TW201414796A - Self-adhering curable silicone adhesive compositions and process for making thereof - Google Patents

Abstract

A self-adhering curable silicone adhesive composition comprising: (A) an alkenyl substituted organopolysiloxane containing on average at least 0.1 alkenyl groups per molecule; (B) an organohydrogenpolysiloxane containing on average at least 2 silicon-bonded hydrogen atoms per molecule in an amount that the molar ratio of the total number of the silicon-bonded hydrogen atoms of component (B) to the total quantity of all alkenyl radicals of component (A) is less than 1.3: 1; (C) a hydrosilylation catalyst; (D) an adhesion promoter; and (E) an adhesion catalyst in the form of microscopic particles comprising: (a) a thermally activated semi-crystalline polymer, and (b) at least one organometallic condensation catalyst having a metal M wherein the organometallic condensation catalyst is either admixed or encapsulated with the thermally activated semi-crystalline polymer. A process for making the adhesion catalyst (E).

Description

Composition of self-bonding curable polyoxynoxy adhesive and method for manufacturing same

Disclosed herein are self-adhesive curable polyoxyxene adhesive compositions and a method of making a self-adhesive curable polyoxyxene adhesive composition, and hardening the self-adhesive curable polyxanthene composition The product formed. More specifically, the present invention relates to a hydrazine hydrogenated hardenable composition which provides low temperature adhesion while maintaining good shelf stability.

The main problem with the single-part thermosetting hydrazine curable curable polyoxyxene adhesive composition is that the temperature at which adhesion is formed is much higher than its hardening temperature. This effect can be problematic when manufacturing a joint design with integrity because the manufacturer cannot confirm the adhesive properties before the component is manufactured. Therefore, it is desirable to have a composition that hardens at a similar temperature and provides adhesion. The present invention provides a composition that hardens at similar temperatures and provides adhesion.

In recent years, organometallic compounds such as metal chelates have been used to reduce the temperatures required to achieve adhesion (and provide improved adhesion) to many engineering plastics. However, the interaction antagonism between organometallic compounds and hydrazine hydride groups in organohydrogenpolysiloxanes affects their hardenability, limits their shelf stability, and reduces thermal stability. The composition of the present invention does not have the interaction antagonism between the organometallic compound and the hydrazine hydride group in the organohydrogenpolyoxyalkylene.

Therefore, there is a need for a simple method for introducing an organometallic compound into a hydrogenated hardenable adhesive composition. The practice in the present invention provides long-term hardenability, shelf stability, and thermal stability.

The present invention relates to a self-adhesive curable polyoxyxene adhesive composition comprising: (A) an alkenyl-substituted organopolyoxane having an average of at least 0.1 alkenyl groups bonded to fluorene per molecule (B) an organohydrogen polyoxyalkylene containing an average of at least 1.5 hydrogen atoms bonded to hydrazine per molecule in an amount such that the total number and composition of hydrogen atoms bonded to hydrazine in component (B) The total number of all alkenyl groups in (A) has a molar ratio of less than 1.3:1; (C) a hydrogenation catalyst; (D) an adhesion promoter; and (E) an adhesion catalyst in the form of microscopic particles, It comprises: (a) a thermally activated semi-crystalline polymer, and (b) at least one organometallic condensation catalyst having a metal M, wherein the organometallic condensation catalyst is doped with the thermally activated semi-crystalline polymer Combined or coated. This composition may be referred to herein as "Stage 1".

The invention also relates to a method of making the adhesive catalyst (E) which comprises forming the adhesive catalyst in a single layer process or a two layer process.

[Details of the Invention]

All quantities, ratios and percentages are by weight unless otherwise indicated. The definitions used in this application are listed below.

The terms "one" and "one" each represent one or more.

The term "crystalline" refers to a polymer having a first-order phase transition characteristic of a crystalline melting point ( T _m ) if analyzed by differential scanning calorimetry (DSC) or equivalent techniques.

The term "amorphous" refers to a polymer, if the differential scanning calorimetry (DSC) or equivalent technical analysis, which has a glass transition phase transition (T _g) of a crystalline melting point and lack features.

The term "semi-crystalline" means a polymer having both crystalline and amorphous characteristics as defined above.

The term "release temperature" refers to the temperature at which the microcapsules melt and the coated catalyst can diffuse into the composition.

The term "thermally activated semi-crystalline polymer" refers to a polymeric composition comprising microscopic particles that are thermally triggered to release the active ingredients therein.

The abbreviation "M" denotes a fluorene oxide unit of the formula R ₃ SiO _1/2 wherein each R independently represents a monovalent atom or group.

The abbreviation "D" denotes a oxoxane unit of the formula R ₂ SiO _2/2 wherein each R independently represents a monovalent atom or group.

The abbreviation "T" denotes a siloxane unit of the formula RSiO _3/2 wherein R represents a monovalent atom or group.

The abbreviation "Q" denotes a siloxane unit of the formula SiO _4/2 .

The abbreviation "Me" stands for monomethyl.

The abbreviation "Vi" stands for a vinyl group.

The component (A), that is, an alkenyl-substituted organopolyoxane, is a polydiorganosiloxane having an average of at least a dialiphatic unsaturated organic group and at least one aromatic group per molecule. The component (A) may be a single polydiorganotoxime or a combination comprising two or more polydiorganooxanes, and at least one of the following properties of the different polyorganosiloxanes is different from each other: structure, viscosity, Average molecular weight, oxane unit and order. The viscosity of component (A) is not critical; however, the viscosity can range from 10 to 1,000,000 mPa. s at 25 ° C, or 100 to 50,000 mPa. s to improve the handling characteristics of the hardened polyoxynene resin prepared from the polyoxynene composition. The amount of the component (A) in the composition may be 10 to 40 or 15 to 30 parts by weight based on the total weight of the composition.

The aliphatically unsaturated organic group in component (A) may be an alkenyl group such as, but not limited to, a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, or a vinyl group. The aliphatically unsaturated organic group can be an alkynyl group such as, but not limited to, an ethynyl group, a propynyl group, and a butynyl group. The aliphatically unsaturated organic group in component (A) can be located at the end, suspended or both at the terminal and in the suspending position. One or more aromatic groups within component (A) may be located at the end, suspended or both at the terminal and in the suspending position. The aromatic group can be, for example but not limited to, ethylbenzyl, naphthyl, phenyl, tolyl, xylyl, benzyl, styryl, 1-phenylethyl, and 2-phenylethyl, or Is a phenyl group. Ingredient (A) contains an average of at least one aromatic group per molecule. However, the component (A) may contain more than 40 mol% or more than 45 mol% of an aromatic group.

If the component (A) contains an organic group remaining bonded to ruthenium, the organic group may be an aromatic-free and aliphatic-free monovalent substituted and unsubstituted hydrocarbon group. Monovalent unsubstituted hydrocarbon groups such as, but not limited to, alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, eleven and ten An octa group, and a cycloalkyl group such as a cyclohexyl group. The monovalent substituted hydrocarbon group is, for example but not limited to, a halogenated alkyl group such as chloromethyl, 3-chloropropyl and 3,3,3-trifluoropropyl, fluoromethyl, 2-fluoropropyl, 3,3,3- Trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl and 8,8,8,7,7-pentafluorooctyl.

The component (A) may have the formula (I): R ¹ ₃ SiO-(R ² ₂ SiO) _a -SiR ¹ ₃ , wherein each R ¹ and each R ² group are independently selected from the above monovalent substituted and unsubstituted hydrocarbon groups, a group consisting of an aliphatic unsaturated organic group and an aromatic group, and the subscript letter a is an integer having a value sufficient to provide a viscosity of the component (A), the viscosity being 10 to 5 at 25 ° C 1,000,000mPa. s, but their premise that R ¹ and / or R ² is an average of at least two unsaturated organic group and R ¹ and / or at least one R ² is an aromatic group. Or at least two R ¹ are an unsaturated organic group, at least one R ² is an aromatic group and the subscript a has a value of from 5 to 1,000. Or the formula (I) is an α,ω -dienyl functional polydiorganosiloxane.

The component (B), that is, the organohydrogenpolysiloxane, is an organohydrogenpolyoxane having an average of at least 2 hydrogen atoms bonded to hydrazine per molecule. Ingredient (B) can be a homopolymer, copolymer or polymer blend. The component (B) may have a straight chain, a branched chain, a cyclic or a resinous structure. The hydrogen atom bonded to the oxime in component (B) may be located at the end, suspended or both at the end and at the suspending position.

