JP5689262B2 - Low coefficient of friction coating for metal surfaces - Google Patents

Description

  The present invention relates to an article or device having at least one metal surface coated with a low coefficient of friction coating. In particular, it relates to an article or device comprising at least one metal surface primed with a silanol functional siloxane at least partially condensation polymerized and subsequently coated with a topcoat of addition polymerized alkenyl functional siloxane. The invention also relates to a method of making such a coated article or device.

  Silicone coatings of metal surfaces of articles such as surgical devices, needles, razors are well known. For example, US Pat. No. 6,210,437 includes a metal surface coated with a first layer of short chain silicone having silicon hydroxide and silicon hydride groups and a second layer of silicone polymer. Disclosed is a medical device in which a first layer of short chain silicone is bonded to a metal via a silicon hydroxide group that is not a terminal of silicon hydride, and a second layer of silicone polymer is bonded to a short layer of the first layer. It is covalently bonded to the silicon hydride group of the chain silicone via a vinyl group.

  US Pat. No. 5,985,355 discloses a surgical needle coating process. The process includes forming a first smooth coating on the surface of the needle by applying a polymethylsiloxane-containing composition that can be condensed to the surface of the needle, and an amino and alkoxy functional siloxane on the first coating. Forming a second slip coating on the smooth coating by applying the containing composition.

US Pat. No. 4,720,521 discloses a film-forming siloxane composition for use in coating hypodermic needles, razor blades, catheters, and the like. The composition comprises a first siloxane polymer having two or more vinyl groups, a second siloxane crosslinked polymer having two or more pendant hydrogen groups, and a second siloxane polymer having two or more terminal hydrogen groups. A reactive component comprising a combination of three siloxane chain-extending polymers, and (R) ₃ SiO (SiR ₂ O) _z Si (R) ₃ wherein R is C1-C20 alkyl, haloalkyl, aryl, haloaryl, cycloalkyl , Silacyclopentyl, aralkyl, and mixtures thereof, and Z is from about 20 to about 1,800].

  US Pat. No. 6,936,297 is based on using a coating mixture of at least one polydialkylsiloxane, aminoalkylsiloxane, at least one other copolymerizable siloxane and at least one other silicon processing material. A method of making a siliconized surgical needle is disclosed.

  U.S. Pat. No. 5,536,582 discloses an aqueous silicone coating composition that can be used on smooth substrates such as suture needles. The coating composition includes a non-reactive polydimethylsiloxane, a reactive siloxane polymer, and at least one dispersant, wherein the reactive siloxane polymer is an aminoalkylsiloxane and at least one other copolymerizable siloxane. And a mixture.

  Unfortunately, some of the coating materials in the prior art require high cure temperatures and long cure periods. For example, US Patent '437 illustrates that the coating disclosed therein is cured at 140 ° C for 4 hours. U.S. Patent '355 discloses that curing of the condensable polymethylsiloxane occurs at a temperature in the range of 130 ° C to 250 ° C for a period in the range of 1 hour to 5 hours. U.S. Pat. No. 297 discloses that the coated needle is placed in a furnace or oven at a temperature of about 100.degree. C. to 200.degree. C. for a period ranging from about 2 hours to about 48 hours.

  To date, cured coating materials have often been unsatisfactory with respect to their ability to covalently bond to metal substrates. Accordingly, the robustness of these coatings will be limited by the risk of delamination from the substrate.

  In addition, some of the prior art coatings have a relatively high coefficient of friction. Such coatings are not suitable for applications that require low friction, such as surgical needles that require the ability to penetrate small tissues and razor blades that require low skin irritation. They are not desirable.

  Accordingly, there is a need in the coatings field for articles or devices having a metal surface coated with a robust, low frictional resistance coating that can be cured at lower temperatures and shorter cure times than the prior art. . The present invention provides a solution to that need.

  In one embodiment, the present invention relates to an article having a metal surface, a primer layer deposited on the metal surface, and a topcoat deposited on the primer layer, wherein the primer layer comprises a silanol-containing organopolysiloxane resin and an alkylsilicyl resin. And a topcoat composition comprising an alkenyl-functional polyorganosiloxane, an organohydrogensiloxane, and a hydrosilylation catalyst.

  The articles of the present invention are suitable for applications such as surgical devices such as surgical needles, razors, cutting / slicing devices, health care related devices for needles and articles. The coating on the article is robust and exhibits a low coefficient of friction. Applying this coating to a device such as a needle can help improve the device's ability to penetrate tissue with less force.

  In another embodiment, the present invention relates to a method of making an article or device having a coated metal surface, the method comprising (1) providing an article or device having at least one metal surface; (2) a primer. Providing a composition and a coating composition, wherein the primer composition comprises a silanol-containing organopolysiloxane resin and a crosslinker that is an alkyl silicate, and wherein the topcoat composition is an alkenyl alkenyl functional group. A step of containing a functional polyorganosiloxane, an organohydrogensiloxane, and a hydrosilylation catalyst, (3) a step of contacting the metal surface with the primer composition to form a primer layer, and (4) a primer layer. Contacting with the topcoat composition to form a topcoat; (5) the undercoat By curing said top coat and, thereby containing the step of making the article or device.

  The article or device of the present invention has at least one metal surface. The material on the metal surface is not particularly limited, but may include any metal or metal alloy commonly used in health care articles or devices. Exemplary metallic materials include stainless steel, tungsten, nickel, cobalt, molybdenum, tin, vanadium, titanium, aluminum, iron, copper, zinc, silver, lead or metal alloys thereof. Preferably the metal surface contains a biocompatible material such as stainless steel or tungsten.

  According to the present invention, the metal surface is coated with a primer layer and a top coat covering the primer layer. Here, the term “top coat” means a coating layer that covers an undercoat layer. As used herein, when it is desired to form a topcoat on the topcoat, it is preferred that one or more additional coating layers be deposited on the topcoat.

  A suitable composition for forming the primer layer contains a silanol-containing organopolysiloxane resin and a crosslinker that is an alkyl silicate. In one embodiment, the primer composition consists essentially of these two components. Preferably, the silanol-containing organopolysiloxane resin is present in the primer composition in an amount ranging from about 70 to 95% by weight, more preferably from 80 to 90% by weight, and the crosslinking agent is from 5 to about 30% by weight. %, More preferably from about 10 to about 20% by weight, which are based on the solid component content of the primer composition.

A silanol-containing organopolysiloxane resin useful in a primer composition comprises a silanol-terminated organopolysiloxane. Suitable silanol-containing organopolysiloxanes have the formula I:
M _a D _b T _c Q _d (Formula I)
Represented by
Where M = R ¹ R ² R ³ SiO _1/2 ; D = R ⁴ R ⁵ SiO _2/2 ; T = R ⁶ SiO _3/2 ; and Q = SiO _4/2 , where subscript The letters a, b, c and d are zero or positive numbers, and the organopolysiloxane resin is about 5 centistokes and 10,000 centistokes based on a solid solution of 50% by weight in an aromatic solvent. And wherein each R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is independently hydrogen, hydroxyl, monovalent C 1 to C 60 Alkyl radicals, C1 to C60 monovalent haloalkyl radicals, C1 to C60 monovalent aryl radicals, C1 to C60 monovalent alkylaryl radicals, and C1 to C60 monovalent haloalkyl radicals. Is selected from the group consisting of Rurajikaru, wherein at least one of R ^1, R ² and R ³ according to the limitation that is hydroxyl. In one embodiment, R ^{1 to} R ⁶ are independently hydroxyl, a C1 to C40 alkyl radical, more preferably a C1 to C20 alkyl radical, even more preferably a C1 to C5 radical, and R ¹ , R ² , Subject to the limitation that at least one of R ³ is hydroxyl.

Preferably, the silanol-containing organopolysiloxane resin suitable for the primer composition of the present invention is of the formula:
_{De TF} (Formula II)
Have
Where D = R ⁷ R ⁸ SiO _2/2 , T = R ⁹ SiO _3/2 , where each R ⁷ , R ⁸ and R ⁹ is independently alkyl, eg, methyl, ethyl Or propyl, preferably methyl, hydroxyl, alkoxy or acyloxy, with the proviso that at least one of R ⁷ , R ⁸ and R ⁹ in one molecule is hydroxyl, and e is from about 160 to about 450 And f is from about 15 to about 50. In a preferred embodiment, it is a methyl silicone resin as defined by formula (II).

