JP2012082429A - Curable coating low in permeability of sulfur containing gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of obtaining a composition substantially impermeable against a gaseous sulfur compound such as hydrogen sulfide, to be applied as a protective coating for various products, in particular, an electronic component, and capable of protecting the various products against an action of the gaseous sulfur compound.SOLUTION: The composition for the coating contains a polyolefin, siloxane or polysiloxane, generates a reaction product of two-component network structure by curing, and is low in a diffusion coefficient of hydrogen sulfide or a diffusion coefficient of methyl mercaptan in 50°C, or both the diffusion coefficients.

Description

  The present invention relates generally to polyisobutylene-containing polymer compositions, including binary network structures and multiblock copolymers useful as coatings. More specifically, the present invention relates to various types, including binary network structures and multiblock copolymers useful as coatings by combining a plurality of polyisobutylene polymer chains with a siloxane compound having two or more SiH moieties. It relates to the synthesis of novel polyisobutylene-containing compositions. Specifically, a two-component network synthesized by combining a polyfunctional polyisobutylene, preferably an allyl-terminated polyisobutylene, with a polyfunctional linear polysiloxane such as a ditelechelic linear SiH-terminated polydimethylsiloxane by hydrosilylation. The structure can be coated on the surface of an electronic device. Similarly, multiblock copolymers can be synthesized by end-linking difunctional allyl-terminated polyisobutylene with a bifunctional SiH-terminated linear polysiloxane such as polydimethylsiloxane by hydrosilylation. Yet another polyisobutylene-containing polymer network is a hydrosilylation of a polyfunctional polyisobutylene, preferably a ditelechelic allyl-terminated polyisobutylene, with a polyfunctional SiH-containing compound, preferably a cyclosiloxane such as hexamethylhexahydrocyclosiloxane. And can be used as a coating.

  The discovery of living cationic polymerization has made it possible to synthesize polyisobutylene (PIB) with controlled molecular weight and quantitative terminal functional groups. Currently, it is known that allyl-terminated polyisobutylene can be end-bound quantitatively by hydrosilylation with a SiH group-containing molecule. This reaction forms a Si—C bond that is stable to hydrolysis. However, previous work on the usefulness of the quantitative end functional groups of polyisobutylene and the ability of allyl-terminated PIBs to be end-linked by hydrosilylation with siloxane compounds has focused on the production of star polymers and star block copolymers. For example, US Pat. No. 5,663,245 teaches the synthesis and properties of multi-arm star polymers in which polyisobutylene arms radiate from a well-defined siloxane core. Star block copolymers have been produced using polyisobutylene-b-polystyrene arms radiating from a well-defined siloxane core. There is very little, if any, research on the usefulness of this synthetic reaction in the production of network structures such as binary and multiblock copolymers.

  The polymer network of the present invention, in particular the binary network (BCN), should be distinguished from the traditional interpenetrating polymer network (IPN). BCN is defined as a single rubber-like elastic network structure in which two kinds of chemically different sequences are covalently bonded, whereas IPN consists of two or more independent unbonded networks. This distinction is significant in that the polymers in IPN are intertwined as two separate networks without chemical bonding. Most binary systems that have been studied previously relate to IPN and few studies have been performed using BCN.

  A multi-block copolymer is similar to BCN in that it consists of two chemically different sequences covalently linked, but it will be apparent that the cross-linking mode differs from that of BCN. A multi-block copolymer is a linear block of two or more kinds of polymers. For example, in the present invention, polyisobutylene (-A-) and bifunctional linear polysiloxane (-B-) are end-bonded to form a multi-block copolymer (- -AB-) n is formed. It should be noted that such a block copolymer is different from a “normal” block copolymer in that the polymers (—A—) and (—B—) are already formed before the end bonds are formed. Is different. However, none of these are crosslinked, rubbery, elastic, and soluble in various solvents, so they are not “two-component network structures” defined as described above. BCN has traditionally been required for two cross-linking components to at least theoretically contribute to the physical and chemical properties of the polymer network. That is, the properties of the two-component network structure reflect the properties of individual components. For example, the two-component network structure containing polyisobutylene and polysiloxane is low in cost, excellent in mechanical properties, extremely low in gas permeability, excellent in environmental resistance, hydrolysis resistance, and high temperature resistance. In contrast to siloxanes, which are known to be relatively expensive and inferior in mechanical properties, they are superior in terms of high gas permeability, low surface energy and biocompatibility. You may be interested.

US Pat. No. 5,663,245 US Patent No. 6005051 U.S. Pat. No. 3,484,468 US Pat. No. 3,159,601 U.S. Pat. No. 3,159,662 U.S. Pat. No. 3,220,972 U.S. Pat. No. 3,715,334 U.S. Pat. No. 3,775,452 U.S. Pat. No. 3,814,730 US Pat. No. 3,635,743 U.S. Pat. No. 3,847,848 US Pat. No. 5,506,289 US Pat. No. 5,922,795 U.S. Pat. No. 5,928,564 US Pat. No. 5,948,339 US Patent No. 6002039 US Pat. No. 6,158,853 US Pat. No. 6,034,199

“Electron Pair Donors in Carbolation Polymerization, III. Carbon Stabilization by External Electron Donors in Isobutylene Polymerization”. al. , J. et al. Macromol. Sci. Chem. , A26, 1099-1114 (1989) “Electrophilic Substitution of Organosilicon Compounds II., Synthesis of Alli- valently quantified by the Quantitative Alkyl , J. et al. Polym, Sci. : Polym. Chem. 25, 3255-3265 (1987) J. et al. L. Spier, “Homogeneous Catalysis of Hydrolysis by Transition Metals”, Advances in Organometallic Chemistry, volume 17, pages 407 thruh. G. A. Stone and R.C. West editors, published by the Academic Press (New York, 1979)

The present invention provides a polymer composition in which two or more chemically distinct components are covalently bonded and is useful as a coating. The present invention also provides a well-defined two-component network or multiblock copolymer comprising a polyfunctional polyisobutylene and a linear polysiloxane such as polydimethylsiloxane useful as a coating. The present invention further provides polymer compositions that are elastomeric and insoluble in solvents. The present invention further provides a method for synthesizing the above two-component network structure by end-linking difunctional allyl-terminated polyisobutylene with polyfunctional SiH-terminated polydimethylsiloxane by hydrosilylation. The present invention further provides a method for synthesizing the multi-block copolymer by end-linking difunctional allyl-terminated polyisobutylene with difunctional SiH-terminated polydimethylsiloxane by hydrosilylation. The present invention synthesizes the polyisobutylene network by end-linking ditelechelic allyl terminated polyisobutylene (or other allyl terminated polyolefin) with a SiH containing compound such as hexamethylhexahydro-cyclosiloxane by hydrosilylation, A method of using the resulting composition as a coating is also provided. At least one or more of the foregoing objectives are achieved by the invention described herein and provide advantages over known techniques for polymer networks and multi-block copolymers, as will be apparent from the remainder of the specification. Become. In general, the present invention provides a composition comprising a hydrosilylation reaction product in which a plurality of multifunctional siloxane compounds having two or more SiH moieties and a plurality of multifunctional allyl terminated polyisobutylenes are combined. The present invention is a two-component network structure comprising a hydrosilylation reaction product in which a plurality of ditelechelic linear polysiloxanes having two or more SiH moieties and a plurality of multifunctional allyl-terminated polyisobutylenes are end-bonded, comprising polyisobutylene and It also provides a binary network having chemical and physical properties determined by both polysiloxanes. The present invention is a multi-block copolymer comprising a hydrosilylation reaction product in which a plurality of ditelechelic linear polysiloxanes having 2 or less SiH moieties and a plurality of ditelechelic allyl terminated polyisobutylenes are end-linked, comprising: Also provided are multi-block copolymers having chemical and physical properties determined by both siloxanes. The present invention further provides a polymer network comprising a hydrosilylation reaction product in which a plurality of polyfunctional siloxane compounds having two or more SiH moieties and a plurality of polyfunctional allyl-terminated polyisobutylenes are bonded. Another object and aspect of the present invention is a polymer network composition useful as a coating comprising combining a plurality of siloxane compounds having two or more SiH moieties and a plurality of multifunctional allyl-terminated polyisobutylenes by hydrosilylation. It can be achieved by synthetic methods.

  The present invention relates to a coating comprising a polymer composition containing a reaction product of polyolefin and siloxane or polysiloxane, wherein the diffusion coefficient of hydrogen sulfide and / or methyl mercaptan at 50 ° C. is low. I will provide a.