Ingredient (B) may comprise a oxoxane unit including, but not limited to, HR ⁶ ₂ SiO _1/2 , R ⁶ ₃ SiO _1/2 , HR ⁶ SiO _2/2 , R ⁶ ₂ SiO _2/2 , R ⁶ SiO _{3 /2} and SiO _4/2 units. In the above formula, each R ⁶ is independently selected from a hydrocarbon group which is not aliphatically unsaturated.

The component (B) may include a compound of the formula R ⁷ ₃ SiO(R ⁷ ₂ SiO) _e (R ⁷ HSiO) _f SiR ⁷ ₃ , R ⁸ ₂ HSiO(R ⁸ ₂ SiO) _g (R ⁸ HSiO) _h SiR ⁸ ₂ H or a combination thereof.

The subscript text e has an average value of 0 to 2000, and the subscript text f has an average value of 2 to 2000. Each R ⁷ system is independently a non-aliphatic unsaturated hydrocarbon group. Suitable aliphatic-unsaturated hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl and butyl groups; aromatic groups such as phenyl, tolyl and xylyl.

The subscript text g has an average value of 0 to 2000, and the subscript text h has an average value of 0 to 2000. Each R ⁸ system is independently a non-aliphatic unsaturated hydrocarbon group. Suitable aliphatic-unsaturated hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl and butyl groups; aromatic groups such as phenyl, tolyl and xylyl.

Examples of component (B) are i) dimethylhydroquinone-terminated polydimethyloxane, ii) dimethylhydroquinone-terminated poly(dimethyloxane/methylhydroquinone) Oxyalkylene), iii) dimethylhydroquinone-terminated polymethylhydroquinone, iv) trimethylphosphonium-terminated poly(dimethyloxane/methylhydrooxane), v) trimethyl methoxy-terminated polymethylhydroquinone, vi) a resin consisting essentially of H(CH ₃ ) ₂ SiO _1/2 units and SiO _4/2 units, and vii) combinations thereof .

Ingredient (B) may be a combination of two or more organohydrogenpolyoxanes having at least one of the following characteristics different from each other: structure, average molecular weight, viscosity, and oxoxane units.

The molar ratio (SiH _B /Vi _A ) of the hydrogen atom bonded to the oxime in the component (B) to the aliphatic unsaturated group in the component (A) is less than 1.3:1, or the ratio may be about 1:1. Or less than 1:1. In other embodiments, the ratio is less than 0.9:1, 0.8:1, 0.7:1, 0.6:1, or 0.5 to 10:1.

The component (C), that is, a ruthenium hydrogenation catalyst, is a ruthenium hydrogenation catalyst for promoting the hydrazine hydrogenation reaction between the components (A) and (B). Component (C) is added to the platinum group metal in an amount of from 0.1 to 1000 ppm, or from 1 to 500 ppm, or from 2 to 200 or from 5 to 150 ppm, based on the weight of the composition. Suitable rhodium hydrogenation catalysts are known in the art and are commercially available. Ingredient (C) may comprise a transition metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, iridium or ruthenium or an organometallic compound thereof or a combination thereof. Examples of the component (C) include compounds such as hydrochloroplatinic acid, hydrochloroplatinic acid hexahydrate, platinum dichloride, and complexes of the compounds with low molecular weight organic polyoxyalkylenes, supported platinum compounds or A platinum compound that is micro-coated within 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. Examples of supported platinum compounds include platinum supported on carbon and platinum supported on alumina.

The component (C) is present in the polyoxymethylene composition in an amount of from 0.01 to 1000 parts per million (ppm), from 0.1 to 1000 ppm, from 0.01 to 500 ppm, from 0.1 to 500 ppm, from 0.5 to 100 ppm or from 1 to 25 ppm to (A) , (B) and (C) total weight.

Ingredient (D) is an adhesion promoter. The component (D) in the composition is added in an amount of from 0.01 to 50 parts by weight based on the weight of the composition.

Ingredient (D) may comprise a combination of an alkoxydecane, an alkoxydecane, and a monohydroxy functional polyorganosiloxane, or a combination thereof. The alkoxydecane can be either unsaturated or epoxy functional. Suitable epoxy functional compounds are known in the art and are commercially available. Ingredient (D) may comprise an unsaturated or epoxy functional alkoxydecane. For example, the functional alkoxydecane may have the formula R ⁹ _i Si(OR ¹⁰ ) _(4-i) wherein the subscript i is 1, 2 or 3, or the subscript i is 1.

Each R ⁹ system is independently a monovalent organic group, provided that at least one R ⁹ is an unsaturated organic group or an epoxy functional organic group. Examples of R ^{9 which} are epoxy functional organic groups are 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Examples of the unsaturated organic group wherein R ⁹ is an unsaturated group include 3-methacryloxypropyl, 3-propenyloxypropyl, and an unsaturated monovalent hydrocarbon group (e.g., vinyl, allyl, hexenyl, eleven). Alkenyl).

Each R ¹⁰ is independently an unsubstituted saturated hydrocarbon group having at least 1 carbon atom. R ¹⁰ may have up to 4 carbon atoms, or up to 2 carbon atoms. Examples of R ¹⁰ are methyl, ethyl, propyl and butyl.

Examples of suitable epoxy functional alkoxydecanes include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, (epoxycyclohexyl)ethyl Dimethoxydecane, (epoxycyclohexyl)ethyldiethoxydecane, and combinations thereof. Examples of suitable unsaturated alkoxydecanes include vinyltrimethoxydecane, allyltrimethoxydecane, allyltriethoxydecane,hexenyltrimethoxydecane,undecyltrimethoxy. Decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propene oxime Oxypropyl triethoxy decane and combinations thereof.

Ingredient (D) may comprise an epoxy functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxy decane, as described above, or a hydroxy-terminated polyorganosiloxane. A physical blend of an epoxy functional alkoxydecane. Ingredient (D) may comprise a combination of an epoxy functional alkoxydecane and an epoxy functional alumoxane. For example, examples of component (D) are 3-glycidoxypropyltrimethoxydecane and hydroxy-terminated methylvinyloxirane and 3-glycidoxypropyltrimethoxydecane. a mixture of reaction products, or a mixture of 3-glycidoxypropyltrimethoxydecane and a hydroxy-terminated methylvinyloxirane, or 3-glycidoxypropyltrimethoxydecane and a hydroxyl group A mixture of terminal methyl vinyl/dimethyl methoxide copolymers. If used in the form of physical blends rather than reaction products, these components can be stored separately in multiple sets. In the group.

Suitable adhesion promoters include organic phosphonium compounds such as organodecane and organopolyoxane having an alkoxy group bonded to a ruthenium atom. Examples of the organic hydrazine compound include alkoxy decane such as tetramethoxy decane, tetraethoxy decane, dimethyl dimethoxy decane, methyl phenyl dimethoxy decane, methyl phenyl di Oxydecane, phenyltrimethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, vinyltrimethoxydecane,allyltrimethoxydecane,allyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane and 3-methacryloxypropyltrimethoxydecane, and a linear siloxane compound or a cyclic siloxane compound (ie, an organic oxane oligo) a polymer having from about 4 to about 30 germanium atoms in one embodiment, or from about 4 to about 20 germanium atoms in another embodiment, and including at least two or three functional groups of one molecule selected from the group consisting of a hydrogen atom (SiH group) bonded to a ruthenium atom, an alkenyl group bonded to a ruthenium atom (for example, a group of Si--CH.dbd.CH.sub.2), an alkoxy fluorenyl group (for example, a trialkoxy group) An anthracenyl group such as a trimethoxyindenyl group and an epoxy group such as a glycidoxypropyl group and a 3,4-epoxycyclohexylethyl group.

In one embodiment, an organooxonium-modified trimel isocyanate compound having the following general formula and/or a hydrolyzed condensate thereof (ie, an organooxane-modified trimel isocyanate compound) is used as an adhesion promoter.

Wherein R ^{22 is} each independently an organic group including a halogen atom (or an organic oxoalkyl group) having the formula:

Or a monovalent hydrocarbon group including an aliphatic unsaturated bond, at least one R ²² is a halogen atomic organic group of the formula (4), each of R ^{23 is} independently a hydrogen or a monovalent hydrocarbon group of 1 to 6 carbon atoms, and the subscript m is An integer from 1 to 6 or from 1 to 4.