A suitable cross-linking agent for the primer layer can be an alkyl silicate. The alkyl silicate used in the present invention is a partially hydrolyzed at least one tetraalkyl silicate represented by the following formula: Si (OR ¹⁰ ) (OR ¹¹ ) (OR ¹² ) (OR ¹³ ) (Formula III) Thus obtained condensate is soluble in at least one organic solvent. In connection with this formula, each of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is an alkyl group containing from 1 to 4 carbon atoms.

  Examples of tetraalkyl silicates are tetramethyl silicate, trimethyl monoethyl silicate, dimethyl diethyl silicate, trimethyl monopropyl silicate, trimethyl monobutyl silicate, monoethyl triethyl silicate, tetraethyl silicate, dimethyl dibutyl silicate , Triethyl monobutyl silicate, triethyl mono-tert-butyl silicate, diethyl dibutyl silicate, diethyl di-tert-butyl silicate, tetrapropyl silicate, tetraisopropyl silicate, monoethyl tributyl silicate, diisopropyl dibutyl silicate, Monoisopropyl triisobutyl silicate, monoisopropyl tri-tert-butyl silicate, tri-sec-butyl mono-tert-butyl Including Likert, tetrabutyl silicate, tetra isobutyl silicate and tetra -sec- butyl silicate and tetra -tert- butyl silicate. Of these, tetraethyl silicate is particularly preferred.

  The condensate is a tetraalkyl silicate condensate that is soluble in organic solvents, in which the tetraalkyl silicate of formula (III) is partially hydrolyzed in an organic solvent in the presence of a suitable catalyst such as hydrochloric acid. It is obtained by partial hydrolysis with the required amount of water. A particularly preferred condensate is a tetraethyl silicate condensate.

  Preferably, no solvent is required in the primer composition. However, if necessary, a solvent may be used in the primer composition. General purpose hydrocarbon solvents such as alkanes, ethers and the like are useful. Preferably the solvent has a low boiling point. In one embodiment, the solvent used is hexane.

  The primer composition may further contain 5 to 1000 ppm of catalyst, based on the total weight of the silanol-containing organopolysiloxane and alkyl silicate in the primer composition. The catalyst promotes a condensation reaction between the components of the primer composition. Suitable catalysts are iron chloride, zinc carboxylate, titanium, tin, zirconium or combinations thereof, such as zinc 2-ethylhexanoate, zinc octylate, titanate, tetraisopropyl titanate, titanate Including such things as tetrabutyl, dibutyltin dilaurate, dimethyltin dineodecanoate, dibutyltin dioctylate, dimethyltin oxide, dimethylhydroxytin oleate, dibutyltin bis (acetylacetonate) and zirconium 2-ethylhexanoate It is not limited to them. In a preferred embodiment, the catalyst is iron chloride.

  A topcoat composition that may be used to form a topcoat layer overlying the primer layer contains an alkenyl functional organopolysiloxane, an organohydrogensiloxane, a hydrosilylation catalyst, and optionally a solvent. The alkenyl functional organopolysiloxane ranges from about 0.5 to about 30%, preferably from about 1 to about 10% by weight in the topcoat composition, based on the solid component content of the topcoat composition. Present in the amount of. The organohydrogensiloxane has a SiH and Si-alkenyl (Vi) functional group in the topcoat composition of 0.8 to 10, and preferably 1.2 to 8, more preferably 1.5 to 5. Present in an amount such that the molar ratio of The hydrosilylation catalyst is present in an amount of about 5 to about 500 ppm, preferably about 10 to about 100 ppm, based on the total weight of the alkenyl functional organopolysiloxane and organohydrogensiloxane in the topcoat composition.

