KR910003842B1 - Aorylic resin having pendant silane groups thereon - Google Patents

Abstract

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Description

Acrylic resin having a silane group of the side chain and its manufacturing method

The present invention provides a poly (meth) acrylate polymer having a pendant alkoxysilane group, a method for producing the same, a method for forming an adhesive coating for coating a substrate with a composition comprising the poly (meth) acrylate polymer, A method for further bonding a resinous sealant composition to the adhesive coating, wherein the composition is used to form the adhesive coating on a substrate, wherein the adhesive coating serves as a primer to the sealant composition; The present invention relates to a substrate having the adhesive polymer coating and a resinous sealant composition bonded to the primer coating thereon.

The term "poly (meth) acrylate" as used herein refers to homopolymers of esters of acrylic acid and esters of methacrylic acid, as well as air formed between the acrylic esters and / or methacrylic esters. Means coalescence.

Ward et al., US Pat. No. 4,146,585 (patented March 27, 1979) describes in detail a specific moisture-curable composition characterized as a "polymerizable adhesion promoter", which compositions 1-3 Silane grafted binary copolymers or terpolymers prepared by reacting isocyanato functional organosilanes containing two silicon-bonded hydrolysable groups with a hydroxy functional copolymer or terpolymer. ) Such copolymer or terpolymer starting materials essentially contain 25-60% by weight of vinyl chloride units polymerized in the material and 10-75% by weight of hydroxyallyl acrylate units copolymerized therewith, It may also optionally contain 0-30% by weight of another comonomer selected from the group consisting of alkyl esters of alpha, beta-ethylenically unsaturated carboxylic acids and vinyl esters of saturated fatty acids. The copolymers or terpolymers containing hydroxy groups of the side chains according to the content of hydroxyalkyl acrylates are reacted with isocyanato functional organosilanes of the following structure.

O = C = NR ³ -SiXnR ⁴ (3-n)

Wherein X is a hydrolyzable group (typically a lower alkoxy group), R ⁴ is hydrogen or lower alkyl up to 4 carbon atoms, n is an integer of 1-3 (preferably 3) and R ³ is It is a divalent aliphatic, aromatic, or aromatic aliphatic organic radical.

When such isocyanato functional organosilane is reacted with some or all of the side chain hydroxyl groups attached to the copolymer or the tripolymer backbone, the hydroxyl groups and the isocyanate groups react to form urethane bonds. The polymer backbone is modified to have a number of organosilane groups (each of which is linked to the polymer backbone by the urethane bonds described above) along the length of the polymer backbone. U.S. Pat. No. 4,146,585, described above, describes a variety of such urethane-bonded R ³ groups (see, eg, column 4). Among the isocyanato functional organosilanes described in the word-patent patent, isocyanate alkylalkoxy silanes which are preferred for use in the present invention, more preferably gamma-isocyanatopropyltriethoxysilane Isocyanate alkyltri (lower alkoxy) silanes.

As described in the word-patent US patent, it is known that the "polymerizable adhesion promoter" in the prior art is adhesively bonded to a non-porous substrate (especially inorganic substrates having oxidative surfaces such as glass and aluminum). In the presence of water, the hydrolyzable groups X present in the side chains on the polymer backbone are hydrolyzed, reacting on the one hand with hydroxy or other oxygen-containing groups present on the substrate, and on the other hand with mutual interaction (possibly Intermediate silanol) to form a crosslinked polymer by the presence of siloxane (—Si—O—Si) bonds. In addition, the U.S. Patent of the above-mentioned word describes that the above-mentioned coating applied to a non-porous substrate can be used as a primer coating for more easily bonding onto another substrate of another resin material.

It is claimed that the coating composition prepared in accordance with the above-mentioned U.S. patent has good weather resistance, but the weatherability of conventional polymers and compositions containing them is significantly behind the weather resistance of the compositions required in modern technology, especially in the automotive industry. Falls. If these compositions are used as adhesives in the manufacture of automobiles or as sealants for the installation of windshields and windshields in automobiles, they are the standards required by the automotive industry for such adhesives and sealants, in particular for heat, moisture and ultraviolet radiation. It does not meet the criteria for low power.