Examples of the monovalent hydrocarbon group including an aliphatic unsaturated bond (represented by R ²² ) include, in one embodiment, an alkenyl group of 2 to 8 carbon atoms, or in another embodiment, 2 to 6 carbon atoms, For example, vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, and cyclohexenyl. The monovalent hydrocarbon group represented by R ²³ includes, in one embodiment, one having from 1 to 8 carbon atoms, or in another embodiment from 1 to 6 carbon atoms, such as an alkyl group such as a methyl group or an ethyl group. , propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl, cycloalkyl such as cyclohexyl, alkenyl such as vinyl, allyl, propenyl and isopropenyl, and An aryl group such as a phenyl group.

Illustrative examples of adhesion promoters include:

In the above example, the subscripts n and p are integers of at least 1, the subscript text q is 0 or more, and in various embodiments, p+q=2 to 50, or p+q=2 to 10 , n+p+q=4 to 20 or n+p+q=2 to 50.

For the organic ruthenium compound, an alkoxy group having a bond to a ruthenium atom in the molecule and an alkenyl group bonded to a ruthenium atom or a hydrogen atom bonded to a ruthenium atom (ie, a SiH group) may be Preferably, the hardened composition is more viscous.

The component (D) in the polyoxyxene adhesive composition is present in an amount of from 0.1 to 10 parts by weight (pbw), or from 0.5 to 7.5 pbw or from 0.75 to 5 pbw, per 100 pbw of (A).

The adhesive catalyst component (E) exhibits a catalytic function in the presence of component D, that is, the adhesion catalyst can have a catalytic effect on the adhesion promoter.

In the practice of the present invention, the components (A) and (B) are reacted with each other in the presence of the component (C). The reaction product plus other ingredients, including (D) an adhesion promoter, a non-essential component (F) filler, and an optional component (G) inhibitor, need to be adhered to a substrate to allow the present invention to be used as a polymerization Oxygen adhesive composition. The compositions (A) to (E) are hardened to a substrate, however, the adhesion temperature is much higher than the hardening temperature. Due to the difference in temperature, the manufacturer cannot confirm the adhesive properties before the parts are manufactured. The adhesion temperature is lowered to the hardening temperature by the addition of the adhesion catalyst (E).

The adhesive catalyst is present in the form of microscopic particles and has an average particle diameter of 0.01 to 100 μm or 0.01 to 50 μm. The adhesion catalyst (E) can be formed by a single layer process or a two layer process. Further, the release temperature of the adhesion catalyst (E) is from 35 ° C to 125 ° C.

The single layer process single layer process comprises melting a heat activated semi-crystalline polymer (E) (a), adding an organometallic condensation catalyst (E) (b) to molten (E) (a), mixing (E) ( a) and (E) (b) to obtain a homogeneous mixture, cooling the homogeneous mixture, adding the cooled homogeneous mixture to a hot aqueous solution to form a hot aqueous mixture, The hot aqueous mixture is emulsified, the hot emulsified aqueous mixture is cooled, and water is removed from the cooled emulsified aqueous mixture to produce a dry powder.

The two-layer process two-layer process comprises melting a heat-activated semi-crystalline polymer (E) (a), preparing a dispersion comprising an organometallic condensation catalyst and a solvent, and comprising an amorphous polymer and a solution of a solvent is combined to form a mixture, and the solvent is removed to form a coated organometallic composition, and the coated organometallic composition is mixed with the thermally activated semi-crystalline polymer (E) (a) Obtaining a homogeneous mixture, cooling the homogeneous mixture, adding the cooled homogeneous mixture to a hot aqueous solution to form a hot aqueous mixture, emulsifying the hot aqueous mixture, cooling the thermally emulsified aqueous mixture, and cooling from The emulsified aqueous mixture removes water to produce a dry powder.

Both of the above procedures use (E) (a) a thermally activated semi-crystalline polymer and (E) (b) at least one organometallic condensation catalyst.

The heat-activated semi-crystalline polymer (E) (a) is selected from the group consisting of polyolefin waxes and natural paraffin waxes. Polyolefin waxes include synthetic paraffin waxes. The polyolefin wax is prepared from a homopolymer of ethylene or propylene or a copolymer of propylene and ethylene or a copolymer of ethylene and propylene or with one or more alpha olefins. The alpha olefin used is a linear or branched olefin having from 3 to 18 carbon atoms or from 3 to 6 carbon atoms. Examples thereof are propylene, 1-butene, 1-hexene, 1-octene or 1-octadecene and styrene. Preferred is ethylene Copolymer with propylene or 1-butene. The content of ethylene in the copolymer is from 70 to 99.9% by weight, preferably from 80 to 99% by weight.

Preferred examples of natural waxes include, but are not limited to, natural waxes selected from the group consisting of palm wax, wax, beeswax, whale wax, water wax, and brown carbon wax.

The organometallic condensation catalyst (E) (b) is at least one organometallic compound MX _k (OR ¹² ) _1-k having the following formula, wherein M is selected from the group consisting of Ti, Al, Zr, Sn, Cu, Ce, Co, Cr, Hf, Mo, Pd, Pt, V and Fe, each X is independently selected from a carboxylate ligand, an organic sulfonate ligand, an organophosphate ligand, a β-ketoate ligand, β- Diketoate ligand, β-ketoester ligand, β-hydroxy acid, α-hydroxy acid, salicyl ligand, fluorine-substituted ligand, and chloride ligand, subscript 1 The oxidation state of M, the subscript text k is a value from 0 to the subscript text 1, each R ¹² is independently hydrogen or a hydrocarbon group selected from a monovalent alkyl group having 1 to 6 carbon atoms, and has 6 to 8 carbons. An aryl group of an atom or a fluorenylalkyl group having the formula -(SiO) _m R ¹⁴ wherein the subscript m is a value of 1 to 8, and R ¹⁴ is independently selected from a hydrogen atom or a monovalent having 1 to 6 carbon atoms alkyl.

Examples of the alkyl group wherein R ¹² is a methyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, and a hexyl group. Examples of the aryl group wherein R ¹² is an aryl group include a phenyl group and a benzyl group.

An example in which R ¹⁴ is an alkyl group having 1 to 6 carbon atoms is as defined above for R ¹² . The subscript text m is a value of 1 to 8 or 1 to 4.

Or R ¹⁴ is independently selected from a hydrogen atom or a monovalent alkyl group having 1 to 6 carbon atoms, or methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl, or Base and ethyl.

X is independently selected from a carboxylate ligand, an organic sulfonate ligand, an organophosphate ligand, a β-ketoate ligand, a β-diketate ligand, a β-ketoester ligand, Β-hydroxy acid, α-hydroxy acid, salicylate ligand, fluorine-substituted ligand, and chloride ligand, or carboxylate ligand, β-diketate ligand, and β-ketone Ester ligand. The carboxylate ligand which can be X has the formula R ¹⁵ COO ^- wherein R ¹⁵ is selected from the group consisting of hydrogen, alkyl, alkenyl and aryl. Examples of the alkyl group which may be R ¹⁵ include an alkyl group having 1 to 18 carbon atoms or 1 to 8 carbon atoms. Examples of the alkenyl group which may be R ¹⁵ include alkenyl groups having 2 to 18 carbon atoms or 2 to 8 carbon atoms, such as a vinyl group, a 2-propenyl group, an allyl group, a hexenyl group, and an octenyl group. Or R ¹⁵ is methyl, 2-propenyl, allyl and phenyl. Non-limiting examples of β-diketonate and β-diketone ester ligands which may be used as X may each have the following structure:

Wherein R ¹⁶ , R ¹⁸ , R ¹⁹ and R ²¹ are selected from the group consisting of alkyl, alkenyl and aryl. Examples of the alkyl group which may be R ¹⁶ , R ¹⁸ , R ¹⁹ and R ²¹ include an alkyl group having 1 to 18 carbon atoms or 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an ethyl trifluoro group, and the like. Tributyl, hexafluoropropyl and undecenyl. Examples of the aryl group which may be R ¹⁶ , R ¹⁸ , R ¹⁹ and R ²¹ include an aryl group having 6 to 18 carbon atoms or 6 to 8 carbon atoms, such as a phenyl group and a tolyl group. Examples of alkenyl groups which may be taken as R ¹⁶ , R ¹⁸ , R ¹⁹ and R ²¹ include alkenyl groups having 2 to 18 carbon atoms or 2 to 8 carbon atoms, such as allyl, hexenyl and octenyl. R ¹⁷ and R ²⁰ are hydrogen or an alkyl group, an alkenyl group and an aryl group. Examples of the alkyl group which may be R ¹⁷ and R ²⁰ include an alkyl group having 1 to 12 carbon atoms or 1 to 8 carbon atoms, such as a methyl group and an ethyl group. Examples of the alkenyl group which may be R ¹⁷ and R ²⁰ include an alkenyl group having 2 to 18 carbon atoms or 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a hexenyl group, and an octenyl group. Examples of the aryl group which may be R ¹⁷ and R ²⁰ include an aryl group having 6 to 18 carbon atoms or 6 to 8 carbon atoms, such as a phenyl group and a tolyl group. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently selected and may be the same or different.

