CA1119056A - Adhesion of a vapor deposited polymer to a substrate by pre-treatment of the substrate with vaporous coupling agents - Google Patents
Adhesion of a vapor deposited polymer to a substrate by pre-treatment of the substrate with vaporous coupling agentsInfo
- Publication number
- CA1119056A CA1119056A CA000284092A CA284092A CA1119056A CA 1119056 A CA1119056 A CA 1119056A CA 000284092 A CA000284092 A CA 000284092A CA 284092 A CA284092 A CA 284092A CA 1119056 A CA1119056 A CA 1119056A
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- xylylene
- coupling agent
- polymer
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
10,985 WRM
IMPROVED ADHESION OF A VAPOR DEPOSITED POLYMER TO A
SUBSTRATE BY PRE-TREATMENT OF THE SUBSTRATE WITH VAPOROUS
COUPLING AGENTS
ABSTRACT OF THE DISCLOSURE
A process is provided for improving the adherence of vapor deposited polymers, such as the poly-p-xylylenes, to solid substrates. The process comprises the vaporization of a coupling agent, for example, an organo-silane, prior to the deposition process. Optionally, water vapor can be introduced to the system to hydrolyze the coupling agent, prior to polymer deposition.
S P E C I F I C A T I O N S
IMPROVED ADHESION OF A VAPOR DEPOSITED POLYMER TO A
SUBSTRATE BY PRE-TREATMENT OF THE SUBSTRATE WITH VAPOROUS
COUPLING AGENTS
ABSTRACT OF THE DISCLOSURE
A process is provided for improving the adherence of vapor deposited polymers, such as the poly-p-xylylenes, to solid substrates. The process comprises the vaporization of a coupling agent, for example, an organo-silane, prior to the deposition process. Optionally, water vapor can be introduced to the system to hydrolyze the coupling agent, prior to polymer deposition.
S P E C I F I C A T I O N S
Description
--- 10,985 ~ 5 ~
This invention relates in general to an improved process for adhering vapor deposited polymers to substrates. In one aspect this invention relates to a proce~s for adher~ng the poly-p-~ylylenes to substrates by pre-treatment of the sub-strate with a coupling agent. In a further aspect, this invention is directed to substrates coated with a poly-p-xylylene wherein the bond between the two is superior to those curre~tly a~ailable.
An important problem encountered in the c~mmercial a~licatlon of vapor deposited polymers such as, poly-p-xylylene has been the difficulty in acquiring the adhesion of the poly-p-xylylene to the surface of the obJect to be coate,d- The poly-p-xylylene family of polymers do not inherently exhibit satisfactory ad-hesion to a wide variety of substrate surfaces such as metals, ceramics and plastics. In the past, specific treatments, such as HCl treatme~t on copper, have promoted poly-p-xylylene ad-hesion. However, such specific treatment was found applica~le only to th?t particular material and was not applicable for adhesion to other types of substrates. Thus, the probl~m of poly-p-xylylene adhesion is complicated by the necessity of 10,985 WRM
~lg~S~
acquiring a & eslon to a variety of substrates using the æame adhesion technique.
A pr~mary area of interest for poly-p-xylylene coating is the electronics field where the substrates consist of a combination ofmaterials such as plastics, metals and ceramics.
In this field, adhesion must be ob~ained without impairing advantages of the poly-p-xylylene coating process such as thinness and substrate conformality while maintaining the necessary electrical properties of the electr~cal and electronic components of the coated substrates. Adhesives, such as tacky gums applied by æolvent dipping are not desirable.
- ' `:
-- 3 o 10,985 ~ 5 ~
Proper adhesion ca~ be acquired using an adhesion promoter to effect bonding between the substrate and the poly-p-xylylene.
Known procedures used for obtaining adhesion using adhesion promoters normally require such techniques as treatment of the sub-strate with an adhesion promoter followed by lamination of a polymer wlth heat and pressure; or reaction of a liquid or solid on an ad-hesion promotéd surface, such as curing of epoxies which generate heat during cure; or incorporation of the adhesion promoter in the liquid or solid, such epoxies, prior ~o the polymerization on a substrate surface with generation of heat from the polymerization reaction. m ese teachings of the prior art are obviously incompat-ible with vapor deposition processes for applying polymer coatings.
