subscript f, h, i, and k have values that satisfy the following conditions: 5 ≥ f ≥ 0, 5 ≥ h ≥ 0, subscript i is 0 or 1, subscript kk is 0 or 1, subscript m > 0, and quantity ( m + n + f + o + h + i + p + kk) ≤ 50, with the proviso that > 90 mol% of all D groups in the blocking agent are linear; and iv) hydrazine hydrogenation catalyst. Starting material i)

The oxirane resin used to prepare the starting material B) is a fluorene resin comprising the formula (R ^{2 '} ₃ SiO _1/2 ) and (SiO _4/2 ) units, wherein each R ^{2 ′ is} independently a monovalent hydrocarbon group, with the proviso that at least one R ^{2 '} per molecule has terminal aliphatic unsaturation, wherein the hafnoxy resin has a (R ^{2 '} ₃ SiO _{1/2 ) unit in the} range of 0.5:1 to 1.5:1 The molar ratio (M:Q ratio) of the ("M" unit) to the (SiO _4/2 ) unit ("Q" unit), the starting material i) may contain an average of 3 to 30 mole percent of aliphatic unsaturation The group, alternatively 0.1 to 30 mole percent, alternatively 0.1 to 5 mole percent, alternatively 3 to 100 mole percent. The aliphatic unsaturated group of R ^{2 '} may have 2 to 18 carbon atoms. The aliphatic unsaturation of R ^{2 '} can be an alkenyl group, an alkynyl group, or a combination thereof. The molar percentage of the aliphatic unsaturated organic group in the decane resin is the ratio of the number of moles of the unsaturated group-containing oxirane unit in the resin to the total number of moles of the oxoxane unit in the resin. . The remaining monovalent hydrocarbon group of R ^{2 '} may be, for example, an alkyl or aryl group of 1 to 18 carbon atoms.

Methods of preparing resins are known in the art. For example, the resin can be prepared by treating the resin copolymer with at least one alkenyl-containing endcapping agent (produced by the dadt et al. cerium oxide hydrosol capping procedure). The method of Daudt et al. is disclosed in U.S. Patent No. 2,676,182.

The method of Daudt et al. involves reacting a cerium oxide hydrosol under acidic conditions with a hydrolyzable triorganosin such as trimethylchloromethane, a decane such as hexamethyldioxane or a mixture thereof, and then A copolymer having M units and Q units is recovered. The resulting copolymer typically contains from 2 to 5 weight percent of hydroxyl groups.

The decane resin (generally containing less than 2% of the hydrazone-bonded hydroxyl group) can be prepared by reacting the product of Daudt et al. with a capping agent containing an unsaturated organic group and a blocking agent containing no aliphatic unsaturation. It is used in an amount sufficient to provide from 3 to 30 mole percent of the unsaturated organic group in the final product. Examples of blocking agents include, but are not limited to, silazane, decane, and decane. Suitable end-capping agents are those well known in the art and are exemplified in U.S. Patent Nos. 4,584,355; 4,591,622; and 4,585,836. A single blocking agent or a mixture of such blocking agents can be used to prepare the decyl alkane resin used as starting material i). Starting material ii)

The polydiorganotoxime used to prepare the starting material B) comprises a formula (R ^{2 '} ₃ SiO _1/2 ) ii and a (R ₂ SiO _2/2 ) _hh unit (D unit), wherein R and R ^2' As described above, the subscript hh is 20 to 1000 and the subscript ii has an average of 2.

Alternatively, the starting material ii) may comprise the formula (I'): R ² R ² SiO(R ₂ SiO) _a (RR ² SiO) _b SiR ² R ² , formula (II'): R ₃ SiO (R ₂ a polydiorganosiloxane having a SiO) _c (RR ² SiO) _d SiR ₃ or a combination of (I') and (II'), wherein R is as described above, and each R ² independently has a terminal aliphatic group Unsaturated monovalent hydrocarbon group as described above for R ^{2 '} . The subscript a can be 0 or a positive number. Alternatively, the subscript a has an average of at least 2. Alternatively, the subscript a may have a value in the range of 2 to 2000. The subscript b can be 0 or a positive number. Alternatively, the subscript b may have an average value in the range of 0 to 2000. The subscript c can be 0 or a positive number. Alternatively, the subscript c may have an average value in the range of 0 to 2000. The subscript d has an average of at least 2. Alternatively, the subscript d has an average value in the range of 2 to 2000. Alternatively, each R is a monovalent hydrocarbon group, and examples thereof are an alkyl group such as a methyl group and an aryl group such as a phenyl group. Alternatively, examples of R ² are alkenyl groups (such as vinyl, allyl, butenyl, and hexenyl); and alkynyl groups (such as ethynyl and propynyl).