を持つ、ビニル鎖末端化ポリシロキサンであり得、
式中、Ｒ^１４は不飽和のない一価の炭化水素ラジカルであり、Ｒ^１５はアルケニル不飽和を持つ炭化水素ラジカルであり、ｘは０から６３００であり、ｙは０から２５０であり、ｘ＋ｙの合計が少なくとも８０であるという条件である。一実施態様において、Ｒは置換のもしくは不置換のアリール、アルカリールもしくはアルキル基を含む。好ましくは、Ｒ^１４は、メチル、エチル、プロピルのようなアルキルであり、好ましくはメチル基であり、そしてＲ^１５はビニルもしくはビニルエーテル基である。 Alkenyl functional organopolysiloxanes suitable for use in the topcoat composition have the general formula:

A vinyl chain terminated polysiloxane having
Where R ¹⁴ is a monovalent hydrocarbon radical without unsaturation, R ¹⁵ is a hydrocarbon radical with alkenyl unsaturation, x is from 0 to 6300, y is from 0 to 250, x + y The total of at least 80. In one embodiment, R comprises a substituted or unsubstituted aryl, alkaryl or alkyl group. Preferably R ¹⁴ is an alkyl such as methyl, ethyl, propyl, preferably a methyl group, and R ¹⁵ is a vinyl or vinyl ether group.

Examples of preferred linear alkenyl functional organopolysiloxanes of the above formula suitable for the topcoat compositions of the present invention are (CH ₂ ═CH) (CH ₃ ) ₂ SiO [Si (CH ₃ ) ₂ O] _{100 [Si (CH 3) (CH} 2 CH 2 CH 2 CH 2 CH = CH 2) O] 2 -Si (CH 3) 2 (CH = CH 2), (CH 2 = CH) (CH 3) 2 SiO [ Si (CH ₃ ) ₂ O] ₁₀₀ [Si (CH ₃ ) (CH═CH ₂ ) O] ₂ Si (CH ₃ ) ₂ (CH═CH ₂ ), (CH ₂ ═CH) (CH ₃ ) ₂ SiO [ Si (CH ₃ ) ₂ O] ₆₃₀₀ [Si (CH ₃ ) (CH═CH ₂ ) O] ₂₅₀ Si (CH ₃ ) ₂ (CH═CH ₂ ), (CH ₂ ═CH) (CH ₃ ) ₂ SiO [ _{Si (CH 3) 2 O]} 6300 [ _{i (CH 3) (CH =} CH 2) O] 6 Si (CH 3) 2 (CH = CH 2), (CH 2 = CH) (CH 3) 2 SiO [Si (CH 3) 2 O] 80 Si (CH ₃ ) ₂ (CH═CH ₂ ), (CH ₂ ═CH) (CH ₃ ) ₂ SiO [Si (CH ₃ ) (CH═CH ₂ ) O] ₁₅₀ Si (CH ₃ ) ₂ (CH═CH ₂ ), And mixtures thereof.

The organohydrogensiloxane of the topcoat composition is
MD _r ^DH _S M
MD ^H _r M
MD _r ^DH _s ^MH
M ^H D _r D ^H _s M ^H and M ^H D _r M ^H
A substantially linear hydrogen siloxane having a formula selected from the group consisting of:
Where
M is defined as R ¹⁶ ₃ SiO _1/2
M ^H is defined as ^{_{H g R 16 3-g SiO}} 1/2,
D = R ¹⁶ R ¹⁶ SiO _2/2 and D ^H = R ¹⁶ HSiO _2/2 ,
Wherein R ¹⁶ is independently 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, and most preferably 1 and carbon atoms. A monovalent hydrocarbon of atoms, the subscripts r and s may be zero or positive numbers, the sum of r and s ranges from about 10 to about 100, and the sum of r and g is at least The condition is 2.

In another embodiment of the invention, R ¹⁶ comprises a substituted or unsubstituted aryl, alkaryl or alkyl group. Preferably R is alkyl, such as a methyl group.

In a preferred embodiment of the invention, the organohydrogensiloxane is MD ^H _k M, wherein k is greater than 0 and less than about 100, preferably 1 to 50, more preferably 2 to 25, and Most preferably, it is 5 to 10. M and ^DH are defined as described above.

  A universal platinum hydrosilylation catalyst catalyzes the addition reaction between carbon-carbon multiple bonds in the alkenyl functional polyorganosiloxanes described above and silicon-bonded hydrogen atoms in the organohydrogensiloxane crosslinkers of the present invention. It may be used as a hydrosilylation catalyst. In general, any hydrosilylation catalyst for addition crosslinking of the silicone composition may be used. Preferably used are metal-containing catalysts such as platinum, palladium, iridium, rhodium and ruthenium, with platinum and platinum compounds being preferred. Particularly preferred are polyorganosiloxane soluble platinum-vinylsiloxane strategies and hexachloroplatinic acid.