  First, the present invention relates to the synthesis of polymer compositions, including binary networks and multiblock copolymers comprising a polyfunctional compound having one or more SiH moieties and a polyfunctional polyisobutylene. More specifically, the present invention utilizes a known hydrosilylation reaction to end-link allyl-terminated polyisobutylenes and SiH-containing molecules such as siloxanes, useful new novel compounds containing polyisobutylene and other polyolefins. The polymer composition is to be obtained. In the present invention, the term “polymer composition” refers to a composition in which two types of chemically different sequences such as polyisobutylene and polysiloxane are covalently bonded. It will be clear that the relevant network structure described in the book is included.

  Binary network structures with well-defined polyisobutylene can be synthesized by end-linking polyfunctional allyl-terminated polyisobutylene with well-defined bifunctional SiH-terminated linear polysiloxane by hydrosilylation. Such a BCN of the present invention is rubbery elastic and insoluble in a solvent, and is considered to have a great ripple effect on the rubber industry.

  Similarly, multi-block copolymers with well-defined polyisobutylene and siloxane can be synthesized by end-linking difunctional allyl-terminated polyisobutylene with bifunctional SiH-terminated linear polysiloxane by hydrosilylation. When using PIB and PDMS, this reaction scheme produces a multi-block PIB / PDMS copolymer, which is illustrated in the following scheme. It is also clear that a new polyisobutylene network is synthesized if the amount of polyisobutylene exceeds the amount of SiH group-containing molecules in the composition. Such polyisobutylene networks include polyfunctional (preferably ditelechelic) allyl-terminated polyisobutylene and SiH-containing siloxane compounds. More specifically, polyisobutylene networks are synthesized by end-linking ditelechelic allyl-terminated polyisobutylene with linear or cyclic hydridosiloxanes or hydrosilanes by hydrosilylation. Such linear or cyclic hydridosiloxanes or hydrosilanes are well known in the art.

  In fact, a well-defined polyisobutylene network is composed of a ditelechelic polyisobutylene having a known number average molecular weight (Mn) and a SiH-containing cyclosiloxane compound having an appropriate functional group (ie, hexamethylhexahydrocyclosiloxane). Synthesized by a hydrosilylation reaction with end linkages, particularly ditelechelic PIB.

It is clear that the ditelechelic PIB component and the siloxane component form a bond. Therefore, if the siloxane component has a sufficient molecular weight and size, the network structure can form a two-component network structure. If the siloxane component composed of cyclosiloxane other than low molecular weight cyclic siloxane (usually volatile) has a sufficient molecular weight and size, a network structure can be formed that does not dissolve in the solvent but swells. To synthesize a polymer composition, a multitelechelic allyl terminated polyisobutylene is first synthesized as is known in the art. The production of allyl-terminated PIB can be accomplished by living polymerizing isobutylene to virtually any chain length (and thus virtually any molecular weight desired), followed by quantitative end functionalization to a terminal olefin group. N as an electron pair donor, N- presence of dimethyl acetamide, by using 2-chloro-2,4,4-trimethylpentane / TiC1 ₄ initiator system, a chlorine terminated polyisobutylene living isobutylene polymerization Obtainable. Details of this method can be found in “Electron Pair Donors in Carbolative Polymerization, III. Carbon Stabilization by External Electron Donors in Isobutylene Polymers”. , J. et al. Macromol. Sci. Chem. , A26, 1099-1114 (1989). After polymerization is complete, allylation of the living polyisobutylene can be achieved by in situ deactivation with excess allyltrimethylsilane, resulting in an allyl-terminated PIB. For more information on this method, "Electrophilic Substitution of Organosilicon Compounds II., Synthesis of Allyl-terminated Polyisobutylenes by Quantitative Alkylation of tert-Chloro-Polyisobutyhlenes with Allyltrimethylsilane", Wilczek et al. , J. et al. Polym, Sci. : Polym. Chem. 25, 3255-3265 (1987). The resulting allyl-terminated PIB can be characterized by H-NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).

  The compositions of the present invention are fully described in US Pat. No. 6,050,051, the disclosure of which is hereby incorporated by reference.

Siloxane polymers can be produced separately from the production of polyisobutylene. For example, difunctional SiH terminated polydimethylsiloxane, can be synthesized by acid-catalyzed equilibration of cyclic tetramer D ₄ in the presence of chain terminating agents tetramethyldisiloxane. Polysiloxanes can be characterized by H-NMR spectroscopy and DSC. If a cyclosiloxane such as hexahydrohexamethylcyclohexasiloxane is desired, it is well known in the art and described in detail in US Pat. No. 3,484,468, the disclosure of which is incorporated herein by reference. It can be produced by hydrolysis of methyldichlorosilane. As used herein, the term siloxane includes siloxane monomers or polymer species having one or more reactive groups that condense on reaction with the olefinic end of a ditelechelic polyolefin. This generally means that the siloxane moiety has one or more, preferably two or more silicon-bonded hydrogen atoms, for example silylhydrides or hydridosiloxanes of the general formula

^{_{M a M H b D c D}} H d T e T H f Q g
In the formula, the silicone structural units M, D, T and Q have the usual definitions as follows.
M = R ¹ R ² R ³ SiO _1/2 ,
M ^H = HR ⁴ R ⁵ SiO _1/2 ,
D = R ⁶ R ⁷ SiO _2/2 ,
D ^H = HR ⁸ SiO _2/2 ,
T = R ⁹ SiO _3/2 ,
T ^H = HSiO _3/2 and Q = SiO _4/2
In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 60 carbon atoms and 1 carbon atom. Selected from the group consisting of ˜60 monovalent organic groups, the subscripts a, b, c, d, e, f and g are b + d + f ≧ 1, preferably b + d + f ≧ 2, more preferably b + d + f ≧ 3, most preferably 0 or a positive integer, provided that b + d + f ≧ 4. The term monovalent organic group having 1 to 60 carbon atoms refers to an organic group in which the carbon-carbon chain is interrupted by a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus. As used herein, the term siloxane is a generic term and includes functionalized and reactive siloxanes.

Since the ditelechelic polyolefins utilized in the coatings of the present invention are reactive, they are reacted to form terminal oxirane groups or terminal epoxide groups, and the hydridosiloxanes described above (eg, M _a M ^H _b D _c D ^H _d T _e T ^H _f Q _g ).

Similarly, terminal carboxylic acid groups can be formed by oxidizing terminal olefin groups. These can be condensed with silanol-containing species such as M _a ^MOH _b D _c D ^OH _{d Te} ^TOH _f Q _g . In this case, the standard structure definition is changed as follows.
M = R ¹ R ² R ³ SiO _1/2 ,
M ^OH = HOR ⁴ R ⁵ SiO _1/2 ,
D = R ⁶ R ⁷ SiO _2/2 ,
D ^OH = HOR ⁸ SiO _2/2 ,
T = R ⁹ SiO _3/2 ,
T ^OH = HOSiO _3/2 and Q = SiO _4/2
In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydroxyl, a monovalent hydrocarbon group having 1 to 60 carbon atoms and a carbon atom. Selected from the group consisting of monovalent organic groups of 1 to 60, and the subscripts a, b, c, d, e, f and g are b + d + f ≧ 1, preferably b + d + f ≧ 2, more preferably b + d + f ≧ 3, most Preferably, it is 0 or a positive integer on condition that b + d + f ≧ 4. The term monovalent organic group having 1 to 60 carbon atoms refers to an organic group in which the carbon-carbon chain is interrupted by a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus.

The coatings of the present invention can be made by reacting a ditelechelic polyolefin, preferably polyisobutylene, with a suitable crosslinkable hydridosiloxane under hydrosilylation conditions. Hydrosilylation is catalyzed by a noble metal, preferably platinum, and many useful compositions of such catalysts are known. Many types of noble metal catalysts for hydrosilylation reactions are known and such catalysts can be used in the reactions of the present invention. Where optical clarity is required, preferred catalysts are those that are soluble in the reaction mixture. With respect to the term noble metal, Ru, Rh, Pd, Os, Ir and Pt are defined herein as noble metals, but Ni known to have hydrogenation activity is also included in this definition. Preferably, the catalyst is a platinum compound, which is a compound of formula (PtCl ₂ olefin), H (PtCl ₂ ) as described in US Pat. No. 3,159,601, the disclosure of which is incorporated herein by reference. ₃ olefins) or H ₂ PtCl ₆ . The olefins shown in the previous two chemical formulas can be almost any type of olefin, but are preferably alkenylene having 2 to 8 carbon atoms, cycloalkenylene having 5 to 7 carbon atoms or styrene. Specific examples of olefins that can be used in these chemical formulas include various isomers of ethylene, propylene, and butylene, octylene, cyclopentene, cyclohexene, cycloheptene, and the like.