It is therefore an object of the present invention to provide polymers useful as adhesives and coatings which can meet the current stringent weather resistance standards as required in the automotive industry and methods of making and using such polymers.

This object can be achieved according to the invention by the development of a poly (meth) acrylate polymer having a side chain hydrolyzable alkoxysilane group thereon, wherein the poly (meth) acrylate has a side chain hydroxyl group thereon. The poly (meth) acrylate polymer is prepared by reacting with an isocyanato functional alkoxysilane in which 1-3 hydrolyzable lower alkoxy groups are present on the silicon atom. Such poly (meth) acrylate polymers are compositions for forming a tacky coating on a substrate (especially a non-porous substrate such as glass), used alone or in combination with a film-forming resin binder of any other material. Used. Such a tacky coating can also be used as a primer coating to easily bond another resinous sealant composition (eg, a water-curable polyurethane sealant) onto a substrate. This sealant may be used as an adhesive to bond the primer treated substrate to any other material, or may serve as a final coating. Adhesive coating made according to the invention using a composition essentially containing a poly (meth) acrylate polymer having a side chain hydrolyzable alkoxysilane group, and an adhesive made with a sealant bonded to such adhesive coating as a primer. Bonding and sealing have good weather resistance, i.e., long-term resistance to deterioration due to harmful effects such as heat, moisture and ultraviolet irradiation.

Poly (meth) acrylate polymers having side chain hydroxyl groups are known in the art and include, for example, "G-cure 867", "G-cure 868", "G-cure 869", and the like. Commercially available under the trademark " acryloid " such as " acryloid AU-608 ", " acryloid OL-42 " resin. These hydroxy functional acrylic and methacryl polymers are dissolved and supplied in different solvents, and examples of the solvent include toluene, xylene, ethylbenzene, aliphatic hydrocarbons, ethylene glycol monoethyl ether acetate. This polymer comprises one or more hydroxyalkyl acrylates or methacrylates having alkylene groups containing 2-6 carbon atoms and one or more alkyl acrylates or methacrylates having 1-8 carbon atoms in the alkyl group. And mixtures were prepared by heating together in a solution of a suitable solvent in the presence of a free radical initiator or the like. Methods for preparing such compounds are described, for example, in US Pat. No. 3,082,367 to O'Brien et al. However, the process according to this patent is particularly relevant for the preparation of compounds of relatively low molecular weight, which is carried out in the presence of a mercaptan which acts as a chain transfer agent and a molecular weight regulator. As is known in the art, relatively high molecular weight products similar to those used in accordance with the present invention can be obtained by reducing or completely eliminating the amount of chain transfer agent present. The weight average molecular weight of the poly (meth) acrylate polymers suitable for use in accordance with the present invention is from about 1000 to about 100,000, preferably from about 20,000 to 60,000.

Poly (meth) acrylate polymers of the type as described immediately above are isocyanato functionalities with hydrolyzable groups, according to known methods and according to the methods described in the above described partial amounts of US Pat. No. 4,146,585. Reacts with organosilanes In order to prevent the isocyanate group from reacting with the water in advance and to prevent coarse condensation of the coarse hydrolysis and hydrolyzable silane groups, it is suitable that the two reactive components are reacted under anhydrous conditions. These materials are reacted at a temperature of 0 ° C.-150 ° C., preferably at 23 ° C.-80 ° C., until no free isocyanate is detected in the reaction mixture by infrared spectrum. This reaction involves a catalyst that promotes the formation of a urethane bond, such as a first tin salt of carboxylic acid (e.g., tin tin octosan, tin oleic acid, tin tin acetate, stannic tin laurate), dicarboxylic acid di It is suitably carried out in the presence of a catalyst such as alkyl tin salts (eg dibutyltin dilaurate, dibutyltin diacetate), tertiary amines, or tin mercaptides. The amount of catalyst is generally used at 0.005-5% by weight of the catalyzed mixture, depending on the nature of the catalyst used.

By simply selecting the equivalent ratio of hydroxy groups to the isocyanate groups to be reacted, half or all of the hydroxy groups of the side chains present on the poly (meth) acrylate polymer backbone are formed to form a urethane bond, It can also be introduced into the side chain hydrolyzable polymer backbone.

The ratio of hydroxyalkyl (meth) acrylate monomers to alkyl (meth) acrylates in the polymer backbone can vary widely, but each polymer has at least two side chain hydroxyl groups, and typically irregularly along the polymer backbone. It contains at least two side chain hydroxyl groups located. The hydroxy equivalents of commercially available materials as described previously vary, for example, from 400 to 1000. In view of the acceptable molecular weight of the material, it is clear that this polymer can contain from 3-4 to 100 or more groups per polymer chain. Some or all of these may be reacted with isocyanato functional organosilanes to form urethane bonds that connect this organosilane graft to the polymer.

In forming the adhesive coating on the substrate, the polymer as described above and the method of its preparation can be applied to the substrate in the form of a polymer solution dissolved in a volatile organic solvent. The solution is applied to the substrate by conventional methods such as coating, spraying, dipping, painting, etc., and then the solvent is removed by evaporation, leaving a film residue of the polymer on the substrate. Prior to application of the polymer, the polymer is kept under anhydrous conditions to inhibit the coarse hydrolysis of the hydrolyzable groups. Of course, the solution to which the polymer is applied is also anhydrous. Once the material is exposed to room temperature atmospheric pressure on the substrate, the polymer is moisture cured in the presence of moisture in the atmosphere. As described above, such curing reactions not only form siloxane groups to crosslink the polymers, but also allow hydrolyzed silanes to be present on the substrate, particularly on substrates such as glass or aluminum. Oxidative groups as present). In addition, the polymers of the present invention may be combined with conventional coating additives that have been carefully dried in advance, examples of which include fillers (eg carbon black), titanium dioxide, surface-treated silica, and auxiliaries (eg ultraviolet light). Stabilizers, antioxidants).

In another embodiment, the polymers of the present invention (with or without conventional fillers and additives in the form as described above) differ from different resinous components, suitably miscible film-forming polymeric binders. It can also be combined. Mixing conventional polymers with these binders can improve the adhesion of the resulting mixture to the substrate and can also promote the adhesion of the compound to another resin (e.g., sealant compound) applied on the mixture. have. An example of a film-forming resin in combination with the polymer of the present invention to form a tacky coating is a poly (meth) acrylate starting material as described above with side chain hydroxyl groups. However, the hydroxyl group of the side chain should not be reacted with any other substance. As another example, the resins of the present invention may be mixed with a wide range of homopolymers and copolymers of poly (meth) acrylates. In addition, the novel polymers of the present invention may be mixed with thermoplastic polyurethanes or used to form a tacky coating on a substrate.

As mentioned above, coatings formed on a substrate using the novel polymers of the present invention can serve as primer coatings for further application of different resinous materials thereon, in which case the different resinous materials for the substrates. The binding of is greatly enhanced by the primers. Such different resinous compositions can be, for example, resinous sealant compositions. That is, the coating composition of the present invention, before the windshield or other automotive glass is bonded to the vehicle body with the polymerizable sealant composition (for example, a composition containing a polyurethane polymer as a main component), such windshield or other As a primer used in the automotive windshield of the can be used in the automotive industry. Suitable polyurethane sealant compositions of this type are described, for example, in US Pat. No. 3,779,794 to De Santis. The adhesion of the sealant to the substrate by the primer is improved by the binding of the primer to the substrate by the reaction as described above, the poly (meth) acrylate backbone of the primer composition, and the organic resin component of the sealant composition applied thereon; It is believed that it is due to the good miscibility of.

Likewise, a sticky coating can be formed on a substrate by a mixture of the novel polymers of the invention with other resins of the type described above, in which case the novel polymers of the invention It acts as an adhesion promoter. In addition, such coatings containing combinations of the polymers of the present invention with other resinous binder materials can also serve as primers for further application of another resinous material thereon.

In all cases as described above, conventional fillers and additives of the type as described above may also be incorporated, wherein such materials are carefully dried prior to mixing with the resin, thereby introducing moisture into the composition. Care should be taken to prevent premature curing due to this.

Hereinafter, the present invention and the advantages of the present invention will be further described with reference to Examples.

Example 1

210 g of a polyacrylate copolymer having a hydroxyl group of side chains in a three branched glass reaction vessel equipped with a condenser connected to a drying tube, a heating mantle, a thermometer and a mechanical stirrer, as a solvent 332 g of tetrahydrofuran, 52 g of gamma-isocyanatopropyltriethoxy silane, and 0.1 g of a dicarboxylic acid dialkyltin catalyst (newly marketed under the trademark "Formez UL-28") were added. The mixture was refluxed for 15 hours, i.e. until no isocyanate absorption peaks at 4.4μ were detected in the infrared stack rum of the reaction mixture. 30% of the contents of the container were solids.

The polyacrylate polymers used are those commercially available under the trademark "acryloid AU-608", and are copolymers having a molar ratio of about 4: 1 between butyl acrylate and hydroxyethyl acrylate. This material with a hydroxy equivalent weight of 600 was added into the reaction mixture as a solution of a mixture of cellosolve acetate and toluene. The weight average molecular weight of resin is about 19,300, and the equivalence ratio of OH and NCO group is 1: 1.

Example 2

According to the method of Example 1, 1703 g of the polyacrylate polymer of Example 1 was subjected to gamma-isocyanatopropyltriethoxy in 1485 g of methylethyl ketone as solvent in the presence of 0.5 g of the "UL-28" catalyst of Example 1 Reaction with 422 g of silane. In this mixture, the equivalent ratio of OH: NCO is 1.0: 1.0. That is, all side chain hydroxyl groups present in the starting polyacrylate polymer were converted to urethane bonds by reaction with isocyanates.

This material was reacted at 80 ° C. for 6 hours until no isocyanate was detected in the infrared spectrum. After the reaction, this solution was diluted by the addition of 1203 g of methylethyl ketone to contain 30% solids.

Example 3

According to the method of Examples 1 and 2, 1391 g of "acryloid AU-608" polyacrylate polymer and gamma-isocy in the presence of 0.4 g of "UL-28" catalyst described in Examples 1 and 2 258 g of anatopropyltriethoxy silane were reacted in 1082 g of methylethyl ketone. In this mixture, the equivalent ratio of OH: NCO is 1.0: 0.75. That is, not all of the side chain hydroxyl groups present in the starting polyacrylate polymer are converted to urethane bonds by reaction with isocyanates. The total amount of solids in this solution is 40%.

Example 4

137 g of "Acryloid AU-608" (polyacrylate polymer) in three branched glass reaction vessels equipped with a condenser connected to a drying tube, a heating mantle, a thermometer, and a mechanical stirrer (hydroxyl equivalent 0.137 ), 202.5 g of tetrahydrofuran as a solvent, 28.1 g of gamma-isocyanatopropyltrimethoxy silane (NCO equivalent 0.137), and 0.1 g of a "Formez UL-28" catalyst were added. This mixture was refluxed for 13 hours until no isocyanate absorption peak at 4.4μ was detected in the infrared spectrum of the reaction mixture. The solids content of the mixture was 30% and the OH: NCO equivalence ratio was 1.0: 1.0.

Example 5

In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, a "G-cure 867" (60% solution in a solvent mixture of 55% by weight cellosolve acetate, 19% by weight ethylbenzene and 26% by weight aliphatic hydrocarbon) A polyacrylic layer having a hydroxyl group of a side chain; 375 g (0.375 equivalents) of hydroxyl equivalent of solid resin = 600), gamma-isocyanatopropyltriethoxy silane (2.6 g90.375 G equivalent), and ethyl 591. 1 g of acetate and 0.16 g of “Formuls UL-28” catalyst were added. This reaction was carried out at 75 ° C. for 15 hours until no isocyanate absorption at 4.4 μ was detected in the infrared spectrum. The OH: NCO equivalence ratio is 1.0: 1.0 and the total solid content is 30% by weight.