The starting material ii) may comprise a polydiorganofluorene, such as i) dimethylvinyloxyl-terminated polydimethyloxane, ii) dimethylvinyloxyl-terminated poly (dimethyl methoxy oxane / methyl vinyl fluorene oxide), iii) dimethylvinyl methoxy-terminated polymethyl vinyl siloxane, iv) trimethyl methoxy-terminated poly ( Dimethyl methoxy oxane / methyl vinyl fluorene oxide), v) trimethyl methoxy-terminated polymethyl vinyl fluorene oxide, vi) dimethyl vinyl hydroxy terminated poly (two Methyl methoxy alkane / methyl vinyl oxirane), vii) dimethylvinyl methoxy-terminated poly(dimethyl methoxy oxane / methyl phenyl oxa oxane), viii) dimethyl Polyvinyl oxy-terminated poly(dimethyl methoxy oxane / diphenyl sulfoxane), ix) phenyl, methyl, vinyl - methoxy-terminated polydimethyl methoxy oxane , x) dimethylhexenyloxy-terminated polydimethyloxane, xi) dimethylhexenyloxy-terminated poly(dimethyloxane/methylhexene矽 oxoxane), xii) dimethylhexenyl oxy-terminated polymethylhexenyl decane, xiii) trimethyl hydrazine Blocked poly(dimethyloxane/methylhexenyl decane), xiv) trimethyl methoxy-terminated polymethylhexenyl decane, xv) dimethylhexenyl- Alkoxy-terminated poly(dimethyloxane/methylhexenyl decane), xvi) dimethylvinyl methoxy-terminated poly(dimethyl methoxy oxane/methyl hexyl) Alkenyl alkane), or xvii) i), ii), iii), iv), v), vi), vii), viii), ix), x), xi), xii), xiii) xiv) A combination of two or more of , xv), and xvi).

Suitable for use as a polydiorganotoxioxane as starting material for the preparation of starting material B), in a process for the preparation thereof (such as hydrolysis and condensation of the corresponding organohalodecane or equilibrium of cyclic polydiorganotoxime) ) is known in the art. Starting material iii)

The starting material iii) is an alkoxy-functional organohydroquinone oligo. The starting material iii) can be prepared by a process comprising the following steps: 1) reacting a starting material comprising: (a) unit formula (I): (HR ₂ SiO _1/2 ) _e (R ₃ SiO _1/2 ) _f (HRSiO _2/2 ) _g (R ₂ SiO _2/2 ) _h (RSiO _3/2 ) _i (HSiO _3/2 ) _jj (SiO _4/2 ) _kk polyorganohydroquinone oligo a polymer wherein R is as described above, and the subscripts e, f, g, h, i, jj, and kk have values satisfying the following conditions: 5 ≥ e ≥ 0, 5 ≥ f ≥ 0, 10 ≥ g ≥ 0,5 ≥ h ≥ 0, subscript i is 0 or 1,5 ≥ jj ≥ 0, subscript kk is 0 or 1, the constraint is the quantity (e + g + jj) ≥ 2, and the quantity (e + f + g + h + i + jj + kk) ≤ 50; (b) Formula (II): R ² (R _c )Si(OR ³ ) _{( 3-c)} aliphatic unsaturated alkoxy decane, wherein R And R ² is as described above, each R ^{3 is} independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and the subscript c is 0 or 1; and (c) a selective hydrogenation catalyst; and optionally 2) separation The alkoxy-functional organohydrogenoxane oligomer prepared in step 1). Starting material iv)