  Other platinum-containing materials that can be used in the compositions of the present invention are the cyclopropane complexes of platinum chloride described in US Pat. No. 3,159,662, the disclosure of which is incorporated herein by reference.

  Other platinum-containing materials include chloroplatinic acid and 2 moles or less of alcohol, ether, 1 g of platinum described in US Pat. No. 3,220,972 (the disclosure of which is incorporated herein by reference) Complexes consisting of those selected from the group consisting of aldehydes and mixtures thereof are mentioned.

  Preferred catalysts for use in liquid injection molding compositions are described in Karstedt US Pat. Nos. 3,715,334, 3,775,452, and 3,814,730. Background art in this field is described in J.A. L. Spier, “Homogeneous Catalysis of Hydrodynamics by Transition Metals” Advances in Organometallic Chemistry, volume 17, pages 407 through 44. G. A. Stone and R.C. It can be found in West editors, published by the Academic Press (New York, 1979). An effective amount of platinum catalyst can be readily determined by one skilled in the art. In general, the effective amount for hydrosilylation is about 0.1 to 50 ppm of the total amount of organopolysiloxane composition, as well as any partial range thereof.

  The ditelechelic polyolefin utilized in the coating of the present invention is alternatively reacted to form an epoxidized terminal olefin group, and the epoxidized ditelechelic olefin is reacted with hydridosiloxane under acid catalyst conditions to crosslink. If a polymer is formed, it can be used as a coating of the present invention.

  In order to obtain high tensile strength with the composition of the present invention, it may be desirable to incorporate a filler into the composition. Specific examples of a number of fillers that can be selected, titanium dioxide, lithopone, zinc oxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, calcium carbonate, fumed silica, silazane-treated silica, precipitated silica, glass fiber, Magnesium oxide, chromium oxide, zirconium oxide, aluminum oxide, α-quartz, calcined clay, asbestos, carbon, graphite, cork, cotton, synthetic fiber and the like.

  The preferred filler to be utilized in the composition of the present invention is either surface-treated fumed silica or precipitated silica. In one surface treatment method, fumed silica or precipitated silica is contacted with a cyclic organopolysiloxane under heat and pressure conditions. Another method of treating the filler is to contact silica with siloxane or silane in the presence of an amine compound.

  A particularly preferred surface treatment method for the silica filler uses a methylsilane or silazane surface treatment agent. Fumed silica or precipitated silica fillers surface treated with methylsilane or silazane exhibit free flowing properties and do not increase the low viscosity of the uncured liquid precursor silicone composition. After curing, the silazane-treated silica improves the tear strength of the cured elastomer. Silazane treatment is disclosed in US Pat. Nos. 3,635,743 and 3,847,848, the disclosure of which is incorporated herein by reference.

  The filler is generally used at a concentration of about 5 to about 70 parts by weight, preferably 15 to 50 parts by weight of filler per 100 parts by weight of the resulting cross-linked or network polymer. Preferred fillers are silazane-treated fumed silica or a mixture of silazane-treated fumed silica and silazane-treated precipitated silica. Particularly preferred is the latter mixture comprising fumed silica and precipitated silica in a weight ratio of about 25/1 to about 1/1, preferably about 10/1 to about 5/1.

  Hydroxy containing organopolysiloxane fluids may be added to extend the shelf life of the crosslinkable organopolysiloxane composition. If a silazane treated precipitated silica filler is present in the composition, a hydroxy-containing organopolysiloxane fluid or resin may be added along with the precipitated silica filler to increase shelf life and release properties. Suitable hydroxy-containing organopolysiloxane fluids are those having a viscosity of about 5 to about 100 centipoise, preferably about 20 to 50 centipoise at 25 ° C. These fluids can be expressed as:

R _j (OH) _k SiO _{(4-jk) / 2}
Wherein R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, j is 0 to about 3, preferably 0.5 to about 2.0, and k is 0.005 to about 2. , J and k are about 0.8 to about 3.0. The hydroxy substitution site of the organopolysiloxane fluid or resin is primarily terminal hydroxy substitution.

