阅读说明：本技术 成膜配制品及其组合物 (Film-forming formulations and compositions thereof ) 是由 道格拉斯·E·穆恩 于 2019-07-19 设计创作，主要内容包括：提供了一种成膜配制品,其包括磷酸与张力环烷氧基硅烷的反应产物。所述磷酸和所述张力环烷氧基硅烷以0.9-3.3:1的分子比存在。所述膜配制品还包括水性溶剂。还提供了一种脱模涂覆组合物,其包括所述成膜配制品、反应性脱模剂、基质和水性溶剂。(A film-forming formulation is provided that includes the reaction product of phosphoric acid and a strained ring alkoxysilane. The phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 0.9 to 3.3: 1. The film formulation also includes an aqueous solvent. Also provided is a release coating composition comprising the film-forming formulation, a reactive release agent, a matrix, and an aqueous solvent.)

1. A film-forming formulation comprising:

a reaction product of phosphoric acid and a strained ring alkoxysilane, wherein the phosphoric acid and strained ring alkoxysilane are present in a molecular ratio of 0.9 to 3.3: 1; and

an aqueous solvent.

2. The formulation of claim 1, wherein the phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 3: 1.

3. The formulation of claim 1, wherein the phosphoric acid is present at from 20 to 40 weight percent of the total weight of the formulation and the tensioaclkoxysilane is present at from 60 to 80 weight percent of the total weight of the formulation.

4. The formulation of claim 1, wherein the phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 3: 2.

5. The formulation of claim 4, wherein the phosphoric acid is present at from 10 to 25 weight percent of the total weight of the formulation and the strained ring alkoxysilane is present at from 70 to 90 weight percent of the total weight of the formulation.

6. The formulation of claim 1, wherein the phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 3: 3.

7. The formulation of claim 6, wherein the phosphoric acid is present at from 5 to 20 weight percent of the total weight of the formulation and the strained ring alkoxysilane is present at from 80 to 95 weight percent of the total weight of the formulation.

8. The formulation of any one of claims 1 to 7, wherein the strained ring alkoxysilane has three alkoxy groups all the same and all methoxy or ethoxy.

9. The formulation of any one of claims 1 to 7, wherein the strained ring alkoxysilane has three alkoxy groups, each independently being one of: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, or decyloxy.

10. The formulation of any one of claims 1 to 7, wherein the reaction product is concentrated to a total non-volatile content of greater than 2.4 weight percent of the total weight of the formulation.

11. The formulation of any one of claims 1 to 7, wherein the reaction product is concentrated to a total non-volatile content of greater than 15 weight percent of the total weight of the formulation.

12. The formulation of any one of claims 1 to 7, wherein the strained ring alkoxysilane has an average molecular weight of less than 4,000 daltons and has formula (I):

(OCH₂CH)-R¹-X-R²-Si-(R³)_a(OR⁴)_3-a (I)

wherein R is¹Is C₁-C₄Alkyl, aromatic, heteroaromatic, or with (OCH)₂CH) together form (OC 6H)₉) (ii) a X is absent or oxygen, R²Is C₂-C₆An alkyl, aromatic or heteroaromatic group; r³Independently at each occurrence is C₁-C₆Alkyl, a is an integer from 0 to 2 inclusive; and R is⁴Independently at each occurrence is C₁-C₆Alkyl or (C)₁-C₄Alkyl) -O- (C₁-C₄Alkyl groups).

13. The formulation according to any one of claims 1 to 7, wherein the strained ring alkoxysilane is 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and combinations thereof.

14. A release coating composition comprising:

the formulation of claim 1;

a reactive mold release agent;

a substrate; and

an aqueous solvent.

15. The composition of claim 14, wherein a first amount of said phosphoric acid and said gamma-glycidoxytrialkoxysilane are present in a molecular ratio of 3:2, and said first amount of said reaction product is present in from 1.0 to 2.5 weight percent of the total weight of said composition.

16. The composition of claim 14, further comprising a second amount of said phosphoric acid and said strained ring alkoxysilane present in a molecular ratio of 3:3, and said second amount of said reaction product present in from 1.0 to 2.5 weight percent of the total weight of said composition.

17. The composition of any of claims 14-16, wherein the second amount of the reaction product is present from 1.5 to 2.0 weight percent of the total weight of the composition.

18. The composition of any of claims 14-16, wherein the reactive mold release agent is present at from 1.5 to 2.0 weight percent of the total weight of the composition.

19. The composition of any one of claims 14 to 16, wherein the reactive mold release agent is a monoepoxide-functional mold release agent.