The starting material iv) is a hydrazine hydrogenation catalyst which is used for the preparation of the catalyst of the starting material iii). Conventional catalysts for catalyzing the rhodium hydrogenation reaction are suitable, are known in the art, and are commercially available. Such an hydrazine hydrogenation catalyst can be a platinum group metal such as platinum. Alternatively, the rhodium hydrogenation catalyst may be a compound of such a metal, such as chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and a complex of such a compound with a low molecular weight organopolyoxane, or micro. A platinum compound encapsulated in a matrix or core/shell structure. The complex of platinum with a low molecular weight organopolyoxane comprises a complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane with platinum. These complexes can be microencapsulated in a resin matrix. Exemplary hydrogenation catalysts are described in U.S. Patent Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,784,879, 5,036,117, and 5,175,325. EP 0 347 895 B. The microencapsulated ruthenium hydrogenation catalyst and the process for the preparation thereof are exemplified in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654. The combination of such starting materials can be carried out at elevated temperatures, such as at 50 ° C to 250 ° C.

The polyalkoxy-functionalized polyoxyxyl-polymer blend is synthesized by reacting starting materials i), ii), and iii) in the presence of catalyst iv) at a temperature in the range of 50 to 250 °C. .

When used, the amount of component B in the adhesive of the present invention is at least 5% by weight, alternatively at least 10% by weight, alternatively at least 15% by weight, but not more than 90% by weight, alternatively not more than 50% by weight The percentage, alternatively, is not greater than 35 weight percent, and all percentages are based on the total of those components A through D used in the adhesive formulation. Component C

An optional component C in the above adhesive composition is a condensation reaction catalyst. The condensation reaction catalyst may be selected from the group of common condensation catalysts which are effective for the sterol-sterol condensation reaction, including organometallic compounds, amines, and a wide range of organic and inorganic bases and acids. Organometallic compounds include tin, titanium, zinc, zirconium, hafnium, and others. The condensation reaction catalyst may be an organotin compound and an organotitanium compound. Exemplary organogermanium compounds can be selected from the group consisting of: a) tin salts of carboxylic acids such as i) dibutyltin dilaurate, ii) dimethyltin dilaurate, iii) diketo acid di-( Di-(n-butyl)tin bis-ketonate, iv) dibutyltin diacetate, v) dibutyltin maleate, vi) dibutyl sulfonium dibutyltin, vii) Dibutyltin dimethoxide, viii) carbomethoxyphenyl tin tris-uberate, ix) dibutyltin dioctoate, x) dibutyltin dicarboxylate, xi) trisinic acid Isobutyl tin triceroate, xii) dimethyltin dibutoxide, xiii) dimethyltin di-n-decanoate, xiv) dibutyltin di-n-decanoate, xv) triethylenetin tartrate, xvi) Dibutyltin benzoate, xvii) butyltin tris-2-ethylhexanoate, xviii) dioctyltin diacetate, xix) tin octoate, xx) tin oleate, xxi) tin butyrate, xxii) tin naphthenate , xxiii) dimethyltin dichloride; b) tin (II) salt of an organic carboxylic acid such as xxiv) tin (II) diacetate, xxv) tin (II) dioctoate, xxvi) tin diethylhexanoate ( II), xxvii) tin (II) dilaurate; c) tin salt of carboxylic acid, such as xxviii) tin octoate, xxix) tin oleate, xxx) tin acetate , xxxi) tin laurate, xxxii) tin stearate, xxxiii) tin naphthenate, xxxiv) tin hexanoate, xxxv) tin succinate, xxxvi) tin octoate, and i) to xxxvi) two or more Combination of people. Exemplary organotitanium compounds can be selected from the group consisting of: i) tetra-n-butyl titanate, ii) tetraisopropyl titanate, iii) tetra-butyl butyl titanate, iv) barium titanate (2) -ethylhexyl)ester, v) acetylacetonate titanate chelate, vi) ethyl acetoacetate titanate chelate, vii) triethanolamine titanate chelate And a combination of two or more of i), ii), iii), iv), v), vi), and vii).