  If formation of a cured composition is desired, the two components, PIB and siloxane prepolymer, are mixed in the presence of a noble metal hydrosilylation catalyst and, optionally, the desired inhibitor to cure the composition. Depending on the inhibitor selected, the composition may be cured by heating.

Once the desired PIB / siloxane prepolymer has been formed, the allyl-terminated PIB precursor can be combined with a well-defined siloxane having the desired number of SiH functional groups by hydrosilylation. At that time, polyisobutylene may be dissolved in toluene (30 wt% PIB), and 1-ethynyl-1-cyclohexanol (Aldrich) may be added as desired to retard or inhibit hydrosilylation. . US Pat. Nos. 5,506,289, 5,922,795, 5,928,564, 5,948,339, 6002039, 6015853, and As taught in US Pat. No. 6,034,199, other inhibitors can control the initiation of the reaction of allyl and hydrosilyl groups, the disclosures of which are incorporated herein by reference. . Then 500 ppm of H ₂ PtCl ₆ catalyst solution is added, the solution is mixed, poured into a Teflon mold, covered, placed in an oven at about 60 ° C. for about 48 hours, and further at about 90 ° C. Heat for 24 hours. The network sample can then be removed from the oven.

  In order to confirm the hydrosilylation efficiency, the amount of the extract (sol fraction) may be obtained after curing. A network sample is weighed and extracted at room temperature for about 48 hours to about 72 hours (soaked in toluene and decanted and replaced every about 8 hours) and de-swelled with a series of toluene / methanol mixtures. What is necessary is just to change the density | concentration of a toluene / methanol liquid mixture so that it may increase by 10% every about 12 to 24 hours so that it may start with the toluene / methanol ratio of about 90/10 and may end with 100% methanol. The network sample is then removed from the solvent and dried to constant weight in a vacuum oven at about 60 ° C. for about 3 days. The amount of sol can be obtained from the difference in weight before and after extraction of the network structure sample.

  The compositions of the present invention are useful as coatings to create vapor or gas impermeable barriers that are impermeable to sulfur-containing species. Therefore, the composition of the present invention is a method for producing a coated product that is resistant to the action of certain corrosive gases or steam (for example, sulfur-containing gases such as hydrogen sulfide, methyl mercaptan, sulfur dioxide, sulfur trioxide). I will provide a. In such a coating process or coating method, a laminate comprising the coating of the present invention and a substrate is produced, and the substrate is an article for which protection of an electronic device, a circuit board or a chip is desired. The coating of the present invention is particularly resistant to or impervious to sulfur-containing gases, so that in electronic components of automobiles, the silver used in the electronic circuit is discolored or corroded with ordinary reactivity. Especially suitable for protection of parts.

  The term opacity can have several different meanings defined for each application. The term impervious as used herein is exposed to 50 ppm (parts per million or parts per million, ppm) of sulfur-containing species such as hydrogen sulfide and methyl mercaptan at temperatures above 50 ° C. for 2 days. Later, it means that it shows no signs of measurable discoloration or corrosion.

  It is clear that the above procedure synthesizes a multi-component polymer composition containing polyisobutylene. However, other olefins (eg, methylpentene, propylene, etc.) can be polymerized such that allyl or olefin end groups are formed. If these materials are crosslinked by hydrosilylation, polymer compositions similar to those obtained with polyisobutylene can be produced. In order to illustrate the practice of the present invention, the following experiment was conducted. The following matters are merely examples of the essence of the present invention and do not limit the technical scope of the present invention. The technical scope of the present invention resides in the invention defined in each claim.

Test membrane or film production procedure
Silicone coating (solvent-free):
1. A release agent was sprayed on a clean glass surface.
2. The coating material was dropped in a line on the glass using a pipette.
3. The line coating material was spread using a drawing bar and set to various desired thicknesses in the range of 10-20 mils.
4). The glass was placed in an oven at 150 ° C. for 15 minutes.
5. The glass was removed from the oven and allowed to cool to room temperature.
6). The cured coating was carefully peeled from the glass and cut into 5 "x 5" (about 12.7 x 12.7 cm) squares.