20. The composition of any one of claims 14 to 16, further comprising at least one of an emulsifier, a catalyst, an antimicrobial agent, a filler, a pigment, a dye, a wetting agent, a surfactant, a thickener, a thixotropic agent, a drying agent, an anti-skinning agent, or a combination thereof.

Technical Field

The present invention relates generally to resin reaction products useful in a wide variety of applications, including adhesion to a variety of substrates; and in particular to a film-forming formulation of the reaction product of phosphoric acid and a tensioacycloalkoxysilane in an aqueous solvent, and a release coating composition containing the same.

Background

Coating compositions comprising organic resins are widely used. There are numerous compositions produced by dissolving one or more film-forming resins in an organic solvent or by blending various emulsified film-forming resins in a semi-aqueous or fully aqueous "medium". Glycidoxy functional film formers have been used as the reactive part of many film forming resin systems and formulations for decades in the past century. Glycidoxy-functional film formers have been used to positively impart a wide variety of properties to a wide variety of substrates including iron, steel, aluminum, glass, plastic, and the like.

Unfortunately, many prior art glycidoxy-functional film formers have handling problems. Thus, there is a need for film-forming formulations and compositions thereof that are not endocrine disruptors and avoid the inclusion of environmentally harmful solvents. In addition, many prior art glycidoxy functional film formers require polymerization. Polymerization requires a large energy input because it utilizes reaction equipment, heat, catalyst, condensation, and further requires recovery of potentially harmful byproducts. Polymerization further exacerbates the hazards to both human health and the environment associated with many prior art glycidoxy functional film formers due to the large energy input requirements and the production of potentially harmful by-products. Thus, film-forming formulations and compositions thereof that avoid these hazards to human health and the environment are highly desirable.

The use of phosphoric acid as a modifier for glycidoxy-functional film formers is well known and has been widely used over the past century for decades. Phosphoric acid has been used as a catalyst for solvent-based "epoxy" and "epoxy-phenolic" coating compositions, including but not limited to internal and/or external coatings for pipes (for transporting materials), tank external coatings, and tank internal coatings. Such solvent-based "epoxy" and "epoxy novolac" coating compositions are also harmful to the environment and human health, as they often contain or are themselves endocrine disruptors (both epoxy and phenol precursors).

U.S. patent No. 4,801,628(Ashing et al) discloses non-water dispersible, ethylene oxide defunctionalized, etherified phosphate esters of epoxy resins for use as varnishes (transparencies) or white enamels for drawn and ironed beer and beverage containers. Phosphoric acid reaction products of "ethylene oxide" (glycidyl) resins were prepared in a water-soluble solvent base containing butyl cellosolve and/or butanol. The ethylene oxide resin used is diglycidyl ether of bisphenol A (DGEBA) or the reaction product of DGEBA with bisphenol A (BPA). Both DGEBA and BPA are known endocrine disruptors.

In view of the state of the art, there is an unmet need for film-forming formulations that avoid the use of excess solvents and the production of harmful by-products that are harmful to the environment, and further avoid the use of endocrine disrupting materials. There is a further need for coating compositions incorporating such film formulations.

Disclosure of Invention

A film-forming formulation is provided that includes the reaction product of phosphoric acid and a strained ring alkoxysilane. The phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 0.9 to 3.3: 1. The film formulation also includes an aqueous solvent.

Also provided is a release coating composition comprising the film-forming formulation of the invention, a reactive release agent, a matrix (base), and an aqueous solvent.

Detailed Description

The following detailed description is merely exemplary in nature and is in no way intended to limit the scope of the invention, its application, or uses (which may vary). The invention is described with respect to non-limiting definitions and terms included herein. These definitions and terms are not intended to serve to limit the scope or practice of the present invention, but are presented for illustrative and descriptive purposes only.

The present invention has utility as a film-forming formulation that avoids the use of excess solvents, endocrine disruptors, and the production of by-products that are harmful to human health and the environment. The formulations of the present invention use phosphoric acid as a "seed" or "center" which serves as a reactant for the strained ring alkoxysilane, which can be reacted in an aqueous solvent under ambient atmospheric conditions to form a film-forming reaction product. Variation of the stoichiometry of the phosphoric acid relative to the strained cycloalkoxysilane provides formulation flexibility. The reaction products are extremely storage stable and tunable when mixed with other functional materials, providing the ability to produce a wide variety of film-forming formulations exhibiting a wide range of physical properties. This adjustability allows flexibility in creating embodiments of the film-forming formulation of the present invention having physical properties specific to a variety of specific materials and substrates. The present invention also has utility as a release coating composition incorporating the film-forming formulation of the present invention.