Further limitation is thus found in obtaining an adhesion promoter which can be applied without impairing the vapor teposition coating process for the poly-p-xylylenes that is conventionally employed.
More recen~ly, other methods have been disclosed in the literature for improving the adhesion, of parylene coatings to substrates. For instance, U.S. Patent 3~600,216 which issued August 17, 1971 to Donald D. Stewart discloses a process for adhering vapor deposited poly-p-xylylene to solid substrates through the use of organo-silane compounds having at least one hydrolyzable or condensible group.
U.S. Patent 3,900,600 which issued August 19, 1976 to E.C.
Spaulding discloses a method for producing dielectric fi~ms by heating an admixture of halogen substitu~ed pdy-p-xylylene dimers and silyl amines and vapor depositing the admixture upon a sub-strate under reduced pressure. This method provides a fi~m which contains the silyl amine throughout the polymer bulk. A disadvantage of this method is that certai~ silyl amines may be susceptible to degradation during the elevated temperatures employed during 10,985 ~ 5~
pyrolysis of the parylene dimer. This could adversely affect the properties of the polymeric layer.
Prior to the present invention one method c~mmonly employed to treat substrates to improve adhesion involved several steps and, although effective, was tedious and time consuming. The method involved 1) i ersing the substrate in isopropanol for 5 to 10 minutes 2) ~mmersing the substrate in a solution of a coupling agent for 30 minutes 3) air drying for 30 minutes 4) rinsing twice with isopropanol and 5) air drying for 30 minutes. This method required meticulous care to insure that the treated substrate was kept free of contaminents. In con-trast, the process of the present invention is simple and pro-vides a rapid and efficient method for treating and coating the substrate with minimal susceptibility to contamination.
Accordingly, one or more of the following objects will be ~chieved by the practice;of this invention. It is an object of this invention to p~ovide an improved process for adhering vapor deposited polymers to substrates. Another ob~ect of this in-vention is to provide a method for contacting the coupling agent with the substrate under conditions wherein contamination is minimized. A still further object is to provide a parylene coated substrate wherein the coating is c~mprised throughout of essentially pure polymer. These and other objects will readily bec~me apparent to those skilled in the art in the light of the teachings hereinafter set forth.
In its broad aspect this invention is directed to a prosessfDr adhering a vapor deposited polymer,such as the poly-p-xylylenes, to solid substrates. The process c~mprises the steps of: (a) placing the substrate in a deposition chamber, (b) c~nt~ing the 10,985 ~ 5 ~
substrate wi~hin the chæmber with at least one vaporous coupling agent, the coupling agent being further characterized as having a vapor pressure sufficiently large to allow its admittance to the deposition chamber under conditions c~mpatible with those normally used to conduct the vapor deposition of the polymer, (c) thereafter contacting the substrate with a vaporous polymer precursor, which upon deposition on the surface of the substrate forms a polymeric coating which adheres to the surface.
Substrates of the present invention can be any organic or inorganic solid which may t~ke any fonm, such as sheet, fiber or particles. Illustrative of the organic and inorganic sub-strates within the purview of this invention are, by way of example, metal substrates such as aluminum, iron, copper, æteel, molybdenum, and the like; metal oxide substrates such as alum-inum oxide, titanium oxides, lead o~ides, copper oxides, iron oxides, berylium oxides, manganese oxides, tungsten oxides, tantalum oxides, vanadium oxides, and the like, non-metal in-organic oxides, such as silicon oxide (e.g. sand, fly ash, hydrated silica, silica, quartz, aerogel, xerogels, fumed silica, and the like); and solid organic substrates such as epoxy con-taining campounds and thermopla tic and thermosetting cumpounds having a lightly oxidizing sur~ace.
Especially suitable substrates for use in the process of the present invention hlve ~en ~hose metal, glass or organic resin substrates having hydroxyl, oxide or epoxy groups on their surfaces.
The apparatus most suitable for producing and depositing the reactive vaporous p-xylyly~ene on the surface of the treated substrate is disclosed in U.S. Patent 3,246,627 to Loeb et al.
