JP6204508B2 - Epoxysiloxane coating composition - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of US 13 / 415,925 filed March 9, 2012, the disclosure of which is hereby incorporated by reference in its entirety.

FIELD OF THE DISCLOSURE The present disclosure relates to epoxy resin-based compositions useful for protective coatings and the like, and more particularly, with conventional epoxy polysiloxane coating formulations with improved properties of flexibility, weather resistance and low shrinkage. It relates to an epoxy-polysiloxane polymer composition having at least equivalent corrosion resistance, compressive strength and chemical resistance.

Background Epoxy coating materials are well known in the maintenance, marine, construction, architecture, aircraft, automotive, flooring and product finishing markets as protective, decorative coatings for steel, aluminum, plating, wood and concrete, and commercial Is recognized. The basic raw materials used to prepare such coatings generally include (a) an epoxy resin, (b) a curing agent, and (c) a pigment, aggregate or other component as essential components. Including.

  Epoxide resins have more than one 1,2-epoxy group per molecule and can be saturated or unsaturated aliphatic, alicyclic or heterocyclic. Epoxy resins generally contain glycidyl ester groups or glycidyl ether groups and have a weight of 100 to 5,000 per epoxide. Curing agents are typically selected from the general types of aliphatic amines or aliphatic amine adducts, polyamides, polyamidoamines, cycloaliphatic amines, aromatic amines, Mannich bases, ketimines, and carboxylic acid derivatives. . Examples of pigments and aggregates include titanium dioxide and other inorganic and organic color pigments, silica, barium sulfate, magnesium silicate, calcium silicate, fumed silica, garnet, feldspar, carbon black and the like.

  Epoxy-based protective coatings are one of the most widely used corrosion control methods. This coating can be used to provide long-term protection of steel, concrete, aluminum and other structures under a wide range of corrosive conditions ranging from atmospheric exposure to complete immersion in strong corrosive liquids. For more than 20 years, this coating has been made using solid or liquid epoxy resins cured with aliphatic polyamines, or polyamide resins such as Shell Epon 1001, or diethylenetriamine (DETA) or Versamid 100 series polyamides. One of the cured Epon 828 epoxy resins is blended. In a typical two-part coating system, the epoxy resin component is usually the vehicle for pigment grinding and dispersion of other aggregates and various additives.

  Epoxy protective coatings have many properties that make them desirable as coating materials. The coating is readily available and is easily applied by various methods such as spraying, rolling and brushing. The coating adheres well to steel, concrete and other substrates, has a low water vapor transmission rate, acts as a barrier to the ingress of water, chloride and sulfate ions and has excellent corrosion under various atmospheric exposure conditions Provides protection and has good resistance to many chemicals and solvents.

  Epoxy-based materials can also be formulated as a primer or flooring material that is applied primarily to concrete. For example, one commercially successful epoxy flooring material uses liquid bisphenol A epoxy resin and modified aliphatic polyamine in combination with graded silica sand aggregate.

  Some specific epoxy-based coating materials and flooring materials may not exhibit good resistance to sunlight weather conditions. The chemical and corrosion resistance of such coatings can be maintained, but when exposed to the ultraviolet (UV) light component of sunlight, as whitening (which changes the retention of both the original coating's color and gloss) Known surface degradation phenomena can result. Where color and gloss retention is desired or required, the epoxy protective coating is typically topcoated with a more weather resistant coating, such as an alkyd, vinyl or aliphatic polyurethane coating. The end result is that there are two or even three coat systems that provide the desired corrosion and weather resistance, but at the same time, the application is labor intensive and expensive.

  Epoxy coating materials and flooring materials are also required to be resistant to mechanical abuse. For example, the coated material can be subjected to impact or bending that can result in cracking or other defects in the epoxy coating. Subsequent exposure to weathering conditions or chemicals may result in contact with the chemical and the underlying surface material, oxidation of the underlying material from the inner surface and / or by peeling of the epoxy coating from the surface, epoxy coating May lead to degradation.

  Epoxy coating materials and flooring materials are widely recognized commercially, but nevertheless improved chemical and corrosion resistance, resistance to mechanical abuse (such as bending or impact), and improved color or gloss There remains a need for epoxy-based materials having a retention of Whenever it can be exposed to sunlight, epoxy coating materials and flooring materials with improved color and gloss retention are needed. Epoxy coatings that do not whiten and do not require a weather resistant top coat are desirable. Coating materials and flooring materials with improved chemical, corrosion, impact, flex and wear resistance are used in both primary and secondary chemical containment structures to protect steel and concrete, Needed in the power generation, railcar, sewage and wastewater treatment, automotive, and paper and pulp processing industries. Improved epoxy flooring materials must be repeatedly cleaned with steam and harsh chemicals in industrial environments where heavy impact loads such as shipping and receiving docks can be expected (eg, for food processing, meat packaging and beverages). Necessary for floors where spilling caustic, acid and highly reactive chemicals cannot be avoided.

  Thus, according to the present disclosure, one of improved chemical resistance, weather resistance, corrosion resistance, resistance to mechanical abuse, flexibility, high extensibility and compressive strength, and excellent impact and wear resistance. Alternatively, several new epoxy coating compositions and flooring compositions are provided.

を有するポリシロキサン；１分子あたり１つより多くの１，２−エポキシド基を有し、エポキシド換算重量が１００〜５，０００である非芳香族エポキシド樹脂；および少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂を含むブレンドを含む硬化系（ここで、ブレンドは１０重量％〜２５重量％のアルコキシ含有量を有する）を含むエポキシ−ポリシロキサンポリマーコーティング組成物を提供する。このポリシロキサン配合物によれば、各Ｒ_１はヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ_２は独立して、水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される。 SUMMARY OF THE INVENTION In accordance with the present disclosure, new epoxy-polysiloxane polymer coating compositions are provided. According to a first embodiment, according to the present disclosure, water, formula:

A non-aromatic epoxide resin having more than one 1,2-epoxide group per molecule and an epoxide equivalent weight of 100 to 5,000; and at least one trialkoxy-functional aminosilane; There is provided an epoxy-polysiloxane polymer coating composition comprising a curing system comprising a blend comprising at least one aminofunctional polysiloxane resin, wherein the blend has an alkoxy content of 10 wt% to 25 wt%. According to this polysiloxane formulation, each R ₁ is a hydroxy group, or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is independently hydrogen, or up to 6 carbons. It is an alkyl or aryl group having an atom, and n is selected such that the molecular weight of the polysiloxane is 400 to 10,000.

を有する２０％〜８０重量％のポリシロキサン；１分子あたり１つより多くの１，２−エポキシド基を有し、エポキシド換算重量が１００〜５，０００である２０％〜８０重量％の非芳香族エポキシド樹脂；オクタン酸塩、ドデカン酸塩またはナフタン酸塩（ｎａｐｈｔｈａｎａｔｅ）の形態のスズ触媒を含む１５重量％までの硬化促進剤；ヒマシ油のグリシジルエーテルに基づき、２００〜１，０００のエポキシド換算重量を有する１５重量％までの軟質エポキシ樹脂；および少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂のブレンドを含む５％〜４０重量％の硬化系（ここで、ブレンドは２．２〜２．８の平均アルコキシ官能基数（ｆｕｎｃｔｉｏｎａｌｉｔｙ ｖａｌｕｅ）を有し、コーティング組成物においてアミン当量対エポキシド当量が０．７：１．０〜１．３：１．０となるのに十分な量で添加される）を含むエポキシ−ポリシロキサンポリマーコーティング組成物を提供する。このポリシロキサン配合物によれば、各Ｒ_１はヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ_２は水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される。アミノ官能性ポリシロキサン樹脂は、一般式

を有し；トリアルコキシ官能性アミノシランは、一般式

を有し；
式中、Ｒ_５は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から選択される二官能性の有機原子団であり、各Ｒ_６は独立して、６個未満の炭素原子を含むアルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルコキシアルキル基であり、各Ｒ_８は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から独立して選択される二官能性の有機原子団であり、各Ｒ_９は独立して、アリール、フェニル、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_１〜Ｃ_４）アルコキシまたは−ＯＳｉ（Ｒ_９）_２Ｒ_８ＮＨ_２基であり、ｍは、ブレンドが１１２〜２５０ｇ／ＮＨのアミン換算重量を有するように選択される。 In another embodiment, according to the present disclosure, water, formula:

20% to 80% by weight of polysiloxane having 20% to 80% by weight of non-aromatic having more than one 1,2-epoxide group per molecule and having an epoxide equivalent weight of 100 to 5,000 Epoxide resin; up to 15% by weight of a curing accelerator containing a tin catalyst in the form of octanoate, dodecanoate or naphthanate; epoxide conversion of 200 to 1,000, based on glycidyl ether of castor oil Up to 15% by weight of a flexible epoxy resin; and 5% to 40% by weight of a curing system comprising a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin, where the blend is An average alkoxy functional group value of 2.2 to 2.8 And is added in an amount sufficient to provide an amine equivalent to an epoxide equivalent of 0.7: 1.0 to 1.3: 1.0 in the coating composition). I will provide a. According to this polysiloxane formulation, each R ₁ is a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is hydrogen or an alkyl having up to 6 carbon atoms. Or it is an aryl group and n is selected so that the molecular weight of polysiloxane may be 400-10,000. Amino-functional polysiloxane resin has the general formula

A trialkoxy-functional aminosilane has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH ₂ and m has an amine equivalent weight of 112 to 250 g / NH in the blend. Selected to do.

  In another embodiment, the present disclosure provides a coated substrate with at least one surface coated with the epoxy-polysiloxane polymer coating composition described herein.

を有するポリシロキサン；１分子あたり１つより多くの１，２−エポキシド基を有し、エポキシド換算重量が１００〜５，０００である非芳香族エポキシド樹脂を含む。このポリシロキサン配合物によれば、各Ｒ_１はヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ_２は水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される。硬化系は、少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂のブレンド；および任意選択で、少なくとも１つの金属触媒を含む硬化促進剤を含む。
例えば、本発明は、以下の項目を提供する。
（項目１）
水；
式

（式中、各Ｒ _１ は独立して、ヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ _２ は独立して、水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される）
を有するポリシロキサン；
１分子あたり１つより多くの１，２−エポキシド基を有し、エポキシド換算重量が１００〜５，０００である非芳香族エポキシド樹脂；および
少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂を含むブレンドを含む硬化系（該ブレンドは１０重量％〜２５重量％のアルコキシ含有量を有する）
を含む、エポキシ−ポリシロキサンポリマーコーティング組成物。
（項目２）
前記トリアルコキシ官能性アミノシランが一般式