The subscript text 1 is the oxidation state of M, which ranges from 1 to 4. Or the subscript text 1 ranges from 2 to 4.

The subscript text k is a value from 0 to the value of the subscript text 1, or a value from 0 to 2 or 0.

Examples of the organometallic compound which can be used in the present invention include cerium acetyl acetonate, chromium acetyl acetonate, cobalt acetyl acetonate, cerium (trifluoroacetate pyruvate), cerium oxalate pyruvate (IV), Ethyl palladium pyruvate, vanadium acetonate pyruvate, titanium tetrapropoxide, titanium tetrabutoxide, tetrapropoxide zirconia and tetrabutyl zirconia, tripropylene alumina, tributyl alumina, phenyl aluminum oxide, copper ethoxide ( II), methoxyethoxy copper (II) oxide, iron (III) oxide, di-n-butyl di-n-butoxy tin, di-n-butyl dimethoxy tin, Tetra-t-butoxy tin, tri-n-butylethoxy tin, titanium oxide, 2-ethylhexyltitanium oxide, titanium oxide, methoxy titanium oxide, n-tellurium titanium oxide, B Zirconium oxide, 2-ethylhexyl zirconia, 2-methyl-2-buty zirconia, 2-methoxymethyl-2-propenyl zirconia, s-butadiene bis(ethylene acetate), Di-s-butyl alumina acetate ethyl acetate, diisopropylaluminum acetonitrile ethyl acetate, acetamidine acetate 9-octadecyl ester diisopropyl aluminum oxide, acetamethylene acetate allyl titanium triisopropoxide , bis(triethanolamine) titanium diisopropoxide, titanium triisopropoxide, Dichlorodiethylene titania, diisopropoxy bis(2,4-pentate) titanium, diisopropyltitanium bis(tetramethylpimelate), diisopropyltitanium dichloride B Ethyl acetate), methacrylate, triisopropoxide, methacryloxyethylacetate, triisopropoxide, trimethacrylate, methoxyethoxytitanium oxide, ginseng Dioctylphosphorus) titanium isopropoxide, ginseng (dodecylbenzenesulfonate) titanium isopropoxide, titanium ruthenium acetate, (bis-2,2'-(allyloxymethyl)-butane oxidation Zirconium) bis(dioctyl phosphate), zirconium diisopropoxide bis(2,2,6,6-tetramethyl-3,5-pimelate), dimethacrylate zirconium pentoxide, Methyl propylene oxyethyl acetonitrile acetate tri-n-propoxide zirconia and zirconium ethoxide acetate.

Many of the organometallic compounds are available from Gelest (Morrisville, PA USA) or Dorf Ketal (Stafford, TX USA).

The amorphous polymer has a _{Tg of} less than 140 °C. Suitable amorphous polymers include, for example, polystyrene, polycarbonate, polyacrylates, polymethacrylates, elastomers such as styrenic block copolymers such as styrene-isoprene-styrene ( SIS), random and block copolymerization of styrene-ethylene/butylene-styrene block copolymer (SEBS), polybutadiene, polyisoprene, polychloroprene, styrene and dienes (for example, styrene-butadiene rubber (SBR)), ethylene-propylene-diene monomer rubber, natural rubber, ethylene propylene rubber, polyethylene terephthalate (PET). Other examples of the amorphous polymer include, for example, polystyrene-polyethylene copolymer, polyethylene cyclohexane, polyvinyl chloride, thermoplastic polyurethane, aromatic epoxide, amorphous polyester, amorphous Polyamide, acrylonitrile-butadiene-styrene (ABS) copolymer, polyphenylene oxide alloy, impact polystyrene, polystyrene copolymer, polymethyl methacrylate (PMMA), fluorination Elastomer, polydimethyl siloxane, amorphous fluoropolymer, amorphous polyolefin, polyphenylene oxide, polyphenylene oxide-polystyrene alloy, copolymer containing at least one amorphous component And mixtures thereof.

The component (E) is present in an amount of from 0.5 to 5 or from 1 to 3 parts by weight based on 100 parts by weight of the component (A).

Adhesion Catalyst (E) Preparation The adhesive catalyst (E) is prepared in a single layer process or a two-layer process. The single layer process comprises the steps of: melting a previously described thermally activated semi-crystalline polymer (E) (a), adding a preceding organometallic condensation catalyst (E) (b) to the molten (E) (a), Mixing (E) (a) and (E) (b) to obtain a homogeneous mixture, cooling the homogeneous mixture, adding the cooled homogeneous mixture to a hot aqueous solution to form a hot aqueous mixture, emulsifying the hot aqueous The mixture, the hot emulsified aqueous mixture is cooled, and water is removed from the cooled emulsified aqueous mixture to produce a dry powder.

The two-layer process includes the steps of: melting a heat-activated semi-crystalline polymer (E) (a), preparing a dispersion comprising an organometallic condensation catalyst and a solvent, and comprising an amorphous polymer And a solution of the solvent is combined to form a mixture, and the solvent is removed to form a coated organometallic composition, and the coated organometallic composition is mixed with the thermally activated semi-crystalline polymer (E) (a) Obtaining a homogeneous mixture, cooling the homogeneous mixture, adding the cooled homogeneous mixture to a hot aqueous solution to form a hot aqueous mixture, emulsifying the hot aqueous mixture, cooling the hot-emulsified aqueous mixture, and cooling from The emulsified aqueous mixture removes water to produce a dry powder.

The above process uses an aqueous melt-emulsification-cooling (MEC) process. In the MEC process, the heat-activated semi-crystalline polymer (E) (a) is heated from 40 ° C up to 200 ° C to melt the heat-activated semi-crystalline polymer (E) (a). The organometallic condensation catalyst (E) (b) is then introduced into the thermally activated semi-crystalline polymer (E) (a) in one of two processes. In the first process, a solvent-free organometallic condensation catalyst (E) (b) is added to the thermally activated semi-crystalline polymer (E) (a) and mixed until a homogeneous mixture is formed. In the second process, the organometallic condensation catalyst (E)(b) is coated with an amorphous polymer and added to the thermally activated semi-crystalline polymer (E)(a), and mixed until a homogeneous mixture is formed. . The method of coating the organometallic condensation catalyst (E) (b) with an amorphous polymer can be carried out by a spray drying method using a suitable solvent to obtain uniformly coated catalyst particles. In either method, the homogeneous mixture of the first process or the second process is cooled to between 5 ° C and 80 ° C.

In the second process, the amorphous polymer has a _{Tg of} less than 140 °C. Suitable amorphous polymers include, for example, polystyrene, polycarbonate, polyacrylates, polymethacrylates, elastomers such as styrenic block copolymers such as styrene-isoprene-styrene ( SIS), random and block copolymerization of styrene-ethylene/butylene-styrene block copolymer (SEBS), polybutadiene, polyisoprene, polychloroprene, styrene and dienes (for example, styrene-butadiene rubber (SBR)), ethylene-propylene-diene monomer rubber, natural rubber, ethylene propylene rubber, polyethylene terephthalate (PET). Other examples of the amorphous polymer include, for example, polystyrene-polyethylene copolymer, polyethylene cyclohexane, polyvinyl chloride, thermoplastic polyurethane, aromatic epoxide, amorphous polyester, amorphous Polyamide, acrylonitrile-butadiene-styrene (ABS) copolymer, polyphenylene oxide alloy, impact polystyrene, polystyrene copolymer, polymethyl methacrylate (PMMA), fluorination Elastomer, polydimethyl siloxane, amorphous fluoropolymer, amorphous polyolefin, polyphenylene oxide, polyphenylene oxide-polystyrene alloy, copolymer containing at least one amorphous component And mixtures thereof.

The amorphous polymer is combined with a solvent to form a solution. A dispersion of the organometallic condensation catalyst (E) (b) and a solvent is added to the solution. A suitable solvent can be easily removed when the amorphous polymer and the solvent and the solution of the organometallic condensation catalyst (E) (b) dispersion and the solvent are treated by a spray drying method for removing the solvent. The coated organometallic composition is formed after solvent removal. Suitable solvents are, for example, low molecular weight ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone and methyl n-butyl ketone; and low molecular weight ethers, whether symmetrical or Asymmetry, for example, is like diethyl ether and methyl ethyl ether.