This patent provides a chamber adapted to receive objects to be 10,985 ~ 5 $
coated, such as the treated substrates~ The chamber and/or the substrate therein is maintained at a temperature below about 200C. The chamber is in communication with a vaporiza-tion-pyrolyzation oven by a labyrinthine exit passageway w~ich emits the p-xylylene mon~mer. The oven is maintained at temper-atures suitable for the vaporization and pyrolyzation of the di-p-xylylene. In operation, the di-p-xylylene-is maintained in the oven for a period of time sufficient to vaporize and pyrolyze the di-p-xylylene to the corresponding p-xylylene monomer. The p-xylylene monomer is then penmitted to emit into evacuated space defined by the walls of the chamber whereby the p-xylylene condenses on the treated surface of the substrate and polymerize to form a poly-p-xylylene coating having improved adhesion to the substrate.
As previously indicated, a wide variety of commercially available coupling agents which are somet~mes also referred to as adhesion promoters can be employed in this invention to ~mprove the adhesive characteristics of the poly-p-xylylene coating to its substrate. The only requirement of the coupling agent is that it must have a suitable vapor pressure and must not react ad-versely with either the substrate or coating while it must promote adhesion between the two. In practice, deposition of the coupling agent will usually be conducted at temperatures of from about - 40C to about rocm tem~erature, and hence the coupling agent should be volatile within this range.
.
Illustrative coupling agents which can be employed include, among others the organic silanes. Typical organic silanes which can be utilized in the process of this invention .
10,985 ~ 5 ~
include among others, ~inyltriethoxysilane, Vinyl-tr.is (beta-.
methoxyethoxy) silane, gamma-Methacryloxypropyltrimethoxy-silane, beta-(3,4-Epoxycyclohexyl3-ethyltrimethox~silane, gamma-Glycidoxypropyltrimethoxy-silane, Vinyltriacetoxysilane, gamma-Mercaptopropyltrimethoxy-silane, gamma-Aminopropyltrie-thoxysilane, N-beta-(Aminoethyl)-gamma-aminopropyltrimethoxr silflne . . - ~
In practice, it has been observed that the process of the present invention for the promotion of adhesion of parylenes can be effected o~er a wide variety of chamber pressures.
Excellen~ resultshave been obtained when pressures of ~rom about 1 micron to about 1 torr have been employed.
10,985 ~3~ ~5 ~
The following examples illustrate at least one of the best modes for presently conducting the process of this invention:
In this example a vapor deposition chamber of a poly-p-xylylene polymerization unit was employed which was 9 inches in length and had a diameter of 9 inches. Into the chamber were placed four 3 x 5 inch pieces of plate glass.
A metal weighing disk containing 5 milliliters of gamma, -methacryloxypropyl-trimethoxysilane was placed in the bottom of the chamber and the chamber pumped down to 6 micro pressure.
After about 10 minutes 20 grams of dichloro di-p-xylylene was vaporized at 158 C at a pressure of ~ nu~ro~s to form _ the monomer, which was introduced into the vapor deposition chamber where it condensed on the silane coated glass platPs to form a poly p-xylylene coating of about 0.5 mil thickness the total time for the deposition was approximately 40 minutes.
Examination of the coated glass plates showed that the coating had an adhesion value of approximately 8 pounds per inch as measured by Hesiometer.
?0 In a manner similar to that employed in Example 1 four 3 x 5 ~nch pieces of plate glass were coated with the dichlorc di-p-xylylene. However, prior to exposure of the glass surfac~s to the silane, and after the unit was pumped down to the 6 micron pressure, a 20 micron air leak was admitted to the chamber. The relative humidity of the air was about 50 percent .
_ g _ 10,985 ~ 5 ~
thereafter, the glass plates were exposed to ~he silane and the vaporous monomer as in the previous example. Excellent ad-hesion was also observed (7 to 11 pounds per inch). Due to the presence of the water vapor the process was conducted in a shorter period of time, that is, much less than the 40 minutes of Example 1.
In a similar manner, sheets of copper and aluminum, circuit boards, and the like were coated with dichloro-di P-xylylene 2nd found to have excellent adhesion values of at least 7 pounds per inch as measured by Hesiometer.