を有し；そして
前記アミノ官能性ポリシロキサン樹脂が一般式

を有し；
式中、Ｒ _５ は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から選択される二官能性の有機原子団であり、各Ｒ _６ は独立して、６個未満の炭素原子を含むアルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルコキシアルキル基であり、各Ｒ _８ は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から独立して選択される二官能性の有機原子団であり、各Ｒ _９ は独立して、アリール、フェニル、（Ｃ _１ 〜Ｃ _４ ）アルキル、（Ｃ _１ 〜Ｃ _４ ）アルコキシまたは−ＯＳｉ（Ｒ _９ ） _２ Ｒ _８ ＮＨ _２ 基であり、ｍは、前記ブレンドが１１２〜２５０ｇ／ＮＨの範囲のアミン換算重量を有するように選択される、
項目１に記載のコーティング組成物。
（項目３）
Ｒ _５ が、（Ｃ _１ 〜Ｃ _６ ）アルキルまたは（Ｃ _１ 〜Ｃ _６ ）アルキルアミノ（Ｃ _１ 〜Ｃ _６ ）アルキル基から選択される二官能性の有機原子団であり、各Ｒ _６ が独立して（Ｃ _１ 〜Ｃ _６ ）アルキル基である、項目２に記載の組成物。
（項目４）
前記少なくとも１つのトリアルコキシ官能性アミノシランが、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルトリプロポキシシラン、アミノネオヘキシルトリメトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルトリメトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルトリエトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン、トリメトキシシリルプロピルジエチレントリアミン、３−（３−アミノフェノキシ）プロピルトリメトキシシラン、アミノエチルアミノメチルフェニルトリメトキシシラン、２−アミノエチル−３−アミノプロピル−トリス−２−エチルヘキソキシシラン、Ｎ−アミノヘキシルアミノプロピルトリメトキシシランおよび／またはトリスアミノプロピルトリスメトキシエトキシシランを含む、項目１に記載の組成物。
（項目５）
前記少なくとも１つのアミノ官能性ポリシロキサン樹脂が、式中のＲ _９ が７０％より多くのフェニル基、３０％未満の（Ｃ _１ 〜Ｃ _４ ）アルキル基および２．０％未満の（Ｃ _１ 〜Ｃ _４ ）アルコキシ基を含む構造を有する、項目１に記載の組成物。
（項目６）
Ｒ _９ が０．５％未満の（Ｃ _１ 〜Ｃ _４ ）アルコキシ基を含む、項目５に記載の組成物。
（項目７）
前記少なくとも１つのアミノ官能性ポリシロキサン樹脂がアミノ官能性フェニルメチルポリシロキサン樹脂を含む、項目１に記載の組成物。
（項目８）
前記少なくとも１つのアミノ官能性ポリシロキサン樹脂が２４０〜２８０ｇ／ＮＨのアミン換算重量を有する、項目７に記載の組成物。
（項目９）
前記硬化系が１５％〜８５重量％の前記少なくとも１つのトリアルコキシ官能性アミノシランと８５％〜１５％の前記少なくとも１つのアミノ官能性ポリシロキサン樹脂を含む、項目１に記載の組成物。
（項目１０）
前記硬化系が、２．２〜２．８の平均アルコキシ官能基数を有するブレンドを含む、項目１に記載の組成物。
（項目１１）
前記コーティング組成物が、２０％〜８０重量％の前記ポリシロキサン、２０％〜８０重量％の前記非芳香族エポキシ樹脂および５％〜４０重量％の前記硬化系を含む、項目１に記載のコーティング組成物。
（項目１２）
前記コーティング組成物が、０．７：１．０〜１．３：１．０の範囲であるアミン当量対エポキシド当量の比を含む、項目１に記載のコーティング組成物。
（項目１３）
前記非芳香族エポキシド樹脂が、水素化シクロヘキサンジメタノールまたは水素化ビスフェノールＡエポキシド樹脂のジグリシジルエーテルを含む脂環式エポキシド樹脂を含む、項目１に記載のコーティング組成物。
（項目１４）
さらに、ヒマシ油のグリシジルエーテルに基づき、２００〜１，０００のエポキシド換算重量を有する軟質エポキシ樹脂を含む、項目１に記載のコーティング組成物。
（項目１５）
前記コーティング組成物が、１５重量％までの前記軟質エポキシ樹脂を含む、項目１４に記載のコーティング組成物。
（項目１６）
さらに、各々がオクタン酸塩、ネオデカン酸塩またはナフタン酸塩の形態の亜鉛、マンガン、ジルコニウム、チタン、コバルト、鉄、鉛および／またはスズ触媒を含む１５％までの硬化促進剤を含む、項目１に記載のコーティング組成物。
（項目１７）
さらに、亜鉛もしくはホスフェート系腐食防止剤または有機系腐食防止剤を含む１つまたは複数の腐食防止剤を含む、項目１に記載のコーティング組成物。
（項目１８）
水；
式

（式中、各Ｒ _１ は、独立して、ヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ _２ は独立して、水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される）
を有する２０％〜８０重量％のポリシロキサン；
１分子あたり１つより多くの１，２−エポキシド基および１００〜５，０００のエポキシド換算重量を含む２０％〜８０重量％の非芳香族エポキシド樹脂；
オクタン酸塩、ドデカン酸塩またはナフタン酸塩の形態のスズ触媒を含む１５重量％までの硬化促進剤；
１５重量％までのヒマシ油のグリシジルエーテルに基づき、２００〜１，０００のエポキシド換算重量を有する軟質エポキシ樹脂；および
少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂のブレンドを含む５％〜４０重量％の硬化系
を含むエポキシ−ポリシロキサンポリマーコーティング組成物であって、
該トリアルコキシ官能性アミノシランが一般式

を有し；
該アミノ官能性ポリシロキサン樹脂が一般式

を有し；
式中、Ｒ _５ は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から選択される二官能性の有機原子団であり、各Ｒ _６ は独立して、６個未満の炭素原子を含むアルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルコキシアルキル基であり、各Ｒ _８ は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルまたはシクロアルキル原子団から独立して選択される二官能性の有機原子団であり、各Ｒ _９ は独立して、アリール、フェニル、（Ｃ _１ 〜Ｃ _４ ）アルキル、（Ｃ _１ 〜Ｃ _４ ）アルコキシまたは−ＯＳｉ（Ｒ _９ ） _２ Ｒ _８ ＮＨ _２ 基であり、ｍは、該ブレンドが１１２〜２５０ｇ／ＮＨのアミン換算重量を有するものとなるように選択され、該ブレンドは２．２〜２．８の平均アルコキシ官能基数を有し、該コーティング組成物においてアミン当量対エポキシド当量が０．７：１．０〜１．３：１．０となるのに十分な量で添加される、
エポキシ−ポリシロキサンポリマーコーティング組成物。
（項目１９）
各Ｒ _６ が独立して（Ｃ _１ 〜Ｃ _６ ）アルキル基であり、Ｒ _５ が（Ｃ _１ 〜Ｃ _６ ）アルキル基または（Ｃ _１ 〜Ｃ _６ ）アルキルアミノ（Ｃ _１ 〜Ｃ _６ ）アルキル基であり、各Ｒ _９ がメチルまたはフェニルである、項目１８に記載のコーティング組成物。
（項目２０）
前記少なくとも１つのトリアルコキシ官能性アミノシランが、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルトリプロポキシシラン、アミノネオヘキシルトリメトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルトリメトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルトリエトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン、トリメトキシシリルプロピルジエチレントリアミン、３−（３−アミノフェノキシ）プロピルトリメトキシシラン、アミノエチルアミノメチルフェニルトリメトキシシラン、２−アミノエチル−３−アミノプロピル−トリス−２−エチルヘキソキシシラン、Ｎ−アミノヘキシルアミノプロピルトリメトキシシランおよび／またはトリスアミノプロピルトリスメトキシエトキシシランを含み；
前記少なくとも１つのアミノ官能性ポリシロキサン樹脂がアミノ官能性フェニルメチルポリシロキサン樹脂である、
項目１８に記載のコーティング組成物。
（項目２１）
項目１に記載のコーティング組成物で被覆された少なくとも１つの表面を含む被覆基材。
（項目２２）
基材の表面を化学薬品、腐食および耐候条件のうちの１つまたは複数の望ましくない結果から：
水；
式

（式中、各Ｒ _１ はヒドロキシ基、または６個までの炭素原子を有するアルキル、アリールもしくはアルコキシ基であり、各Ｒ _２ は水素、または６個までの炭素原子を有するアルキルもしくはアリール基であり、ｎは、ポリシロキサンの分子量が４００〜１０，０００となるように選択される）
を有するポリシロキサン；
１分子あたり１つより多くの１，２−エポキシド基および１００〜５，０００の範囲のエポキシド換算重量を含む非芳香族エポキシド樹脂
を含む樹脂成分を調製する工程；
該樹脂成分に硬化系を添加し、十分に硬化したエポキシ変性ポリシロキサンコーティング組成物を形成する工程であって、該硬化系は：
少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂のブレンド
；および
任意選択で、少なくとも１つの金属触媒を含む硬化促進剤
を含み、
該ブレンドは２．２〜２．８の平均アルコキシ官能基数を有する工程；ならびに
該コーティング組成物が十分に硬化した状態になる前に、該コーティング組成物を保護対象の基材の表面に塗布する工程
を含む方法によって調製されるコーティング組成物で該表面をコーティングすることにより保護する方法。
（項目２３）
前記樹脂成分がさらに、ヒマシ油のグリシジルエーテルに基づき、２００〜１，０００のエポキシド換算重量を有する軟質エポキシ樹脂を含む、項目２２に記載のコーティング組成物。 In another embodiment, the present disclosure provides for the step of preparing a resin composition from the undesirable result of one or more of chemical, corrosion and weathering conditions on the surface of a substrate, adding a curing system to the resin component Forming a fully cured epoxy-modified polysiloxane coating composition, wherein the blend has an average number of alkoxy functional groups of 2.2 to 2.8, and the coating composition is fully cured Before becoming, a method of protecting by coating a surface with a coating composition prepared by a method comprising the step of applying the composition to the surface of a substrate to be protected is provided. The resin composition is water, formula:

A non-aromatic epoxide resin having more than one 1,2-epoxide group per molecule and an epoxide equivalent weight of 100 to 5,000. According to this polysiloxane formulation, each R ₁ is a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is hydrogen or an alkyl having up to 6 carbon atoms. Or it is an aryl group and n is selected so that the molecular weight of polysiloxane may be 400-10,000. The curing system includes a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin; and, optionally, a curing accelerator that includes at least one metal catalyst.
For example, the present invention provides the following items.
(Item 1)
water;
formula

Wherein each R ₁ is independently a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is independently hydrogen or up to 6 carbon atoms. And n is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
A polysiloxane having
A non-aromatic epoxide resin having more than one 1,2-epoxide group per molecule and having an epoxide equivalent weight of 100 to 5,000; and
Curing system comprising a blend comprising at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin (the blend has an alkoxy content of 10% to 25% by weight)
An epoxy-polysiloxane polymer coating composition comprising:
(Item 2)
The trialkoxy-functional aminosilane has the general formula

And having
The aminofunctional polysiloxane resin has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH a ₂ group, m is an amine conversion range the blend of 112~250g / NH Selected to have a calculated weight,
Item 4. The coating composition according to Item 1.
(Item 3)
R ₅ is a bifunctional organic atomic group selected from (C ₁ -C ₆ ) alkyl or (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl groups, and each R ₆ is independently The composition according to item 2, wherein the composition is a (C ₁ -C ₆ ) alkyl group.
(Item 4)
The at least one trialkoxy-functional aminosilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminonehexyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3- (3-aminophenoxy) propyltrimethoxysilane, aminoethylaminomethylphenyltri Methoxysilane, 2-aminoethyl-3-aminopropyl-tris-2-ethylhexoxysilane, N-aminohexylaminopropyltrimethoxysilane and / or trisami Including tris methoxyethoxy silane composition of claim 1.
(Item 5)
Wherein at least one amino-functional polysiloxane resin is more phenyl groups from _{R 9} is 70% wherein less than 30% _(C 1 ~C ₄₎ alkyl group and less than 2.0% _(C 1 ~ C ₄₎ having a structure containing an alkoxy group the composition of claim 1.
(Item 6)
R ₉ comprises a _(C 1 _{~C 4)} alkoxy groups of less than 0.5% The composition of claim 5.
(Item 7)
The composition of claim 1, wherein the at least one aminofunctional polysiloxane resin comprises an aminofunctional phenylmethylpolysiloxane resin.
(Item 8)
Item 8. The composition according to Item 7, wherein the at least one aminofunctional polysiloxane resin has an amine equivalent weight of 240 to 280 g / NH.
(Item 9)
The composition of claim 1, wherein the curing system comprises 15% to 85% by weight of the at least one trialkoxy-functional aminosilane and 85% to 15% of the at least one amino-functional polysiloxane resin.
(Item 10)
The composition of item 1, wherein the curing system comprises a blend having an average number of alkoxy functional groups of 2.2 to 2.8.
(Item 11)
The coating of claim 1, wherein the coating composition comprises 20% to 80% by weight of the polysiloxane, 20% to 80% by weight of the non-aromatic epoxy resin and 5% to 40% by weight of the curing system. Composition.
(Item 12)
The coating composition of claim 1, wherein the coating composition comprises an amine equivalent to epoxide equivalent ratio in the range of 0.7: 1.0 to 1.3: 1.0.
(Item 13)
Item 2. The coating composition of item 1, wherein the non-aromatic epoxide resin comprises an alicyclic epoxide resin comprising a diglycidyl ether of hydrogenated cyclohexanedimethanol or hydrogenated bisphenol A epoxide resin.
(Item 14)
Furthermore, the coating composition of item 1 containing the soft epoxy resin which has an epoxide conversion weight of 200-1,000 based on the glycidyl ether of castor oil.
(Item 15)
15. A coating composition according to item 14, wherein the coating composition comprises up to 15% by weight of the soft epoxy resin.
(Item 16)
Item 1 further comprising up to 15% cure accelerator each comprising zinc, manganese, zirconium, titanium, cobalt, iron, lead and / or tin catalysts in the form of octanoate, neodecanoate or naphthanate A coating composition according to claim 1.
(Item 17)
The coating composition of claim 1, further comprising one or more corrosion inhibitors comprising a zinc or phosphate corrosion inhibitor or an organic corrosion inhibitor.
(Item 18)
water;
formula