  Optionally, the topcoat composition contains a hydrosilylation metal catalyst inhibitor. Inhibitors are well known in the organosilicon field. Examples of various types of such metal catalyst inhibitors include unsaturated organic compounds such as ethylenically or aromatic unsaturated amides (US Pat. No. 4,337,332), acetylene compounds (US Pat. 3,445,420, US Pat. No. 4,347,346 and US Pat. No. 5,506,289), ethylenically unsaturated isocyanate (US Pat. No. 3,882,083), olefin siloxane (US No. 3,989,667), unsaturated hydrocarbon diesters (US Pat. No. 4,256,870, US Pat. No. 4,476,166 and US Pat. No. 4,562,096) and conjugated ene- In (U.S. Pat. No. 4,465,818 and U.S. Pat. No. 4,472,563), hydroperoxide (U.S. Pat. No. 4,061,609), (US Pat. No. 3,418,731), sulfoxide, amine, phosphine, phosphite, nitrile (US Pat. No. 3,344,111), diaziridine (US Pat. No. 4,043,977) half ester and Other organic compounds such as half amide (US Pat. No. 4,533,575), and various salts (such as US Pat. No. 3,461,185). The compositions of the present invention can contain inhibitors from any of these types of inhibitors.

  Inhibitors include ethylenically unsaturated amides, aromatic unsaturated amides, acetylene compounds, ethylenically unsaturated isocyanates, olefin siloxanes, unsaturated hydrocarbon diesters, unsaturated acid unsaturated hydrocarbon monoesters, conjugated enynes, hydroperoxides , Ketone, sulfoxide, amine, phosphine, phosphite, nitrile and diaziridine.

  Optionally, a solvent can be used in the topcoat composition. In a preferred embodiment, it contains from about 70 to about 95% by weight of inert solvent, preferably from about 80 to about 95% by weight. Suitable solvents include alkyl or aromatic hydrocarbons or mixtures thereof. Exemplary solvents include but are not limited to heptane, hexane and xylene. Optionally, ethers and alcohols are included in small amounts, usually less than 25% of the solvent system. Exemplary alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethylene glycol butyl ether, or combinations thereof. Other water miscible organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether and 2-butoxyethanol can also be utilized in small amounts if desired.

  Both the primer composition and the top composition can be made by simply mixing the components described above. Once the primer and topcoat compositions are made, they can be applied to the metal surface of the article or device.

  According to another embodiment of the present invention, (1) providing an article or device having at least one metal surface, (2) providing a primer composition and a coating composition according to the present invention, (3) said Contacting a metal surface with the undercoat composition to form an undercoat layer; (4) contacting the undercoat layer with the topcoat composition to form a topcoat; and (5) the undercoat. There is provided a method of making an article or device having a coated metal surface, comprising the steps of curing a layer and the topcoat, thereby making the article or device.

  The primer composition may be formed using a technique known to those skilled in the art, such as dip coating, brushing, wiping, spraying, total immersion, and the like. It can be applied to the surface and dip coating and spray coating are preferred techniques. If the primer composition contains a solvent, it is preferred to first evaporate the solvent before applying the topcoat composition to the substrate.

  The topcoat composition can be applied to the primed metal surface by techniques such as dip coating, brush coating, wipe coating, spray coating, full dip coating, and the like. Preferably, the needle can be dipped into the topcoat composition to form a topcoat on the needle.

  Curing of the primer and topcoat can be accomplished by conventional methods well known to those skilled in the art, such as, for example, heat curing in an oven. Suitable curing conditions depend on the coating composition. A preferred curing condition is to heat the coated substrate at 80 to 300 ° C. for a period of 1 or 2 seconds to about 20 minutes. A more preferred curing condition is to heat the coated substrate at 80 ° C. to 200 ° C. for a period of about 5 seconds to about 5 minutes.