In this example a parylene production coating unit baving a capacity of 3400 cubic inches was employed. G?ass plates measuring 9 x 9 inches were employed as the substrate. The gamma-methacrylox~ropyl trimethoxysilane was admitted through a 0.5 inch pipe into the post pyrolysis zone for about 15 minutes at 30 microns pressure - thereafter, the val~e was shut and the pressure lowered to 100 microns. In a manner similar to that of the previous examples, 81 grams of dichloro di-p-xylylene was vaporized at 200-C at a pressure of 25 microns to form the monomer which was then introduced into the vapor deposi~i~n chamber where it condensed on the silane coated plates to form poly-p-xylylene coating of about 0.6 mil thickness. Examlnation of the coated glass plates showed that the coating had an adhesion value of 7.5 0.5 pounds per inch as measured by Hesiometer for all substrate surface.
Although the invention has been illustrated by the preceding examples, it is not to be construed as being 10,~85 ~ 5 ~
limlted thereto, but rather the invention is directed to the generic area as hereinbefore disclosed. Various modificatio~s and embodiments may be made without departing fr~m the spirit and scope thereof.
This invention relates in general to an improved process for adhering vapor deposited polymers to substrates. In one aspect this invention relates to a proce~s for adher~ng the poly-p-~ylylenes to substrates by pre-treatment of the sub-strate with a coupling agent. In a further aspect, this invention is directed to substrates coated with a poly-p-xylylene wherein the bond between the two is superior to those curre~tly a~ailable.
An important problem encountered in the c~mmercial a~licatlon of vapor deposited polymers such as, poly-p-xylylene has been the difficulty in acquiring the adhesion of the poly-p-xylylene to the surface of the obJect to be coate,d- The poly-p-xylylene family of polymers do not inherently exhibit satisfactory ad-hesion to a wide variety of substrate surfaces such as metals, ceramics and plastics. In the past, specific treatments, such as HCl treatme~t on copper, have promoted poly-p-xylylene ad-hesion. However, such specific treatment was found applica~le only to th?t particular material and was not applicable for adhesion to other types of substrates. Thus, the probl~m of poly-p-xylylene adhesion is complicated by the necessity of 10,985 WRM
~lg~S~
acquiring a & eslon to a variety of substrates using the æame adhesion technique.
A pr~mary area of interest for poly-p-xylylene coating is the electronics field where the substrates consist of a combination ofmaterials such as plastics, metals and ceramics.
In this field, adhesion must be ob~ained without impairing advantages of the poly-p-xylylene coating process such as thinness and substrate conformality while maintaining the necessary electrical properties of the electr~cal and electronic components of the coated substrates. Adhesives, such as tacky gums applied by æolvent dipping are not desirable.
- ' `:
-- 3 o 10,985 ~ 5 ~
Proper adhesion ca~ be acquired using an adhesion promoter to effect bonding between the substrate and the poly-p-xylylene.
Known procedures used for obtaining adhesion using adhesion promoters normally require such techniques as treatment of the sub-strate with an adhesion promoter followed by lamination of a polymer wlth heat and pressure; or reaction of a liquid or solid on an ad-hesion promotéd surface, such as curing of epoxies which generate heat during cure; or incorporation of the adhesion promoter in the liquid or solid, such epoxies, prior ~o the polymerization on a substrate surface with generation of heat from the polymerization reaction. m ese teachings of the prior art are obviously incompat-ible with vapor deposition processes for applying polymer coatings.
Further limitation is thus found in obtaining an adhesion promoter which can be applied without impairing the vapor teposition coating process for the poly-p-xylylenes that is conventionally employed.
More recen~ly, other methods have been disclosed in the literature for improving the adhesion, of parylene coatings to substrates. For instance, U.S. Patent 3~600,216 which issued August 17, 1971 to Donald D. Stewart discloses a process for adhering vapor deposited poly-p-xylylene to solid substrates through the use of organo-silane compounds having at least one hydrolyzable or condensible group.
U.S. Patent 3,900,600 which issued August 19, 1976 to E.C.
Spaulding discloses a method for producing dielectric fi~ms by heating an admixture of halogen substitu~ed pdy-p-xylylene dimers and silyl amines and vapor depositing the admixture upon a sub-strate under reduced pressure. This method provides a fi~m which contains the silyl amine throughout the polymer bulk. A disadvantage of this method is that certai~ silyl amines may be susceptible to degradation during the elevated temperatures employed during 10,985 ~ 5~
pyrolysis of the parylene dimer. This could adversely affect the properties of the polymeric layer.