In either method, the cooled homogeneous phase mixture is then added to the hot water surfactant solution (the temperature of which is at most the boiling point of the solution) to obtain a hot mixture. The surfactant may be cationic (based on quaternary ammonium cations), anionic (based on sulfuric acid, sulfonic acid or carboxylate anions), nonionic or amphoteric. Examples of surfactants include, but are not limited to, sodium dodecyl sulfate (SDS) and other alkyl sulfates, sodium lauryl polyoxyether sulfate (also known as sodium lauryl ether sulfate (SLES)), alkyl benzene sulfonate. Acid, soap, fatty acid salt, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC) and other alkyltrimethylammonium salts, cetylpyridinium chloride (CPC), poly Oxidized bovine amine (POEA), benzalkonium chloride (BAC), benzethonium chloride (BZT), zwitterionic (amphoteric), dodecyl betaine, dodecyl dimethylamine oxide, alkyl hydrazine Copolymer of amine betaine, coco ampho glycinate, nonionic alkyl poly(ethylene oxide), poly(ethylene oxide) and poly(propylene oxide) (commercial name) Is Poloxamers, Pluronics or Poloxamines), alkyl polyglucosides, including: octyl glucoside, thioglycoside, fatty alcohol, cetyl alcohol, oleyl alcohol, cocoamine MEA, cocoamine DEA, sorbitol ester or A fatty acid or a combination thereof. The surfactant is present in the aqueous solution in an amount of from 0.25 to 3% by weight.

In either method, the hot mixture is subsequently emulsified by mechanical agitation. Then it was cooled to below 45 °C. Water is then removed from the cooled emulsified mixture to obtain (E) a powder. The method of removing water may be selected from the group consisting of freeze drying, spray drying, spray cooling, and filtration. In the first process, the final particles comprise a catalyst having a single coating, while in the second process, the final particles comprise a catalyst having two different coatings.

Non-essential components In addition to the components (A) to (E), one or more optional components may be added to the composition. Suitable non-essential ingredients include (F) fillers, (G) inhibitors, (H) void reducing agents, (I) pigments, (J) rheology modifiers, (K) spacers, and combinations thereof.

(F) Filler Non-essential component (F) is a reinforcing and compatibilizing inorganic filler. Examples of the aforementioned inorganic filler (F) are as follows: glass fiber, mineral fiber, alumina fiber, ceramic fiber containing alumina and alumina, boron fiber, zirconium fiber, tantalum carbide fiber, metal fiber or other fibrous filler Agent; molten bauxite, crystalline bauxite, precipitated bauxite, fume bauxite, bake bauxite, zinc oxide, baking clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, hydroxide Aluminum, magnesium hydroxide, barium sulfate, titanium dioxide, aluminum nitride, boron nitride, tantalum carbide, aluminum oxide, magnesium oxide, titanium oxide, cerium oxide, kaolin, mica, zirconium and other powdery fillers. These fillers may be used in combination of two or more. Or the filler (F) is spherical alumina having an average particle diameter of 0.1 to 40 μm.

In another embodiment, the filler is a thermally conductive filler that is used to provide conductivity to the compositions of the present invention. It may be, for example, aluminum powder, copper powder, nickel powder or other metal powder; alumina powder, magnesium oxide powder, cerium oxide powder, chromium oxide powder, titanium oxide powder or the like metal oxide powder; boron nitride powder, nitrogen Aluminum powder or similar nitride powder; boron carbide powder, titanium carbide powder, tantalum carbide powder or similar metal carbide powder; metal oxide powder for coating it with a metal-containing substance to provide conductivity to the surface Or a mixture of two or more of the above. Thermally conductive filler The particles may have a spherical shape, a circular shape, a needle shape, a disk shape, a rod shape or an irregular shape. If the crosslinked body of the composition or the composition needs to have electrical insulation, it is preferred to use a metal oxide type powder, a metal nitride type powder or a metal carbonate type powder, particularly an alumina powder. The average particle diameter of the thermally conductive filler is not particularly limited, but it is recommended that the average particle diameter is from 0.1 to 100 μm and preferably from 0.1 to 50 μm. If alumina powder is used as the thermal conductive filler, it is recommended that the thermal conductive filler be a spherical or round alumina powder having an average particle diameter of 5 to 50 μm and a spherical or irregularly shaped alumina powder having an average particle diameter of 0.1 to 5 μm. mixture. Further, it is recommended that in the mixture of the components, the former accounts for 30 to 90% by weight and the latter accounts for 10 to 70% by weight.

The component (F) is present in an amount of 10 to 200 and or 75 to 150 parts by weight per 100 parts by weight of the component (A).

(G) Inhibitor The self-adhesive curable polyoxyxene adhesive composition of the present invention may optionally include an inhibitor (G). Ingredient (G) is any material known or useful for inhibiting the catalytic activity of component (C). As used herein, a term inhibitor is a material that inhibits catalyst activity at room temperature but does not affect the properties of the catalyst at elevated temperatures. Examples of suitable inhibitors include ethylenically or aromatic unsaturated decylamines, acetylenic compounds, thiolated acetylenic compounds, ethylenically unsaturated isocyanates, olefin oxiranes, unsaturated hydrocarbon monoesters and diesters, conjugated olefins. - alkyne, hydroperoxide, nitrile and diazocyclopropane.

Typical inhibitors include acetylenic alcohols, examples of which are 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol , 2-ethynyl-isopropanol, 2-ethynyl-butan-2-ol, and 3,5-dimethyl-1-hexyn-3-ol, thiolated acetylenic alcohol, examples of which are trimethyl (3,5-Dimethyl-1-hexyn-3-oxy)decane, dimethyl-bis-(3-methyl-1-butynyloxy)decane, methylvinyl bis (3 -Methyl-1-butyn-3-oxy)decane and ((1,1-dimethyl-2-propynyl)oxy)trimethylnonane, not sufficient And carboxylic acid esters, examples of which are diallyl maleate, dimethyl maleate, diethyl fumarate, diallyl fumarate and bis-2- Methoxy-1-methylethyl maleate, mono-octyl maleate, mono-isooctyl maleate, mono-allyl maleate, mono- Methyl maleate, mono-ethyl fumarate, mono-allyl fumarate and 2-methoxy-1-methylethyl maleate Examples of conjugated alkene-alkynes are 2-isobutyl-1-butene-3-yne, 3,5-dimethyl-3-hexene-1-yne, 3-methyl-3-pentene 1-yne, 3-methyl-3-hexene-1-yne, 1-ethynylcyclohexene, 3-ethyl-3-butene-1-yne, and 3-phenyl-3-butene 1-yne, vinylcyclodecane, such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, and the aforementioned conjugated alkyne and the aforementioned A mixture of vinylcyclodecanes. Typical inhibitors are diallyl maleate, bis-2-methoxy-1-methylethyl maleate, 1-ethynyl-1-cyclohexanol, and 3,5- Dimethyl-1-hexyn-3-ol.

The component (G) is present in an amount of from 0.5 to 5 or from 1 to 3 parts by weight per 100 parts by weight of the component (A).

(H) The void reducing agent component (H) is a void reducing agent. The amount of component (H) added to the composition is sufficient to reduce voids. Suitable void-reducing agents are known in the art and are commercially available, see, for example, EP 0 850 997 A2 and U.S. Patents 4,273,902 and 5,684,060. Suitable void reducing agents may include zeolites, anhydrous aluminum sulfate, molecular sieves (preferably having a pore size of 10 Å or less), diatomaceous earth, silicone, activated carbon, palladium compounds, such as palladium metal, palladium metal, supported on a substrate (eg, Carbon or alumina) and organic palladium compounds.

(I) The pigment component (I) is a pigment. The amount of the component (I) added to the composition depends on the kind of the selected pigment. The amount of the component (I) added to the composition may be 0.001% to 30% by weight of the composition. Pigments are known in the art and are commercially available. Suitable pigments include carbon black (eg, LB-1011C carbon black, available from Williams), chromium oxide pigments (eg, Harcros G-6099), titanium dioxide (eg, available from DuPont), and UV reactive dyes (eg, (thiophene diyl)). Bis(tert-butyl benzoate Azole), available from Ciba Specialty Chemicals under the trade name UVITEX OB).

(J) The rheology modifier component (J) is a rheology modifier. A rheology modifier can be added to alter the rocking properties of the composition. Examples of component (J) are flow control additives; reactive diluents; anti-settling agents; alpha olefins; hydroxyl terminated polyoxyn organic copolymers including, but not limited to, hydroxyl terminated polyepoxy propylene-dimethyl oxime An alkane copolymer; and combinations thereof.