Wherein each R ₁ is independently a hydroxy group, or an alkyl, aryl, or alkoxy group having up to 6 carbon atoms, and each R ₂ is independently hydrogen, or up to 6 carbons. An alkyl or aryl group having an atom, and n is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
20% to 80% by weight of polysiloxane having:
20% to 80% by weight non-aromatic epoxide resin containing more than one 1,2-epoxide group per molecule and epoxide equivalent weight of 100 to 5,000;
Up to 15% by weight of a curing accelerator comprising a tin catalyst in the form of octanoate, dodecanoate or naphthanate;
A soft epoxy resin having an epoxide equivalent weight of 200 to 1,000, based on glycidyl ether of castor oil up to 15% by weight; and
5% to 40% by weight cure system comprising a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin
An epoxy-polysiloxane polymer coating composition comprising:
The trialkoxy-functional aminosilane has the general formula

Having
The aminofunctional polysiloxane resin has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH a ₂ group, m is the blend is an amine-equivalent weight of 112~250g / NH And the blend has an average number of alkoxy functional groups of 2.2 to 2.8 and an amine equivalent to epoxide equivalent of 0.7: 1.0 to 1.3 in the coating composition. : Added in an amount sufficient to be 1.0,
Epoxy-polysiloxane polymer coating composition.
(Item 19)
Each R ₆ is independently a (C ₁ -C ₆ ) alkyl group, and R ₅ is a (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl group 19. A coating composition according to item 18 , wherein each R ₉ is methyl or phenyl.
(Item 20)
The at least one trialkoxy-functional aminosilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminonehexyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3- (3-aminophenoxy) propyltrimethoxysilane, aminoethylaminomethylphenyltri Methoxysilane, 2-aminoethyl-3-aminopropyl-tris-2-ethylhexoxysilane, N-aminohexylaminopropyltrimethoxysilane and / or trisami It includes tris methoxyethoxy silane;
The at least one aminofunctional polysiloxane resin is an aminofunctional phenylmethylpolysiloxane resin;
Item 19. The coating composition according to Item 18.
(Item 21)
A coated substrate comprising at least one surface coated with a coating composition according to item 1.
(Item 22)
From the undesirable result of one or more of chemical, corrosion and weathering conditions on the surface of the substrate:
water;
formula

Wherein each R ₁ is a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is hydrogen or an alkyl or aryl group having up to 6 carbon atoms , N is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
A polysiloxane having
Non-aromatic epoxide resin containing more than one 1,2-epoxide group per molecule and epoxide equivalent weight in the range of 100 to 5,000
Preparing a resin component comprising:
Adding a curing system to the resin component to form a fully cured epoxy-modified polysiloxane coating composition, the curing system comprising:
Blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin
;and
Optionally a cure accelerator comprising at least one metal catalyst
Including
The blend has an average alkoxy functionality of 2.2 to 2.8; and
Applying the coating composition to the surface of the substrate to be protected before the coating composition is sufficiently cured
Protecting the surface by coating with a coating composition prepared by a method comprising:
(Item 23)
Item 23. The coating composition according to Item 22, wherein the resin component further comprises a soft epoxy resin having an epoxide equivalent weight of 200 to 1,000 based on glycidyl ether of castor oil.

DETAILED DESCRIPTION The present disclosure provides an epoxy-modified polysiloxane coating composition that exhibits improved properties compared to conventional epoxy polysiloxane materials. When formulated as a coating material, the compositions according to various embodiments of the present disclosure have improved properties on surfaces coated with the coating composition compared to surfaces coated with conventional epoxy-modified polysiloxane coating compositions. For example, but not limited to, resistance to chemicals, resistance to corrosion or oxidation and / or improved weather resistance.

  It should also be understood that any numerical range recited herein is intended to encompass any sub-range included within that range. For example, the range “1-10” is between the stated minimum value 1 and the stated maximum value 10 (inclusive), ie, a minimum value equal to 1 or greater than 1 to a maximum equal to 10 or less than 10. It is intended to encompass any sub-range that has a value.

  In this application, the use of the singular includes the plural and the plural includes the singular unless specifically stated otherwise. In addition, in this application document, the use of “or (or)” means “and / or” even if “and / or” is explicitly used in some cases, unless otherwise specified. . Including means “including but not limited to”.

  As used herein, unless expressly specified otherwise, all numbers such as those indicating a value, range, quantity or percentage may be read as if prefixed with the word “about” (the term Even if is not explicitly indicated). Accordingly, unless stated to the contrary, the numerical values and ranges set forth in the following specification and claims may vary depending on the desired properties sought to be practiced by the practice of the present invention. To say the least, not as an attempt to limit the application of the doctrine to the scope of the claims, each numerical parameter is interpreted at least by applying the usual rounding method in view of the reported significant digits. I want.

  Although the numerical ranges and parameters indicating the wide range of various embodiments of the present disclosure are approximate, the numerical values shown in the specific examples are reported as closely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

  According to various embodiments, the present disclosure provides an epoxy-polysiloxane polymer coating composition suitable for surface coating and imparting improved chemical, corrosion and / or resistance to weathering conditions. The epoxy-polysiloxane polymer coating may comprise water, a resin component comprising polysiloxane and a non-aromatic epoxide resin, and a curing system, wherein the combined composition is reacted to form a crosslinked epoxy-polysiloxane polymer structure. Is formed. In some specific embodiments, the coating composition may further comprise a soft epoxy resin (rein) based on glycidyl ether of castor oil. In other embodiments, the coating composition can optionally include a cure accelerator comprising at least one metal catalyst.

を有するものが挙げられ、式中、各Ｒ_１は、ヒドロキシ基ならびに６個までの炭素原子を有するアルキル、アリールおよびアルコキシ基からなる群より選択され得る。各Ｒ_２は、水素ならびに６個までの炭素原子を有するアルキルおよびアリール基からなる群より選択され得る。式Ｉにおいて、ｎは、ポリシロキサンの分子量が４００〜１０，０００ダルトンの範囲になるように選択される整数であり得る。特定の実施形態では、Ｒ_１およびＲ_２には、例えば、ポリシロキサンの急速な加水分解（この反応は加水分解のアルコール類似体生成物の揮発性によって駆動され得る）を助長するために６個未満の炭素原子を有する基が包含され得る。一部の特定の実施形態では、６個より多い炭素原子を有するＲ_１およびＲ_２基では、各アルコール類似体の比較的低い揮発性のため、ポリシロキサンの加水分解が障害されることがあり得る。特定の実施形態では、分子量が４００〜２０００になるように選択されたｎを有するメトキシ官能性、エトキシ官能性およびシラノール官能性のポリシロキサンが本開示のコーティング組成物の配合に使用され得る。 With respect to the resin component, the resin can include a blend of polysiloxane, epoxide resin, and optionally an organooxysilane. With respect to the polysiloxane used to constitute the resin component, various embodiments of the polysiloxane include, but are not limited to, Formula I:

Wherein each R ₁ may be selected from the group consisting of hydroxy groups and alkyl, aryl and alkoxy groups having up to 6 carbon atoms. Each R ₂ may be selected from the group consisting of hydrogen and alkyl and aryl groups having up to 6 carbon atoms. In Formula I, n can be an integer selected such that the molecular weight of the polysiloxane is in the range of 400 to 10,000 daltons. In certain embodiments, R ₁ and R ₂ include, for example, 6 to facilitate rapid hydrolysis of the polysiloxane (this reaction can be driven by the volatility of the alcohol analog product of hydrolysis). Groups having fewer than carbon atoms can be included. In some specific embodiments, R ₁ and R ₂ groups having more than 6 carbon atoms may impair polysiloxane hydrolysis due to the relatively low volatility of each alcohol analog. obtain. In certain embodiments, methoxy-functional, ethoxy-functional, and silanol-functional polysiloxanes having n selected to have a molecular weight of 400-2000 can be used in formulating the coating compositions of the present disclosure.

  According to various embodiments, suitable methoxy functional polysiloxanes include: DC-3074 and DC-3037 (commercially available from Dow Corning Corp. (Midland, MI)); GE SR191 and SY-550 (Wacker, located at Commercially available from Adrian, MI). Silanol functional polysiloxanes include, but are not limited to, Dow Corning DC840, Z6018, Q1-2530 and 6-2230 intermediates. According to various embodiments, the coating composition may comprise 20% to 80% by weight polysiloxane. In other embodiments, the coating composition may comprise 15% to 65% by weight polysiloxane. In one embodiment, the coating composition may include approximately 31% by weight polysiloxane.

  Suitable epoxy resins useful for forming the coatings of embodiments of the present disclosure include non-aromatic epoxies that contain more than one per molecule, and in some specific embodiments, two 1,2-epoxy groups. Resins may be mentioned. As used herein, the terms “epoxide resin” and “epoxy resin” are used interchangeably. In a special embodiment, the epoxide resin can be liquid rather than solid, with an epoxide equivalent weight of 100-5,000, in other embodiments 100-2,000, and in other embodiments 100-500. And has a reactivity of about 2.

  In some specific embodiments, the epoxide resin is a diglycidyl ether of non-aromatic hydrogenated cyclohexanedimethanol and hydrogenated bisphenol A type epoxide resin, such as Eponex 1510, and Eponex 1513 (hydrogenated bisphenol A-epichloro Hydrine epoxy resin) (commercially available from Shell Chemical (Houston, TX)); Santolink LSE-120 (commercially available from Monsanto (Springfield, Mass.)); Araldite XUGY358 and PY327 (Ciba Geigy (Hawthorne, NY)) Epirez 505 (available from Rhone-Poulenc (Lousville, KY)); Aroflint 393 and 607 (available from Reichold (Pensacola, FL)); and ERL 4221 (available from Union Carbide (Tarrytown, NY)) . Other suitable non-aromatic epoxy resins may include EP-4080E (alicyclic epoxy resin) (commercially available from Adeka, Japan); DER 732 and DER 736. In a particular embodiment, the epoxy resin can be EP-4080E. Such non-aromatic hydrogenated epoxide resins may be desired due to their limited reactivity of about 2, which promotes the formation of linear epoxy polymers and inhibits the formation of crosslinked epoxy polymers. While not intending to be limited to a particular interpretation, linear epoxy polymers formed and formed by adding a curing agent to an epoxide resin can be responsible, at least in part, for improving the weather resistance of the composition. it is conceivable that.

  According to various embodiments, the coating composition may include 20% to 80% by weight epoxide resin, and in other embodiments 15% to 45% by weight epoxide resin. According to one embodiment, the coating composition may comprise about 26% by weight non-aromatic epoxide resin.

  Various embodiments of the coating composition include a curing system. According to some particular embodiments, the curing system may include a blend of one or more alkoxy functional amino silanes. In other embodiments, the curing system can include a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin, where the blend has an alkoxy content of 10 wt% to 25 wt%. Have In some specific embodiments, the blend comprising an alkoxy functional amino silane or the blend comprising at least one trialkoxy functional amino silane and at least one amino functional polysiloxane resin ranges from 2.0 to 2.8. It can have an average number of alkoxy functional groups. In other embodiments, a blend of alkoxy-functional aminosilanes or a blend comprising at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin has an average alkoxy functionality in the range of 2.2 to 2.8. Can have. In certain embodiments, the curing system may comprise 5% to 40% by weight of the coating composition, and in other embodiments 10% to 30% by weight of the coating composition. According to one embodiment, the curing system may constitute about 14% by weight of the coating composition. In some specific embodiments, the curing system has a ratio of amine equivalents to epoxide equivalents in the coating composition of 0.7: 1.0 to 1.3: 1.0, and in other embodiments, the ratio Is added in an amount sufficient to be 0.95: 1.00 to 1.05: 1.00.