Prior to the present invention one method c~mmonly employed to treat substrates to improve adhesion involved several steps and, although effective, was tedious and time consuming. The method involved 1) i ersing the substrate in isopropanol for 5 to 10 minutes 2) ~mmersing the substrate in a solution of a coupling agent for 30 minutes 3) air drying for 30 minutes 4) rinsing twice with isopropanol and 5) air drying for 30 minutes. This method required meticulous care to insure that the treated substrate was kept free of contaminents. In con-trast, the process of the present invention is simple and pro-vides a rapid and efficient method for treating and coating the substrate with minimal susceptibility to contamination.
Accordingly, one or more of the following objects will be ~chieved by the practice;of this invention. It is an object of this invention to p~ovide an improved process for adhering vapor deposited polymers to substrates. Another ob~ect of this in-vention is to provide a method for contacting the coupling agent with the substrate under conditions wherein contamination is minimized. A still further object is to provide a parylene coated substrate wherein the coating is c~mprised throughout of essentially pure polymer. These and other objects will readily bec~me apparent to those skilled in the art in the light of the teachings hereinafter set forth.
In its broad aspect this invention is directed to a prosessfDr adhering a vapor deposited polymer,such as the poly-p-xylylenes, to solid substrates. The process c~mprises the steps of: (a) placing the substrate in a deposition chamber, (b) c~nt~ing the 10,985 ~ 5 ~
substrate wi~hin the chæmber with at least one vaporous coupling agent, the coupling agent being further characterized as having a vapor pressure sufficiently large to allow its admittance to the deposition chamber under conditions c~mpatible with those normally used to conduct the vapor deposition of the polymer, (c) thereafter contacting the substrate with a vaporous polymer precursor, which upon deposition on the surface of the substrate forms a polymeric coating which adheres to the surface.
Substrates of the present invention can be any organic or inorganic solid which may t~ke any fonm, such as sheet, fiber or particles. Illustrative of the organic and inorganic sub-strates within the purview of this invention are, by way of example, metal substrates such as aluminum, iron, copper, æteel, molybdenum, and the like; metal oxide substrates such as alum-inum oxide, titanium oxides, lead o~ides, copper oxides, iron oxides, berylium oxides, manganese oxides, tungsten oxides, tantalum oxides, vanadium oxides, and the like, non-metal in-organic oxides, such as silicon oxide (e.g. sand, fly ash, hydrated silica, silica, quartz, aerogel, xerogels, fumed silica, and the like); and solid organic substrates such as epoxy con-taining campounds and thermopla tic and thermosetting cumpounds having a lightly oxidizing sur~ace.
Especially suitable substrates for use in the process of the present invention hlve ~en ~hose metal, glass or organic resin substrates having hydroxyl, oxide or epoxy groups on their surfaces.
The apparatus most suitable for producing and depositing the reactive vaporous p-xylyly~ene on the surface of the treated substrate is disclosed in U.S. Patent 3,246,627 to Loeb et al.
This patent provides a chamber adapted to receive objects to be 10,985 ~ 5 $
coated, such as the treated substrates~ The chamber and/or the substrate therein is maintained at a temperature below about 200C. The chamber is in communication with a vaporiza-tion-pyrolyzation oven by a labyrinthine exit passageway w~ich emits the p-xylylene mon~mer. The oven is maintained at temper-atures suitable for the vaporization and pyrolyzation of the di-p-xylylene. In operation, the di-p-xylylene-is maintained in the oven for a period of time sufficient to vaporize and pyrolyze the di-p-xylylene to the corresponding p-xylylene monomer. The p-xylylene monomer is then penmitted to emit into evacuated space defined by the walls of the chamber whereby the p-xylylene condenses on the treated surface of the substrate and polymerize to form a poly-p-xylylene coating having improved adhesion to the substrate.
As previously indicated, a wide variety of commercially available coupling agents which are somet~mes also referred to as adhesion promoters can be employed in this invention to ~mprove the adhesive characteristics of the poly-p-xylylene coating to its substrate. The only requirement of the coupling agent is that it must have a suitable vapor pressure and must not react ad-versely with either the substrate or coating while it must promote adhesion between the two. In practice, deposition of the coupling agent will usually be conducted at temperatures of from about - 40C to about rocm tem~erature, and hence the coupling agent should be volatile within this range.