(K) The spacer component (K) is a spacer. The spacer may include organic particles, inorganic particles, or a combination thereof. The spacer can be thermally conductive, electrically conductive, or both. The spacer may have a particle size of from 25 micrometers to 250 micrometers. The spacer can include monodisperse beads. The amount of ingredient (K) depends on various factors including particle distribution, pressure applied when the composition is placed, placement temperature, and other factors. The composition may contain up to 15% or up to 5% of the ingredient (K).

Other non-essential ingredients may be added with other non-essential ingredients, which are additionally added or used to replace all or part of the aforementioned ingredients, provided that the non-essential ingredients do not prevent the composition from hardening to form the aforementioned preferred adhesion and chemical resistance. Polyoxyl product. Examples of other non-essential ingredients include, but are not limited to, acid acceptors; antioxidants; stabilizers such as magnesium oxide, calcium hydroxide, metal salt additives (as disclosed in EP 0 950 685 A1), thermal stabilizers, and ultraviolet (UV) a stabilizer; a flame retardant; a thiolating agent such as 4-(trimethyldecyloxy)-3-propen-2-one and N-(t-butyldimethylmethyl)-N- Methyl trifluoroacetamide; dehydrating agent such as zeolite, anhydrous aluminum sulfate, molecular sieve (preferably having a pore size of 10 Å or less), diatomaceous earth, tannin and activated carbon; and a foaming agent such as water, methanol, ethanol , isopropanol, benzyl alcohol, 1,4-butanediol, 1,5-pentanediol, 1,7-g Glycols and sterols.

The following is a representative example of the formation of the adhesive catalyst (G).

Example 1 - Single Layer Process 50 parts of heat activated semi-crystalline polymer (E) (a), which is Polywax 655, available from Baker Petrolite and having a molecular weight of 655, was added to a mixing vessel. The semi-crystalline polymer is heated until it is melted. 50 parts of the organometallic condensation catalyst (E) (b), which is ground cerium zirconium pyruvate (GZAA), was added to the molten polymer. The contents were mixed by hand to obtain a homogeneous mixture, which was then cooled. A hot water surfactant solution containing 890 parts water and 10 parts cetyltrimethylammonium chloride was prepared, and the cooled mixture was added to the hot surfactant solution and mixed until the homogeneous mixture melted. The emulsion was mixed using a Silverson rotor stator mixer at 5000 revolutions per minute (rpm) for 10 minutes. The emulsion was cooled to room temperature while stirring with a top mixer. Dry powder was obtained by freeze drying.

Example 2 - Two-layer process In this example, the organometallic condensation catalyst (E) (b) was coated with an amorphous polymer using a spray drying process. An amorphous polymer of polymethyl methacrylate (PMMA) (0.6 wt/vol%) was dissolved in acetone. The organometallic condensation catalyst (E) (b), which is 2.4 wt/vol% of ground cerium zirconium pyruvate, was added to the acetone solution. The contents were mixed and spray dried to yield GZAA coated with PMMA. 40 parts of the heat-activated semi-crystalline polymer (E) (a), which is a synthetic paraffin 80, was heated until it was melted. 40 parts of PMMA coated with GZAA were added to the molten (E) (a). The contents were mixed by hand to obtain a homogeneous mixture, which was then cooled. A hot water surfactant solution containing 890 parts water and 10 parts cetyltrimethylammonium chloride was prepared, and the cooled mixture was added to the hot surfactant solution and mixed until the homogeneous mixture melted. The emulsion was mixed using a Silverson rotor stator mixer at 5000 revolutions per minute (rpm) for 10 minutes. Cool the emulsion to room temperature while stirring with a top mixer mix. Dry powder was obtained by freeze drying.

The following Examples 3 and 4 are used to illustrate the invention because they contain components (A) to (E).

Example 3 100 parts of an organic polydecane resin (substantially composed of CH ₂ =CH(CH ₃ ) ₂ SiO _1/2 units, (CH ₃ ) ₃ SiO _1/2 units, and SiO _4/2 units, Wherein the CH ₂ =CH(CH ₃ ) ₂ SiO _1/2 unit together with the molar ratio of the (CH ₃ ) ₃ SiO _1/2 unit to the SiO _4/2 unit is 0.7, and the weight average molecular weight of the resin is 22,000, polydisperse 5 as a component and containing 1.8% by weight (5.5 mol%) of vinyl) as component (A), 6.8 parts of trimethyldecyloxy-terminated poly(dimethyloxane/methylhydroquinoxane) ) (having an average of 3 dimethyl methoxyoxane units per molecule and 5 methylhydroquinone units, and containing 0.8% of hydrogen atoms bonded to hydrazine) as a mixture of component (B) and 0.3 parts (Platinum (IV) complex containing 1% 1,1-divinyl-1,1,3,3-tetramethyldioxane, 92% dimethylvinyl decyloxy terminated Polydimethylsiloxane (viscosity 0.45 Pa.s at 25 ° C) and 7% tetramethyldivinyldioxane) as a mixture of component (C) and 2.5 parts (containing 46% of 3) - glycidoxypropyltrimethoxydecane, 40% hydroxy-terminated methylvinyl fluorene, 7% cyclomethylvinyl decane Hydroxy-terminated methylvinyl siloxane and the silicon 3-glycidoxypropyl 6% a reaction product of trimethoxy Silane and 1% methanol) as the component (D) (wherein the viscosity of the mixture 0.000015m ² / s (15 cSt) at 25 ° C, 60 parts of hexamethyldioxane treated alumina (with a BET surface area of 200 and 250 m ² /g (m ² /g), a pH of 4.5 to 6.5 and The moisture content measured by gravity analysis at 105 ° C does not exceed 0.6%, and the trade name is Cab-O-Sil TS-530, purchased from Cabot Corporation as component (F), 0.35 parts of double -2- Methoxy-1-methylethyl maleate was added as a component (G) and 0.86 parts of component E as a product of Example 1 to a mixing vessel. The contents were mixed using a dispersion mixer.

Example 4 The procedure of Example 3 was repeated except that 0.86 parts of component E was used as the product of Example 2 (double layer process) instead of 0.86 parts of component E as the product of Example 1 (single layer process).

A comparative example was also prepared using the weights of the above Examples 3 and 4, but the ingredient (E) was absent.

The compositions of Examples 3 and 4 and the comparative examples were separately applied to a polybutylene terephthalate (Ticona Celanex ® 3300D PBT) plate, followed by venting for 5 minutes to remove air bubbles which may be introduced during the application. A No. 18 copper wire was placed in the adhesive composition at each end of the PBT board. A 76.2 micron (3 mil) aluminum foil was then placed over the sample. The sample was placed on a hot gradient hot plate and allowed to harden for one hour. Allow the sample to cool to room temperature. The aluminum foil was then peeled off using a 90° peel adhesion test method for each sample. Based on the measured displacement during the peel test and the linear equation derived from the applied thermal gradient, the temperature at which the adhesive hardens (T _C ) and the temperature adhered to the substrate (T _A , expressed as a cohesive failure mode) are calculated.

Further, the composition was aged at 5 ° C for 6 months and tested again according to the above method.

Table 1 below shows the T _C °C and T _A ° _{C for} both cases at the initial preparation of the plate sample and during the 6 month ripening period.

Embodiments of the invention also include the following numbering aspects:

2. The composition of aspect 1, wherein component (A) comprises an alkenyl-substituted organopolyoxane having the formula R ¹ ₃ SiO(R ¹ ₂ SiO) _a (R ¹ R ² SiO) _b SiR ¹ ₃ , R ³ ₂ R ⁴ SiO(R ³ ₂ SiO) _c (R ³ R ⁴ SiO) _d SiR ³ ₂ R ⁴ or a combination thereof; wherein the subscript letter a has an average value of 0 to 2000, subscript text b Having an average value of at least 0.1 to 2000, each R ¹ is independently a hydrocarbon group, each R ² is independently an unsaturated monovalent organic group, and the subscript c has an average value of at least 0.1 to 2000, and the subscript The text d has an average value of from 0 to 2000, and each of the R ³ groups is independently a hydrocarbon group, and each of the R ⁴ groups is independently an unsaturated monovalent group.