  The coated articles or devices of the present invention can be used in many applications. The coating on the article is robust and exhibits a low coefficient of friction so that the coating is in healthcare-related articles or devices such as, for example, surgical devices, needles, preferably surgical needles, razors, and cutting / slicing devices. It is particularly useful. Applying this coating to a device such as a surgical needle can help improve the performance of the device that penetrates tissue with less force and is therefore a preferred embodiment.

  The following examples are illustrative and do not limit the invention disclosed and claimed herein. Unless otherwise stated, all parts and percentages are on a weight basis and all temperatures are in degrees Celsius. All patent applications, patents and other references cited herein are hereby incorporated by reference in their entirety.

Examples Examples 1-7 and Comparative Examples (a)-(g)
Part 1: components having the following structure preparation of the primer composition is mixed to form a subbing composition: 84.23 wt% of _{(T 89.5 D 9) x OH} , 0.5 wt% x ~ 2~5,15.70% by weight, based on the OH content of the _{T (OCH} 2 _{CH 3) ~2.5} and 725ppm iron chloride.

Second Part: Preparation of Topcoat Composition The following ingredients were mixed to form a topcoat composition: 96.67 parts hexane, 3.33 parts vinyl functional polydimethylsiloxane gum (48.34). Parts M ^vi D ₆₃₀₀ D ^vi ₂₅₀ M ^vi and 51.66 parts M ^vi D ₆₃₀₀ D ^vi ₆ M ^vi ), 0.033 parts crosslinker M ^vi Dl ₁₅₀ M ^vi and 0.028 parts platinum catalyst.

Part 3: Preparation of coated metal substrate 14 stainless steel panels (Q panel RS-14, 1.5 millimeters (0.06 inches) x 2.54 cm (1 inch) x 10.2 cm ( 4 inches)) set was cleaned. The primer composition prepared in the first part was wiped on 7 panels with a clean cloth and air dried for 10 minutes.

  The topcoat composition described in Part 2 of Examples 1-7 of seven primed panels and comparative examples (a)-(g) of the remaining seven unprimed panels using a dip coating technique Painted with objects.

  The coated panel was then placed in a forced air oven set at 190 ° C. and cured for 2, 2.5, 3, 3.5, 4, 4.5 and 5 minutes. They were removed from the oven and allowed to cool to room temperature. The dynamic coefficient of friction (CoF) for each coating polyurethane substrate was measured and the results are shown in Table 1. An Instrumentor SP-101B slip / peel tester was used to perform a CoF test according to ASTM standard D-1894. The results show that the presence of the subbing layer helps reduce the coefficient of friction of the coating. For example, as seen in Example 7 and Comparative Example (g), the dynamic friction coefficient decreased from 0.027 to 0.009 when the metal panel was primed compared to the unprimed substrate.

  Although the present invention has been described above with reference to specific embodiments thereof, it will be apparent that many changes, modifications and variations may be made without departing from the inventive concepts disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims.

Claims (22)