.
Illustrative coupling agents which can be employed include, among others the organic silanes. Typical organic silanes which can be utilized in the process of this invention .
10,985 ~ 5 ~
include among others, ~inyltriethoxysilane, Vinyl-tr.is (beta-.
methoxyethoxy) silane, gamma-Methacryloxypropyltrimethoxy-silane, beta-(3,4-Epoxycyclohexyl3-ethyltrimethox~silane, gamma-Glycidoxypropyltrimethoxy-silane, Vinyltriacetoxysilane, gamma-Mercaptopropyltrimethoxy-silane, gamma-Aminopropyltrie-thoxysilane, N-beta-(Aminoethyl)-gamma-aminopropyltrimethoxr silflne . . - ~
In practice, it has been observed that the process of the present invention for the promotion of adhesion of parylenes can be effected o~er a wide variety of chamber pressures.
Excellen~ resultshave been obtained when pressures of ~rom about 1 micron to about 1 torr have been employed.
10,985 ~3~ ~5 ~
The following examples illustrate at least one of the best modes for presently conducting the process of this invention:
In this example a vapor deposition chamber of a poly-p-xylylene polymerization unit was employed which was 9 inches in length and had a diameter of 9 inches. Into the chamber were placed four 3 x 5 inch pieces of plate glass.
A metal weighing disk containing 5 milliliters of gamma, -methacryloxypropyl-trimethoxysilane was placed in the bottom of the chamber and the chamber pumped down to 6 micro pressure.
After about 10 minutes 20 grams of dichloro di-p-xylylene was vaporized at 158 C at a pressure of ~ nu~ro~s to form _ the monomer, which was introduced into the vapor deposition chamber where it condensed on the silane coated glass platPs to form a poly p-xylylene coating of about 0.5 mil thickness the total time for the deposition was approximately 40 minutes.
Examination of the coated glass plates showed that the coating had an adhesion value of approximately 8 pounds per inch as measured by Hesiometer.
?0 In a manner similar to that employed in Example 1 four 3 x 5 ~nch pieces of plate glass were coated with the dichlorc di-p-xylylene. However, prior to exposure of the glass surfac~s to the silane, and after the unit was pumped down to the 6 micron pressure, a 20 micron air leak was admitted to the chamber. The relative humidity of the air was about 50 percent .
_ g _ 10,985 ~ 5 ~
thereafter, the glass plates were exposed to ~he silane and the vaporous monomer as in the previous example. Excellent ad-hesion was also observed (7 to 11 pounds per inch). Due to the presence of the water vapor the process was conducted in a shorter period of time, that is, much less than the 40 minutes of Example 1.
In a similar manner, sheets of copper and aluminum, circuit boards, and the like were coated with dichloro-di P-xylylene 2nd found to have excellent adhesion values of at least 7 pounds per inch as measured by Hesiometer.
In this example a parylene production coating unit baving a capacity of 3400 cubic inches was employed. G?ass plates measuring 9 x 9 inches were employed as the substrate. The gamma-methacrylox~ropyl trimethoxysilane was admitted through a 0.5 inch pipe into the post pyrolysis zone for about 15 minutes at 30 microns pressure - thereafter, the val~e was shut and the pressure lowered to 100 microns. In a manner similar to that of the previous examples, 81 grams of dichloro di-p-xylylene was vaporized at 200-C at a pressure of 25 microns to form the monomer which was then introduced into the vapor deposi~i~n chamber where it condensed on the silane coated plates to form poly-p-xylylene coating of about 0.6 mil thickness. Examlnation of the coated glass plates showed that the coating had an adhesion value of 7.5 0.5 pounds per inch as measured by Hesiometer for all substrate surface.
Although the invention has been illustrated by the preceding examples, it is not to be construed as being 10,~85 ~ 5 ~
limlted thereto, but rather the invention is directed to the generic area as hereinbefore disclosed. Various modificatio~s and embodiments may be made without departing fr~m the spirit and scope thereof.