The amount of condensation reaction catalyst in the adhesive composition depends on various factors, including the choice of other starting materials (whether or not any additional starting materials are added), and the end use of the adhesive composition. However, when used, the condensation reaction catalyst is preferably at least 0.01% by weight, more preferably at least 0.1% by weight, and in some cases, based on the total of those components A to D used in the adhesive formulation. At least 0.5% by weight in the embodiment, but preferably not more than 25% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight, still more preferably not more than 5% by weight, and most preferably It is present in an amount of no more than 1% by weight in some embodiments. Component D

Component D in the above adhesive composition is a radical initiator. The radical initiator may comprise an azo compound or an organic peroxide compound. Suitable azo compounds include azobenzene, p-azobenzenesulfonic acid, azobisdimethylvaleronitrile, azobisisobutyronitrile, and combinations thereof. Suitable organic peroxide compounds include dialkyl peroxides, diaryl peroxides, dinonyl peroxides, alkyl hydroperoxides, and aryl hydroperoxides. Specific examples of the organic peroxide compound are benzamidine peroxide; benzamidine peroxide; 4-monochlorobenzidine peroxide; dicumyl peroxide; tert-butyl peroxybenzoate; peroxidation Tertiary butyl cumene; tertiary butoxide 2,5-dimethyl-2,5-di-tertiary butyl peroxyhexane; 2,4-dichlorobenzamide peroxy; di-three Butyl peroxy-diisopropylbenzene; 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane; 2,5-di-tertiary butyl Oxyhexane-3,2,5-dimethyl-2,5-bis(tributylperoxy)hexane; cumyl-tertiary butyl peroxide; or two or more thereof The combination.

The starting amount of free radical added to the adhesive composition depends on a number of factors, including the type and amount of catalyst selected for the condensation reaction, as well as the choice of other starting materials in the adhesive composition, however, as an adhesive formulation The radical initiator may be at least 0.1% by weight, alternatively 0.2% by weight, and preferably 0.3% by weight but not more than 5% by weight, alternatively not greater than the total weight of those components A to D used in the use. It is present in an amount of 3% by weight, and alternatively no more than 2% by weight. Optional additive

The above adhesive composition may further comprise one or more optional ingredients (other than the above-mentioned components A), B), C), and D) and additionally added in addition to these components. The optional ingredients are selected from the group consisting of: E) dual cure compounds, F) adhesion promoters, G) corrosion inhibitors, H) rheology modifiers, I) desiccants, J) crosslinkers, K Filler, L) spacer, M) acid scavenger, N) decyl functional polydiorganosiloxane, O) fluorescent optical brightener, P) chain transfer agent, Q) (meth) acrylate , R) polyalkoxy-terminated polydiorganotoxime, S) colorant, and E), F), G), H), I), J), K), L), M) Two or more of N, O), P), Q), R), and S).

Adhesives are used simply by applying an adhesive and curing. The curing of the adhesive can be achieved thermally in the range of 50 to 170 ° C, preferably 70 ° C or higher. Adhesive compositions provide superior performance on a variety of metals that are not primed or surface treated. It also has satisfactory adhesion properties on plastics with medium to high surface energy. It can be used for metal-metal bonding and metal-plastic bonding. Ingredients and components A method of measuring the surface wetness of an adhesive.

The adhesive film of the present invention was made on an aluminum Q-panel (3.5 x 10 inch) from Q-Lab with a 50 mil gap (1.27 mm) draw-down bar. The film was allowed to cure in air at 100 ° C for one hour in an oven. The film was allowed to cool to room temperature for 15 minutes, after which the surface wetness of the film was measured.

Surface wetness is quantified by impact testing.

Impact testing was performed on a drop impact tester (Qualtech Prodcuts). Pre-weighed filter paper (Gilman, quantitative, Grade 2) was placed on a cured adhesive film (thickness: 50 mils, 1.27 mm) which was attached to aluminum Q-panel (3.5 x 10'') . The steel block (0.3 Kg) was dropped from a height of 30 cm onto a cylindrical metal rod, which caused marks on the filter paper. Repeat the drop several times in different areas of the filter paper. Carefully peel the filter paper from the sample and weigh it. The difference before and after the impact (in milligrams) is the surface wetness of the sample. Synthesis Example 1 (Comparative Example) A. Preparation of a siloxane having a terminal cluster and an alkyl acrylate-only reactive group. (Comparative example)