3. The composition of any of the preceding aspects, wherein component (A) comprises an MQ resin selected from the group consisting of R ⁵ ₃ SiO _1/2 units and SiO _4/2 units, a unit selected from R ⁵ SiO _3/2 units and R ⁵ ₂ SiO _2/2 unit TD resin, one MT resin selected from R ⁵ ₃ SiO _1/2 unit and R ⁵ SiO _3/2 unit, and one selected from R ⁵ ₃ SiO _1/2 unit, R ⁵ SiO _{3 a /} D unit and an MTD resin of R ⁵ ₂ SiO _2/2 unit or a combination thereof, wherein each R ⁵ is a monovalent organic group having 1 to 20 carbon atoms, and the resin comprises an average of 3 to 30 mole percent Unsaturated organic groups.

4. The composition of any of the preceding aspects, wherein component (B) comprises a oxoxane unit selected from the group consisting of HR ⁶ ₂ SiO _1/2 , R ⁶ ₃ SiO _1/2 , HR ⁶ SiO _2/2 , R ⁶ ₂ SiO _2/2 , R ⁶ SiO _3/2 , SiO _4/2 or a combination thereof; wherein each R ⁶ is independently selected from the group consisting of aliphatically unsaturated monovalent organic groups.

A composition according to any one of the preceding aspects, wherein the component (B) comprises an organohydrogen polyoxymethane compound having the formula: R ⁷ ₃ SiO(R ⁷ ₂ SiO) _e (R ⁷ HSiO) _f SiR ⁷ ₃ , R ⁸ ₂ HSiO(R ⁸ ₂ SiO) _g (R ⁸ HSiO) _h SiR ⁸ ₂ H or a combination thereof, wherein the subscript text e has an average value of 0 to 2000, and the subscript word f has an average value of 2 Up to 2000, each R ⁷ system is independently a non-aliphatic unsaturated monovalent organic group, the subscript g has an average value of 0 to 2000, and the subscript h has an average value of 0 to 2000, and each R ^{The 8} series is independently a monovalent organic group free of aliphatic unsaturation.

6. The composition of any of the preceding aspects, wherein the hydrazine hydrogenation catalyst (C) comprises a platinum metal, a ruthenium metal or an organometallic compound.

7. The composition of any of the preceding aspects, wherein component (D) is selected from the group consisting of monounsaturated alkoxydecane, monoepoxy functional alkoxydecane, monoepoxy functional alkoxyne or combinations thereof.

8. The composition of any of the preceding aspects, wherein component (D) comprises an alkoxydecane having the formula R ⁹ _i Si(OR ¹⁰ ) _(4-i) wherein the subscript i is 1, 2 or 3, each R ⁹ is independently a monovalent organic group, provided that at least one R ⁹ is an unsaturated organic group or an epoxy functional group, and each R ¹⁰ is independently one having at least one carbon. An unsubstituted saturated hydrocarbon group of an atom.

9. The composition of any of the preceding aspects, wherein component (D) is selected from the group consisting of 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, (ring) Oxycyclohexyl)ethyldimethoxydecane, (epoxycyclohexyl)ethyldiethoxydecane, vinyltrimethoxydecane, allyltrimethoxydecane, allyltriethoxydecane, Hexenyltrimethoxydecane, undecyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3- Propylene methoxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxy Decane and its combination.

10. The composition of any of the preceding aspects, wherein component (D) is selected from the group consisting of a reaction product of a monohydroxyl-terminated polyorganosiloxane and an epoxy functional alkoxysilane or an unsaturated alkoxydecane, Physical conjugates of monohydroxy terminated polyorganosiloxanes with an epoxy functional alkoxy decane or monounsaturated alkoxy decane and combinations thereof.

11. The composition of any of the preceding aspects, wherein the thermally activated semi-crystalline polymer (E) (a) is selected from the group consisting of synthetic polyolefin waxes, natural paraffin waxes, and synthetic paraffin waxes.

12. The composition of any of the preceding aspects, wherein the thermally activated semi-crystalline polymer (E) (a) is selected from the group consisting of synthetic polyethylene waxes and synthetic paraffins.

13. The composition of any of the preceding aspects, wherein the organometallic condensation catalyst (E)(b) is represented by the formula MX _k (OR ¹² ) _1-k

Wherein M is selected from the group consisting of Ti, Al, Zr, Sn, Cu, Ce, Co, Cr, Hf, Mo, Pd, Pt, V, and Fe, and each X system is independently selected from a carboxylate ligand and an organic sulfonate coordination. Suborganic, organophosphate ligand, β-ketoate ligand, β-diketate ligand, β-ketoester ligand, β-hydroxy acid, α-hydroxy acid, salicyl ligand, The fluorine-substituted ligand and the chloride ion ligand, the subscript text 1 is the oxidation state of M, the subscript text k is the value from 0 to the subscript text 1, and each R ¹¹ is independently one with 1 to 18 An alkyl group of a carbon atom, each R ¹² is independently selected from a monovalent alkyl group having 1 to 6 carbon atoms, an aryl group, and a polyether group (R ¹³ O) _m R ^{14 of the} following formula.

Wherein the subscript text m is 1 to 4, each R ¹³ is independently selected from a divalent alkylene group having 2 to 6 carbon atoms, and R ¹⁴ is selected from a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Monovalent alkyl group.

14. The composition of any of the preceding aspects, wherein the organometallic condensation catalyst (E)(b) has a ligand selected from the group consisting of a single tooth mass, a double tooth mass, a tridentate group, and a multidentate group. Its combination.

A composition according to any one of the preceding aspects, wherein the organometallic compound (E) (b) in the component (E) is in the range of from 1 to 75 wt.%.

16. The composition of any of the preceding aspects, wherein the component (E) has an average particle diameter of from 0.01 to 100 μm.

17. The composition of any of the preceding aspects, wherein component (E) (a) has an average particle size of less than 50 microns.

18. The composition of any of the preceding aspects, wherein the component (E) has a release temperature of from 35 ° C to 125 ° C.

19. A method of producing an adhesive catalyst (E) according to any of the foregoing aspects, comprising forming the adhesive catalyst in a single layer process or a two layer process.

20. The method of claim 19, wherein the adhesion catalyst (E) is formed by a single layer process comprising melting a heat activated semi-crystalline polymer (E) (a) and adding an organometallic condensation Catalyst (E) (b) to the molten (E) (a), mixing (E) (a) and (E) (b) to obtain a homogeneous mixture, cooling the homogeneous mixture, which will be cooled The homogeneous mixture is added to a hot aqueous solution to form a hot aqueous mixture, the hot aqueous mixture is emulsified, the hot emulsified aqueous mixture is cooled, and water is removed from the cooled emulsified aqueous mixture to produce a dry powder.

21. The method of aspect 19, wherein the adhesive catalyst (E) is formed by a two-layer process a method comprising: melting a heat-activated semi-crystalline polymer (E) (a), preparing a dispersion comprising an organometallic condensation catalyst (E) (b) and a solvent, and comprising an amorphous material a solution of a polymer and a solvent are combined to form a mixture, and the solvent is removed to form a coated organometallic composition, and the coated organometallic composition is mixed with the thermally activated semi-crystalline polymer (E) (a) obtaining a homogeneous mixture, cooling the homogeneous mixture, adding the cooled homogeneous mixture to a hot aqueous solution to form a hot aqueous mixture, emulsifying the hot aqueous mixture, cooling the thermally emulsified aqueous mixture, and Water is removed from the cooled emulsified aqueous mixture to produce a dry powder.

22. The method of aspect 21, wherein the amorphous polymer is selected from the group consisting of polyacrylates, polymethacrylates, polystyrenes, polycarbonates, and mixtures thereof.

23. The method of aspect 21, wherein the amorphous polymer has a glass transition temperature Tg of less than 140 °C.

24. The method of aspect 20 or 21, wherein the hot aqueous solution comprises from 0.25 to 3.0 wt% of a surfactant, and wherein the temperature of the hot aqueous solution is at most the boiling point of the solution.

25. The method of aspect 20 or 21 wherein the means for removing water is selected from the group consisting of freeze drying, spray drying, spray cooling, and filtration.

While the invention has been described in terms of the preferred embodiments and aspects thereof therefore, It is to be understood that the invention disclosed herein is intended to cover such modifications and may fall within the scope of the appended claims.