を有し得る。このジアルコキシ官能性アミノシランの構造によれば、Ｒ_５は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルおよびシクロアルキル原子団からなる群より独立して選択される二官能性の有機原子団であり得、アルキル、アリール、シクロアルキルおよびアルコキシ基の各々は６個までの炭素原子を含み、各Ｒ_６およびＲ_７は独立して、アルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルコキシアルキル基から選択され得、ここで、Ｒ_６およびＲ_７基のアルキル、アリール、シクロアルキルおよびアルコキシ基の各々は６個までの炭素原子を含む。特定の実施形態によれば、各Ｒ_６およびＲ_７基は独立して（Ｃ_１〜Ｃ_６）アルキル基から選択され得、各Ｒ_５は独立して、（Ｃ_１〜Ｃ_６）アルキル基および（Ｃ_１〜Ｃ_６）アルキルアミノ（Ｃ_１〜Ｃ_６）アルキル基から選択される。例えば、好適なジアルコキシ官能性アミノシランとしては、アミノプロピルメチルジメトキシシラン、アミノプロピルエチルジメトキシシラン、アミノプロピルエチルジエトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルメチルジメトキシシラン、Ｎ−２−アミノエチル−３−アミノイソブチル−メチルジメトキシシラン、およびアミノネオヘキシルメチルジメトキシシランが挙げられ得る。好適な市販のジアルコキシ官能性アミノシランの例としては、ＤＹＮＡＳＹＬＡＮ（登録商標）１５０５（８１．５７のアミン換算重量を有するアミノプロピルメチルジメトキシシラン（Ｅｖｏｎｉｋ Ｄｅｇｕｓｓａ Ｃｏｒｐ．（ＵＳＡ）から市販））およびＳＩＬＱＵＥＳＴ（登録商標）Ａ−２６３９（１０２．７のアミン換算重量を有するアミノネオヘキシルメチルジメトキシシラン（Ｃｒｏｍｐｔｏｎ ＯＳｉ Ｓｐｅｃｉａｌｔｉｅｓ（Ｓｏｕｔｈ Ｃｈａｒｌｅｓｔｏｎ，ＷＶ）から市販））、およびＳＩＬＱＵＥＳＴ（登録商標）Ａ−２１２０（Ｎ−ベータ−（アミノエチル）−ガンマ−アミノプロピルメチルジメトキシシラン）が挙げられる。 In one embodiment, the blend of alkoxy functional amino silanes can include at least one dialkoxy functional amino silane, the blend having an average number of alkoxy functional groups of about 2.0. According to such an embodiment, the at least one dialkoxy-functional aminosilane has the structure:

Can have. According to this dialkoxy-functional aminosilane structure, R ₅ is a difunctional organic atom independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl and cycloalkyl groups. Each of the alkyl, aryl, cycloalkyl and alkoxy groups contains up to 6 carbon atoms, and each R ₆ and R ₇ is independently from an alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group Wherein each of the alkyl, aryl, cycloalkyl and alkoxy groups of the R ₆ and R ₇ groups contains up to 6 carbon atoms. According to certain embodiments, each R ₆ and R ₇ group can be independently selected from a (C ₁ -C ₆ ) alkyl group, and each R ₅ is independently a (C ₁ -C ₆ ) alkyl group. And a (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl group. For example, suitable dialkoxy-functional aminosilanes include aminopropylmethyldimethoxysilane, aminopropylethyldimethoxysilane, aminopropylethyldiethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-2- Mention may be made of aminoethyl-3-aminoisobutyl-methyldimethoxysilane and aminoneohexylmethyldimethoxysilane. Examples of suitable commercially available dialkoxy-functional aminosilanes include DYNASYLAN® 1505 (aminopropylmethyldimethoxysilane having an amine equivalent weight of 81.57 (commercially available from Evonik Degussa Corp. (USA))) and SILQUEST ( A-2639 (aminoneohexylmethyldimethoxysilane (commercially available from Crompton OSi Specialties (South Charleston, WV)) with an amine equivalent weight of 102.7) and SILQUEST A-2120 (N-beta) -(Aminoethyl) -gamma-aminopropylmethyldimethoxysilane).

を有し得、本明細書に記載の種々の実施形態における使用のための好適なトリアルコキシ官能性アミノシランは構造：

を有し得る。このジアルコキシ官能性アミノシランおよびトリアルコキシ官能性アミノシランの構造によれば、Ｒ_５は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルおよびシクロアルキル原子団からなる群より独立して選択される二官能性の有機原子団であり得、アルキル、アリール、シクロアルキルおよびアルコキシ基の各々は６個までの炭素原子を含み、各Ｒ_６およびＲ_７は独立して、アルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルコキシアルキル基から選択され得、ここで、Ｒ_６およびＲ_７基のアルキル、アリール、シクロアルキルおよびアルコキシ基の各々は６個までの炭素原子を含む。特定の実施形態によれば、各Ｒ_６およびＲ_７基は独立して（Ｃ_１〜Ｃ_６）アルキル基から選択され得、各Ｒ_５は独立して、（Ｃ_１〜Ｃ_６）アルキル基および（Ｃ_１〜Ｃ_６）アルキルアミノ（Ｃ_１〜Ｃ_６）アルキル基から選択される。好適なジアルコキシ官能性アミノシランは本明細書に記載する。好適なトリアルコキシ官能性アミノシランとしては、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルトリプロポキシシラン、アミノネオヘキシルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピル（ｐｒｏｐｙ）トリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン、トリメトキシシリルプロピルジエチレントリアミン、３−（３−アミノフェノキシ）プロピルトリメトキシシラン、アミノエチルアミノメチルフェニルトリメトキシシラン、２−アミノエチル−３−アミノプロピル−トリス−２−エチルヘキソキシシラン、Ｎ−アミノヘキシルアミノプロピルトリメトキシシラン、およびトリスアミノプロピルトリスメトキシエトキシシランが挙げられ得る。好適な市販のジアルコキシ官能性アミノシランの例としては、ＳＩＬＱＵＥＳＴ（登録商標）Ａ−１１００（８９．７のアミン換算重量を有するアミノプロピルトリメトキシシラン）、ＳＩＬＱＵＥＳＴ（登録商標）Ａ−１１１０（１１１のアミン換算重量を有するアミノプロピルトリエトキシシラン）、ＳＩＬＱＵＥＳＴ（登録商標）Ａ−１１２０（Ｎ−ベータ−（アミノエチル）−ガンマ−アミノプロピルトリメトキシシラン）、およびＳＩＬＱＵＥＳＴ（登録商標）Ａ−１６３７（Ｃｒｏｍｐｔｏｎ ＯＳｉ Ｓｐｅｃｉａｌｔｉｅｓ（Ｓｏｕｔｈ Ｃｈａｒｌｅｓｔｏｎ，ＷＶ）から市販）が挙げられる。他の好適なトリアルコキシ官能性アミノシランとしては、米国特許第７，４５９，５１５号の第１０欄、３８〜６５行目（引用により本明細書に組み込まれる）に示されたものが挙げられる。 According to other embodiments, the curing system may include a blend of at least one dialkoxy functional aminosilane and at least one trialkoxy functional aminosilane. According to such embodiments, the curable blend may have an average number of alkoxy functional groups ranging from 2.2 to 2.8, and in some specific embodiments from 2.28 to 2.73. Suitable dialkoxy-functional aminosilanes for use in the various embodiments described herein have the structure:

A suitable trialkoxy-functional aminosilane for use in the various embodiments described herein can have the structure:

Can have. According to this dialkoxy-functional aminosilane and trialkoxy-functional aminosilane structure, R ₅ is independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl, and cycloalkyl groups. Can be difunctional organic groups, each of the alkyl, aryl, cycloalkyl and alkoxy groups containing up to 6 carbon atoms, each R ₆ and R ₇ being independently alkyl, hydroxyalkyl, alkoxyalkyl Or it may be selected from hydroxyalkoxyalkyl groups, wherein each of the alkyl, aryl, cycloalkyl and alkoxy groups of the R ₆ and R ₇ groups contains up to 6 carbon atoms. According to certain embodiments, each R ₆ and R ₇ group can be independently selected from a (C ₁ -C ₆ ) alkyl group, and each R ₅ is independently a (C ₁ -C ₆ ) alkyl group. And a (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl group. Suitable dialkoxy-functional aminosilanes are described herein. Suitable trialkoxy functional aminosilanes include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminonehexyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl (propy). ) Trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3- (3-aminophenoxy) propyltrimethoxysilane, Aminoethylaminomethylphenyltrimethoxysilane, 2-aminoethyl-3-aminopropyl-tris-2-ethylhexoxysilane, N-aminohexylaminopropyltrimethoxysilane, and Scan aminopropyl tris methoxyethoxy silane may be cited. Examples of suitable commercially available dialkoxy-functional aminosilanes include SILQUEST® A-1100 (aminopropyltrimethoxysilane having an amine equivalent weight of 89.7), SILQUEST® A-1110 (111 Aminopropyltriethoxysilane with amine equivalent weight), SILQUEST® A-1120 (N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane), and SILQUEST® A-1637 (Crompon) OSI Specialties (commercially available from South Charleston, WV). Other suitable trialkoxy functional aminosilanes include those shown in US Pat. No. 7,459,515 at column 10, lines 38-65 (incorporated herein by reference).

  According to embodiments in which the curing system comprises a blend of at least one dialkoxy functional aminosilane and at least one trialkoxy functional aminosilane, the aminosilanes are mixed together in a ratio that provides the desired average number of alkoxy functional groups. At least one dialkoxy-functional aminosilane has an average alkoxy functionality of 2.0, at least one trialkoxy-functional aminosilane has an average alkoxy functionality of 3.0, and the blend of alkoxyaminosilanes is 2. Having an average number of alkoxy functional groups in the range of 2 to 2.8. For example, the blend may comprise 20% to 80% by weight dialkoxy functional aminosilane and 80% to 20% by weight trialkoxy functional aminosilane based on the total weight of aminosilanes in the blend. In other embodiments, the blend may comprise 27% to 73% by weight dialkoxy functional aminosilane and 72% to 28% by weight trialkoxy functional aminosilane, based on the total weight of the aminosilanes in the blend.

を有し得る。このアミノ官能性ポリシロキサン樹脂の構造によれば、各Ｒ_８は、アリール、アルキル、ジアルキルアリール、アルコキシアルキル、アルキルアミノアルキルおよびシクロアルキル原子団からなる群より独立して選択される二官能性の有機原子団であり得、各Ｒ_９は独立して、アリール、フェニル、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_１〜Ｃ_４）アルコキシ、および−ＯＳｉ（Ｒ_９）_２Ｒ_８ＮＨ_２からなる群より選択され得る。ポリシロキサンは、ブレンドが１１２〜２５０の範囲のアミン換算重量を有するようにｍが選択された構造を有し得る。種々の実施形態において、硬化系は、１０％から２５重量％のアルコキシ含有量（アルコキシｗｔ％）を有することになる。一部の特定の実施形態では、硬化系ブレンドは２．２〜２．８、一部の特定の実施形態では２．２６〜２．７８の範囲の平均アルコキシ官能部を有し得る。特定の実施形態では、Ｒ_９は、フェニル、メチル、メトキシ、−ＯＳｉ（Ｒ_９）_２Ｒ_８ＮＨ_２基およびその任意の混合物から選択され得る。特定の実施形態では、アミノ官能性ポリシロキサン樹脂はＲ_９にメチル、フェニルおよび−ＯＳｉ（Ｒ_９）_２Ｒ_８ＮＨ_２基の置換を含み得る。例えば、一実施形態によれば、アミノ官能性ポリシロキサン樹脂は、２３０〜２５５グラム／ＮＨのアミン換算重量を有するアミノ官能性メチルフェニルシリコーン樹脂であるＳＩＬＲＥＳ（登録商標）ＨＰ２０００（Ｗａｃｋｅｒ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ（Ａｄｒｉａｎ，Ｍｉｃｈｉｇａｎ）から市販）であり得る。特定の実施形態では、アミノ官能性ポリシロキサン樹脂は、２５０〜２７０グラム／ＮＨのアミン当量を有する軟質アミノ官能性フェニルメチルシリコーン樹脂（ＣＡＳ Ｎｏ．１２４２６１９−２３−３）であるＤＯＷ ＣＯＲＮＩＮＧ（登録商標）３０５５樹脂（Ｄｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐ．（Ｍｉｄｌａｎｄ，Ｍｉｃｈｉｇａｎ）から市販）であり得る。また、Ｒ_９にメチル置換およびフェニル置換を有する他の市販または専売のアミノ官能性ポリシロキサン樹脂も硬化系の種々の実施形態に適し得る。一部の特定の実施形態では、少なくとも１つのトリアルコキシ官能性アミノシランとアミノ官能性ポリシロキサン樹脂を含む硬化系は、１５％〜８５重量％のトリアルコキシ官能性アミノシランおよび８５％〜１５％のアミノ官能性ポリシロキサン樹脂を含み得る。特定の実施形態では、硬化系は、７０％〜８５％のトリアルコキシ官能性アミノシランおよび１５％〜３０％のアミノ官能性ポリシロキサン樹脂を含み得る。 In other embodiments, the curing system can include at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin. According to the curing system of such an embodiment, the at least one trialkoxy-functional aminosilane can have a structure as shown herein. Amino-functional polysiloxane resin has a general structure