In a general synthesis, MB-2030 (2897 g), SFD-120 polymer (1636 g), OS-20 fluid (271 g), and ETS-900 (also known as OFS-) were added to a 10 liter Turello mixer. 1579, 4.89 g). The mixture was inerted with a nitrogen purge and stirred for 10 minutes (dissolved blade = 500 rpm; doctor blade = 20 rpm). Butylated hydroxytoluene (1.4 g), MH-1109 (98.8 g), and allyl methacrylate (233 g) were added to the homogenized mixture. The mixture was stirred at room temperature for an additional 10 minutes (250 rpm; 20 rpm) at which time a platinum catalyst (2-0707, 6.4 g) was added to the mixture. The mixture was stirred for an additional 10 minutes (250 rpm; 20 rpm), after which the temperature was set at 60 °C. The temperature was maintained at 60 ° C for 30 minutes before cooling, and diallyl maleate (6.4 g) was added when the temperature dropped below 50 °C. The mixture was then cooled to below 30 ° C, after which MTM (Z-6070, 44.2 g) was added. The mixture was then heated to 60 ° C for 30 minutes (250 rpm; 20 rpm) with the temperature raised to 85 ° C and a vacuum of 5 to 6 Torr applied for 40 minutes. This polymer was obtained as a white viscous paste. Yield: 4500 g. B. Preparation of Adhesive from Component A (Comparative Example)

The polymer of Part A of Comparative Example 1 (2200 g), IT EA-3013 ETM resin/polymer (593 g), 3-1719 (3 g), and Tinopal OB (0.61) in a 10 liter Turello mixer. g) loaded. The mixture was mixed at 10 ° C for 10 minutes (200 rpm; 20 rpm). To the homogenized mixture, benzoyl peroxide paste (Perkadox L-50S-ps, 90.48 g), Z-6030 decane (60.4 g), triallyl isocyanurate (15 g), and 2 were added. a solution of mercaptobenzothiazole (4.6 g) in A186 (also known as KBM-303, 18.1 g). The mixture was again mixed at 10 ° C for 10 minutes (200 rpm; 20 rpm). A solution of tri-n-butyl titanate (18.7 g) in IBTMS (Z-2306, 56.7 g) and a solution of A1110 (3.4 g) in IBTMS (3.4 g) were added. The preparation was again mixed at 10 ° C for 10 minutes (200 rpm; 20 rpm). The final product was degassed at 10 ° C for 30 minutes under a vacuum of 200 Torr.

Comparative Examples a and b were actually prepared after Synthesis Example 1. Synthesis Example 2. Preparation of the adhesive of the present invention. A. Synthesis of alkoxythiol-modified polymers with cyclic clustered end groups

In a general synthesis, MB-2030 (2897 g), SFD-120 polymer (1636 g), OS-20 fluid (271 g), and ETS-900 (also known as OFS-) were added to a 10 liter Turello mixer. 1579, 4.89 g). The mixture was inerted with a nitrogen purge and stirred for 10 minutes (dissolved blade = 500 rpm; doctor blade = 20 rpm). To the homogenized mixture was added butylated hydroxytoluene (1.4 g), stripped MH-1109 (98.8 g), vinyl functional alkoxy decane (5 to 25% based on allyl methacrylate) Mol), and allyl methacrylate (217.5 g). The mixture was stirred at room temperature for an additional 10 minutes (250 rpm; 20 rpm) at which time a platinum catalyst (2-0707, 6.4 g) was added to the mixture. The mixture was stirred for an additional 10 minutes (250 rpm; 20 rpm), after which the temperature was set at 60 °C. The temperature was maintained at 60 ° C for 30 minutes before cooling, and diallyl maleate (6.4 g) was added when the temperature dropped below 50 °C. The mixture was then cooled to below 30 ° C, after which MTM (Z-6070, 44.2 g) was added. The mixture was then heated to 60 ° C for 30 minutes (250 rpm; 20 rpm) with the temperature raised to 85 ° C and a vacuum of 5 to 6 Torr applied for 40 minutes. A dumbbell-shaped polymer modified with an alkoxy thiol group in a white viscous paste was obtained. Yield: 4500 g. B. After comparing the step B in Synthesis Example 1, the alkoxythiol-modified dumbbell-shaped polymer was formulated into an adhesive. Samples 1 to 6 were prepared after Synthesis Example 2. Comparative Synthesis Example 3. An adhesive was prepared by using a dumbbell-shaped polymer modified with an alkyl decane. A. Synthesis of dumbbell-shaped polymer modified by alkyl thiol