PIB coating (ISOPAR C as solvent, boiling point approx. 100 ° C)
Procedures 1, 2, and 3 are the same as the above silicone coating.
4). The glass was placed in an oven at 100 ° C. for 1 hour.
5. The glass was removed from the oven and allowed to cool to room temperature.

  The cured coating was carefully removed from the glass and cut into 5 "x 5" squares.

Transmission Test Procedure Cut the film to be tested and attach it to the transmission cell. The cell has a lower chamber into which a load gas (H ₂ S or methyl mercaptan in nitrogen) is introduced and an upper chamber for sampling. When the load gas passes through the membrane and moves from the lower part of the cell to the upper part, the load gas is trapped by the sweep gas and carried to the detector for quantitative analysis. The cell has an inlet and an outlet for allowing a continuous sweep of the load gas and sampling gas at atmospheric pressure.

Permeation Test Procedure Cut the film to be tested and attach it to cover the lower chamber of the two-chamber permeation cell. The lower chamber has inlet and outlet passages, and the load gas flows freely through the chamber without creating back pressure. The load gas is a mixture of 50 ppm H ₂ S or methyl mercaptan in nitrogen.

  A groove is cut in the mating surface of the lower chamber. An O-ring is accommodated in this groove. When the upper chamber is placed over the lower chamber, the film covering the lower chamber and overlapping the “O” ring forms a seal. The upper chamber is held in place with the pressurizer.

The upper chamber also has inlet and outlet passages. Purge nitrogen through this passage at a rate of 45 cc / min. As the load gas (H ₂ S or methyl mercaptan) permeates through the film, it is swept into the detector by a nitrogen purge.

When analyzing the H ₂ S, draw the purge gas in a special designed analyzer for low levels of _{H 2} S detection (Arizona Instrument Co. Jerome-X631-0101 Gold Film Hydrogen Sulfide Analyzer ).

  When analyzing methyl mercaptan, a purge gas is drawn into a gas injector and introduced into a gas chromatogram equipped with a quantitative measurement PID.

  There are several ASTM methods for permeation of liquid or gas through the barrier, none of which are specific to the present application. The reference method used is ASTM F739.

  The liquid from the circulating bath was pumped through a passage in the cell so that the cell could be cooled or heated.

  The above results indicate that the hydrogen sulfide permeability or diffusion rate of membranes or films of various thicknesses from about 10 mils to about 30 mils is about 0.0003 g hydrogen sulfide / square meter membrane / day. . The above results also show that the film has a much higher permeation resistance to methyl mercaptan, with virtually no mercaptan permeating the membrane during the 4 day test period (96 hours). . A useful permeation rate is about 0.0010 g hydrogen sulfide / square meter membrane / day or less, preferably about 0.0007 g hydrogen sulfide / square meter membrane / day, more preferably about 0.0005 g hydrogen sulfide / day at 50 ° C. Permeation rate of not more than square meter membrane / day, most preferably about 0.0003 g hydrogen sulfide / square meter membrane / day or less. Useful permeation rates at 50 ° C. are about 0.0010 g methyl mercaptan / square meter membrane / day or less, preferably about 0.0007 g methyl mercaptan / square meter membrane / day, more preferably about 0.0005 g methyl mercaptan / day. Permeation rate of less than square meter membrane / day, most preferably about 0.0003 g methyl mercaptan / square meter membrane / day. These permeation rates can be used alone or in combination to define preferred operating parameters.

Claims (24)