Claims (10)

A self-adhesive curable polyoxyxene adhesive composition comprising: (A) an alkenyl-substituted organopolyoxyalkylene having an average of at least 0.1 alkenyl groups per molecule; (B) an organohydrogen polyoxyalkylene, It contains, on average, at least 1.5 hydrogen atoms bonded to ruthenium in an amount such that the total number of hydrogen atoms bonded to ruthenium in component (B) and the total number of all alkenyl groups in component (A) a molar ratio of less than 1.3:1; (C) a hydrogenation catalyst; (D) an adhesion promoter; and (E) an adhesion catalyst in the form of microscopic particles, comprising: (a) a thermally activated semi-crystalline polymer, And (b) at least one organometallic condensation catalyst having a metal M, wherein the organometallic condensation catalyst is blended or coated with the thermally activated semi-crystalline polymer. The composition of claim 1, wherein the component (A) comprises an alkenyl-substituted organopolyoxane having the formula R ¹ ₃ SiO(R ¹ ₂ SiO) _a (R ¹ R ² SiO) _b SiR ¹ ₃ , R ³ ₂ R ⁴ SiO(R ³ ₂ SiO) _c (R ³ R ⁴ SiO) _d SiR ³ ₂ R ⁴ , or a combination thereof; wherein the subscript letter a has an average value of 0 to 2000, subscript text b The average value is at least 0.1 to 2000, each R ¹ is independently a hydrocarbon group, and each R ² is independently an unsaturated monovalent organic group, the subscript c has an average value of at least 0.1 to 2000, and the subscript d has an average value. The value is from 0 to 2000, each R ³ is independently a hydrocarbon group, and each R ⁴ is independently an unsaturated monovalent group; or wherein the component (A) comprises a unit selected from the group consisting of R ⁵ ₃ SiO _1/2 units and SiO _4/2 units. MQ resin, TD resin selected from R ⁵ SiO _3/2 unit and R ⁵ ₂ SiO _2/2 unit, MT resin selected from R ⁵ ₃ SiO _1/2 unit and R ⁵ SiO _3/2 unit, selected from R ⁵ ₃ SiO _1/2 units, R ⁵ SiO _3/2 units and R ⁵ ₂ SiO _2/2 units of MTD resin or a combination thereof, wherein each R ⁵ is a monovalent having 1 to 20 carbon atoms of an organic group, and The resin contains an average of 3 to 30 mole percent of unsaturated organic groups The composition according to any of the preceding claims, wherein the component (B) comprises a member selected from the group consisting of HR ⁶ ₂ SiO _1/2 , R ⁶ ₃ SiO _1/2 , HR ⁶ SiO _2/2 , R ⁶ ₂ SiO _{2 a oxoxane} unit of _/2 , R ⁶ SiO _3/2 , SiO _4/2 or a combination thereof; wherein each R ⁶ is independently selected from a non-aliphatic unsaturated monovalent organic group; or wherein component (B) comprises an organic a hydrogen polyoxymethane compound having the formula: R ⁷ ₃ SiO(R ⁷ ₂ SiO) _e (R ⁷ HSiO) _f SiR ⁷ ₃ , R ⁸ ₂ HSiO(R ⁸ ₂ SiO) _g (R ⁸ HSiO) _h SiR ⁸ ₂ H, or a combination thereof, wherein the subscript text e has an average value of 0 to 2000, the subscript letter f has an average value of 2 to 2000, and each R ⁷ system is independently a monovalent organic group free from aliphatic unsaturation. The subscript text g has an average value of 0 to 2000, the subscript word h has an average value of 0 to 2000, and each R ⁸ is independently a monovalent organic group free from aliphatic unsaturation. The composition of claim 1 wherein component (D) is selected from the group consisting of unsaturated alkoxy decane, epoxy functional alkoxy decane, epoxy functional oxane or combinations thereof; or component (D) An alkoxydecane having the formula R ⁹ _i Si(OR ¹⁰ ) _(4-i) wherein the subscript i is 1, 2 or 3, and each R ⁹ is independently a monovalent organic group, provided that At least one R ⁹ is an unsaturated organic group or an epoxy functional group, and each R ¹⁰ is independently an unsubstituted saturated hydrocarbon group having at least 1 carbon atom; or wherein component (D) is selected from 3 Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, (epoxycyclohexyl)ethyldimethoxydecane, (epoxycyclohexyl)ethyldi Ethoxy decane, vinyl trimethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, hexenyl trimethoxy decane, undecyl trimethoxy decane, 3-methyl Propylene methoxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethyl Oxydecane and combinations thereof; or wherein component (D) is selected from the group consisting of a reaction product of a hydroxyl terminated polyorganosiloxane and an epoxy functional alkoxysilane or an unsaturated alkoxydecane, a hydroxyl terminated polyorganoquinone Physical conjugates of oxane with epoxy functional alkoxy decane or unsaturated alkoxy decane and combinations thereof. The composition of claim 1, wherein the heat-activated semi-crystalline polymer (E) (a) is selected from the group consisting of synthetic polyolefin waxes, natural paraffin waxes, and synthetic paraffin waxes; or wherein the heat-activated semi-crystalline polymer ( E) (a) is selected from the group consisting of synthetic polyethylene wax and synthetic paraffin; or wherein the organometallic condensation catalyst (E) (b) is represented by the following formula MX _k (OR ¹² ) _1-k wherein M is selected from Ti , Al, Zr, Sn, Cu, Ce, Co, Cr, Hf, Mo, Pd, Pt, V and Fe, each X series is independently selected from a carboxylate ligand, an organic sulfonate ligand, an organic phosphate Position, β-ketoate ligand, β-diketate ligand, β-ketoester ligand, β-hydroxy acid, α-hydroxy acid, salicyl ligand, coordination with fluorine substitution And the chloride ion ligand, the subscript text 1 is the oxidation state of M, the subscript text k is the value of 0 to the subscript text 1, and each R ¹¹ is independently an alkyl group having 1 to 18 carbon atoms, each R ¹² is independently selected from the group consisting of a monovalent alkyl group having 1 to 6 carbon atoms, an aryl group, and a polyether group (R ¹³ O) _m R ^{14 of the} following formula wherein the subscript m is from 1 to 4, and each R ¹³ is independently Selected from two with 2 to 6 carbon atoms Alkylene group, and R ¹⁴ is selected from a hydrogen atom or a monovalent having from 1 to 6 carbon atoms, the alkyl group; or wherein the organometallic condensation catalyst (E) (b) has a seat with which group selected from a single tooth , a double tooth mass, a tridentate group, and a multidentate group and combinations thereof; or wherein the organometallic compound (E) (b) in the component (E) is in the range of 1 to 75 wt.%; or a component thereof (E) The average particle diameter is 0.01 to 100 μm; or the average particle diameter of the component (E) (a) is less than 50 μm; or the release temperature of the component (E) is 35 ° C to 125 ° C. A method of producing the adhesive catalyst (E) according to claim 1, which comprises forming the adhesive catalyst in a single layer process or a two layer process. The method of claim 6, wherein the adhesive catalyst (E) is formed by a single layer process comprising melting the heat activated semi-crystalline polymer (E) (a) and adding an organometallic condensation catalyst ( E) (b) to the molten (E) (a), mixing (E) (a) and (E) (b) to obtain a homogeneous mixture, cooling the homogeneous mixture, and cooling the homogeneous mixture Adding to the hot aqueous solution to form a hot aqueous mixture, emulsifying the hot aqueous mixture, cooling the thermally emulsified aqueous mixture, and removing water from the cooled emulsified aqueous mixture to produce a dry powder; or wherein the adhesive catalyst (E) is Formed by a two-layer process, the two-layer process includes Melting the heat-activated semi-crystalline polymer (E) (a), preparing a dispersion including the organometallic condensation catalyst (E) (b) and a solvent, and combining it with a solution including an amorphous polymer and a solvent to form a mixture, and removing the solvent to form a coated organometallic composition, mixing the coated organometallic composition with the melted heat-activated semi-crystalline polymer (E) (a) to obtain a homogeneous mixture, and cooling The homogeneous mixture, the cooled homogeneous phase mixture is added to the hot aqueous solution to form a hot aqueous mixture, the hot aqueous mixture is emulsified, the hot emulsified aqueous mixture is cooled, and water is removed from the cooled emulsified aqueous mixture. Dry powder. The method of claim 7, wherein the amorphous polymer is selected from the group consisting of polyacrylates, polymethacrylates, polystyrenes, polycarbonates, and mixtures thereof; or wherein the glass transition temperature of the amorphous polymer The Tg system is less than 140 °C. The method of claim 7 or 8, wherein the hot aqueous solution comprises from 0.25 to 3.0% by weight of a surfactant, and wherein the temperature of the hot aqueous solution is at most the boiling point of the solution. The method of claim 7 or 8, wherein the method of removing water is selected from the group consisting of freeze drying, spray drying, spray cooling, and filtration.