In a general synthesis, MB-2030 (2897 g), SFD-120 polymer (1636 g), OS-20 fluid (271 g), and ETS-900 (also known as OFS-) were added to a 10 liter Turello mixer. 1579, 4.89 g). The mixture was inerted with a nitrogen purge and stirred for 10 minutes (dissolved blade = 500 rpm; doctor blade = 20 rpm). To the homogenized mixture was added butylated hydroxytoluene (1.4 g), stripped MH-1109 (98.8 g), alkyl decane having a vinyl functional or hydrocarbon alkene (based on allyl methacrylate) 5 to 25% mol), and allyl methacrylate (217.5 g). The mixture was stirred at room temperature for an additional 10 minutes (250 rpm; 20 rpm) at which time a platinum catalyst (2-0707, 6.4 g) was added to the mixture. The mixture was stirred for an additional 10 minutes (250 rpm; 20 rpm), after which the temperature was set at 60 °C. The temperature was maintained at 60 ° C for 30 minutes before cooling, and diallyl maleate (6.4 g) was added when the temperature dropped below 50 °C. The mixture was then cooled to below 30 ° C, after which MTM (Z-6070, 44.2 g) was added. The mixture was then heated to 60 ° C for 30 minutes (250 rpm; 20 rpm) with the temperature raised to 85 ° C and a vacuum of 5 to 6 Torr applied for 40 minutes. A dumbbell-shaped polymer modified with an alkyl thiol group in a white viscous paste was obtained. Yield: 4500 g. B. After comparing step B in Synthesis Example 1, the alkyl thiol-modified dumbbell-shaped polymer was formulated into an adhesive.

Comparative Samples 7 to 8 were prepared after Synthesis Example 3. Example 4. Efficacy of alkoxythiol-modified dumbbell-shaped polymer

The surface wettability of the unmodified adhesive (Comparative Examples a, b) and vinyl trimethoxy decane (VTMS) modified adhesive was compared at three different loadings (samples 1 to 3). As shown, the VTMS modified adhesive dries in 22 hours or less, and more than 200 hours compared to the adhesive such as that from Comparative Example 1. Table 1. Performance comparison of unmodified adhesives (Comparative Examples a, b) with VTMS modified adhesives (Samples 1 to 3).

The surface wettability of the unmodified adhesive (Comparative Examples a, b) and the allyltrimethoxydecane (ATMS) modified adhesive was compared at three different loadings (samples 4 through 6). As shown in the table, the ATMS modified adhesive of the present invention dries in less than about 20 hours, compared to more than 200 hours in Comparative Example 1. Table 2. Comparison of the performance of the unmodified adhesives of Comparative Examples a and b with the ATMS modified adhesives (samples 4 to 6 ) . Example 5. Alkoxyfluorenyl p-alkyl fluorenyl.

The 1-octene and allyl trimethyl decane modified adhesive was prepared according to Example 3 (Samples 7 and 8). The surface wetness of the new adhesive (sample 6) modified with ATMS and the samples 7 and 8 (Table 3) were compared. The loading of all modifiers was 12.5% mol. This example shows that having a hydrolyzable functional group is important for shortening the drying time because allyl methyl decane and 1-octene modified adhesives still have a drying time of more than 40 hours. table 3. Example 6. Adhesion performance.

The adhesion properties of Comparative Examples a, b and Samples 1 through 8 are compared in Table 4. Adhesion strength is determined by the lap shear method. Table 4.