It will be understood that where a range of values is provided, the range is intended to cover not only the end points of the range, but also the middle values of the range, as explicitly included within the range and as varied by the number of significant digits at the end of the range. For example, a recited range of from 1 to 4 is intended to include 1-2, 1-3, 2-4, 3-4, and 1-4.

In at least one embodiment, the film-forming formulation of the present invention comprises the reaction product of phosphoric acid with a strained ring alkoxysilane (where γ -glycidoxytrialkoxysilanes represent a subset of such silanes effective herein, which react in aqueous solvents at ambient atmospheric conditions) and avoids the use of excess solvents, endocrine disruptors and the production of by-products that are harmful to human health and the environment. It will be appreciated that the phosphoric acid and strained ring alkoxysilane are present in a molecular ratio of 0.9 to 3.3: 1. It will further be appreciated that the variation in the molecular ratio of phosphoric acid to strained ring alkoxysilane provides flexibility, allowing the formulation of the present invention to be tailored to achieve desired physical properties with respect to a variety of target substrates and materials. By way of non-limiting example, embodiments of the film-forming formulation of the present invention have particular utility as a base material in mold release compositions for elastomers and other molding media. It will be appreciated that the formulations of the present invention have a pH between 3.0 and 8.0. It should also be appreciated that adjusting the formulation pH in the range of 3.0 to 8.0 provides another mode of tunability. It will further be appreciated that another mode of tunability of the film-forming formulations of the present invention may also be provided by varying the type of alkoxy groups of the strained ring alkoxysilanes. A tensioacycloalkoxysilane useful herein is a monomer or oligomer of formula (I) typically having an average molecular weight of less than 4,000 daltons:

(OCH₂CH)-R¹-X-R²-Si-(R³)_a(OR⁴)_3-a (I)

wherein R is¹Is C₁-C₄Alkyl, aromatic, heteroaromatic, or with (OCH)₂CH) together form (OC 6H)₉) (ii) a X is absent or oxygen, R²Is C₂-C₆An alkyl, aromatic or heteroaromatic group; r³Independently at each occurrence is C₁-C₆Alkyl, a is an integer from 0 to 2 inclusive; r⁴Independently at each occurrence is C₁-C₆Alkyl or (C)₁-C₄Alkyl) -O- (C₁-C₄Alkyl) groups, wherein the alkyl ether groups are not necessarily the same. It will be understood that alkyl as used herein is straight chain, branched chain or cyclic, provided that cyclic alkyl is C₄-C₆. The strained ring alkoxysilanes useful herein illustratively include 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and combinations thereof.

In at least one embodiment, the phosphoric acid and the strained ring alkoxysilane of the film-forming formulation of the present invention are present in a molecular ratio of 3: 1. In at least one preferred embodiment, when present in a molecular ratio of 3:1, the phosphoric acid is present from 20 to 40 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 60 to 80 weight percent of the total weight of the formulation. In another preferred embodiment, when present in a molecular ratio of 3:1, the phosphoric acid is present from 25 to 35 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 65 to 75 weight percent of the total weight of the formulation.

In at least one embodiment, the phosphoric acid and the strained ring alkoxysilane of the film-forming formulation of the present invention are present in a molecular ratio of 3: 2. In at least one preferred embodiment, when present in a molecular ratio of 3:2, the phosphoric acid is present from 10 to 25 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 70 to 90 weight percent of the total weight of the formulation. In another preferred embodiment, when present in a molecular ratio of 3:2, the phosphoric acid is present from 15 to 20 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 75 to 85 weight percent of the total weight of the formulation.

In at least one embodiment, the phosphoric acid and the strained ring alkoxysilane of the film-forming formulation of the present invention are present in a molecular ratio of 3: 3. In at least one preferred embodiment, when present in a molecular ratio of 3:3, the phosphoric acid is present from 5 to 20 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 80 to 95 weight percent of the total weight of the formulation. In another preferred embodiment, when present in a molecular ratio of 3:3, the phosphoric acid is present from 10 to 15 weight percent of the total weight of the formulation, and the strained ring alkoxysilane is present from 85 to 90 weight percent of the total weight of the formulation.

The inventors have discovered the use of a reaction product of a monofunctional glycidoxy-functional alkoxysilane with phosphorus to overcome many of the disadvantages of prior art glycidoxy film-forming formulations and systems. By way of non-limiting example, it has been found that the reaction products of the film formulations of the present invention are formed without the use of excess solvents, endocrine disrupting materials and the production of harmful by-products relative to the prior art. This has the benefit of reducing the generation and presence of these hazardous materials (materials that are hazardous to both human health and the environment) in the film-forming formulations of the invention. In at least one embodiment, the reaction product is concentrated to a total non-volatile content of greater than 2.4 weight percent of the total weight of the formulation. In at least one preferred embodiment, the reaction product is concentrated to a total non-volatile content of greater than 15 weight percent of the total weight of the formulation. In yet another preferred embodiment, the reaction product is concentrated to a total non-volatile content of greater than 30 weight percent of the total weight of the formulation.