Example 6

In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, "G-cure 868" (60% in a solvent mixture of 55% by weight cellosolve acetate, 19% by weight ethylbenzene and 26% by weight aliphatic hydrocarbon) As a solution, 200.0 g (0.15 equivalent) of hydroxyl equivalent-800 of a solid resin, 30.8 g (0.15 equivalent) of gamma-isocyanatopropyl trimethoxy silane, 271 .9 g of tetrahydrofuran, and 0.06 g of "Formuls UL-28 'catalyst. This reaction was carried out at 65 ° C. for 6 hours until no isocyanate absorption at 4.4 μ was detected in the infrared spectrum. The OH: NCO equivalence ratio is 1.0: 1.0, and the total amount of solids is 30% by weight.

Example 7

The silane grafted polyacrylate of Example 1 was synthesized to be used as a primer suitable for use in glass as follows.

100 g of the 30% silane grafted polyacrylate solution of Example 1 was mixed with 27.5 g of anhydrous carbon black in a ball mill of 1 quilt steel. This material was ground in a ball mill for at least 7½ Hegman fineness for 16 hours.

Thereafter, 62.5 g of the silane grafted polyacrylate solution of Example 1 was added to the black powder, followed by 37.5 g of anhydrous toluene, and the mixture was further ball milled under anhydrous conditions for 2 hours.

Example 8

The silane grafted polyacrylate of Example 2 was synthesized to be used as a primer suitable for use in glass as follows:

100 g of a 30% solution of silane grafted polyacrylate synthesized in methylethyl ketone as in Example 2 was mixed with 27.5 g of anhydrous carbon black in a 1 quart rigid ball mill. This material was ground in a ball mill for at least 7½ hegman powder for 16 hours.

Then, a solution obtained by dissolving 25 g of a polymethyl methacrylate copolymer commercially available under the trademark "acryloid B-48N" in 75 g of anhydrous toluene was added to the black powder, and the mixture was further ball milled for 2 hours under anhydrous conditions. It was.

Example 9

The silane grafted polyacrylate of Example 2 was synthesized to be used as a primer suitable for use in glass as follows:

50 g of a commercially available polymethyl methacrylate polymer ("acryloid A-11") was mixed with 55 g of anhydrous carbon black and 150 g of anhydrous methyl ethyl ketone in a 1 quart steel ball mill. This material was ground in a ball mill for at least 7½ hegman powder for 16 hours.

Thereafter, 200 g of the 30% silane grafted polyacrylate solution of Example 2 was added to the black powder, followed by 30 g of anhydrous methanol, and the mixture was further ball milled under anhydrous conditions for 2 hours.

Example 10

The silane grafted polyacrylate of Example 4 was synthesized to be used as a primer suitable for use in glass as follows:

50 g of a commercially available polymethyl methacrylate polymer ("acryloid B-50") was mixed with anhydrous carbon black 56 and 150 g of toluene anhydrous in a 1 quart steel ball mill. This material was ground in a ball mill to more than 7½ hegman powder for 16 hours.

Then, 200 g of the 30% silane grafted polyacrylate solution of Example 4 was added to the black powder, and the mixture was further ball milled under anhydrous conditions for 1 hour.

Example 11

The silane grafted polyacrylate of Example 3 (saccharide ratio of OH: NCO = 1: 0.75) was synthesized to be used as a primer suitable for use in glass as follows:

50 g of a commercially available polymethyl methacrylate polymer ("acryloid B-50") was mixed with 55 g of anhydrous carbon black and 150 g of anhydrous toluene in a 1 quart steel ball mill. This material was ground in a ball mill for at least 7½ hegman powder for 16 hours.

Thereafter, 200 g of the 40% silane-grafted polyacrylate solution of Example 3 was added to the black powder, followed by 20 g of anhydrous methanol, and the mixture was further ball milled for 1 hour under anhydrous conditions.

Example 12

The silane grafted polyacrylate of Example 1 was synthesized to be used as a primer suitable for use in glass as follows:

387 g of butyl acrylate and hydroxyethyl acrylated "acryloid AU-608" copolymer used as starting materials in the preparation of the polymer of Example 1 were 554 g of methyl ethyl ketone and anhydrous carbon black in a 1 gallon ball mill. Mix with 261 g. This material was ground in a ball mill to more than 7½ hegman powder.