Metal surface, an undercoat layer deposited on the metal surface layer, and saw including a topcoat deposited on the undercoat layer, wherein the subbing layer is the silanol-containing organopolysiloxane resin and alkyl silicate It is formed from the undercoating composition containing a crosslinking agent, and a wherein an article said topcoat Ru is formed from a top coat composition containing an alkenyl-functional polyorganosiloxane, organo hydrogencarbonate siloxane and a hydrosilylation catalyst,
The alkyl silicate in the primer composition has the following formula:
Si (OR ¹⁰ ) (OR ¹¹ ) (OR ¹² ) (OR ¹³ )
[Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each represents an alkyl group containing 1 to 4 carbon atoms]
A condensate obtained by partially hydrolyzing at least one tetraalkylsilicate represented by
Goods.   The metal surface contains a metal selected from the group consisting of stainless steel, tungsten, nickel, cobalt, molybdenum, tin, vanadium, titanium, aluminum, iron, copper, zinc, silver, lead and combinations thereof. Item according to Item 1.   The article of claim 2, wherein the metal surface is made of stainless steel.   The article of claim 2, wherein the metal surface contains tungsten. The silanol-containing organopolysiloxane resin in the undercoat composition has the general formula:
M _a D _b T _c Q _d (Formula I)
Represented by
Where M = R ¹ R ² R ³ SiO _1/2 ; D = R ⁴ R ⁵ SiO _2/2 ; T = R ⁶ SiO _3/2 ; and Q = SiO _4/2 , where subscript Letters a, b, c and d are zero or positive numbers and the resin is between 5 centistokes and 10,000 centistokes based on a 50 wt% solids solution in an aromatic solvent And wherein each R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is independently hydrogen, hydroxyl, monovalent alkyl of C1 to C60 Radicals, C1-C60 monovalent haloalkyl radicals, C1-C60 monovalent aryl radicals, C1-C60 monovalent alkylaryl radicals and C1-C60 monovalent haloalkylaryl radicals? Is selected from the group consisting, wherein at least one of R ^1, R ² and R ³ according to the limitation that a hydroxyl,
The article according to any one of claims 1 to 4 . The silanol-containing organopolysiloxane has the general formula (II):
_{De TF} (Formula II)
Represented by
Wherein D = R ⁷ R ⁸ SiO _2/2 , T = R ⁹ SiO _3/2 , where each R ⁷ , R ⁸ and R ⁹ is independently alkyl, hydroxyl, alkoxy or acyloxy There is a condition that at least one of ^R 7, ^{R 8} and ^{R 9} in each molecule is hydroxyl, e is up to 1 60 or et 4 50, and is f 1 5, 4, and 5 0,
The article according to claim 5. The article according to any one of claims 1 to 6 , wherein the alkyl silicate is a condensate of tetraethyl silicate. The article according to any one of claims 1 to 7 , wherein the undercoat composition further contains a condensation catalyst. The article of claim 8 , wherein the catalyst is iron chloride. The alkenyl functional organopolysiloxane has the general formula:

A vinyl chain-terminated polysiloxane having
Wherein R ¹⁴ is a monovalent hydrocarbon radical having no unsaturation, R ¹⁵ is a hydrocarbon radical having alkenyl unsaturation, x is 0 to 6300, y is 0 to 250, and x + y Where the sum of is at least 80.
The article according to any one of claims 1 to 9 . The article of claim 10 , wherein R ¹⁴ is methyl and R ¹⁵ is vinyl or vinyl ether. The organohydrogensiloxane is
MD _r ^DH _S M
MD ^H _r M
MD _r ^DH _s ^MH
M ^H D _r D ^H _s M ^H and M ^H D _r M ^H
A substantially linear hydrogen siloxane having a formula selected from the group consisting of:
Where
M is defined as R ¹⁶ ₃ SiO _1/2
M ^H is defined as _{^{H g R 16 3-g SiO}} 1/2,
D = R ¹⁶ R ¹⁶ SiO _2/2 and D ^H = R ¹⁶ HSiO _2/2 ,
Where R ¹⁶ is independently a monovalent hydrocarbon of 1 to 40 carbon atoms, the subscripts r and s may be zero or positive, and the sum of r and s is 1 in the range of 0 to 1 00, with the proviso that the sum of r and g is at least 2,
The article according to any one of claims 1 to 11 . The organo hydrogensulfate siloxane is ^MD _{H k} M, where, k is greater than 0, not smaller than element 1 00 An article according to claim 12. The article according to any one of claims 1 to 13 , wherein the hydrosilylation catalyst is a platinum-based complex. The article according to any one of claims 1 to 14 , wherein the topcoat composition contains a solvent. The article according to any one of the preceding claims, wherein the article is a surgical needle. The article according to any one of the preceding claims, wherein the article is a surgical device. A method of making an article or device having a coated metal surface, (1) providing an article or device having at least one metal surface, (2) priming composition and the topcoat composition of claim 1 Providing a product, (3) contacting the metal surface with the primer composition to form a primer layer, and (4) contacting the primer layer with the topcoat composition to form a topcoat. (5) curing the subbing layer and the topcoat, thereby producing the article or device. 19. The method of claim 18 , wherein the step of contacting the metal surface with a primer composition is selected from the group consisting of dip coating, spray coating, brushing or wiping. 20. A method according to any of claims 18 to 19, wherein the method further comprises the step of drying the primer composition to form a primer layer. 21. A method according to any one of claims 18-20, wherein the subbing layer and the topcoat are cured at a temperature of 80 to 300 <0> C for a period of 2 seconds to 20 minutes. An article or device made by the method according to any one of claims 18-21 .