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Claims (15)

A curable siloxane polymer comprising a backbone of the following oxane repeating units: Wherein j is an integer of at least 50, and R ¹ is independently H or an alkyl group of 1 to 4 carbon atoms or an aryl group of 6 to 12 carbon atoms at each occurrence, wherein the characteristics of the siloxane polymer The end groups are formed from clusters of oxoxane units and the groups are functionalized by the presence of at least two functionally reactive groups per cluster, and at least one functionally reactive group is free radicals a polymeric group and at least one functionally reactive group is an alkenyl alkoxy decane group, and the amount of free radical polymerizable group is at least 2 mole percent of the total moles of functionally reactive groups in the polymer . The polymer of claim 1 wherein each cluster has at least 3 functional reactive groups. The polymer of any one of the preceding claims, wherein the amount of the radical polymerizable group is less than 30 moles based on the total number of moles of the functionally reactive group. The polymer of claim 1 which has the formula Wherein D ¹ is a single bond or a divalent hydrocarbon group of 1 to 20 carbon atoms, k is independently 0 to 12 at each occurrence, and R is independently (a) a monovalent hydrocarbon group or a halogen or a hetero atom, such as a monovalent hydrocarbon group substituted with oxygen or nitrogen, (b) a radical polymerizable group, or (c) an alkenyl alkoxyalkyl group, with the proviso that at least two R groups on each ring are selected from ( b) and (c), and in terms of the total number of moles of the free radical polymerizable group and the alkenyl alkoxyalkyl group present, the amount of the alkenyl alkoxydecane is at least 2 mole percent and not More than 30 mole percent. The polymer of claim 4, wherein k is 1 or 2. A polymer according to any one of the preceding claims, wherein the radical polymerizable group is a group containing an acrylate or an alkyl acrylate. The polymer according to any of the preceding claims, wherein the alkenyl alkoxyalkylene group is selected from the group consisting of vinyl trimethoxy decane, vinyl methyl dimethoxy decane, olefin Propyltrimethoxydecane, allylmethyldimethoxydecane, 3-butenyltrimethoxynonane, 3-butenylmethyldimethoxydecane, 4-pentenyltrimethoxydecane , 4-pentenylmethyldimethoxydecane, 5-hexenyltrimethoxydecane, 5-hexenylmethyldimethoxydecane, 6-heptenyltrimethoxydecane, 6-g Alkenylmethyldimethoxydecane, 7-octenyltrimethoxydecane, 7-octenylmethyldimethoxydecane, 8-decenyltrimethoxydecane, 8-decenylmethyl Dimethoxy decane, 9-nonenyl trimethoxy decane, 9-nonenyl methyl dimethoxy decane, 10-undecenyl trimethoxy decane, and 10-undecenylmethyl Methoxy decane. The polymer according to any one of the preceding claims, wherein the radical polymerizable group is selected from the group consisting of methyl methacrylate, methyl acrylate, butyl methacrylate, 2-ethyl acrylate Hexyl hexyl ester, and 2-ethylhexyl methacrylate. The polymer according to any one of claims 4 to 8, wherein the alkenyl alkoxy decane is not more than the total number of moles of the radical polymerizable group and the alkenyl alkoxyalkyl group present. 15 mole percentage. An adhesive comprising the polymer of any one of claims 1 to 9 and a radical initiator. An adhesive according to claim 10, which further comprises a polyalkoxy-terminated polyoxyl resin-polymer blend. The adhesive of claim 10 or 11, which further comprises a condensation reaction catalyst. The adhesive of claim 12, wherein the total weight of the polymer, the polyalkoxy-terminated polyoxyl resin-polymer blend, the condensation reaction catalyst, and the radical initiator are The amount of the polymer a is at least 10% by weight, and the amount of the polyalkoxy-terminated polyoxynoxy resin-polymer blend is in the range of 10 to 50% by weight, and the amount of the condensation reaction catalyst is It is in the range of 0.1 to 5 weight percent, and the amount of the radical initiator is in the range of 0.1 to 3 weight percent. The adhesive according to any one of claims 10 to 13, which further comprises one or more of the following components: a dual curing compound, an adhesion promoter, a corrosion inhibitor, a rheology modifier, a desiccant, a crosslinking agent , fillers, spacers, acid scavengers, sterol-functional polydiorganosiloxanes, fluorescent optical brighteners, chain transfer agents, (meth) acrylate monomers, polyalkoxy-terminated polydiorganic Alkane, a coloring agent. A procedure comprising applying an adhesive according to any one of claims 10 to 14 to a substrate and curing at a temperature of at least 70 °C.