Thereafter, 1951 g of a 30% solution of the silane grafted polyacrylate of Example 1 was added to the black powder, and further ball milled for 1 hour under anhydrous conditions.

Example 13

The silane grafted polyacrylate of Example 5 was synthesized to be used as a primer suitable for use in glass as follows.

40 g of "acryloid B-50" polymethylmethacrylate used as binder in Example 10 were mixed with 120 g of anhydrous toluene and 45 g of anhydrous carbon black in a 1 quart ball mill. This material was ground in a ball mill to more than 7½ hegman powder.

Then, 30% solution black powder of the silane grafted polyacrylate of Example 5 was added, followed by 20 g of anhydrous methanol, and further ball milling for 1 hour under anhydrous conditions.

Example 14

The silane grafted polyacrylate of Example 6 is suitable for use in glass by using the silane grafted polyacrylate of Example 6 in place of the silane grafted polyacrylate of Example 5 in the primer composition of Example 13. It was synthesized to be used as a primer.

Example 15

Each of the black synthesized compositions described in Examples 7-14 was applied by a brush onto each untreated clean glass plate of 1 "x 4" (2.54 cm x 10.16 cm) and dried for 5-10 minutes to a film. Formed. By storing this blackcoat for 7 days at room temperature under ambient atmospheric conditions, the blackcoat was aged and fully crosslinked in the presence of moisture in the atmosphere. The adhesive strength of this coating was tested by attaching and detaching the adhesive tape labeled "Scotch". If the tape does not remove the coating from the glass substrate, the adhesion is good. The weathering test was then performed by storing the aged and coated glass plates in a wet cabinet at 100% relative humidity and 100 ^° F (about 38 ° C.) for three weeks.

In each of these eight coatings, there was no appreciable effect on the adhesion even under extreme conditions of temperature and humidity. That is, in each case, when the coating was removed from the glass substrate using the adhesive tape as described above, each coating did not fall from the glass substrate.

Example 16

The compositions of Examples 7-14 were each coated with a brush on a 1 "x 4" (2.54 cm x 10.16 cm) glass plate and aged at room temperature as in Example 15, then these glass plates were atlas twin enclosed. The carbon etc. "Weather-O-Meter" model was exposed to UV and humidity and heat by maintaining the temperature by 190 ^° F (approx. 88 ° C.) H by means of interstitial water spray while placed in the CDMC for 1000 hours.

When the glass plates thus coated were examined after being tested, the adhesive properties of the coatings were not changed at all by the adhesive tapes as in Example 15. That is, in each case, the adhesive tape before and after the gas phase action as described above did not remove the coating from the glass substrate.

Example 17

In this Example, it is an Example about using the composition of this invention as a primer which continues to apply an adhesive sealant composition.

The clean, untreated glass surface and painted metal surface were bonded together as follows:

Using the method of Example 15, one by one of the primer compositions of Examples 7 to 14 were individually coated on a 1 " x 4 " (10.16 cm x 2.54 cm) glass plate, respectively. Thereafter, a mixture of carbon black and an inorganic filler further mixed with a mixture of polyoxypropylene diol and polyoxyflopylenetriol as described in US Pat. No. 3,779,794 is reacted with diphenylmethane-4,4'-diisocyanate. The beads and primers of the resulting water-curable polyurethane composition (0.64 cm wide, .085 cm high) were placed across the 1 "(2.54 cm) edge of each of the coated glass plates to obtain a 1" sealant and a primer. A contact was made over an area of 4 " (2.54 cm x 0.64 cm).

Thereafter, 1 ″ × 4 ″ (2.54 cm × 10.16 cm) painted metal plates were placed on each seal bead and the seal beads were compressed to 1/4 ”(0.64 cm) in height.

The laminate thus obtained was moisture-cured for 1 day at room temperature and humidity conditions.

Thereafter, the bonded composite was left to stand in a humidity box having a relative humidity of 100% and a temperature of 100 ^° F (about 38 ° C.) for 7 days, thereby measuring the resistance of the composite to humidity. Laminate shear strength was then inspected using an "Instron" tester, in which case the bond of the polyurethane sealant was broken at a shear strength value of 500 psi.