a) a telechelic polyolefin and b) a siloxane, a reaction product having a two-component network structure is formed by curing, and a diffusion rate of hydrogen sulfide gas of the reaction product measured under the following conditions is 0.0010 g hydrogen sulfide Composition for coating electronic circuits of electronic components that is less than / square meter membrane / day.
<Diffusion rate measurement conditions>
Film thickness: 10-30 mils Measurement temperature: 50 ° C
Load gas: 50 ppm H ₂ S mixture standard: ASTM F739   The composition for coating an electronic circuit of an electronic component according to claim 1, wherein the diffusion rate is less than 0.0005 g hydrogen sulfide / square meter film / day.   The composition for coating an electronic circuit of an electronic component according to claim 1, wherein the diffusion rate is less than 0.0003 g hydrogen sulfide / square meter film / day. a) a telechelic polyolefin and b) a siloxane, a reaction product having a two-component network structure is formed by curing, and a diffusion rate of methyl mercaptan gas of the reaction product measured under the following conditions is 0.0010 g methyl mercaptan Composition for coating electronic circuits of electronic components that is less than / square meter membrane / day.
<Diffusion rate measurement conditions>
Film thickness: 10-30 mils Measurement temperature: 50 ° C
Load gas: 50 ppm methyl mercaptan mixture standard: ASTM F739   The composition for coating an electronic circuit of an electronic component according to claim 4, wherein the diffusion rate is less than 0.0005 g methyl mercaptan / square meter film / day.   The composition for coating an electronic circuit of an electronic component according to claim 1, wherein the polyolefin is polyisobutylene.   The composition for coating an electronic circuit of an electronic component according to claim 1, wherein the polyolefin is polypropylene.   The composition for coating an electronic circuit of an electronic component according to claim 1, wherein the polyolefin is polymethylpentene.   The composition for coating an electronic circuit of an electronic component according to claim 6, wherein the diffusion rate is less than 0.0005 g hydrogen sulfide / square meter film / day.   The composition for coating an electronic circuit of an electronic component according to claim 6, wherein the diffusion rate is less than about 0.0003 g hydrogen sulfide / square meter film / day. The hydrogen sulfide gas of the reaction product measured under the following conditions, in which an electronic circuit is coated with a reaction product of a two-component network structure formed by a curing reaction of a composition comprising a) telechelic polyolefin and b) siloxane An electronic component comprising an electronic circuit having a diffusion rate of less than 0.0010 g hydrogen sulfide / square meter film / day.
<Diffusion rate measurement conditions>
Film thickness: 10-30 mils Measurement temperature: 50 ° C
Load gas: 50 ppm H ₂ S mixture standard: ASTM F739   The product of claim 11, wherein the diffusion rate is less than 0.0005 g hydrogen sulfide / square meter membrane / day.   The product of claim 11, wherein the diffusion rate is less than 0.0003 g hydrogen sulfide / square meter membrane / day. A methyl mercaptan gas of the reaction product measured under the following conditions when an electronic circuit is coated with a reaction product of a two-component network structure formed by a curing reaction of a composition comprising a) telechelic polyolefin and b) siloxane An electronic component comprising an electronic circuit having a diffusion rate of less than 0.0010 g methyl mercaptan / square meter membrane / day.
<Diffusion rate measurement conditions>
Film thickness: 10-30 mils Measurement temperature: 50 ° C
Load gas: 50 ppm methyl mercaptan mixture standard: ASTM F739   The electronic component comprising an electronic circuit according to claim 14, wherein the diffusion rate is less than 0.0005 g methyl mercaptan / square meter membrane / day.   The electronic component comprising an electronic circuit according to claim 14, wherein the polyolefin is polyisobutylene.   The electronic component comprising an electronic circuit according to claim 14, wherein the polyolefin is polypropylene.   The electronic component comprising an electronic circuit according to claim 14, wherein the polyolefin is polymethylpentene.   The electronic component comprising an electronic circuit according to claim 16, wherein the diffusion rate is less than 0.0005 g hydrogen sulfide / square meter film / day.   The electronic component comprising an electronic circuit according to claim 16, wherein the diffusion rate is less than 0.0003 g hydrogen sulfide / square meter film / day. A method for protecting an electronic circuit of an electronic component from hydrogen sulfide,
1) curing a composition comprising telechelic polyolefin and 2) siloxane to form a reaction product having a two-component network structure on an electronic circuit, and sulfiding the reaction product measured under the following conditions: A method wherein the diffusion rate of hydrogen gas is less than 0.0010 g hydrogen sulfide / square meter membrane / day at 50 ° C.
<Diffusion rate measurement conditions>
Film thickness: 10-30 mils Measurement temperature: 50 ° C
Load gas: 50 ppm H ₂ S mixture standard: ASTM F739   The method of claim 21, wherein the polyolefin is polyisobutylene. A method for protecting an electronic circuit of an electronic component from methyl mercaptan,
1) curing a composition containing telechelic polyolefin and 2) siloxane to form a reaction product having a two-component network structure on an electronic circuit, and measuring the methyl of the reaction product measured under the following conditions: A process wherein the diffusion rate of mercaptan gas is less than 0.0010 g methyl mercaptan / square meter membrane / day at 50 ° C. 24. The method of claim 23, wherein the polyolefin is polyisobutylene.