A release coating composition is also provided. In at least one embodiment of the present invention, a release coating composition includes the film-forming formulation of the present invention, a reactive release agent, a matrix, and an aqueous solvent. In at least one embodiment, the coating composition has a pH between 3.0 and 8.0. In at least one embodiment of the release coating composition of the present invention, the first amount of phosphoric acid and the strained ring alkoxysilane are present in a molecular ratio of 3:2, and the first amount of reaction product is present from 1.0 to 2.5 weight percent of the total weight of the composition. In another embodiment of the present invention, the first amount of the reaction product is present from 1.5 to 2.0 weight percent of the total weight of the composition. In at least one embodiment of the present invention, the release coating composition has a second amount of phosphoric acid and a tensioacycloalkoxysilane (present in a 3:3 molecular ratio) in addition to the first amount, wherein the second amount of reaction product is present from 1.0 to 2.5 weight percent of the total weight of the composition. In another embodiment, the second amount of reaction product is present from 1.5 to 2.0 weight percent of the total weight of the composition.

In at least one embodiment, a reactive release agent is provided and is present at from 1.5 to 2.0 weight percent of the total weight of the formulation. In at least one embodiment of the present invention, the reactive mold release agent is a monoepoxide-functional mold release agent. It will be appreciated that the release coating composition of the present invention functions as a semi-permanent release agent in some applications. In the context of the present invention, semi-permanent is intended to define coatings of the release coating compositions of the present invention that are applied to the mold surface and provide more than one release per application.

In at least one embodiment of the present invention, the reaction product is aged between 12 and 36 months. In another embodiment of the present invention, the reaction product is aged for 18 to 24 months. It will be appreciated that the aged reaction product renders the release coating compositions of the present invention extremely storage stable.

In at least one embodiment of the present invention, the release coating composition of the present invention comprises at least one of an emulsifier, a catalyst, an antimicrobial agent, a filler, a pigment, a dye, a wetting agent, a surfactant, a thickener, a thixotropic agent, a drying agent, an anti-skinning agent, or a combination thereof.

Thixotropic agents that are effective in some inventive embodiments of the present invention illustratively include fumed silica, organoclays, inorganic clays, and precipitated silicas. Polyfunctional alcohols are commonly used to enhance thixotropic properties.

Fillers useful in the present invention illustratively include talc, mica, alumina trihydrate, calcium sulfate, calcium carbonate, magnesium sulfate, magnesium carbonate, barium sulfate, and microspheres.

In some inventive embodiments of the present invention, a desiccant additive is provided to adjust the drying rate of the formulation. Desiccants effective in some inventive embodiments of the present invention illustratively include transition metal carboxylates (for which medium to long chain linear or branched carboxylic acids-most commonly 2-ethylhexanoic acid-or various naphthenic acids-are used as ligands), and combinations thereof. Transition metals typically include cobalt, zirconium, and manganese; and are commonly used as drying accelerators in the printing industry.

The invention is further illustrated with respect to the following non-limiting examples:

example 1

The comparative release coating composition is compared to a release composition of the present invention containing the same reactive release agent. The comparative release coating composition was comprised of 87 total weight percent deionized water, 11 total weight percent 3-glycidoxypropyltrimethoxysilane (which had been alcoholyzed in acidified water), and 2 total weight percent of a monoepoxide functional polydimethylsiloxane emulsion polymer. The inventive release composition was identical to the comparative release coating composition except that 3 times the stoichiometric amount of phosphoric acid relative to 3-glycidoxypropyltrimethoxysilane was substituted for the same weight of water.

Is prepared from 100 portionsThe 3 parts zinc oxide, 30 parts carbon black, 3 parts ethylene/acrylic elastomer and 3 parts organic peroxide molded article are peroxide cured fluoroelastomers that are difficult to demold. The article was molded in the mold cavity that had been coated with the comparative release composition. The molded article does not come out of the mold and must be cut off. In contrast, the release coating composition of the present invention was applied to a hot mold and the same difficult to release fluoroelastomer was molded and free released. The release coating compositions of the present invention provide at least three releases of the same fluoroelastomer. Subsequent reapplication ("repair") of the release coating composition of the present invention provides at least three additional releases for each "repair".

While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the described embodiments in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiment or exemplary embodiments, and it will be appreciated by those skilled in the art that changes and modifications may be made to the preferred embodiments of the invention without departing from the scope of the invention as defined in the appended claims.