Can have. According to the structure of this aminofunctional polysiloxane resin, each R ₈ is a bifunctional group independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl and cycloalkyl groups. Each R ₉ can independently be an aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, and —OSi (R ₉ ) ₂ R ₈ NH _2. Can be selected from the group consisting of The polysiloxane may have a structure where m is selected such that the blend has an amine equivalent weight in the range of 112-250. In various embodiments, the curing system will have an alkoxy content (alkoxy wt%) of 10% to 25% by weight. In some specific embodiments, the curable blend may have an average alkoxy functionality ranging from 2.2 to 2.8, and in some specific embodiments from 2.26 to 2.78. In certain embodiments, R ₉ can be selected from phenyl, methyl, methoxy, —OSi (R ₉ ) ₂ R ₈ NH ₂ groups and any mixtures thereof. In certain embodiments, the amino-functional polysiloxane resin may include substitution of methyl, phenyl and _{-OSi (R 9) 2 R 8} NH 2 group in _{R 9.} For example, according to one embodiment, the aminofunctional polysiloxane resin is SILRES® HP2000 (Wacker Chemical Corporation (Adrian), an aminofunctional methylphenylsilicone resin having an amine equivalent weight of 230-255 grams / NH. , Commercially available from Michigan). In a particular embodiment, the aminofunctional polysiloxane resin is DOW CORNING®, which is a soft aminofunctional phenylmethylsilicone resin (CAS No. 1242619-23-3) having an amine equivalent weight of 250-270 grams / NH. ) 3055 resin (commercially available from Dow Corning Corp. (Midland, Michigan)). Also other commercially available or proprietary amino functional polysiloxane resins having methyl and phenyl substitution at R ₉ may be suitable for various embodiments of the curing system. In some specific embodiments, the curing system comprising at least one trialkoxy functional aminosilane and an aminofunctional polysiloxane resin comprises 15% to 85% by weight trialkoxy functional aminosilane and 85% to 15% amino. A functional polysiloxane resin may be included. In certain embodiments, the curing system may comprise 70% to 85% trialkoxy-functional aminosilane and 15% to 30% amino-functional polysiloxane resin.

In some specific embodiments, the at least one aminofunctional polysiloxane resin is independently a (C ₁ -C ₄ ) alkyl group, phenyl group, (C ₁ -C) for each R ₉ in the formula. ₄ ) It may have a structure that can include an alkoxy group and —OSi (R ₉ ) ₂ R ₈ NH ₂ . In certain embodiments, the at least one aminofunctional polysiloxane resin has a substitution of phenyl groups in which R ₉ is greater than 70%, less than 30% (C ₁ -C ₄ ) alkyl groups and 2 It may have a structure comprising less than 0.0% (C ₁ -C ₄ ) alkoxy group substitution, and in certain embodiments less than 0.5% (C ₁ -C ₄ ) alkoxy group substitution. In particular embodiments, the at least one aminofunctional polysiloxane resin can be an aminofunctional phenylmethylpolysiloxane resin, such as, but not limited to, SILRES® HP2000 or DOW CORNING® 3055. In certain embodiments, the latter at least one aminofunctional polysiloxane resin may have an amine equivalent weight of 230-280 g / NH, in other embodiments 240-280 g / NH, or even 250-270 g / NH. .

を有する少なくとも１つの金属触媒が挙げられ得る。式中、「Ｍｅ」は金属であり、Ｒ_１０およびＲ_１１は独立して、アシル基、アルキル基、アリール基またはアルコキシ基から選択され得、アシル、アルキル、アリールおよびアルコキシ基は各々、１２個までの炭素原子を有し得る。Ｒ_１２およびＲ_１３は、Ｒ_１０およびＲ_１１について示した基から、または無機原子、例えば、ハロゲン、イオウもしくは酸素から選択され得る。特定の実施形態では、Ｒ_１０、Ｒ_１１、Ｒ_１２およびＲ_１３基は、ブチル、酢酸基、ラウリン酸基、オクタン酸基、ネオデカン酸基またはナフタン酸基から選択され得る。特定の実施形態では、硬化促進剤は、有機金属スズ触媒またはチタン触媒、例えば、ジブチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズジアセチルジアセトネート、ジオクチルスズジラウレート、ジオクチルスズジアセテート、またはオルガノチタネートなどであり得る。一部の特定の実施形態では、硬化系は、硬化系の総重量に対して１０重量％までの硬化促進剤、他の実施形態では０．０２％〜７重量％の硬化促進剤を含み得る。 Certain embodiments of the curing system may further include a curing accelerator. The cure accelerator can be a metal catalyst in the form of an organometallic catalyst comprising one or more metals. A cure accelerator comprising at least one organometallic catalyst may be useful for the purpose of further accelerating the cure rate that makes the coating composition a protective coating over a wide temperature range. In some specific uses where curing of the coating composition is required at ambient temperatures, organometallic catalyzed curing accelerators can provide an accelerated cure rate at ambient temperatures. Suitable curing accelerators include metals selected from zinc, manganese, zirconium, titanium, cobalt, iron, lead, bismuth or tin, and the formula

There may be mentioned at least one metal catalyst having Wherein “Me” is a metal and R ₁₀ and R ₁₁ may be independently selected from an acyl group, an alkyl group, an aryl group, or an alkoxy group, each having 12 acyl, alkyl, aryl, and alkoxy groups. Can have up to carbon atoms. R ₁₂ and R ₁₃ may be selected from the groups indicated for R ₁₀ and R ₁₁ or from inorganic atoms such as halogen, sulfur or oxygen. In certain embodiments, the R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ groups can be selected from butyl, acetic acid groups, lauric acid groups, octanoic acid groups, neodecanoic acid groups or naphthenic acid groups. In certain embodiments, the cure accelerator can be an organometallic tin catalyst or a titanium catalyst, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetyldiacetate, dioctyltin dilaurate, dioctyltin diacetate, or organotitanate. . In some specific embodiments, the curing system may include up to 10% by weight of the curing accelerator, in other embodiments 0.02% to 7% by weight of the curing accelerator, based on the total weight of the curing system. .

  In the epoxy polysiloxane coating composition of the present disclosure, the ratio of the curing system to the resin component can vary over a wide range. The coating composition, according to one embodiment described herein, is 20% to 80% by weight polysiloxane, 20% to 80% by weight non-aromatic epoxy resin and 5% to 40% by weight curing system. Can be included.

In certain embodiments, the coating composition of the present disclosure further includes a soft epoxy resin, for example, a soft resin CAS No. 2 based on glycidyl ether of castor oil. 74398-71-3 may be included. For example, in some specific embodiments, the soft epoxy resin can be a glycidyl ether of castor oil having an epoxide equivalent weight of 200 to 1,000. Examples of suitable glycidyl ethers of castor oil include, but are not limited to, Heloxy ™ 505 (available from Momentive Specialty Chemicals (Columbus, OH)), a castor oil polyglycidyl ether having an epoxide equivalent weight of 200-500, and CAS. No. Other commercially available castor oil polyglycidyl ethers at 74398-71-3. Other suitable soft epoxy resins include Erisys GE-22 cycloglycan dimethanol diglycidyl ether, Erisys GE-36 polyoxypropylene glycol diglycidyl ether, Erisys GE-60 sorbitol glycidyl ether (Erisys line diglycidyl ether is CVC Specialty Chemicals (commercially available from Moorestown, NJ) and CoatOSil ^* 2810 di-epoxy functional polydimethylsiloxane (commercially available from Momentive Specialty Chemicals (Columbus, OH)). Soft epoxy resins can be included in the coating composition, in which case the coating composition includes up to 15% by weight of the soft epoxy resin. In other embodiments, the coating composition may comprise 2% to 15% by weight soft epoxy resin, or even 5% to 15% by weight soft epoxy resin.

を有し得る。式中、Ｒ_１０は、６個までの炭素原子を含むアルキルもしくはシクロアルキル基または１０個までの炭素原子を含むアリール基から選択され得る。Ｒ_１１は独立して、６個までの炭素原子を含むアルキル、ヒドロキシアルキル、アルコキシアルキルまたはヒドロキシアルキル（ａｌｋｙ）オキシアルキル基 から選択される。一実施形態では、Ｒ_１１には、例えば、オルガノオキシシランの急速な加水分解（この反応は加水分解のアルコール類似体生成物の気化によって駆動され得る）を助長するために６個までの炭素原子を有する基が包含され得る。限定されることを意図しないが、６個より多くの炭素原子を有するＲ_１１基では、各アルコール類似体の比較的低い揮発性のため、オルガノオキシシランの加水分解が障害されることがあり得ると考えられる。オルガノオキシシランを含む特定の実施形態では、シランはトリアルコキシシラン、例えば、Ｕｎｉｏｎ ＣａｒｂｉｄｅのＡ−１６３（メチルトリメトキシシラン）、Ａ−１６２およびＡ−１３７ならびにＤｏｗ ＣｏｒｎｉｎｇのＺ６０７０およびＺ６１２４であり得る。オルガノオキシシランを含み得る実施形態によれば、コーティング組成物は１％〜１０重量％のオルガノオキシシランを含み得る。一実施形態では、コーティング組成物は任意選択で、０．１％〜１０重量％のオルガノオキシシランまたはさらには０．７％〜５重量％のオルガノオキシシランを含み得る。 According to some specific embodiments, the coating composition can optionally include one or a number of organooxysilanes. For the optional organooxysilane used in some specific embodiments, the organooxysilane has the general formula:

Can have. Wherein R ₁₀ may be selected from alkyl or cycloalkyl groups containing up to 6 carbon atoms or aryl groups containing up to 10 carbon atoms. R ₁₁ is independently selected from alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkyl (alkyl) oxyalkyl groups containing up to 6 carbon atoms. In one embodiment, R ₁₁ includes, for example, up to 6 carbon atoms to facilitate rapid hydrolysis of the organooxysilane (this reaction can be driven by vaporization of the alcohol analog product of hydrolysis). Groups having can be included. Without intending to be limited, R ₁₁ groups having more than 6 carbon atoms can interfere with the hydrolysis of organooxysilanes due to the relatively low volatility of each alcohol analog. it is conceivable that. In certain embodiments comprising an organooxysilane, the silane can be a trialkoxysilane, for example, Union Carbide A-163 (methyltrimethoxysilane), A-162 and A-137, and Dow Corning Z6070 and Z6124. According to embodiments that may include an organooxysilane, the coating composition may include 1% to 10% by weight organooxysilane. In one embodiment, the coating composition may optionally comprise 0.1% to 10% by weight organooxysilane or even 0.7% to 5% by weight organooxysilane.

  According to various embodiments, one or more other components in the coating composition, such as, but not limited to, mono- and di-epoxides, corrosion inhibitors, moisture scavengers, pigments, aggregates, rheology modifiers, Plasticizer, antifoaming agent, adhesion promoter, suspending agent, thixotropic agent, catalyst, pigment wetting agent, bitumen and asphalt extender pigment, anti-settling agent, diluent, UV light stabilizer, degassing agent, dispersion aid Agents, solvents, surfactants, or any mixture thereof may be included. Those skilled in the art of resin coating compositions will appreciate that other common ingredients can be incorporated into the coating composition within the scope of the various embodiments of the disclosure described herein. Let's get it. In certain embodiments, the epoxy polysiloxane coating composition can include up to 10% by weight of such components.

  In some specific embodiments, the coating composition may further include one or more corrosion inhibitors. Examples of suitable corrosion inhibitors include, but are not limited to, zinc phosphate based corrosion inhibitors such as micronized HALOX® SZP-391, HALOX® 430 calcium phosphate, HALOX® ZP phosphorus Zinc oxide, HALOX® SW-111 strontium phosphosilicate, HALOX® 720 mixed metal phosphor-carbonate, and HALOX® 550 and 650 proprietary organic corrosion inhibitors (Halox (Hammond, IN)) Commercially available). Other suitable corrosion inhibitors may include HEUCOPHOS® ZPA zinc aluminum phosphate and HEUCOPHOS® ZMP zinc molybdenum phosphate (commercially available from Heukotech Ltd (Fairless Hills, PA)). Corrosion inhibitors can be included in the coating composition in amounts of 1% to 7% by weight. Various embodiments of the coating composition may further include one or more light stabilizers, such as liquid hindered amine light stabilizers (“HALS”) or UV light stabilizers. Examples of suitable HALS include, for example, TINUVIN® HALS compounds such as TINUVIN® 292, TINUVIN® 123, TINUVIN® 622, TINUVIN® 783, TINUVIN ( Registered trademark) 770 (commercially available from BASF (Ludwigshafen, Germany)). Examples of suitable UV light stabilizers include, for example, CYASORB® light stabilizers such as CYASORB® UV-1164L (2,4-bis (2,4-dimethylphenyl) -6- ( 2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine) (commercially available from Cytec Industries (Woodland Park, NJ)) and TINUVIN® 1130 and TINUVIN® 328 (BASF ( Commercially available from Ludwigshafen, Germany). One or more light stabilizers may be included in the coating composition in an amount of 0.25% to 4.0% by weight.

  Suitable pigments for coating compositions of some specific embodiments may be selected from organic or inorganic colored pigments, such as titanium dioxide, carbon black, lamp black, zinc oxide, natural and synthetic petals , Iron yellow, iron oxide powder and iron black, toluidine and benzidine yellow, phthalocyanine blue and green, and carbazole violet, and extender pigments such as ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica And mica-like iron oxide, calcium carbonate, zinc powder, aluminum and aluminum silicate, gypsum, feldspar and the like. It will be appreciated that the amount of pigment that can be used to form the composition will vary depending on the particular composition application, and may be zero if a transparent composition is desired. obtain. In various embodiments, the epoxy polysiloxane composition can include up to 50 weight percent of fine particle size pigments and / or aggregates. In some embodiments, the use of greater than 50 weight percent fine particle size pigments and / or aggregate components can create compositions that may be too viscous to apply. Some specific compositions where it is desirable to have more than 50% pigment or aggregate in the final composition, such as 90 in a dry film or flooring composition that may contain up to 80% pigment / aggregate. For zinc-rich primers containing up to% zinc, the pigment or aggregate can be packaged separately as a third component. Depending on the specific end use, the coating composition of some specific embodiments may comprise 20% to 35% by weight of fine particle size aggregate and / or pigment.

  The pigment and / or aggregate component can typically be added to the epoxy resin portion of the resin component by dispersing, for example, using a Cowles mixer to at least 3 Hegman grinds, or alternatively ball milling. Alternatively, the polysiloxane component may be added after achieving the same degree of grinding by sand mill treatment. In some specific embodiments, the choice of fine particle size pigments or aggregates and dispersion or milling to 3 Hegman friability allows conventional air, air assisted airless, airless electrostatic of mixed resin and cured components. Atomization in painting equipment is possible, and after application, a smooth and uniform surface appearance can be provided.

  The epoxy-polysiloxane compositions of various embodiments of the present disclosure can be formulated for application with conventional air, airless, air-assisted airless electrostatic coating equipment, brushes or rollers. The composition of some specific embodiments can be used in dry film thicknesses ranging from 25 micrometers to 2 millimeters as protective coatings on steel, plating, aluminum, concrete and other substrates. Thus, pigments or aggregate components useful in forming the compositions of the present disclosure include, but are not limited to, at least 90% by weight of 325 mesh US. S. It can be selected from fine particle size materials that are larger than the sieve size.

  In various embodiments, the coating composition of the present invention may include water, which may be present in an amount sufficient to provide both hydrolysis of the polysiloxane and subsequent condensation of the silanol. Non-limiting sources of water can include atmospheric moisture and moisture adsorbed on the pigment or aggregate material. For example, additional water may be added to accelerate curing depending on ambient conditions (such as the use of coating and flooring compositions in a dry environment). In certain specific embodiments, the epoxy-polysiloxane composition can include up to a stoichiometric amount of water to facilitate hydrolysis. Compositions prepared without the addition of water may not contain the amount of moisture required for hydrolysis and condensation reactions and are therefore resistant to UV, corrosion and chemicals. May result in insufficient composition products. Compositions prepared with greater than about 2 weight percent water tend to hydrolyze and polymerize to form undesirable gels prior to application. In certain embodiments, the epoxy-polysiloxane composition can be prepared with approximately 1% by weight of water.

  If desired, water may be added to the epoxy-polysiloxane resin. Other sources of water may include trace amounts present in epoxide resins, curing systems, diluent solvents or other components. Regardless of its source, the total amount of water used should be the stoichiometric amount required to facilitate the hydrolysis reaction. Water above the stoichiometric amount can be undesirable because excess water can act to reduce the surface gloss of the final cured composition product.

（式中、Ｒ_１、Ｒ_２およびｎは本明細書に記載したとおりである）を有する２０％〜８０重量％のポリシロキサン、１分子あたり１つより多くの１，２−エポキシド基を有し、エポキシド換算重量が１００〜５，０００である２０％〜８０重量％の非芳香族エポキシド樹脂、オクタン酸塩、ドデカン酸塩またはナフタン酸塩の形態のスズ有機金属触媒を含む１５重量％までの硬化促進剤、ヒマシ油のグリシジルエーテルに基づき、２００〜１，０００のエポキシド換算重量を有する１５重量％までの軟質エポキシ樹脂、および少なくとも１つのトリアルコキシ官能性アミノシランと少なくとも１つのアミノ官能性ポリシロキサン樹脂のブレンドを含む５％〜４０重量％の硬化系を含むエポキシ−ポリシロキサンポリマーコーティング組成物であって、ブレンドは２．０〜２．８の範囲の平均アルコキシ官能基数を有し、コーティング組成物においてアミン当量対エポキシド当量の比が０．７：１．０〜１．３：１．０となるのに十分な量で添加され、合わせたコーティング組成物を反応させると架橋エポキシポリシロキサンポリマー構造が形成される、エポキシ−ポリシロキサンポリマーコーティング組成物を提供する。このような実施形態によれば、トリアルコキシ官能性アミノシランは、構造

を有し得、式中、各Ｒ_５、Ｒ_６およびＲ_７は独立して本明細書に記載のとおりであり、アミノ官能性ポリシロキサン樹脂は、構造

を有し得、式中、各Ｒ_８は本明細書に記載の構造から選択される二官能性の有機原子団であり、各Ｒ_９は独立して、アリール、フェニル、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_１〜Ｃ_４）アルコキシおよび−ＯＳｉ（Ｒ_９）_２Ｒ_８ＮＨ_２から選択され、ｍは、ブレンドが１１２〜２５０ｇ／ＮＨのアミン換算重量を有するものとなるように選択される。特定の実施形態では、少なくとも１つのアミノ官能性ポリシロキサン樹脂は、本明細書に記載のようなアミノ官能性フェニルメチルポリシロキサン樹脂であり得る。 According to certain embodiments, according to the present disclosure, water, general formula I

20% to 80% by weight of polysiloxane having (wherein R ₁ , R ₂ and n are as described herein) having more than one 1,2-epoxide group per molecule. Up to 15% by weight containing a tin organometallic catalyst in the form of 20% to 80% by weight non-aromatic epoxide resin having an epoxide equivalent weight of 100 to 5,000, octanoate, dodecanoate or naphthanate Up to 15% by weight of a soft epoxy resin based on glycidyl ether of castor oil and having an epoxide equivalent weight of 200 to 1,000, and at least one trialkoxy-functional aminosilane and at least one amino-functional poly Epoxy-polysiloxane polymer coating composition comprising 5% to 40% by weight cure system comprising a blend of siloxane resins And the blend has an average number of alkoxy functional groups in the range of 2.0 to 2.8, and the ratio of amine equivalents to epoxide equivalents in the coating composition is 0.7: 1.0 to 1.3: 1.0. An epoxy-polysiloxane polymer coating composition is provided that is added in an amount sufficient to yield a cross-linked epoxy polysiloxane polymer structure upon reaction of the combined coating composition. According to such an embodiment, the trialkoxy-functional aminosilane has the structure

Wherein each R ₅ , R ₆ and R ₇ is independently as described herein, and the aminofunctional polysiloxane resin has the structure

Wherein each R ₈ is a difunctional organic group selected from the structures described herein, and each R ₉ is independently aryl, phenyl, (C ₁ -C _{4) alkyl, (C} 1 -C ₄₎ is selected from alkoxy and _{-OSi (R 9) 2 R 8} NH 2, m is chosen to be one blend having an amine-equivalent weight of 112~250g / NH Is done. In certain embodiments, the at least one aminofunctional polysiloxane resin can be an aminofunctional phenylmethyl polysiloxane resin as described herein.

  Epoxy-polysiloxane compositions according to various embodiments of the present disclosure are generally low in viscosity and can be spray applied without the addition of solvents. However, in certain embodiments, flow, leveling and / or to improve atomization and application in electrostatic coating equipment or when applied with a brush, roller or standard air and airless spray equipment. Organic solvents can be added to improve the appearance. Exemplary solvents useful for this purpose include, but are not limited to, esters, ethers, alcohols, ketones, glycols, and the like. In some specific embodiments, the amount of solvent added to the composition of the present disclosure may be limited to approximately 420 grams of solvent per liter of composition, due to government regulations under the US Clean Air Act.

  The epoxy-polysiloxane composition of some specific embodiments of the present disclosure can be supplied as a two-part system, for example, in a moisture resistant container. The first package can contain an epoxy resin, a polysiloxane resin, and optionally pigment and / or aggregate components, additives and / or solvents (if any). The second package can include a curing system comprising one or more of dialkoxyaminosilane, trialkoxyaminosilane, amino-functional polysiloxane, and / or optionally a catalyst or promoter. The coating composition of some specific embodiments of the present disclosure may be supplied as a three-part system, in which case, for example, pigments and / or bones for flooring / concrete protection formulations or zinc-rich primer coatings. The material is supplied in a separate package.

  Epoxy-polysiloxane compositions according to the present disclosure can be fully cured at ambient temperature conditions ranging from −6 ° C. to 50 ° C. when applied. Curing can be slowed at temperatures below -18 ° C. However, the coating compositions of the various embodiments of the present disclosure may be applied under firing or curing temperatures from 40C to 120C.

  While not wishing to be bound by any particular theory, the epoxy-polysiloxane coating compositions of the embodiments described herein are: (1) an epoxy polymer chain is formed by the reaction of an epoxy resin and a curing system. (2) an alcohol-polysiloxane polymer is produced by hydrolytic polycondensation of the polysiloxane component; and (3) a sufficiently cured epoxy-polysiloxane polymer by copolymerization of the epoxy polymer chain and the polysiloxane polymer. It is believed that the composition is cured by forming. When an aminosilane or aminofunctional polysiloxane is used to form a curing system, the amine portion of the aminosilane or aminofunctional polysiloxane undergoes an epoxy-amine addition reaction, and the silane portion of the aminosilane or aminofunctional polysiloxane is combined with the polysiloxane. It undergoes hydrolytic polycondensation. In the cured form, the epoxy-polysiloxane coating composition is cross-linked by continuous polysiloxane polymer chains, thereby providing a non-interpenetrating polymer network (IPN) chemical structure (which is significant compared to conventional epoxy systems). Can be present as a sequence of uniformly dispersed linear epoxy chain fragments formed).

  In preparing the epoxy polysiloxane coating composition of various embodiments of the present disclosure, the ratio of curable composition to resin component can vary over a wide range. In general, the epoxy resin can be cured using a sufficient curing system, in which case the amine hydrogen reacts with the epoxide group of the epoxy resin to form an epoxy chain polymer and reacts with the polysiloxane to form a polysiloxane polymer. The crosslinked epoxy polysiloxane polymer composition may be formed by copolymerizing and curing the epoxy chain polymer and the polysiloxane polymer. In some specific embodiments, the epoxy resin component can be cured using a sufficient curing system to provide an amine equivalent weight of 0.7 to 1.3 for an epoxide equivalent weight of 1.0. . In other embodiments, the epoxy resin component may be cured using a sufficient curing system that provides a 0.95 to 1.05 amine equivalent weight for an epoxide equivalent weight of 1.0.

  When two-component or three-component components are combined, the cured silane moiety condenses with the polysiloxane component, and the epoxy resin undergoes chain extension due to reaction with amino groups suspended from the polysiloxane, sufficiently It is believed that a cured epoxy-polysiloxane polymer composition is formed. In such a reaction, it is believed that the epoxy resin functions as a crosslinking improver that increases the crosslink density of the composition without diminishing the beneficial features of the polysiloxane.

  Finally, the chemical and physical properties of the disclosed epoxy-polysiloxane compositions are affected by judicious selection of epoxy resins, polysiloxanes, curing systems and other optional components such as pigments or aggregate components. obtain. Various embodiments of the epoxy-polysiloxane coating composition that can be prepared by combining the components described herein exhibit improved resistance to caustic, weather resistance, corrosion resistance, flexibility, infinite Heavy coat compatibility is possible, resulting in better abrasion resistance than conventional epoxy-polysiloxane coating compositions. The epoxy-polysiloxane coating composition of the present disclosure can exhibit unexpected and surprising improvements in chemical corrosion and weatherability, as well as high extensibility and compressive strength, flexibility and excellent impact and abrasion resistance. .

  Also, certain specific embodiments of the present disclosure can include a coated substrate comprising a substrate having at least one surface coated with a coating composition according to one embodiment described herein. . The coating composition of the present disclosure can be applied to the surface of a desired substrate to protect the surface from weathering conditions, impact, and corrosion and / or exposure to chemical (s). Illustrative substrates that can be treated with the coating compositions described herein include, but are not limited to, wood, plastic, concrete, vitreous surfaces, and metal surfaces. The coating composition according to embodiments described herein may be disposed directly on the top surface of the substrate surface itself, or one or more pre-coatings or other priming to achieve the desired purpose. It can also be useful as a top coating, either disposed on a coating (eg, an inorganic or organic primer coating disposed on the surface of a substrate).

  In accordance with embodiments of the present disclosure, the surface of the substrate (eg, as described herein) from the undesirable result of one or more of chemical (s), corrosion and weathering conditions. At least one surface of the substrate), forming a resin component, adding a curing system to the resin component to form a fully cured epoxy-modified polysiloxane coating composition, and the coating composition sufficiently Provided is a method of protecting by coating with a coating composition prepared by a method comprising applying the coating composition to at least one surface of a substrate to be protected before being cured. The resin component is water, a polysiloxane having formula I, and a non-aromatic epoxide resin having more than one 1,2-epoxide group per molecule and having an epoxide equivalent weight in the range of 100 to 5,000. Can be formed. The curing system can be as described herein, and in one embodiment comprises a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin and optionally at least one metal catalyst. A cure accelerator can be included, where the blend has an average alkoxy functionality in the range of 2.2 to 2.8. In various embodiments, the curing system blend may have an amine equivalent weight in the range of 112 to 250 g / NH. In some specific embodiments, the resin component may further include a soft epoxy resin having an epoxide equivalent weight in the range of 200 to 1,000, based on glycidyl ether of castor oil.

  The coating compositions of the various embodiments described herein can be applied to the surface to be treated by conventional techniques, such as spraying or brushing, typically 50-250 micrometers thick when applied. Now, in some embodiments, the film will be up to 1.5 millimeters thick. If necessary, multiple layers of the coating composition may be applied to the surface to be protected. For example, for use with wooden substrates (eg, the furniture industry), the coating can be applied at a dry film thickness of 75-125 micrometers to provide the desired degree of protection to the underlying surface. . Other surface structures can be applied with an appropriate thickness of coating to provide the desired level of protection. Once applied to at least one surface of the substrate, the coating composition may be cured at ambient temperature until fully cured, or alternatively at elevated temperatures (from ambient temperature to 150 ° C. to 200 ° C.), for example, coating The substrate may be cured by placing it in a drying furnace or a curing furnace. The substrate may be removed from the oven after complete curing of the coating composition, removed after partial curing of the coating composition, and then allowed to cure on the substrate at ambient temperature until complete curing is obtained. You may continue.

  These and other features of various embodiments of the present disclosure will become more apparent upon review of the following examples. The various embodiments of the disclosure described in the following examples should not be construed to limit the invention to the details thereof. In the examples and throughout this specification, all parts and percentages are by weight unless otherwise indicated.

  The following examples describe the preparation of various embodiments of coating compositions used for coating purposes.

In this example, an exemplary epoxy siloxane coating system according to the present disclosure is formulated and tested for weatherability, durability, corrosion resistance, and chemical resistance and compared to a comparative coating system.
Example 1-Preparation of resin component formulation A

The resin component of the formulation was prepared as follows. An alicyclic epoxy resin (Adeka EP-4080E, 256.3 g, commercially available from Adeka Co., Ltd., Tokyo, Japan) was weighed into a 1 liter stainless steel mixing tank and placed under a Hockmeyer mixer fitted with a Cowles blade. . Surfactant (RHODAFAC® RE 610, 4.2 g, commercially available from Solvay, Rhodia Group (New Brunswick, NJ)) and antifoam agent (Foamtrol, 4.4 g, commercially available from Munning NA (Bloomfield, NJ) Was added to the mixing vessel under low speed mixing, followed by the addition of thixotropic agent (CRAYVALLAC® extra, 16.3 g, commercially available from Palmer Holland Inc. (North Olmsted, OH)). The batch was then dispersed at high speed while the temperature of the mixture was brought to 71 ° C. (160 ° F.). This condition was maintained for 30 minutes. The batch was then cooled to 49 ° C. (120 ° F.) under low agitation. A sufficient proportion of titanium dioxide to avoid agglomeration (TIOXIDE® TR60, 401.8 g, commercially available from Huntsman (The Woodlands, TX)). After the addition of TiO ₂ , the batch was mixed at high speed for 20 minutes until a Hegman grind degree of 6 was obtained. Remaining ingredients such as corrosion inhibitors (HALOX® SZP-391 JM, 55.5 g, commercially available from Halox, Hammond, IN); silicone resins (DC-3074, 384.8 g, Dow Corning (Midland, Midland, (Commercially available from MI); soft epoxy resin (HELOXY ™ 505, 71.6 g, commercially available from Momentary Specialty Chemicals (Columbus, OH)); HALS light stabilizer (TINUVIN® 292, 40.0 g, BASF ( Ludwigshafen, Germany); and silicone additives BYK-307 (3.9 g) and BYK-361N (6.0 g) (commercially available from BYK (Wallingford, Conn.)) Were then added to the mixture. The batch was mixed until uniform and then poured as a resin component A into a 1-quart can for storage. Ingredients and weights are shown in Table 1.
Example 2-Preparation of resin component formulation B

The resin component of the formulation was prepared as follows. An alicyclic epoxy resin (Adeka EP-4080E, 570.3 g, commercially available from Adeka Corporation (Tokyo, Japan)) was weighed into a 1 liter stainless steel mixing tank and placed under a Hockmeyer mixer fitted with a Cowles blade. . Surfactant (RHODAFAC® RE 610, 4.2 g, commercially available from Solvay, Rhodia Group (New Brunswick, NJ)) and antifoam agent (Foamtrol, 4.4 g, commercially available from Munning NA (Bloomfield, NJ) Was added to the mixing vessel under low speed mixing, followed by the addition of thixotropic agent (CRAYVALLAC® extra, 16.3 g, commercially available from Palmer Holland Inc. (North Olmsted, OH)). The batch was then dispersed at high speed while the temperature of the mixture was brought to 71 ° C. (160 ° F.). This condition was maintained for 30 minutes. The batch was then cooled to 49 ° C. (120 ° F.) under low agitation. A sufficient proportion of titanium dioxide to avoid agglomeration (TIOXIDE® TR60, 401.8 g, commercially available from Huntsman (The Woodlands, TX)). After the addition of TiO ₂ , the batch was mixed at high speed for 20 minutes until a Hegman grind degree of 6 was obtained. The remaining ingredients, for example, corrosion inhibitors (HALOX® SZP-391 JM, 55.5 g, commercially available from Halox (Hammond, IN); silicone resin (DC-3074, 113.0 g, Dow Corning (Midland, MI) Soft epoxy resin (HELLOXY ™ 505, 70.0 g, commercially available from Momentary Specialty Chemicals (Columbus, OH)); HALS light stabilizer (TINUVIN® 292, 40.0 g, BASF (Ludwigshafen) ), And silicone additives DC-57 (4.1 g, commercially available from Dow Corning (Midland, MI)) and BYK-361N (11.0 g, BYK (Wall) Ngford, was added to the mixture is then commercially available) from the CT), and mixed until uniform batch, then, shown in one quart cans for storage was injected as the resin component B. The ingredients and weight in Table 1.
Example 3-Preparation of Comparative Resin Component Formulation C

実施例４−硬化系の調製 The resin component of the formulation was prepared as follows. Alicyclic epoxy resin (Adeka EP-4080E, 355.4 g, commercially available from Adeka Co., Ltd., Tokyo, Japan) was weighed into a 1 liter stainless steel mixing tank and placed under a Hockmeyer mixer fitted with a Cowles blade. . Surfactant (RHODAFAC (R) RE610, 5.0 g, commercially available from Solvay, Rhodia Group (New Brunswick, NJ)) and antifoaming agent (Foamtrol, 5.3 g, Munning NA (Bloomfield, NJ)) After addition to the mixing vessel under low speed mixing, a thixotropic agent (DISPARLON® 6500, 7.7 g, commercially available from King Industries, Norwalk, Conn.) Was added. The batch was then dispersed at high speed while the temperature of the mixture was brought to 71 ° C. (160 ° F.). This condition was maintained for 30 minutes. The batch was then cooled to 49 ° C. (120 ° F.) under low agitation. A sufficient proportion of titanium dioxide to avoid agglomeration (TIOXIDE® TR60, 401.4 g, commercially available from Huntsman (The Woodlands, TX)). After the addition of TiO ₂ , the batch was mixed at high speed for 20 minutes until a Hegman grind degree of 6 was obtained. Remaining ingredients such as silicone resin (DC-3074, 402.6 g, commercially available from Dow Corning (Midland, MI)); HALS light stabilizer (TINUVIN® 292, 22.9 g, BASF (Ludwigshafen, Germany) And silicone additives DC-57 (4.1 g, commercially available from Dow Corning (Midland, MI)) and BYK-361N (11.0 g, commercially available from BYK (Wallingford, Conn.)) Were then added to the mixture. The batch was mixed until uniform and then poured as a comparative resin component C into a 1-quart can for storage. Ingredients and weights are shown in Table 1.

Example 4-Curing system preparation

  In this example, cure systems 1, 2, 3, 4, 5 and 6 according to embodiments of the present disclosure were prepared with comparative cure systems 7 and 8. The components and amounts of each curing system are shown in Table 2. The ingredients were weighed into a pint container, sealed and placed on a shaker for 5 minutes. Curing systems 1, 2, 3, 4, 5 and 6 and comparative curing systems 7 and 8 were obtained.

  Curing system 1 comprises dialkoxy-functional aminosilane (DYNASYLAN® 1505, 93.2 g, commercially available from Evonik Degussa Corp (USA)) as a metal catalyst curing accelerator (T-1, dibutyltin diacetate, 6.8 g, Prepared by combining with Air Products (commercially available from Allentown, PA). The resulting cured system had an average alkoxy functionality of 2.0, an average alkoxy weight percent of 34.7%, and an average amine equivalent weight of 87.6 g / NH.

  Curing system 2 comprises dialkoxy functional aminosilane (DYNASYLAN® 1505, 25.0 g, commercially available from Evonik Degussa Corp (USA)) and trialkoxy functional aminosilane (SILQUEST® A1110, 68.2 g, Crompton). It was prepared by combining OSi Specialties (commercially available from South Charleston, WV) with a metal catalyst curing accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA). The resulting cured system had an average alkoxy functionality of 2.73, an average alkoxy weight percent of 44.6%, and an average amine equivalent weight of 94.3 g / NH.

  Curing system 3 consists of dialkoxy functional aminosilane (DYNASYLAN® 1505, 67.3 g, commercially available from Evonik Degussa Corp (USA)) and trialkoxy functional aminosilane (SILQUEST® A1110, 25.9 g, Crompton). It was prepared by combining OSi Specialties (commercially available from South Charleston, WV) with a metal catalyst curing accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA). The resulting cured system had an average alkoxy functionality of 2.28, an average alkoxy weight percent of 41.6%, and an average amine equivalent weight of 90.0 g / NH.

  Curing system 4 consists of trialkoxy-functional aminosilane (SILQUEST® A1110, 23.2 g, commercially available from Crompton OSi Specialties (South Charleston, WV)) and aminofunctional polysiloxane resin (SILRES® HP-2000). 70.0 g, commercially available from Wacker Chemical Corporation (Adrian, MI) with a metal catalyst cure accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA). did. The resulting cured system had an average alkoxy functionality of 2.8, an average alkoxy weight percent of 16.9%, and an average amine equivalent weight of 183.8 g / NH.

  Curing system 5 consists of trialkoxy-functional aminosilane (SILQUEST® A1110, 73.2 g, commercially available from Crompton OSi Specialties (South Charleston, WV)) and aminofunctional polysiloxane resin (DOW CORNING® 3055 Resin). , 20.0 g, commercially available from Dow Corning Corporation (Midland, MI) with a metal catalyst curing accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA). did. The resulting cured system had an average alkoxy functionality of 2.78, an average alkoxy weight percent of 37.8%, and an average amine equivalent weight of 112.2 g / NH.

  Curing system 6 consists of trialkoxy-functional aminosilane (SILQUEST® A1110, 24.0 g, commercially available from Crompton OSi Specialties (South Charleston, WV)) and an aminofunctional polysiloxane resin (DOW CORNING® 3055 Resin). , 69.2 g, commercially available from Dow Corning Corporation (Midland, MI) with a metal catalyst curing accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA). did. The resulting cure system had an average alkoxy functionality of 2.26, an average alkoxy weight percent of 12.3%, and an average amine equivalent weight of 169.8 g / NH.

Comparative curing system 7 comprises an aminofunctional polysiloxane resin (DOW CORNING® 3055 Resin, 96.0 g, commercially available from Dow Corning Corporation (Midland, MI)) as a metal catalyst curing accelerator (T-1, dibutyltin Acetate, 4.0 g, commercially available from Air Products (Allentown, Pa.). The resulting cured system had an average alkoxy functionality of less than 0.1, an average alkoxy weight percent of less than 0.1%, and an average amine equivalent weight of 255.8 g / NH.

Comparative curing system 8 is a metal catalyst curing accelerator (T-1, dibutyltin diacetate, commercially available from SILQUEST® A1100, 93.2 g, Crompton OSi Specialties (South Charleston, WV)). 6.8 g, commercially available from Air Products (Allentown, PA). The resulting cured system had an average alkoxy functionality of 3.0, an average alkoxy weight percent of 50.1%, and an average amine equivalent weight of 109.8 g / NH.
Example 5-Coating formulation

  Coating formulations according to some specific embodiments of the present invention were prepared using resin components (comparative resins of Examples 1 and 2 and Example 3) and a curing system (Example 4). Four exemplary coating formulations and a comparative coating formulation were prepared as follows. In coating formulation 1, resin A (100 g) was combined with cure system 1 (8.8 g). For coating formulation 2, resin A (100 g) was combined with cure system 2 (9.4 g). In coating formulation 3, resin A (100 g) was combined with cure system 3 (8.9 g). In coating formulation 4, resin B (100 g) was combined with cure system 4 (39.3 g). In comparative coating formulation 5, resin C (100 g) was combined with cure system 8 (18.1 g). In coating formulation 6, resin A (100 g) was combined with cure system 5 (11.7 g). In coating formulation 7, resin A (100 g) was combined with cure system 6 (17.7 g). In comparative coating formulation 8, resin A (100 g) was combined with cure system 7 (26.6 g). The coating formulations have the following amine equivalents to epoxy equivalents: 0.96: 1.00, 0.96: 1 .. for coating formulations 1, 2, 3, 4, 5, 6, 7, and 8, respectively. 00, 0.96: 1.00, 1.00: 1.00, 1.03: 1.00, 1.00: 1.00, 1.00: 1.00 and 1.00: 1.00 Mix at stoichiometric ratio. The resin component and the curing system were weighed into a container and stirred with a metal spatula until sufficiently mixed to obtain a coating composition.

  The resulting coating composition was sprayed onto a steel panel using a DEVILBISS® spray gun to cure the coating and make it hard (ASTM D1640). Panels coated with the composition of the coating formulation were tested for elongation percentage (Cone Mandrel, ASTM D522). An epoxy siloxane formulation (6 mils) was coated on a 3 mil zinc-rich epoxy primer and tested for 5000 hours for resistance to salt spray (spray / fog) (ASTM B117). After 5000 hours, the panels were analyzed for surface blisters (ASTM D714), surface rust generation (ASTM D1654), and scribe creepage (ASTM D1654). In a separate test, an epoxy siloxane formulation (6 mil) was coated on a 3 mil zinc-rich epoxy primer and tested for 5000 hours for resistance to Prohesion (ASTM D5894). After 5000 hours, the panels were analyzed for surface blisters (ASTM D714), surface rusting (ASTM D1654) and scribe creep pages (ASTM D1654). Panels with the coating composition were exposed to QUV accelerated weathering conditions with a UV 313B bulb using a 4 hour UV exposure / 4 hour moisture alternating cycle (ASTM G53), with a 60 degree gloss change after 5 weeks and 10 weeks. After and after 15 weeks. The results of the test are shown in Table 3.

The data show that epoxy siloxane coating compositions made according to the present disclosure exhibit improved flexibility over prior art comparative compositions as measured by conical mandrel elongation, particularly after aging. Weather and corrosion resistance tests have shown that the epoxysiloxane coating exhibits improved properties compared to prior art comparative compositions.

  While specific embodiments of the present invention have been described above for purposes of illustration, those skilled in the art will make various modifications to the various embodiments described herein without departing from the broad inventive concept of the invention. It will be recognized that it can be broken. Accordingly, it is to be understood that this description is not intended to be limited to the particular embodiments disclosed, but is to be construed as including modifications which are within the spirit and scope of the invention as defined by the appended claims. Like.

Claims (20)

water;
formula

Wherein each R ₁ is independently a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is independently hydrogen or up to 6 carbon atoms. And n is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
20% to 80% by weight of polysiloxane having:
20% to 80% by weight of a non-aromatic epoxide resin having more than one 1,2-epoxide group per molecule and having an epoxide equivalent weight of 100 to 5,000; and at least one trialkoxy functionality 5% to 40% by weight curing system comprising a blend of aminosilane and at least one aminofunctional polysiloxane resin , wherein the trialkoxyfunctional aminosilane is of the general formula

And having
The aminofunctional polysiloxane resin has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH ₂ groups, and m is an amine conversion in which the blend is in the range of 112 to 250 g / NH. And the blend has an average alkoxy functionality of 2.2 to 2.8 and an alkoxy content of 10 to 25% by weight)
An epoxy-polysiloxane polymer coating composition comprising: R ₅ is a bifunctional organic atomic group selected from (C ₁ -C ₆ ) alkyl or (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl groups, and each R ₆ is independently The composition according to claim 1 , which is a (C ₁ -C ₆ ) alkyl group. The at least one trialkoxy-functional aminosilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminonehexyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3- (3-aminophenoxy) propyltrimethoxysilane, aminoethylaminomethylphenyltri Methoxysilane, 2-aminoethyl-3-aminopropyl-tris-2-ethylhexoxysilane, N-aminohexylaminopropyltrimethoxysilane and / or trisami Including tris methoxyethoxy silane composition of claim 1. The at least one aminofunctional polysiloxane resin has a R ₉ of greater than 70% phenyl groups, less than 30% (C ₁ -C ₄ ) alkyl groups and less than 2.0% (C _1- C ₄₎ having a structure containing an alkoxy group the composition of claim 1. The composition according to claim 4 , wherein R _{9 comprises} less than 0.5% (C ₁ -C ₄ ) alkoxy groups. The composition of claim 1, wherein the at least one aminofunctional polysiloxane resin comprises an aminofunctional phenylmethylpolysiloxane resin. 7. The composition of claim 6 , wherein the at least one aminofunctional polysiloxane resin has an amine equivalent weight of 240-280 g / NH. The composition of claim 1, wherein the curing system comprises 15% to 85% by weight of the at least one trialkoxy functional aminosilane and 85% to 15% of the at least one aminofunctional polysiloxane resin. The coating composition of claim 1, wherein the coating composition comprises a ratio of amine equivalents to epoxide equivalents ranging from 0.7: 1.0 to 1.3: 1.0. The coating composition of claim 1, wherein the non-aromatic epoxide resin comprises an alicyclic epoxide resin comprising a diglycidyl ether of hydrogenated cyclohexanedimethanol or hydrogenated bisphenol A epoxide resin. The coating composition according to claim 1, further comprising a soft epoxy resin having an epoxide equivalent weight of 200 to 1,000, based on glycidyl ether of castor oil. The coating composition of claim 11 , wherein the coating composition comprises up to 15% by weight of the soft epoxy resin. Furthermore, it comprises up to 15% of a curing accelerator each comprising zinc, manganese, zirconium, titanium, cobalt, iron, lead and / or tin catalysts in the form of octanoate, neodecanoate or naphthanate. The coating composition according to 1. The coating composition of claim 1 further comprising one or more corrosion inhibitors including zinc or phosphate based corrosion inhibitors or organic based corrosion inhibitors. water;
formula

Wherein each R ₁ is independently a hydroxy group, or an alkyl, aryl, or alkoxy group having up to 6 carbon atoms, and each R ₂ is independently hydrogen, or up to 6 carbons. An alkyl or aryl group having an atom, and n is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
20% to 80% by weight of polysiloxane having:
20% to 80% by weight non-aromatic epoxide resin containing more than one 1,2-epoxide group per molecule and epoxide equivalent weight of 100 to 5,000;
Up to 15% by weight of a curing accelerator comprising a tin catalyst in the form of octanoate, dodecanoate or naphthanate;
A soft epoxy resin based on glycidyl ether of castor oil up to 15% by weight and having an epoxide equivalent weight of 200 to 1,000; and a blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin An epoxy-polysiloxane polymer coating composition comprising 5% to 40% by weight of a curing system comprising:
The trialkoxy-functional aminosilane has the general formula

Having
The aminofunctional polysiloxane resin has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH a ₂ group, m is the blend is an amine-equivalent weight of 112~250g / NH And the blend has an average number of alkoxy functional groups of 2.2 to 2.8 and an amine equivalent to epoxide equivalent of 0.7: 1.0 to 1.3 in the coating composition. : Added in an amount sufficient to be 1.0,
Epoxy-polysiloxane polymer coating composition. Each R ₆ is independently a (C ₁ -C ₆ ) alkyl group, and R ₅ is a (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl group 16. A coating composition according to claim 15 wherein each R ₉ is methyl or phenyl. The at least one trialkoxy-functional aminosilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminonehexyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3- (3-aminophenoxy) propyltrimethoxysilane, aminoethylaminomethylphenyltri Methoxysilane, 2-aminoethyl-3-aminopropyl-tris-2-ethylhexoxysilane, N-aminohexylaminopropyltrimethoxysilane and / or trisami It includes tris methoxyethoxy silane;
The at least one aminofunctional polysiloxane resin is an aminofunctional phenylmethylpolysiloxane resin;
The coating composition according to claim 15 . A coated substrate comprising at least one surface coated with the coating composition of claim 1. The surface of a substrate is coated with a coating composition according to claim 1 prepared from a undesirable result of one or more of chemical, corrosion and weathering conditions by a method comprising the following steps: In which the step comprises:
water;
formula

Wherein each R ₁ is a hydroxy group or an alkyl, aryl or alkoxy group having up to 6 carbon atoms, and each R ₂ is hydrogen or an alkyl or aryl group having up to 6 carbon atoms , N is selected so that the molecular weight of the polysiloxane is 400 to 10,000)
A polysiloxane having
Preparing a resin component comprising a non-aromatic epoxide resin comprising more than one 1,2-epoxide group per molecule and an epoxide equivalent weight in the range of 100 to 5,000;
A process of adding a cure system for the resin component in order to form an epoxy-modified polysiloxane coating composition cured in ten minutes, the curing system:
A blend of at least one trialkoxy-functional aminosilane and at least one amino-functional polysiloxane resin; and, optionally, a curing accelerator comprising at least one metal catalyst;
The trialkoxy-functional aminosilane has the general formula

And having
The aminofunctional polysiloxane resin has the general formula

Having
In which R ₅ is a difunctional organic group selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups, each R ₆ being independently less than 6 An alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl group containing 5 carbon atoms, each R ₈ is independently selected from aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl or cycloalkyl groups A difunctional organic group, each R ₉ is independently aryl, phenyl, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or —OSi (R ₉ ) ₂ R ₈ NH _{There are two} groups, and m is an amine conversion in which the blend is in the range of 112 to 250 g / NH. Selected to have weight,
The blend has an average number of alkoxy functional groups of 2.2 to 2.8 and an alkoxy content of 10% to 25% by weight ; and before the coating composition is fully cured the in claim 1 comprising the step of applying a coating composition according to the surface of the substrate to be protected, how. 20. The method of claim 19 , wherein the resin component further comprises a soft epoxy resin having an epoxide equivalent weight of 200 to 1,000, based on glycidyl ether of castor oil.