The weather resistance of the bonded composite was tested by exposure to humidity and ultraviolet light for 1000 hours while passing ultraviolet light through a glass plate in an "Twin-O-Meter" model CDMC such as the Atlas Twin Enclosed Carbon. When the liver blood test, the temperature was maintained at 190 ^o F (about 88 ℃) by water powder. When tested for moderate partial strength in an "instro" tester, in each case the bond was broken at a shear force of 600 psi.

For both humidity and weather resistance tests, the primers according to the invention remained intact and maintained complete adhesion on the glass surface to which it was applied.

Claims (13)

With one or more hydroxyalkyl acrylates or methacrylates having alkylene groups containing 2 to 6 carbon atoms and one or more alkyl acrylates or methacrylates having 1 to 8 carbon atoms in the alkyl group At least 75 equivalent% of the hydroxy group of the poly (meth) acrylate polymer having 3 to 100 side chain hydroxyl groups per molecule, which is a copolymer formed from the monomer mixture constituted, isocyanate of the following general formula (1) It is prepared by reacting an isocyanate group of an iso functional alkoxysilane, and has a packed average molecular weight of about 1,000 to about 100,000, and has a side chain hydrolyzable alkoxysilane group attached to a poly (meth) acrylate backbone by a urethane bond. Poly (meth) acrylate polymers. OCN-R ³ -Six _n R ⁴ (3-n) (I) Wherein X is lower alkoxy, R ⁴ is hydrogen or lower alkyl, n is an integer from 1 to 3, and R ⁴ is a divalent aliphatic, aromatic or aliphatic organic radical. The polymer of claim 1, wherein the alkoxysilane is isocyanatoalkyltri (lower monoxoxy) silane. The polymer of claim 1, wherein the alkoxysilane is gamma isocyanatopropyltriethoxysilane. The polymer of claim 1, wherein the alkoxysilane is gamma isocyanatopropyltriethoxysilane. The polymer of claim 1 wherein the weight average molecular weight is 20,000 to 60,000. Some or all of the hydroxyl groups of the poly (meth) acrylate polymer having a hydroxyl group of the side chain are reacted with an isocyanate group of the isocyanate functional alkoxysilane of the following general formula (I), A poly (meth) acrylate polymer having a side chain hydrolyzable alkoxysilane group grafted to a meta) acrylate backbone. OCN-R ³ -Six _n R ⁴ (3-n) (I) Wherein X is alkoxy, R ⁴ is hydrogen or alkyl, n is an integer from 1 to 3, and R ³ is a divalent aliphatic, aromatic or aromatic aliphatic organic radical. Poly (meth) acrylates prepared by reacting poly (meth) acrylate polymers having side chain hydroxyl groups with isocyanato functional alkoxysilanes having 1 to 3 hydrolyzable lower alkoxy groups present on silicon atoms A poly (meth) acrylate polymer having a hydrolyzable alkoxysilane group grafted onto the main chain. Side chain hydrolyzable, consisting of reacting a poly (meth) acrylate polymer having a side chain hydroxyl group with an isocyanato functional alkoxysilane having 1 to 3 hydrolyzable lower alkoxy groups present on the silicon atom. The manufacturing method of the said poly (meth) acrylate polymer of Claim 7 which has an alkoxysilane group. Consisting of applying a resinous composition comprising the poly (meth) acrylate polymer of claim 7 having a side chain hydrolyzable alkoxysilane group to a substrate, and then hydrolyzing the side chain hydrolyzable alkoxysilane group in the presence of moisture, A method of forming a weather resistant adhesive coating on a substrate. 10. The method of claim 9, wherein the resinous composition optionally comprises a film-forming resinous binder component different from the poly (meth) acrylate polymer. 10. The method of claim 9, wherein the substrate is glass. 10. The method of claim 9, wherein a resinous sealant composition is further applied onto the adhesive coating, wherein the adhesive coating acts as a primer to the sealant composition. 10. The method of claim 9, wherein the resinous sealant composition is a moisture curable polyurethane sealant.