Claims (5)
1. A process for adhering vapor deposited polymers to a solid substrate which comprises the steps of:
(a) placing said substrate in a deposition chamber, (b) contacting said substrate within said chamber with at least one vaporous siloxane coupling agent, said coupling agent being selected from the group consisting of vinyltris(beta-methoxy-ethoxy)silane, gamma-methacryloxy-propyltriemethoxy-silane, and vinyltriethoxy-silane characterized as having a vapor pressure sufficiently great to allow its admittance to the deposition chamber under conditions compatible with those normally used to conduct the vapor deposition of said polymer, (c) thereafter contacting said substrate with a vaporous polymer precursor, said polymer being a poly-p-xylylene, which upon deposition on the surface of said substrate forms a polymeric coating which adheres to said surface.
(a) placing said substrate in a deposition chamber, (b) contacting said substrate within said chamber with at least one vaporous siloxane coupling agent, said coupling agent being selected from the group consisting of vinyltris(beta-methoxy-ethoxy)silane, gamma-methacryloxy-propyltriemethoxy-silane, and vinyltriethoxy-silane characterized as having a vapor pressure sufficiently great to allow its admittance to the deposition chamber under conditions compatible with those normally used to conduct the vapor deposition of said polymer, (c) thereafter contacting said substrate with a vaporous polymer precursor, said polymer being a poly-p-xylylene, which upon deposition on the surface of said substrate forms a polymeric coating which adheres to said surface.
2. The process of claim 1 wherein said polymer is a poly-p-xylylene homopolymer.
3. The process of claim 1 wherein said polymer is a poly-p-xylylene copolymer.
4. The process of claim 1 wherein said coupling agent undergoes hydrolysis and forms at least a monolayer of hydrolyzed coupling agent on said substrate surface.
5. The process of claim 4 wherein the hydrolysis of said coupling agent is achieved by the introduction of water vapor into said deposition chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71656876A | 1976-08-23 | 1976-08-23 | |
| US716,568 | 1976-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119056A true CA1119056A (en) | 1982-03-02 |
Family
ID=24878533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000284092A Expired CA1119056A (en) | 1976-08-23 | 1977-08-04 | Adhesion of a vapor deposited polymer to a substrate by pre-treatment of the substrate with vaporous coupling agents |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5856371B2 (en) |
| BE (1) | BE857999A (en) |
| CA (1) | CA1119056A (en) |
| DE (1) | DE2737792C3 (en) |
| GB (1) | GB1542566A (en) |
| NL (1) | NL7709243A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045209A3 (en) * | 1996-05-31 | 1998-02-12 | Specialty Coating Systems Inc | Chambers for promoting surface adhesion under vacuum and methods of using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248944A (en) * | 1979-12-21 | 1981-02-03 | Union Carbide Corporation | Seals for electrochemical cells |
| US4588609A (en) * | 1984-11-26 | 1986-05-13 | Leyden Richard N | Process for the photochemical vapor deposition of aromatic polymers |
| GB2248072B (en) * | 1990-09-22 | 1994-03-09 | Gec Ferranti Defence Syst | A method of fabricating coaxial cable components and coaxial cable components fabricated thereby |
| JP2019059209A (en) * | 2017-09-28 | 2019-04-18 | 大日本印刷株式会社 | Heat-sealable laminate excellent in releasability, and packaging material and packaging bag formed of the laminate |
-
1977
- 1977-08-04 CA CA000284092A patent/CA1119056A/en not_active Expired
- 1977-08-22 DE DE19772737792 patent/DE2737792C3/en not_active Expired
- 1977-08-22 JP JP52099634A patent/JPS5856371B2/en not_active Expired
- 1977-08-22 GB GB3513577A patent/GB1542566A/en not_active Expired
- 1977-08-22 NL NL7709243A patent/NL7709243A/en not_active Application Discontinuation
- 1977-08-22 BE BE180341A patent/BE857999A/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045209A3 (en) * | 1996-05-31 | 1998-02-12 | Specialty Coating Systems Inc | Chambers for promoting surface adhesion under vacuum and methods of using same |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7709243A (en) | 1978-02-27 |
| JPS5327700A (en) | 1978-03-15 |
| DE2737792B2 (en) | 1978-11-16 |
| BE857999A (en) | 1978-02-22 |
| JPS5856371B2 (en) | 1983-12-14 |
| DE2737792C3 (en) | 1979-07-12 |
| GB1542566A (en) | 1979-03-21 |
| DE2737792A1 (en) | 1978-03-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |