CA1187239A - Coating composition and primer - Google Patents
Coating composition and primerInfo
- Publication number
- CA1187239A CA1187239A CA000409330A CA409330A CA1187239A CA 1187239 A CA1187239 A CA 1187239A CA 000409330 A CA000409330 A CA 000409330A CA 409330 A CA409330 A CA 409330A CA 1187239 A CA1187239 A CA 1187239A
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Abstract
Abstract What is disclosed is a new and novel primer composition comprising a silicone modified epoxy resin and an organotitanium acid ester. These compositions are useful for priming solid substrates to allow the adherence of room temperature cured silicone rubber to the substrate. The compositions are also useful as protective coatings.
Description
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COATING COMPOSITION AND PRIMER
Background of the Invention ` This invention deals with primer and coa-ting compositions. In particular, this invention deals wlth primer compositions which are used with room temperature curable silicone rubber and room temperature-curable silicone-modified organic rubbers in order to obtaih excellent adhesion to a variety of substrates. In particular, it also deals with compositions, similar -to the primer compositions, which are useful as coatings on various substrates. The compositions have the ability to be stored over a long period of time in the absence of moisture and they can be cured at room temperature in the presence of moistureO The compositions exhibit excellent adhesiveness with a variety of substrates.
In recent years, due to the superior durability of room temperature-curable silicone rubbers in comparison with other rubbers such as organic rubbers, they have become widely used as sealants in construction.
Room temperature curable silicone-modified organic rubbers have recently been introduced and are also being used as sealants in construction. Such construction may employ various substrate materials, for example, metals such as aluminum, steel and stainless stee]; aluminum when coated with acrylic resin, urethane resin or epoxy resin; hard inorganic materials such as glass, tile, stone and porous inorganic base materials such as mortar and concreteO Thus, a firm adhesion by the room temperature-curable silicone rubbers and room temperature~curable silicone-modified organic rubbers used as sealants has become an important problem.
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A wi.del.y used method is the applica-tion of various primers to the suhstrate followed by -the applica-tion of the room temperature curable silicone rubber or room temperature curable silicone-modified organic rubber. However, several of the above-mentioned substrates are difficult to adhere to, such as, for example, pure aluminum, surface-treated aluminum, stainless steel, aluminum coated with various resins and mortar. As a sealant, the silicone rubber or silicone-modified organic rubber peels off at the interface of the substrate before it deteriorates or loses its elasticity. Thus, primers which would main-tain superior adhesive strength for lengthy periods are desired.
Conventionally, primers composed of epoxy resins and organofunctional silanes are well known.
Ilowever, since the mutual miscibility of epoxy resins and the silane is poor, a durable and uniform adhesive film canno-t be obtained.
The inventors discovered the present invention in an attempt to overcome the above-mentioned drawbacks.
As a result, it was found that, by using an organotitanium acid ester to cure a silicone-modified epoxy resin which is itself obtained by a reaction between hydroxyl groups on an epoxy resin and the alkoxy groups of a silicone compound, a sturdy and transparent film can be formed. This film has superior adhesive strength when used as a primer for room temperature-curable silicone rubber and room temperature-curable silicone-modified organic rubber.
Thus, one aspect of this invention concerns primer compositions comprising (A) 100 parts by weight of a silicone modified epoxy resin which contains both epoxy 23~
groups and silicon-bonded alkoxy groups wherein the modified epoxy resin is obtained by contacting and reacting (a! a compound having the unit formula RaSiXb(4 a b) wherein R is a substituted or unsubstitu-ted monovalent hydrocarbon radical, X is an alkoxy radical having the formula R'O- wherein R' is an alkyl radical of 1 to 4 carbon atoms or the radical R2oR3- wherein R2 is an alkyl radical of 1 to 4 carbon atoms and R3 is a divalent alky]ene radical of 1 to 3 carbon atoms; a has a value of O to 2; _ has a value of 1 to 4 and the sum of a + b has a value of 1 to 4 with (b) an epo~y resin containing at least one epoxy group and at least one hydroxy group per molecule; and (B) 0.1 to 100 parts by weight of an organotitanium acid ester.
Componen-t (A) is a primary component of the primer composition along with component (B).
Taking componen-t (A) first, it should be noted that component (A) is prepared from two subcomponents, components (a) and (b). Component (a) prior to reaction with component (b) consists of a compound having the unit formula a b (4-a-b) R in component (a) is a substituted or unsubstituted monovalent hydrocarbon radical. The groups which have been found useful in this invention are, for example, alkyl groups such as methyl, ethyl, propyl and octadecyl;
alkenyl groups such as vinyl and allyl and aryl groups such as phenyl. The substituted monovalent hydrocarbon 3~
radicals useful in this invention are those wherein -the above disclosed unsubstituted monovalent hydrocarbon radicals are substitu-ted by such yroups as halogen, cyano, mercapto and hydroxyl groups or by organofunctional groups such as methacryloxy, acry]oxy or the 3, 4-epoxycyclohexyl groups.
X in the above formula is an alkoxy radical having the formula R'O- wherein R' is an alkyl radical of 1 to 4 carbon atoms or the R2oR3- radical. Thus, X can be R'O- such as methoxy, ethoxy or propoxy. X can also be R2oR30- wherein R2 is an alkyl radical of 1 to 4 carbon atoms and R3 is a divalent alkylene radical of 1 to 3 carbon atoms R can be for example, methyl, ethyl or propyl and R , for example can be methylene, ethylene or propylene. An example of R OR O- can be, for example, rnethoxyethoxy-.
For purposes of this invention, a has a value of 0 to 2; b has a value of 1 to 4. Thus, included within the scope of this invention are compounds wherein R is not necessarily present. The reason for the values of a and b as set forth above is that there cannot be too few alkoxy groups in the resulting reacted product from (a) and (b). Components with too few alkoxy groups in the reacted product result in insufficient curing and insufficient adhesion in the final product. Thus, it is preferable that there be at least two X groups in ~a) and at least 3 X groups be present in (A). Component (a) can be a silane, a polysiloxane or a siloxane oligomer.
Polysiloxanes having a moderate degree of polyrnerization are preferred for this invention. The polysiloxane may be linear, branched chain or a network siloxane. In addition to the alkoxy radicals, this material can also ~3~
contain small amoullts of hydroxyl groups, halogen groups or hydrogen atoms.
Examples of silanes useful as component (a) are such silanes as me-thyltrimethoxysilane, dimethyldie-thoxysilane, e-thyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(methoxyethoxy)silane, allyltripropoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma--glycidoxy-propyltrimethoxysilane, beta-(3,9-epoxycyclohexyl)ethyltri-methoxysilane, tetrame-thoxysilane, tetrae-thoxysilane, -tetra-propoxysilane, tetrabutoxysilane, the partial hydro]ysis condensation products of any of the preceding compounds and ethyl polysilicate. These compounds may be used individually or by mixing with each other. Based on the reactivity with -the hydroxyl groups of -the epoxy resin, low molecular weight organoalkoxysilanes such as methyltrime-thoxysilane and ethyltrimethoxysilane, are desirable. Also, based on their excellent effec-t in improving the adhesion with the base material, gamma-mercaptopropyltrimethoxysilane and gamma-glycidoxy-propyltrimethoxysilane, are desirable. The epoxy resin (b), -the other component of (A), must have at least one hydroxyl group and at least one epoxy group per mo]ecule.
Either the bisphenol type epoxy resins or the novolak type of epoxy resins are usable. The bisphenol resins are preferred. In particular, epoxy resins obtained by the condensation of bisphenol A and epichlorohydrin are preferred. These are expressed by the average formula 23~
rH -CH-CH ~---o--- ~ -C(CH3)2- ~ -OCH2CHCH~-----o--C(CH ) ~ -OCH---CH2 (n is an integer ~ 3 2 ~ \ / between 1 and 19).
A hydroxyl equivalence in the range of 100 to 220 is desirable. When the hydroxyl equivalence is less than this range, the quantity of component (b) modified by the silicone compound becomes small, resulting in difficulty in the formation of a satisfactory film. When the hydroxyl equivalence is greater than 220, under the ordinary conditions of the condensation reaction of components (a) and (b), unreacted hydroxyl groups tend to remain which may lower the storage s-tability ~hen the organotitanium acid ester of component (B) is present in (A). Also, in the condensation reaction this will cause problems of increased viscosity and gelation.
Furthermore, although the epoxy groups generally do not participate in the condensation reaction with the alkoxy groups of component (a) and hydroxyl groups of component (b), an epoxy equivalence in the range of 180 to 4,000 is desirable in order to increase the adhesive efEect of the primer composition. It is preferred that average molecular weight be 300 to 3,000 and particularly 700 to 1,400. Component (A) can be obtained by mixing the above-mentioned components (a) and ~b) at a temperature above the boiling point of the by-produced alcohol. The two components condense liberating the alkoxy groups of component (a) and the hydroxyl groups of component (b) as alcohol. Generally, it is easier to carry out this d ~23~
-tion catalyst at 80 to 160C with continuous removal of the liberated alcohol. A solvent or diluent such as toluene, xylene or ethyl acetate may be used during the reaction. It should be noted that after -the reaction, no hydroxyl groups should remain on the epoxy resin. For this reason, it is advantageous to use a small amount of a catalyst. During the condensation of components (a) and (b), it is desirable that the reaction be carried out under the conditions wherein the ratio of mols of alkoxy groups in component (a) to the mols of hydroxyl groups in component (b) is 1 or greater. When the reac-tion is carried out at below 1 and especially when the organotitanium acid ester of component (B) is added -to component (A), gelation is easily effected~ Thus, in order to obtain a durable, homogeneous liquid primer composition, the reac-tion should be carried out at the above-mentioned molar ratios. It is preferred that component (A) contain at least 3 alkoxy groups.
Component (B), the organotitanium acid ester, after reacting with the alkoxy groups of component (A), will not only cure the primer composition and provide air dryabili-ty, but also will remarkably improve the adhesive strength, especially the adhesive durability, be-tween the substrate and the room temperature-curable silicone rubbers or room temperature-curable silicone--modified organic rubbers. Examples of titanium compounds useful in this invention are as follows: tetraisopropyl ti-tanate, tetra-n-butyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, diethoxytitanium acetylacetonate, titanium diacetylacetonate, octylene glycol titanate, titanium lactate, titanium ethyl lactate, ethanolamine titanate, titanium chelates such as beta-diketonate chelates of dialkoxytitaniums, ketoacid Z3~
e~s-ter chelates of dialkoxy-titaniums or -their partial hydrolysis condensa-tion products. Component (B~ may be used as individual compounds or mix-tures of individual compounds. The amount of Componen-t (B) useful in -this invention is 0.1 to 100 parts by weight per 100 parts of component (A). From the viewpoint of curabili-ty, adhesion and storage stability, 5 to 25 parts by weight is desirable.
Simple mixing of -these componen-ts will provide the primer composition of this invention.
Furthermore, in an attempt to irnprove the adhesion, especially the adhesion durabili-ty of the primer, and also to improve the air dryability and thus increase the productivity, the addition of an additional silane or i-ts par-tial hydrolysis condensa-tion produc-t expressed by the following average formula, is effective:
R Si(OR )3 wherein R4 represents organic groups such as alkyl groups such as methyl and ethyl; monovalent unsaturated aliphatic hydrocarbon groups such as vinyl and methacryloxy and organofunctional groups such as glycidyl and mercaptopropyl; R5 is represented by alkyl groups such as methyl, ethyl and propyl or alkoxyalkyl groups.
Several examples of these compounds are methyltrimethoxysilane, dimethyldiethoxy-silane, ethyltriethoxysilane, phenyltrime-thoxysilane, vinyltrimethoxysilane, allyltripropoxysilane, gamma-methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the partial hydrolysis and condensation products of the preceding compounds and ethyl polysilicate. The silane or partial 723~
hydrolysis condensation product should be selec-ted accord:ing to the intended application of the primer composition.
When applying -the primer composition to the substrate and the viscosity is too high or a thin film is desired, it is possible to use an organic solvent for dilution. For example, toluene, xylene or ethyl aceta-te may be used as the organic solvent. In an attempt to further increase the postcure film strength, various inorganic fillers may be added to the primer compositionsl for example, a powdered silica may be added. Other fillers suitable for this purpose are hydrophobic silicas with a trimethylsilylated surface.
Moreover, any generally well known heat s-tabilizer or colorants such as red iron oxicle, cerium oxide, fa-tty acid salts of iron, titanium oxide or other agents may be optionally added provided interference with the purpose of -this invention is not caused.
The primer of this invention is sui-table for use as a pre-process treatment for substrates in order to increase the adhesion and durability of room temperature-curable silicone rubbers and room temperature-curable silicone-modified organic rubbers with various substrates throughout the curing process.
The room temperature-curable silicone rubber may be a single package or two package type. Any -type involving liberation of alcohol, oxime, ketone, amine, hydroxylamine or carboxylic acid may be used. The room temperature-curable silicone-modified organic rubbers may also be single or two package typesO Examples are as follows: alko~ysilyl-terminated polyether rubbers, alkoxysilyl-terminated polybutadiene rubbers and alkoxysilyl-terminated polyure-thane rubbers.
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By using these primer compositions as a pre-process treatment for poorly adhering base materials such as pure aluminum, surface-treated aluminum, coated aluminum, stainless steel, mortar and concre-te, the above-mentioned rubber can be adhered firmly and durably.
The sealing of different substrates in construc-tion can be carried out smoothly.
Materials similar to those discussed above are also appropriate for use as coatings for various substrates. Therefore, this invention also deals with coating compositions. More particularly, this aspect of the invention deals with compositions which can be stored over a long period of time in the absence of moisture but can be cured at room temperature in the presence of moisture as coatings. These compositions exhibit excellent adhesion to various substrates.
Generally, silicones exhibit excellent heat resistance and electrical insula-ting properties and they have -therefore been widely used for heat-resistant paints and varnishes for electrical insulation. However, silicones have some disadvantages. For example, silicones require high -temperatures and long term heating for curing. In addition, they can be adhered satisfactorily to metal plates such as soft s-teel and stainless steel, but they cannot be easily adhered to plasticsO
The inventors pursued the present investigation in an attempt to overcome the above-mentioned disadvantages of silicones. It was found that compositions can be obtained which can be stored for long periods of -time in the absence of moisture bu-t which can be cured at room temperature in the presence of moisture 23~
to form coatings which exhibit excellent adhesiveness with a variety of substrates such as metals and plastics.
This invention therefore deals with coating compositions whi.ch consist of a coating composition comprising (I) 100 parts by weight of a silicone modified epoxy resin containing silicon-bonded alkoxy groups wherein the modified epoxy resin is ob-tained b~
contac-ting and reacting a compound (a) containing at least two silicon-bonded alkoxy groups per molecule having the unit formula c iXd(4-c-d) wherein R6 is a substituted or unsubstitu-ted monovalent hydrocarbon radical, X' is an alkoxy radical having the formula R70- wherein R7 is an alky] radical of 1 -to 4 carbon atoms or -the radical R80R9- wherein R8 is an alkyl radical of 1 to 4 carbon atoms and R9 is divalen-t alkylene radical of 1 to 3 carbon atoms, c has a value of 0 to 2; d has a value of 1 to 4 and the sum of c + d has a value of 1 to ~, with (b) an epoxy resin containing at least one epoxy group and at least one hydroxyl group per molecule and w.herein prior to contacting and reacti.ng components (a) and (b)~ the ratio of alkoxy groups in component (a) to the hydroxy groups in component (b) is equal to or greater than l; and (II) 0.1 to 100 parts by weight of an organotitanium compound.
Component I of this invention is prepared from two reactive materials I(a) and I(b). Specifically, Component (I) of the composition is a product of the condensation reaction between the silicon~bonded alkoxy groups in component I(a) and the hydroxyl groups in component I(b). This material is a primary component of 3~
-the coating compositions of this invention. Componen-t I(a) is a si]ane or polysiloxane containiny at least two silicon-bonded alkoxy groups per molecule and has the unit formula RlsiXfO~4--e-f)-The alkoxy groups undergo a condensation reaction with the hydroxyl groups in the epoxy, component I(b). In the formula, R10 represents substituted or unsubstituted monovalent hydrocarbon radicals bonded to silicon atoms.
Examples of these groups are alkyl groups such as me-thyl, ethyl, propyl and octadecyl; alkenyl groups such as vinyl and allyl; aryl grou-ps such as phenyl and naphthyl and their derivatives in which some of the hydrogen atoms are substituted with halogen atoms, cyano groups, hydroxyl groups or mercapto groups or in which some of the hydrogen atoms on alkyl groups are substituted with functional groups sueh as methacryloxy acryloxy, glycidyl and 3,4-epoxycyclohexyl. X" for purposes of -this invention is a silicon-bonded alkoxy group represen-ted by the formula R O- wherein R1 is an alkyl radical of 1 to 4 carbon a-toms or the radical R120~13- whe~eirl R12 is an alkyl radical of 1 to 4 carbon atoms and R is a divalent alkylene radical of 1 -to 3 carbon atoms.
Examples of these groups are methoxy, ethoxy, propoxy and methoxyethoxy. For purposes of this inven-tion, e has a value of 0 to 2 and f has a value of 1 to 4 and the sum of e ~ f has a value of 1 -to 4 The fact -that e has a value of 0 to 2 indica-tes that R is not necessarily present in component I~a). However, e must be 2 or less and f must be 1 or more. Each molecule must contain at least two silicon-bonded alkoxy groups. The reason for 23~
this is tha-t if the number of alkoxy groups is too low, -the degree of condensation with the hydroxyl groups i.n component l(b) will be decreased and the number of silicon-bonded alkoxy groups in component (I) will be less which results in insufficient curing. In this sense, it is desirable that at least three X groups be presen-t in component (I) after the reaction of componen-ts I (a) and I (b).
Component I(a) can be either a silane or a polysiloxane. If it is a polysiloxane, the degree of polymerization must be ~ or greater. The molecular configuration of the polysiloxane can be linear, branched chain or network. In addition to the reactive alkoxy groups, it can contain small amounts of silicon-bonded hydroxyl groups, halogen atoms or hydrogen atoms.
Examples of component I(a) are silanes such as methyltrimethoxy-si.lane, methyltripropoxysilane, dimethyldiethoxysilane, ethyltri~ethoxysi]ane, pheny]trimethoxysilane, diphenyldi-methoxysi.lane, phenylmethyldiethoxysilane, vinyltrimethoxy-silane, allyltripropoxysilane, vinyltri(methoxye-thoxy~-silane, methylvinyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropylmethyldimethoxysilane, gamma-glycidyl~
propyl-trimethoxysilane, gamma-glycidylpropylme-thyldie-thoxy-silane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryl-oxypropylmethyldiethoxvsilane and gamma-acryloxypropyltri-7~3~D
methoxysilane; partial hydrolysis and condensation products of one or two or more of these silanes; partial hydrolysis and condensation products of -these silanes with other organosilanes such as trimethoxyethoxysilane and ethyl polysilicate.
Component I(b) is the same as that used for the primer composition discussed above and is an epoxy resin containing at least one epoxy group and hydroxyl group per molecule. Both bisphenol type resins and novolak type resin are applicable. Component I(b) preferably possesses the following structural formula with a molecular weight ranging -from 300 to 6000.
CH2~CH-CH2~ O ~ -C- ~ OH
~3 C ~ \o/
Examples of commercial epoxy resins useful herein are Epikote( ) 815, 820, 828, 834, 864, 1001, 1004 and 1007, all products of the Shell Chemical Corporation.
Component (I) is a silicone-modi-fied epoxy resin containing silicon-bonded alkoxy groups which is obtained by a condensation reaction between components I(a) and I(b) wherein the ratio of alkoxy groups in component I(a) to the hydroxyl groups in component I(b) is equal to or greater than 1. If this ratio is less than 1, gelation is likely to occur during the condensation reaction between components I(a) and I(b).
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Although gelation may not occur during the condensation reaction, gelation is likely to occur when the organotitanium compound, component (II), is added thereto and a satisfactory storage stability therefore cannot be achieved. As the above-mentioned ratio increases, the chances of gelation occurring during the reaction becomes less. In addition, the storage stability of the coating composition, when component (IT) is added, increases.
The condensation reaction between components I(a) and I(b) is preferably carried out at 80-250C using a small amount of a conventional catalyst such as organotitanium acid esters. When this condensation reaction is carried out, an organic solvent which can dissolve both components I(a) and I(b) can be used.
However, the use of an organic solvent is undesirable for some coating applications owing to deterioration of the substrates by the solvent. In such cases the reaction is preferably carried out in the presence of an excess of low boiling alkoxysilane.
Component (II) is a compound which makes component (I) room-temperature curable in the presence of moisture. Examples of such compounds: titanium acid esters of monohydric alcohols such as methanol, e-thanol, isopropanol, butanol, cyclohexanol, octanol and octadecyl alcohol; titanium acid esters of dihydric alcohols such as ethylene glycol, propylene glycol, octylene glycol, diethylene glycol, tripropylene glycol and tetraethylene glycol; titanium acid esters of trihydric alcohols such as glycerin; alkoxy titanium chelates such as diisopropoxybis(acetylacetonato)titanium and di-n-butoxybis(triethanolaminato)titanium and dihydroxybis(lactato)titanium~
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In terms of the amount of component ~II) to be added, the curing rate slows down when the amount of component II is too small. In con-trast, if too much is added, the cured film becomes brittle and cracks are easily produced. Thus, an appropriate amount ranges from 0.1 parts by weight to 100 parts by weight per 100 parts by weight of component (I). From a consideration of curability, adhesiveness and storage stability, the amount preferably ranges from 5 to 90 parts by weight.
The,coating compositions of this invention can be obtained from components (I) and (II) by simply mixing them together. However, in order to increase the storage stability, both components are preferably mixed together in the absence of moisture and the product is stored in a moisture-impermeable container after mixing and degassing treatments.
Optionally, additional components such as organic solvents, inorganic fillers, pigments and heat-resisting agents can be added. In particular, additional organotrialkoxysilane such as has been disclosed for component I(a) can be added in an amount of 5 to 500 parts by weight per 100 parts by weight of component (II) after components I(a~ and I(b) have been reacted and after component II has been added. The organic radicals in the organotrialkoxysilane are identical to the above-mentioned R10 radicals and the alkoxy radicals are also identical to the above~mentioned X". The coating compositions of this invention can be stored over a long period in the absence of moisture. In the presence of moisture, curing occurs even at room temperature to form a strong heat-resistant and weather-resistant film which is firmly adhered on substrates such as various types of metals, plastics and 3~
woods. Thus, the compositions are very useEul as protective coating agents for these substrates.
Several examples illustrating the invention follow: The viscosity unless indicated otherwise was measured at 25C.
"Parts" in the examples denotes "parts by weight." The finger touch drying time, adhesiveness and pencil hardness were determined under the following conditions:
Finger touch drying time: the finger touch drying time was defined by the time in which the coated surface ceases to be tacky after being coated on the substrate ancl a fingerprint no longer imprints on the surface. Pencil hardness: the pencil hardness was measured according to JIS K 5400.
Adhesiveness (Cross-cut adhesion test3: one hundred, 1 mm squares, were cut in a l cm square of the cured coating using a razor blade and a cornmercial cellophane tape was firmly pressed and adhered over the cut squares.
The number of squares remaining out of lOO squares was counted after the tape had been quickly peeled. The number of remaining squares was recorded as the numerator and the number of cut squares was recorded as the denominator.
23~3i Example 1 (A) Synthesis of a partial hydrolysis condensation product of methyltrimethoxysilane 136 g (1 mol) methyltrimethoxysilane and 18 g (1 mol) water and 0.1 g acetic acid were placed in a 300 ml three-neck flask equipped with reflux condenser, stirrer and thermometer. A reaction was carried out for 5 hours at reflux. The reaction by-product, methyl alcohol, and unreacted methyltrimethoxysilane were then removed under vacuum at 10 mm Hg and 150C to give a liquid polysiloxane containing 30 wt% methoxy groups with a viscosity of .000046 m2/s.
(B) Synthesis of a silicone-modified epoxy resin 700 g of an epoxy resin (Epikote 1001, Shell Chemical Co.) with an average molecular weight of 900 to 1000, hydroxyl equivalence of 115 and epoxy equivalence of 500; 300 g of the partial hydrolysis condensation product produced in Example l(A), 1,500 g toluene and 0.15 g tetraisopropyl titanate as catalyst were placed in a 5000 ml three-neck flask equipped with reflux condenser, stirrer and thermometer. With continuous stirring, the flask was heated to 100C gradually and a condensation reaction was carried out at reflux (105 to 110C). The essentially nontransparent reaction mixture gradually became transparent. During the reaction, samples were taken each hour and applied to a glass plate. The reaction was continued until the film on the glass plate, obtained by evaporating the low boiling substances by baking at 150C, became transparentO This film became transparent after a reaction of 3 hours.
Reflux was continued while the methyl alcohol by product was continuously removed from the system through distillation. The residue from the reaction was a ~IL !37%3~
transparent liquid with a viscosity of .00015 m /s at 25 containing 37 weight percent nonvolatile components. Gel permeation chromatography and infrared spectroscopy revealed that this nonvolatile component was a silicone-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. Infrared spectroscopy and boiling point data showed that the volatile component was toluene.
(C) Adding and mixing 10 g of tetra-n-butyl orthotitanate into 100 g of the product of Example l(B) gave a uniform transparant liquid (composition C). This composition C was stable, after sealing to exclude moisture, in storage for more than 2 months. The above-mentioned composition C was then applied to 2 each of mortar blocks and aluminum panels (JIS-H4000) with a brush. An amino~y-liberating two package room temperature-curable silicone rubber (Toray Silicone Co., Ltd. product, SH792 Sealant) was applied to these blocks and panels to form adhesion test samples according to the specification in "Construction Sealing Materials,"
JIS-A5758, section 5.12. After these test samples had been maintained at room temperature for 14 days, the initial properties and the properties after another 7 days immersion in 20C water were investigated.
For comparison, composition l(B~ was used as a primer to form the same kind of test samples and the properties were investigated. Maintenance and measurement of the properties were according to the above-mentioned JIS-A5758, section 5.12. The results are shown in Table 1.
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1:'~ u~ ,_ ~ ~ R ~ ~ R
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! I O ~1 (~ O O ~1 (~ O O
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H E ~ u~ n Ll C) ` ,1 S l O ` ,1 h ,1 .~1 p, O ~
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.
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a) ~ ~ .1~ ~ N ~I O ~J
~1 ~ ~ r~
~3 1~ H O r~ I ~1 ~) a~ _ E~ ~ :~ ~ 1 ,-i ,_i dP ~ X
O U~ ~rY
, ~1 ~ n~ h~rl u~ rY~:: X ~ D7 Q 3 o o ,~ ~ ~ ~n ~n o ~ O ~ O ~ Ul 8 ~ m ~ m ~ ~ ~ ~ o ~ ~ u~
s~s~ ~ ~ ~ u~ o R
::~O ~ O ~ rl X t~
~n ~ ~ ~ u~
~ a~ o.,, a~
~ ~ E~
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S~ U~ U~
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Example 2 100 g of an epoxy resin (Epikote 834, Shell Chemical Co.) with an average molecular weight of 450, hydroxyl equivalence of 105 and epoxy equivalence of 300 to 375 and 10 g of methyltrimethoxysilane, 100 g toluene and 0.15 g tetraisopropyl titanate as catalyst were placed in a 500 ml three-neck flask equipped with stirrer, reflux condenser and thermometer. With continuous stirring, the flask was heated to 100C gradually and a condensation reaction was carried out at reflux (105 to 110C). The essentially nontransparent reaction mixture gradually became transparent. Reflux was continued for 2 hours while the methyl alcohol by-product and unreacted methyltri~ethoxysilane were constantly removed from the system by distillation.
The residue obtained from this reactlon was a transparent liquid with a viscosity of .OD2 M2/s and contained 75 weight percent nonvolatiles. Gel permeation gas chromatography and infrared spectroscopy revealed that this nonvolatile component was a silione-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. Adding and mixing 100 g toluene and 5 g tetra-n-butyl titanate dimer into 100 g of the above-mentioned residue gave a uniform transparent liquid (composition D). Composition D was then applied to 2 each of mortar blocks and aluminum panels (JIS-H4000) with a brush. After being dried at 20C for 5 hours, these blocks and panels were tested as in Example 1 according to the specifications listed in JIS-A5758, section 5.12. The initial properties and the properties 7;23~
after 7 days water immersion were investigated and the results are shown in Table 2.
Table 2 Composition D Test Results Item Initial AEter Immersion in Water Substrate M50 T E M50 T E
Mortar Block 1.1 5.0 750 1.0 5.0 670 Aluminum Panel 1.1 5.3 750 1.0 5.3 870 Example 3 100 g of~the same epoxy resin as was used in Example 1 (Epikote 1001, Shell Chemical Co.), 250 g methyltriethoxysilane, 250 g toluene and 0.10 g tetra-n-butyl titanate were placed in a 1000 ml three-neck flask equipped with stirrer, reflux condenser and thermometer. Under continuous stirrin~, the flask was gradually heated to 100C and a condensation reaction was carried out at reflux. The essentially nontransparent reaction mixture gradually became transparent. Reflux was continued for 3 hours while the ethyl alcohol by-product and unreacted methyltriethoxysilane were constantly removed from the system by distillation.
The reaction residue contained 75 weight percent nonvolatiles. Gel permeation chromatography and 23~
infrared spectroscopy revealed that the nonvolatile component contained primarily a silicone~modified epoxy resin possessing epoxy groups and silicon-bonded ethoxy groups.
Adding and mixing 10 g of tetrabutyl titanate dimer to 100 g of this reaction residue gave a uniform transparent liquid (composition E). Composition E was then applied to 2 each of mortar blocks, aluminum panels (JIS~H4000) and stainless steel panels (SUS 304~ as in Example 2 and they were dried at 20C for 2 hours.
Experimental adhesion test samples were then produced as in Example 1 according to the specifications of JIS-A5758, section 5.12. The initial properties and properties after a 7 day water immersion were investigated and the results are shown in Table 3.
Table 3 Composition E Test Results Item Initial After Immersion in Water Substrate M50T E M50 T E
Mortar Block 1.15.1 750 l.0 5.0 640 ~luminum Panel l.15.5 900 l.0 S.2 950 .__ ~
Stainless Steel l.l5.5 870 l.0 5.3 910 .. _. ___ ._ ... _ __ Example 4 100 g of the epoxy resin of Example 1 ~Epikote lO01, Shell Chemical Co.), lO0 g gamma-mercap-topropyl--trimethoxysilane, lO0 g toluene and 0.15 tetraisopropylor-thotitanate were placed in a 500 ml three-neck flask equipped with stirrer, re~lux condenser and thermometer. With continuous stirring, the flask was heated gradually to 100C and a condensation reaction was carried out at reflux. The essentially nontransparent reaction mixture gradually became transparent. Refluxing was continued for 4 hours while the methyl alcohol by-product was constantly removed from the sys~em by distillation.
The reaction residue was a transparent liquid containing 65 weight percent solids. Gel per~eation gas chromatography and infrared spectroscopy revealed that 7;Z~
this nonvolatile component was a silicone-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. The volatile component was primarily toluene.
Adding and mixing 10 g of diisopropoxytitanium bis(acetylacetonate) to 100 g of this reaction residue gave a uniform liquid (composition F). Composition F was then applied to various panels as in Example 1 and dried at 20C for 2 hours. The same type of experimental adhesion test samples as in Example 1 were then produced.
The initial properties and those after a 7 day water immersion were investigated and the results are shown in Table 4.
~B7Z3~
Table 4 Composition F Test Results Item Initlal After Immerslon in Water . . ._ Substrate M50 T E M50 T E
._ . _ _ _ .. _ Stainless S-teel Panel 1.1 4.5 820 1.0 4.3 880 . . ~
Aluminum Panel 1.2 5.5 830 1.0 5.1 860 Acrylic _ _ Coated Panel 1.1 5.3 870 1.1 5.0 870 ..
Urethane Coated Panel 1.1 4.2 820 1.0 5.0 920 _ . .. _ _ . __ Mortar Block 1.1 5.1 730 1.0 2.0 560 .. .__ . . _ .. _ .... _ ... __ Tile 1.0 4.8 810 1.0 4.7 970 _ .. _ _ ._ ...
Glass Plate 1.0 5.6 960 1.2 5.2 850 Example 5 100 g of an allyl terminated polyoxypropylene polymer (average molecular weight 400) were placed in an autoclave. Under nitrogen gas, 23 g of methyldimethoxysilane and 0.006 g of a platinum-ethylene catalyst complex were added followed by stirring at 100C
for 1 hour. Then, 120 g calcium carbonate, 40 g fumed silica filler, 40 g dioctyl phthalate and 2 g dibutyltin dilaurate were added to this reaction mixture to produce a polyether type room temperature-curable rubber.
The composition E obtained in Example 3 was applied -to 2 each of mortar blocks and aluminum panels with a brush and dried at room temperature for 4 hours.
After that, the above-mentioned room temperature-curable rubber was applied on these experimental panels and blocks as a bead. After being maintained for 14 days, the experimental panels and blocks were checked for adhesion and it was observed that in all cases peeling occurred in the rubber layer and there was 100% cohesive failure.
Example 6 For this example, 0.020 g of a silane with -the formula (CH30)3SiCH2CH(CH3)CH2SH
were added to 7 g of a 20 weight ~ xylene solution of a hydroxyl-terminated polybutadiene with a molecular weight appropriate for curing to a rubber. After heating at 100C for 24 hours, an alkoxysilyl-terminated polybutadiene was formed. To this modified polybutadiene were added 0.163 g methyltrimethoxysilane and 0.082 g titanium acetonylacetate to produce a room temperature-curable rubber. Composition E of Example 3 was applied to 2 each of mortar blocks and aluminum panels with a brush. These blocks and panels were dried -'7~3~
at 20~C for 4 hours. The above-mentioned room temperature-curable rubber was then applied to these plates as a bead. After being maintained for 14 days, these experimental blocks and panels were checked for adhesion and it was observed that in all cases peeling occurred in the rubber layer and there was lO0~ cohesive failure.
Example 7 An oxime-liberating single package silicone sealant (SH780 Sealant by Toray Silicone Co., Ltd.) and an alcohol-liberating single package silicone sealant (SH9145 Sealant by Toray Silicone Co., Ltd.) were used as room temperature-curable silicone rubbers. Composition C
of Example l was used as the primer composition. The adhesion was tested under the same conditions as in Example 6 and identical results were obtained.
Coating Composition Examples Example 8 A condensation reaction was carried out using Epikote lOOl(R) by Shell Chemical Corporation and methyltrimethoxysilane for the compositions shown in Table 5. In this case, tetrabutyl titanate was added as the condensation reaction accelerating catalyst and toluene was used as the solvent. These components were placed in a three-neck flask equipped with a reflux condenser, thermometer and stirrer. A reaction was carried out at 90C under reflux for 5 hours. After the reaction, low boiling fractions were removed by distillation and the mixture was then cooled. A light yellow, transparent silicone-modified epoxy resin containing silicon-bonded methoxy groups was obtained as a result. Tetrabutyl titanate (2 parts) was added to 20 parts of the resin produced above. This is sample l. In 3g~
the case of sample 3 which used sample 1 with a methoxy group/hydroxyl group ratio of less than 1, gelation occurred immediately. In the case of sample 4 which used sample 2 in which the same ratio was 6.9, thickening was not observed. When sample 4 was stored in a sealed glass bottle, a homogeneous liquid was maintained after 3 months. The composition of sample 4 into which tetrabutyl titanate was compounded was coated over a stainless steel plate. The coated surface was no longer tacky after 10 minutes. The coated film adhered well on the stainless steel plate.
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Example 9 Epikote 1001(R) by Shell Chemical Corporation (hydroxyl group equivalents: 1.44) (450 parts), methyltrime-thoxysilane (1050 parts)(methoxyl group equivalents: 23.2) and tetrabutyl titanate (0.1 part) were placed in a three-neck 2000 ml flask. The system was gradually heated to reflux. Ref]ux was achieved at abou-t 88~C. The reaction was carried out under reflux for 5 hours. After the reaction, low boiling fractions (108 parts) were removed by distillation and a light yellow, transparent silicone-modified epoxy resin I
containing silicon-bonded methoxy groups with a nonvolatile fraction of 37.7% was obtained resulting in a yield of 1,390 parts.
On the basis of the solids content, the silicone content in the silicone-modified epoxy resin was calculated to be approximately 14 weight percent. In this case, the volatile fraction in the residue was methyltrimethoxysilane and tetrabutyl titanate were compounded as shown in Table 6 to prepare five compositions. These compositions were respectively coated over a stainless steel panel ~(SUS 304), a methacrylic resin panel and a polycarbonate panel. The finger touch drying time~ adhesiveness after curing for 48 hours (cross-cut adhesion test) and pencil hardness were evaluated. The results are presented in Table 6.
As shown ~'7~3~
in Table 6, when too llttle tetrabutyl titanate was added, drying required too many hours. When too much was added, the coated film became brittle and cracks were easily produced. The adhesion on the methacrylic resin panel and stainless steel panel were found to be impaired.
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Example 10 A coating composition was prepared by compounding methyltrimethoxysilane t260 parts) and tetrabutyl titanate (26 parts) in 100 parts ~solid content) of silicone-modified epoxy resin I. The resulting composition was coated over various base materials as shown in Table 7 and cured by allowing the film to stand at room temperature for 48 hours. The adhesiveness with these base materials and the film hardness were examined. The results are presented in Table 7.
~7~3~
Table 7 Adhesion on Various Subs-trates Adhesiveness ICross-cut Pencll Base Materials Adhesion Test) Hardness . _ Aluminum panel (JISH4000 A1050P) 100/100 HB
Aluminum panel (JISH4000 A1050P) 100/100 HB
(sealed by alumite sulfate treatment) Aluminum panel (JISH400 A1050P) 100/100 HB
(nonsealing by alumite sulfate treatment~
Aluminum panel (JISH4000 A6061S) 100/100 H
Aluminum panel (baked with an 100/100 H
acrylic resin) Aluminum panel (V-Chroma treatment 100/100 H
(note below) Stainless steel panel (SUS 304) 100/100 H
Soft steel panel 100/100 H
Polycarbonate resin panel 100/100 H
Methacrylic resin panel100/100 H
Vinyl chloride panel 100/100 HB
Note: A single~ uid polyurethane resin paint for curtain walls (by DaiNippon Toryo ~.K.) was used.
~87~3~31 Example ll tl) Preparation o~ a silicone-modified epoxy resin II
~ ethyltrimethoxysilane was hydrolyzed and condensed in the presence of an acid catalyst and low boiling fractions were removed by distillation.
Methylmethoxypolysiloxane (144 parts, methoxy group equivalent 1.39) containing 30 weight percent methoxy groups and with a viscosity at 25C of .000042 M2/s~
Epikote 1001(R) by Shell Chemical Corporatlon (576 parts, OH group equivalent 1.84), tetrabutyl titanate (0.2 parts) and toluene (1080 parts~ were placed in a 2000 ml three-neck flask equipped with a stirrer, reflux condenser and thermometer. The temperature was slowly raised to 105C. While the methanol produced at this tempera-ture was removed by distillation, the mixture was continuously stirred. The reaction was continued until compatability was obtained (compatability was judged to be the point at which a sample, taken every hour, formed a transparent film on glass when the sample on the glass plate was devolatized). After compatability had been obtained, low boiling fractions (300 ml) were removed by distillation. The temperature was subsequently reduced to 80C. When the temperature reached 80C or less, methyltrimethoxysilane (130 parts, methoxy group equivalent 3.03) was added. The ratio of total methoxy equivalents/hydroxvl equivalents was 2.4. The mixture was slowly heated and a reaction was carried out at reflux for 6 hours. ~fter the reaction, the mixture was cooled and a transparent liquid silicone-modified epoxy resin II was obtained with a nonvolatile content of 43~.
COATING COMPOSITION AND PRIMER
Background of the Invention ` This invention deals with primer and coa-ting compositions. In particular, this invention deals wlth primer compositions which are used with room temperature curable silicone rubber and room temperature-curable silicone-modified organic rubbers in order to obtaih excellent adhesion to a variety of substrates. In particular, it also deals with compositions, similar -to the primer compositions, which are useful as coatings on various substrates. The compositions have the ability to be stored over a long period of time in the absence of moisture and they can be cured at room temperature in the presence of moistureO The compositions exhibit excellent adhesiveness with a variety of substrates.
In recent years, due to the superior durability of room temperature-curable silicone rubbers in comparison with other rubbers such as organic rubbers, they have become widely used as sealants in construction.
Room temperature curable silicone-modified organic rubbers have recently been introduced and are also being used as sealants in construction. Such construction may employ various substrate materials, for example, metals such as aluminum, steel and stainless stee]; aluminum when coated with acrylic resin, urethane resin or epoxy resin; hard inorganic materials such as glass, tile, stone and porous inorganic base materials such as mortar and concreteO Thus, a firm adhesion by the room temperature-curable silicone rubbers and room temperature~curable silicone-modified organic rubbers used as sealants has become an important problem.
~,23~
A wi.del.y used method is the applica-tion of various primers to the suhstrate followed by -the applica-tion of the room temperature curable silicone rubber or room temperature curable silicone-modified organic rubber. However, several of the above-mentioned substrates are difficult to adhere to, such as, for example, pure aluminum, surface-treated aluminum, stainless steel, aluminum coated with various resins and mortar. As a sealant, the silicone rubber or silicone-modified organic rubber peels off at the interface of the substrate before it deteriorates or loses its elasticity. Thus, primers which would main-tain superior adhesive strength for lengthy periods are desired.
Conventionally, primers composed of epoxy resins and organofunctional silanes are well known.
Ilowever, since the mutual miscibility of epoxy resins and the silane is poor, a durable and uniform adhesive film canno-t be obtained.
The inventors discovered the present invention in an attempt to overcome the above-mentioned drawbacks.
As a result, it was found that, by using an organotitanium acid ester to cure a silicone-modified epoxy resin which is itself obtained by a reaction between hydroxyl groups on an epoxy resin and the alkoxy groups of a silicone compound, a sturdy and transparent film can be formed. This film has superior adhesive strength when used as a primer for room temperature-curable silicone rubber and room temperature-curable silicone-modified organic rubber.
Thus, one aspect of this invention concerns primer compositions comprising (A) 100 parts by weight of a silicone modified epoxy resin which contains both epoxy 23~
groups and silicon-bonded alkoxy groups wherein the modified epoxy resin is obtained by contacting and reacting (a! a compound having the unit formula RaSiXb(4 a b) wherein R is a substituted or unsubstitu-ted monovalent hydrocarbon radical, X is an alkoxy radical having the formula R'O- wherein R' is an alkyl radical of 1 to 4 carbon atoms or the radical R2oR3- wherein R2 is an alkyl radical of 1 to 4 carbon atoms and R3 is a divalent alky]ene radical of 1 to 3 carbon atoms; a has a value of O to 2; _ has a value of 1 to 4 and the sum of a + b has a value of 1 to 4 with (b) an epo~y resin containing at least one epoxy group and at least one hydroxy group per molecule; and (B) 0.1 to 100 parts by weight of an organotitanium acid ester.
Componen-t (A) is a primary component of the primer composition along with component (B).
Taking componen-t (A) first, it should be noted that component (A) is prepared from two subcomponents, components (a) and (b). Component (a) prior to reaction with component (b) consists of a compound having the unit formula a b (4-a-b) R in component (a) is a substituted or unsubstituted monovalent hydrocarbon radical. The groups which have been found useful in this invention are, for example, alkyl groups such as methyl, ethyl, propyl and octadecyl;
alkenyl groups such as vinyl and allyl and aryl groups such as phenyl. The substituted monovalent hydrocarbon 3~
radicals useful in this invention are those wherein -the above disclosed unsubstituted monovalent hydrocarbon radicals are substitu-ted by such yroups as halogen, cyano, mercapto and hydroxyl groups or by organofunctional groups such as methacryloxy, acry]oxy or the 3, 4-epoxycyclohexyl groups.
X in the above formula is an alkoxy radical having the formula R'O- wherein R' is an alkyl radical of 1 to 4 carbon atoms or the R2oR3- radical. Thus, X can be R'O- such as methoxy, ethoxy or propoxy. X can also be R2oR30- wherein R2 is an alkyl radical of 1 to 4 carbon atoms and R3 is a divalent alkylene radical of 1 to 3 carbon atoms R can be for example, methyl, ethyl or propyl and R , for example can be methylene, ethylene or propylene. An example of R OR O- can be, for example, rnethoxyethoxy-.
For purposes of this invention, a has a value of 0 to 2; b has a value of 1 to 4. Thus, included within the scope of this invention are compounds wherein R is not necessarily present. The reason for the values of a and b as set forth above is that there cannot be too few alkoxy groups in the resulting reacted product from (a) and (b). Components with too few alkoxy groups in the reacted product result in insufficient curing and insufficient adhesion in the final product. Thus, it is preferable that there be at least two X groups in ~a) and at least 3 X groups be present in (A). Component (a) can be a silane, a polysiloxane or a siloxane oligomer.
Polysiloxanes having a moderate degree of polyrnerization are preferred for this invention. The polysiloxane may be linear, branched chain or a network siloxane. In addition to the alkoxy radicals, this material can also ~3~
contain small amoullts of hydroxyl groups, halogen groups or hydrogen atoms.
Examples of silanes useful as component (a) are such silanes as me-thyltrimethoxysilane, dimethyldie-thoxysilane, e-thyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(methoxyethoxy)silane, allyltripropoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma--glycidoxy-propyltrimethoxysilane, beta-(3,9-epoxycyclohexyl)ethyltri-methoxysilane, tetrame-thoxysilane, tetrae-thoxysilane, -tetra-propoxysilane, tetrabutoxysilane, the partial hydro]ysis condensation products of any of the preceding compounds and ethyl polysilicate. These compounds may be used individually or by mixing with each other. Based on the reactivity with -the hydroxyl groups of -the epoxy resin, low molecular weight organoalkoxysilanes such as methyltrime-thoxysilane and ethyltrimethoxysilane, are desirable. Also, based on their excellent effec-t in improving the adhesion with the base material, gamma-mercaptopropyltrimethoxysilane and gamma-glycidoxy-propyltrimethoxysilane, are desirable. The epoxy resin (b), -the other component of (A), must have at least one hydroxyl group and at least one epoxy group per mo]ecule.
Either the bisphenol type epoxy resins or the novolak type of epoxy resins are usable. The bisphenol resins are preferred. In particular, epoxy resins obtained by the condensation of bisphenol A and epichlorohydrin are preferred. These are expressed by the average formula 23~
rH -CH-CH ~---o--- ~ -C(CH3)2- ~ -OCH2CHCH~-----o--C(CH ) ~ -OCH---CH2 (n is an integer ~ 3 2 ~ \ / between 1 and 19).
A hydroxyl equivalence in the range of 100 to 220 is desirable. When the hydroxyl equivalence is less than this range, the quantity of component (b) modified by the silicone compound becomes small, resulting in difficulty in the formation of a satisfactory film. When the hydroxyl equivalence is greater than 220, under the ordinary conditions of the condensation reaction of components (a) and (b), unreacted hydroxyl groups tend to remain which may lower the storage s-tability ~hen the organotitanium acid ester of component (B) is present in (A). Also, in the condensation reaction this will cause problems of increased viscosity and gelation.
Furthermore, although the epoxy groups generally do not participate in the condensation reaction with the alkoxy groups of component (a) and hydroxyl groups of component (b), an epoxy equivalence in the range of 180 to 4,000 is desirable in order to increase the adhesive efEect of the primer composition. It is preferred that average molecular weight be 300 to 3,000 and particularly 700 to 1,400. Component (A) can be obtained by mixing the above-mentioned components (a) and ~b) at a temperature above the boiling point of the by-produced alcohol. The two components condense liberating the alkoxy groups of component (a) and the hydroxyl groups of component (b) as alcohol. Generally, it is easier to carry out this d ~23~
-tion catalyst at 80 to 160C with continuous removal of the liberated alcohol. A solvent or diluent such as toluene, xylene or ethyl acetate may be used during the reaction. It should be noted that after -the reaction, no hydroxyl groups should remain on the epoxy resin. For this reason, it is advantageous to use a small amount of a catalyst. During the condensation of components (a) and (b), it is desirable that the reaction be carried out under the conditions wherein the ratio of mols of alkoxy groups in component (a) to the mols of hydroxyl groups in component (b) is 1 or greater. When the reac-tion is carried out at below 1 and especially when the organotitanium acid ester of component (B) is added -to component (A), gelation is easily effected~ Thus, in order to obtain a durable, homogeneous liquid primer composition, the reac-tion should be carried out at the above-mentioned molar ratios. It is preferred that component (A) contain at least 3 alkoxy groups.
Component (B), the organotitanium acid ester, after reacting with the alkoxy groups of component (A), will not only cure the primer composition and provide air dryabili-ty, but also will remarkably improve the adhesive strength, especially the adhesive durability, be-tween the substrate and the room temperature-curable silicone rubbers or room temperature-curable silicone--modified organic rubbers. Examples of titanium compounds useful in this invention are as follows: tetraisopropyl ti-tanate, tetra-n-butyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, diethoxytitanium acetylacetonate, titanium diacetylacetonate, octylene glycol titanate, titanium lactate, titanium ethyl lactate, ethanolamine titanate, titanium chelates such as beta-diketonate chelates of dialkoxytitaniums, ketoacid Z3~
e~s-ter chelates of dialkoxy-titaniums or -their partial hydrolysis condensa-tion products. Component (B~ may be used as individual compounds or mix-tures of individual compounds. The amount of Componen-t (B) useful in -this invention is 0.1 to 100 parts by weight per 100 parts of component (A). From the viewpoint of curabili-ty, adhesion and storage stability, 5 to 25 parts by weight is desirable.
Simple mixing of -these componen-ts will provide the primer composition of this invention.
Furthermore, in an attempt to irnprove the adhesion, especially the adhesion durabili-ty of the primer, and also to improve the air dryability and thus increase the productivity, the addition of an additional silane or i-ts par-tial hydrolysis condensa-tion produc-t expressed by the following average formula, is effective:
R Si(OR )3 wherein R4 represents organic groups such as alkyl groups such as methyl and ethyl; monovalent unsaturated aliphatic hydrocarbon groups such as vinyl and methacryloxy and organofunctional groups such as glycidyl and mercaptopropyl; R5 is represented by alkyl groups such as methyl, ethyl and propyl or alkoxyalkyl groups.
Several examples of these compounds are methyltrimethoxysilane, dimethyldiethoxy-silane, ethyltriethoxysilane, phenyltrime-thoxysilane, vinyltrimethoxysilane, allyltripropoxysilane, gamma-methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the partial hydrolysis and condensation products of the preceding compounds and ethyl polysilicate. The silane or partial 723~
hydrolysis condensation product should be selec-ted accord:ing to the intended application of the primer composition.
When applying -the primer composition to the substrate and the viscosity is too high or a thin film is desired, it is possible to use an organic solvent for dilution. For example, toluene, xylene or ethyl aceta-te may be used as the organic solvent. In an attempt to further increase the postcure film strength, various inorganic fillers may be added to the primer compositionsl for example, a powdered silica may be added. Other fillers suitable for this purpose are hydrophobic silicas with a trimethylsilylated surface.
Moreover, any generally well known heat s-tabilizer or colorants such as red iron oxicle, cerium oxide, fa-tty acid salts of iron, titanium oxide or other agents may be optionally added provided interference with the purpose of -this invention is not caused.
The primer of this invention is sui-table for use as a pre-process treatment for substrates in order to increase the adhesion and durability of room temperature-curable silicone rubbers and room temperature-curable silicone-modified organic rubbers with various substrates throughout the curing process.
The room temperature-curable silicone rubber may be a single package or two package type. Any -type involving liberation of alcohol, oxime, ketone, amine, hydroxylamine or carboxylic acid may be used. The room temperature-curable silicone-modified organic rubbers may also be single or two package typesO Examples are as follows: alko~ysilyl-terminated polyether rubbers, alkoxysilyl-terminated polybutadiene rubbers and alkoxysilyl-terminated polyure-thane rubbers.
23~
By using these primer compositions as a pre-process treatment for poorly adhering base materials such as pure aluminum, surface-treated aluminum, coated aluminum, stainless steel, mortar and concre-te, the above-mentioned rubber can be adhered firmly and durably.
The sealing of different substrates in construc-tion can be carried out smoothly.
Materials similar to those discussed above are also appropriate for use as coatings for various substrates. Therefore, this invention also deals with coating compositions. More particularly, this aspect of the invention deals with compositions which can be stored over a long period of time in the absence of moisture but can be cured at room temperature in the presence of moisture as coatings. These compositions exhibit excellent adhesion to various substrates.
Generally, silicones exhibit excellent heat resistance and electrical insula-ting properties and they have -therefore been widely used for heat-resistant paints and varnishes for electrical insulation. However, silicones have some disadvantages. For example, silicones require high -temperatures and long term heating for curing. In addition, they can be adhered satisfactorily to metal plates such as soft s-teel and stainless steel, but they cannot be easily adhered to plasticsO
The inventors pursued the present investigation in an attempt to overcome the above-mentioned disadvantages of silicones. It was found that compositions can be obtained which can be stored for long periods of -time in the absence of moisture bu-t which can be cured at room temperature in the presence of moisture 23~
to form coatings which exhibit excellent adhesiveness with a variety of substrates such as metals and plastics.
This invention therefore deals with coating compositions whi.ch consist of a coating composition comprising (I) 100 parts by weight of a silicone modified epoxy resin containing silicon-bonded alkoxy groups wherein the modified epoxy resin is ob-tained b~
contac-ting and reacting a compound (a) containing at least two silicon-bonded alkoxy groups per molecule having the unit formula c iXd(4-c-d) wherein R6 is a substituted or unsubstitu-ted monovalent hydrocarbon radical, X' is an alkoxy radical having the formula R70- wherein R7 is an alky] radical of 1 -to 4 carbon atoms or -the radical R80R9- wherein R8 is an alkyl radical of 1 to 4 carbon atoms and R9 is divalen-t alkylene radical of 1 to 3 carbon atoms, c has a value of 0 to 2; d has a value of 1 to 4 and the sum of c + d has a value of 1 to ~, with (b) an epoxy resin containing at least one epoxy group and at least one hydroxyl group per molecule and w.herein prior to contacting and reacti.ng components (a) and (b)~ the ratio of alkoxy groups in component (a) to the hydroxy groups in component (b) is equal to or greater than l; and (II) 0.1 to 100 parts by weight of an organotitanium compound.
Component I of this invention is prepared from two reactive materials I(a) and I(b). Specifically, Component (I) of the composition is a product of the condensation reaction between the silicon~bonded alkoxy groups in component I(a) and the hydroxyl groups in component I(b). This material is a primary component of 3~
-the coating compositions of this invention. Componen-t I(a) is a si]ane or polysiloxane containiny at least two silicon-bonded alkoxy groups per molecule and has the unit formula RlsiXfO~4--e-f)-The alkoxy groups undergo a condensation reaction with the hydroxyl groups in the epoxy, component I(b). In the formula, R10 represents substituted or unsubstituted monovalent hydrocarbon radicals bonded to silicon atoms.
Examples of these groups are alkyl groups such as me-thyl, ethyl, propyl and octadecyl; alkenyl groups such as vinyl and allyl; aryl grou-ps such as phenyl and naphthyl and their derivatives in which some of the hydrogen atoms are substituted with halogen atoms, cyano groups, hydroxyl groups or mercapto groups or in which some of the hydrogen atoms on alkyl groups are substituted with functional groups sueh as methacryloxy acryloxy, glycidyl and 3,4-epoxycyclohexyl. X" for purposes of -this invention is a silicon-bonded alkoxy group represen-ted by the formula R O- wherein R1 is an alkyl radical of 1 to 4 carbon a-toms or the radical R120~13- whe~eirl R12 is an alkyl radical of 1 to 4 carbon atoms and R is a divalent alkylene radical of 1 -to 3 carbon atoms.
Examples of these groups are methoxy, ethoxy, propoxy and methoxyethoxy. For purposes of this inven-tion, e has a value of 0 to 2 and f has a value of 1 to 4 and the sum of e ~ f has a value of 1 -to 4 The fact -that e has a value of 0 to 2 indica-tes that R is not necessarily present in component I~a). However, e must be 2 or less and f must be 1 or more. Each molecule must contain at least two silicon-bonded alkoxy groups. The reason for 23~
this is tha-t if the number of alkoxy groups is too low, -the degree of condensation with the hydroxyl groups i.n component l(b) will be decreased and the number of silicon-bonded alkoxy groups in component (I) will be less which results in insufficient curing. In this sense, it is desirable that at least three X groups be presen-t in component (I) after the reaction of componen-ts I (a) and I (b).
Component I(a) can be either a silane or a polysiloxane. If it is a polysiloxane, the degree of polymerization must be ~ or greater. The molecular configuration of the polysiloxane can be linear, branched chain or network. In addition to the reactive alkoxy groups, it can contain small amounts of silicon-bonded hydroxyl groups, halogen atoms or hydrogen atoms.
Examples of component I(a) are silanes such as methyltrimethoxy-si.lane, methyltripropoxysilane, dimethyldiethoxysilane, ethyltri~ethoxysi]ane, pheny]trimethoxysilane, diphenyldi-methoxysi.lane, phenylmethyldiethoxysilane, vinyltrimethoxy-silane, allyltripropoxysilane, vinyltri(methoxye-thoxy~-silane, methylvinyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropylmethyldimethoxysilane, gamma-glycidyl~
propyl-trimethoxysilane, gamma-glycidylpropylme-thyldie-thoxy-silane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryl-oxypropylmethyldiethoxvsilane and gamma-acryloxypropyltri-7~3~D
methoxysilane; partial hydrolysis and condensation products of one or two or more of these silanes; partial hydrolysis and condensation products of -these silanes with other organosilanes such as trimethoxyethoxysilane and ethyl polysilicate.
Component I(b) is the same as that used for the primer composition discussed above and is an epoxy resin containing at least one epoxy group and hydroxyl group per molecule. Both bisphenol type resins and novolak type resin are applicable. Component I(b) preferably possesses the following structural formula with a molecular weight ranging -from 300 to 6000.
CH2~CH-CH2~ O ~ -C- ~ OH
~3 C ~ \o/
Examples of commercial epoxy resins useful herein are Epikote( ) 815, 820, 828, 834, 864, 1001, 1004 and 1007, all products of the Shell Chemical Corporation.
Component (I) is a silicone-modi-fied epoxy resin containing silicon-bonded alkoxy groups which is obtained by a condensation reaction between components I(a) and I(b) wherein the ratio of alkoxy groups in component I(a) to the hydroxyl groups in component I(b) is equal to or greater than 1. If this ratio is less than 1, gelation is likely to occur during the condensation reaction between components I(a) and I(b).
3~
Although gelation may not occur during the condensation reaction, gelation is likely to occur when the organotitanium compound, component (II), is added thereto and a satisfactory storage stability therefore cannot be achieved. As the above-mentioned ratio increases, the chances of gelation occurring during the reaction becomes less. In addition, the storage stability of the coating composition, when component (IT) is added, increases.
The condensation reaction between components I(a) and I(b) is preferably carried out at 80-250C using a small amount of a conventional catalyst such as organotitanium acid esters. When this condensation reaction is carried out, an organic solvent which can dissolve both components I(a) and I(b) can be used.
However, the use of an organic solvent is undesirable for some coating applications owing to deterioration of the substrates by the solvent. In such cases the reaction is preferably carried out in the presence of an excess of low boiling alkoxysilane.
Component (II) is a compound which makes component (I) room-temperature curable in the presence of moisture. Examples of such compounds: titanium acid esters of monohydric alcohols such as methanol, e-thanol, isopropanol, butanol, cyclohexanol, octanol and octadecyl alcohol; titanium acid esters of dihydric alcohols such as ethylene glycol, propylene glycol, octylene glycol, diethylene glycol, tripropylene glycol and tetraethylene glycol; titanium acid esters of trihydric alcohols such as glycerin; alkoxy titanium chelates such as diisopropoxybis(acetylacetonato)titanium and di-n-butoxybis(triethanolaminato)titanium and dihydroxybis(lactato)titanium~
23~
In terms of the amount of component ~II) to be added, the curing rate slows down when the amount of component II is too small. In con-trast, if too much is added, the cured film becomes brittle and cracks are easily produced. Thus, an appropriate amount ranges from 0.1 parts by weight to 100 parts by weight per 100 parts by weight of component (I). From a consideration of curability, adhesiveness and storage stability, the amount preferably ranges from 5 to 90 parts by weight.
The,coating compositions of this invention can be obtained from components (I) and (II) by simply mixing them together. However, in order to increase the storage stability, both components are preferably mixed together in the absence of moisture and the product is stored in a moisture-impermeable container after mixing and degassing treatments.
Optionally, additional components such as organic solvents, inorganic fillers, pigments and heat-resisting agents can be added. In particular, additional organotrialkoxysilane such as has been disclosed for component I(a) can be added in an amount of 5 to 500 parts by weight per 100 parts by weight of component (II) after components I(a~ and I(b) have been reacted and after component II has been added. The organic radicals in the organotrialkoxysilane are identical to the above-mentioned R10 radicals and the alkoxy radicals are also identical to the above~mentioned X". The coating compositions of this invention can be stored over a long period in the absence of moisture. In the presence of moisture, curing occurs even at room temperature to form a strong heat-resistant and weather-resistant film which is firmly adhered on substrates such as various types of metals, plastics and 3~
woods. Thus, the compositions are very useEul as protective coating agents for these substrates.
Several examples illustrating the invention follow: The viscosity unless indicated otherwise was measured at 25C.
"Parts" in the examples denotes "parts by weight." The finger touch drying time, adhesiveness and pencil hardness were determined under the following conditions:
Finger touch drying time: the finger touch drying time was defined by the time in which the coated surface ceases to be tacky after being coated on the substrate ancl a fingerprint no longer imprints on the surface. Pencil hardness: the pencil hardness was measured according to JIS K 5400.
Adhesiveness (Cross-cut adhesion test3: one hundred, 1 mm squares, were cut in a l cm square of the cured coating using a razor blade and a cornmercial cellophane tape was firmly pressed and adhered over the cut squares.
The number of squares remaining out of lOO squares was counted after the tape had been quickly peeled. The number of remaining squares was recorded as the numerator and the number of cut squares was recorded as the denominator.
23~3i Example 1 (A) Synthesis of a partial hydrolysis condensation product of methyltrimethoxysilane 136 g (1 mol) methyltrimethoxysilane and 18 g (1 mol) water and 0.1 g acetic acid were placed in a 300 ml three-neck flask equipped with reflux condenser, stirrer and thermometer. A reaction was carried out for 5 hours at reflux. The reaction by-product, methyl alcohol, and unreacted methyltrimethoxysilane were then removed under vacuum at 10 mm Hg and 150C to give a liquid polysiloxane containing 30 wt% methoxy groups with a viscosity of .000046 m2/s.
(B) Synthesis of a silicone-modified epoxy resin 700 g of an epoxy resin (Epikote 1001, Shell Chemical Co.) with an average molecular weight of 900 to 1000, hydroxyl equivalence of 115 and epoxy equivalence of 500; 300 g of the partial hydrolysis condensation product produced in Example l(A), 1,500 g toluene and 0.15 g tetraisopropyl titanate as catalyst were placed in a 5000 ml three-neck flask equipped with reflux condenser, stirrer and thermometer. With continuous stirring, the flask was heated to 100C gradually and a condensation reaction was carried out at reflux (105 to 110C). The essentially nontransparent reaction mixture gradually became transparent. During the reaction, samples were taken each hour and applied to a glass plate. The reaction was continued until the film on the glass plate, obtained by evaporating the low boiling substances by baking at 150C, became transparentO This film became transparent after a reaction of 3 hours.
Reflux was continued while the methyl alcohol by product was continuously removed from the system through distillation. The residue from the reaction was a ~IL !37%3~
transparent liquid with a viscosity of .00015 m /s at 25 containing 37 weight percent nonvolatile components. Gel permeation chromatography and infrared spectroscopy revealed that this nonvolatile component was a silicone-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. Infrared spectroscopy and boiling point data showed that the volatile component was toluene.
(C) Adding and mixing 10 g of tetra-n-butyl orthotitanate into 100 g of the product of Example l(B) gave a uniform transparant liquid (composition C). This composition C was stable, after sealing to exclude moisture, in storage for more than 2 months. The above-mentioned composition C was then applied to 2 each of mortar blocks and aluminum panels (JIS-H4000) with a brush. An amino~y-liberating two package room temperature-curable silicone rubber (Toray Silicone Co., Ltd. product, SH792 Sealant) was applied to these blocks and panels to form adhesion test samples according to the specification in "Construction Sealing Materials,"
JIS-A5758, section 5.12. After these test samples had been maintained at room temperature for 14 days, the initial properties and the properties after another 7 days immersion in 20C water were investigated.
For comparison, composition l(B~ was used as a primer to form the same kind of test samples and the properties were investigated. Maintenance and measurement of the properties were according to the above-mentioned JIS-A5758, section 5.12. The results are shown in Table 1.
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Example 2 100 g of an epoxy resin (Epikote 834, Shell Chemical Co.) with an average molecular weight of 450, hydroxyl equivalence of 105 and epoxy equivalence of 300 to 375 and 10 g of methyltrimethoxysilane, 100 g toluene and 0.15 g tetraisopropyl titanate as catalyst were placed in a 500 ml three-neck flask equipped with stirrer, reflux condenser and thermometer. With continuous stirring, the flask was heated to 100C gradually and a condensation reaction was carried out at reflux (105 to 110C). The essentially nontransparent reaction mixture gradually became transparent. Reflux was continued for 2 hours while the methyl alcohol by-product and unreacted methyltri~ethoxysilane were constantly removed from the system by distillation.
The residue obtained from this reactlon was a transparent liquid with a viscosity of .OD2 M2/s and contained 75 weight percent nonvolatiles. Gel permeation gas chromatography and infrared spectroscopy revealed that this nonvolatile component was a silione-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. Adding and mixing 100 g toluene and 5 g tetra-n-butyl titanate dimer into 100 g of the above-mentioned residue gave a uniform transparent liquid (composition D). Composition D was then applied to 2 each of mortar blocks and aluminum panels (JIS-H4000) with a brush. After being dried at 20C for 5 hours, these blocks and panels were tested as in Example 1 according to the specifications listed in JIS-A5758, section 5.12. The initial properties and the properties 7;23~
after 7 days water immersion were investigated and the results are shown in Table 2.
Table 2 Composition D Test Results Item Initial AEter Immersion in Water Substrate M50 T E M50 T E
Mortar Block 1.1 5.0 750 1.0 5.0 670 Aluminum Panel 1.1 5.3 750 1.0 5.3 870 Example 3 100 g of~the same epoxy resin as was used in Example 1 (Epikote 1001, Shell Chemical Co.), 250 g methyltriethoxysilane, 250 g toluene and 0.10 g tetra-n-butyl titanate were placed in a 1000 ml three-neck flask equipped with stirrer, reflux condenser and thermometer. Under continuous stirrin~, the flask was gradually heated to 100C and a condensation reaction was carried out at reflux. The essentially nontransparent reaction mixture gradually became transparent. Reflux was continued for 3 hours while the ethyl alcohol by-product and unreacted methyltriethoxysilane were constantly removed from the system by distillation.
The reaction residue contained 75 weight percent nonvolatiles. Gel permeation chromatography and 23~
infrared spectroscopy revealed that the nonvolatile component contained primarily a silicone~modified epoxy resin possessing epoxy groups and silicon-bonded ethoxy groups.
Adding and mixing 10 g of tetrabutyl titanate dimer to 100 g of this reaction residue gave a uniform transparent liquid (composition E). Composition E was then applied to 2 each of mortar blocks, aluminum panels (JIS~H4000) and stainless steel panels (SUS 304~ as in Example 2 and they were dried at 20C for 2 hours.
Experimental adhesion test samples were then produced as in Example 1 according to the specifications of JIS-A5758, section 5.12. The initial properties and properties after a 7 day water immersion were investigated and the results are shown in Table 3.
Table 3 Composition E Test Results Item Initial After Immersion in Water Substrate M50T E M50 T E
Mortar Block 1.15.1 750 l.0 5.0 640 ~luminum Panel l.15.5 900 l.0 S.2 950 .__ ~
Stainless Steel l.l5.5 870 l.0 5.3 910 .. _. ___ ._ ... _ __ Example 4 100 g of the epoxy resin of Example 1 ~Epikote lO01, Shell Chemical Co.), lO0 g gamma-mercap-topropyl--trimethoxysilane, lO0 g toluene and 0.15 tetraisopropylor-thotitanate were placed in a 500 ml three-neck flask equipped with stirrer, re~lux condenser and thermometer. With continuous stirring, the flask was heated gradually to 100C and a condensation reaction was carried out at reflux. The essentially nontransparent reaction mixture gradually became transparent. Refluxing was continued for 4 hours while the methyl alcohol by-product was constantly removed from the sys~em by distillation.
The reaction residue was a transparent liquid containing 65 weight percent solids. Gel per~eation gas chromatography and infrared spectroscopy revealed that 7;Z~
this nonvolatile component was a silicone-modified epoxy resin containing epoxy groups and silicon-bonded methoxy groups. The volatile component was primarily toluene.
Adding and mixing 10 g of diisopropoxytitanium bis(acetylacetonate) to 100 g of this reaction residue gave a uniform liquid (composition F). Composition F was then applied to various panels as in Example 1 and dried at 20C for 2 hours. The same type of experimental adhesion test samples as in Example 1 were then produced.
The initial properties and those after a 7 day water immersion were investigated and the results are shown in Table 4.
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Table 4 Composition F Test Results Item Initlal After Immerslon in Water . . ._ Substrate M50 T E M50 T E
._ . _ _ _ .. _ Stainless S-teel Panel 1.1 4.5 820 1.0 4.3 880 . . ~
Aluminum Panel 1.2 5.5 830 1.0 5.1 860 Acrylic _ _ Coated Panel 1.1 5.3 870 1.1 5.0 870 ..
Urethane Coated Panel 1.1 4.2 820 1.0 5.0 920 _ . .. _ _ . __ Mortar Block 1.1 5.1 730 1.0 2.0 560 .. .__ . . _ .. _ .... _ ... __ Tile 1.0 4.8 810 1.0 4.7 970 _ .. _ _ ._ ...
Glass Plate 1.0 5.6 960 1.2 5.2 850 Example 5 100 g of an allyl terminated polyoxypropylene polymer (average molecular weight 400) were placed in an autoclave. Under nitrogen gas, 23 g of methyldimethoxysilane and 0.006 g of a platinum-ethylene catalyst complex were added followed by stirring at 100C
for 1 hour. Then, 120 g calcium carbonate, 40 g fumed silica filler, 40 g dioctyl phthalate and 2 g dibutyltin dilaurate were added to this reaction mixture to produce a polyether type room temperature-curable rubber.
The composition E obtained in Example 3 was applied -to 2 each of mortar blocks and aluminum panels with a brush and dried at room temperature for 4 hours.
After that, the above-mentioned room temperature-curable rubber was applied on these experimental panels and blocks as a bead. After being maintained for 14 days, the experimental panels and blocks were checked for adhesion and it was observed that in all cases peeling occurred in the rubber layer and there was 100% cohesive failure.
Example 6 For this example, 0.020 g of a silane with -the formula (CH30)3SiCH2CH(CH3)CH2SH
were added to 7 g of a 20 weight ~ xylene solution of a hydroxyl-terminated polybutadiene with a molecular weight appropriate for curing to a rubber. After heating at 100C for 24 hours, an alkoxysilyl-terminated polybutadiene was formed. To this modified polybutadiene were added 0.163 g methyltrimethoxysilane and 0.082 g titanium acetonylacetate to produce a room temperature-curable rubber. Composition E of Example 3 was applied to 2 each of mortar blocks and aluminum panels with a brush. These blocks and panels were dried -'7~3~
at 20~C for 4 hours. The above-mentioned room temperature-curable rubber was then applied to these plates as a bead. After being maintained for 14 days, these experimental blocks and panels were checked for adhesion and it was observed that in all cases peeling occurred in the rubber layer and there was lO0~ cohesive failure.
Example 7 An oxime-liberating single package silicone sealant (SH780 Sealant by Toray Silicone Co., Ltd.) and an alcohol-liberating single package silicone sealant (SH9145 Sealant by Toray Silicone Co., Ltd.) were used as room temperature-curable silicone rubbers. Composition C
of Example l was used as the primer composition. The adhesion was tested under the same conditions as in Example 6 and identical results were obtained.
Coating Composition Examples Example 8 A condensation reaction was carried out using Epikote lOOl(R) by Shell Chemical Corporation and methyltrimethoxysilane for the compositions shown in Table 5. In this case, tetrabutyl titanate was added as the condensation reaction accelerating catalyst and toluene was used as the solvent. These components were placed in a three-neck flask equipped with a reflux condenser, thermometer and stirrer. A reaction was carried out at 90C under reflux for 5 hours. After the reaction, low boiling fractions were removed by distillation and the mixture was then cooled. A light yellow, transparent silicone-modified epoxy resin containing silicon-bonded methoxy groups was obtained as a result. Tetrabutyl titanate (2 parts) was added to 20 parts of the resin produced above. This is sample l. In 3g~
the case of sample 3 which used sample 1 with a methoxy group/hydroxyl group ratio of less than 1, gelation occurred immediately. In the case of sample 4 which used sample 2 in which the same ratio was 6.9, thickening was not observed. When sample 4 was stored in a sealed glass bottle, a homogeneous liquid was maintained after 3 months. The composition of sample 4 into which tetrabutyl titanate was compounded was coated over a stainless steel plate. The coated surface was no longer tacky after 10 minutes. The coated film adhered well on the stainless steel plate.
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Example 9 Epikote 1001(R) by Shell Chemical Corporation (hydroxyl group equivalents: 1.44) (450 parts), methyltrime-thoxysilane (1050 parts)(methoxyl group equivalents: 23.2) and tetrabutyl titanate (0.1 part) were placed in a three-neck 2000 ml flask. The system was gradually heated to reflux. Ref]ux was achieved at abou-t 88~C. The reaction was carried out under reflux for 5 hours. After the reaction, low boiling fractions (108 parts) were removed by distillation and a light yellow, transparent silicone-modified epoxy resin I
containing silicon-bonded methoxy groups with a nonvolatile fraction of 37.7% was obtained resulting in a yield of 1,390 parts.
On the basis of the solids content, the silicone content in the silicone-modified epoxy resin was calculated to be approximately 14 weight percent. In this case, the volatile fraction in the residue was methyltrimethoxysilane and tetrabutyl titanate were compounded as shown in Table 6 to prepare five compositions. These compositions were respectively coated over a stainless steel panel ~(SUS 304), a methacrylic resin panel and a polycarbonate panel. The finger touch drying time~ adhesiveness after curing for 48 hours (cross-cut adhesion test) and pencil hardness were evaluated. The results are presented in Table 6.
As shown ~'7~3~
in Table 6, when too llttle tetrabutyl titanate was added, drying required too many hours. When too much was added, the coated film became brittle and cracks were easily produced. The adhesion on the methacrylic resin panel and stainless steel panel were found to be impaired.
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Example 10 A coating composition was prepared by compounding methyltrimethoxysilane t260 parts) and tetrabutyl titanate (26 parts) in 100 parts ~solid content) of silicone-modified epoxy resin I. The resulting composition was coated over various base materials as shown in Table 7 and cured by allowing the film to stand at room temperature for 48 hours. The adhesiveness with these base materials and the film hardness were examined. The results are presented in Table 7.
~7~3~
Table 7 Adhesion on Various Subs-trates Adhesiveness ICross-cut Pencll Base Materials Adhesion Test) Hardness . _ Aluminum panel (JISH4000 A1050P) 100/100 HB
Aluminum panel (JISH4000 A1050P) 100/100 HB
(sealed by alumite sulfate treatment) Aluminum panel (JISH400 A1050P) 100/100 HB
(nonsealing by alumite sulfate treatment~
Aluminum panel (JISH4000 A6061S) 100/100 H
Aluminum panel (baked with an 100/100 H
acrylic resin) Aluminum panel (V-Chroma treatment 100/100 H
(note below) Stainless steel panel (SUS 304) 100/100 H
Soft steel panel 100/100 H
Polycarbonate resin panel 100/100 H
Methacrylic resin panel100/100 H
Vinyl chloride panel 100/100 HB
Note: A single~ uid polyurethane resin paint for curtain walls (by DaiNippon Toryo ~.K.) was used.
~87~3~31 Example ll tl) Preparation o~ a silicone-modified epoxy resin II
~ ethyltrimethoxysilane was hydrolyzed and condensed in the presence of an acid catalyst and low boiling fractions were removed by distillation.
Methylmethoxypolysiloxane (144 parts, methoxy group equivalent 1.39) containing 30 weight percent methoxy groups and with a viscosity at 25C of .000042 M2/s~
Epikote 1001(R) by Shell Chemical Corporatlon (576 parts, OH group equivalent 1.84), tetrabutyl titanate (0.2 parts) and toluene (1080 parts~ were placed in a 2000 ml three-neck flask equipped with a stirrer, reflux condenser and thermometer. The temperature was slowly raised to 105C. While the methanol produced at this tempera-ture was removed by distillation, the mixture was continuously stirred. The reaction was continued until compatability was obtained (compatability was judged to be the point at which a sample, taken every hour, formed a transparent film on glass when the sample on the glass plate was devolatized). After compatability had been obtained, low boiling fractions (300 ml) were removed by distillation. The temperature was subsequently reduced to 80C. When the temperature reached 80C or less, methyltrimethoxysilane (130 parts, methoxy group equivalent 3.03) was added. The ratio of total methoxy equivalents/hydroxvl equivalents was 2.4. The mixture was slowly heated and a reaction was carried out at reflux for 6 hours. ~fter the reaction, the mixture was cooled and a transparent liquid silicone-modified epoxy resin II was obtained with a nonvolatile content of 43~.
(2) Preparation of coating compositions and adhesion testing on various substrates
3~
Methyltrimethoxysilane (230 parts) and tetrabutyl titanate or diisopropoxytitanium bis(acetylacetonate) (24 parts) were compounded with 100 parts (solid content) of silicone-modified resin II. The resulting composition was coated onto a s-tainless steel panel, a soft steel panel, polycarbonate resin panel and methacrylic resin panel and cured by allowincJ the coated film to stand a-t room temperature for 48 hours. The( adhesion was examined by the cross-cut adhesion test.
The results were 100/100. Thus, the above-mentioned coating composition exhibited excellent adhesion. The composition had not thickened after storage in a glass bottle at room temperature after 3 months.
Methyltrimethoxysilane (230 parts) and tetrabutyl titanate or diisopropoxytitanium bis(acetylacetonate) (24 parts) were compounded with 100 parts (solid content) of silicone-modified resin II. The resulting composition was coated onto a s-tainless steel panel, a soft steel panel, polycarbonate resin panel and methacrylic resin panel and cured by allowincJ the coated film to stand a-t room temperature for 48 hours. The( adhesion was examined by the cross-cut adhesion test.
The results were 100/100. Thus, the above-mentioned coating composition exhibited excellent adhesion. The composition had not thickened after storage in a glass bottle at room temperature after 3 months.
Claims (9)
1. A primer composition comprising (A) 100 parts by weight of a silicone modified epoxy resin which contains both epoxy groups and silicon-bonded alkoxy groups wherein the modified epoxy resin is obtained by contacting and reacting (a) a compound having the unit formula wherein R is a substituted or unsubstituted monovalent hydrocarbon radical, X is an alkoxy radical having the formula R'O- wherein R' is an alkyl radical of 1 to 4 carbon atoms or the radical R20 R3- wherein R2 is an alkyl radical of 1 to 4 carbon atoms and R3 is a divalent alkylene radical of 1 to 3 carbon atoms; a has a value of O to 2; b has a value of 1 to 4 and the sum of a + b has a value of 1 to 4, with (b) an epoxy resin containing at least one epoxy group and at least one hydroxy group per molecule;
and (B) 0.1 to 100 parts by weight of an organotitanium acid ester.
and (B) 0.1 to 100 parts by weight of an organotitanium acid ester.
2. A primer composition as claimed in claim 1 wherein there is present 5 to 25 parts by weight of component (B) for 100 parts of component (A).
3. A primer composition as claimed in claim 1 wherein the component (B) is a titanium chelate.
4. A primer composition as claimed in claim 3 wherein the titanium chelate is a beta-diketonate chelate of dialkoxytitanium compounds.
5. A primer composition as claimed in claim 3 wherein the titanium chelate is a ketoacid ester chelate of dialkoxytitanium compounds.
6. A solid substrate when primed with the primer of claim 1.
7. A solid substrate as claimed in claim 6 when surmounted by a room temperature curable silicone rubber composition.
8. A solid substrate as claimed in claim 6 when surmounted by a room temperature curable silicone--modified organic rubber.
9. A coating composition comprising (I) 100 parts by weight of a silicone modified epoxy resin containing silicon-bonded alkoxy groups wherein the modified epoxy resin is obtained by contacting and reacting (a) a compound containing at least two silicon-bonded alkoxy groups per molecule having the unit formula wherein R6 is a substituted or unsubstituted monovalent hydrocarbon radical, X' is an alkoxy radical having the formula R70- wherein R7 is an alkyl radical of 1 to 4 carbon atoms or the radical R8OR9- wherein R8 is an alkyl radical of 1 to 4 carbon atoms and R9 is a divalent alkylene radical of 1 to 3 carbon atoms; c has a value of 0 to 2; d has a value of 1 to 4 and the sum of c + d has a value of 1 to 4, with (b) an epoxy resin containing at least one epoxy group and at least one hydroxyl group per molecule and wherein prior to contacting and reacting components (a) and (b), the ratio of alkoxy groups in component (a) to the hydroxy groups in component (b) is equal to or greater than 1; and (II) 0.1 to 100 parts by weight of an organotitanium compound.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP149107/81 | 1981-09-21 | ||
| JP56149107A JPS5852350A (en) | 1981-09-21 | 1981-09-21 | Primer composition |
| JP15145281A JPS5852365A (en) | 1981-09-25 | 1981-09-25 | Coating agent composition |
| JP151452/81 | 1981-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187239A true CA1187239A (en) | 1985-05-14 |
Family
ID=26479104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000409330A Expired CA1187239A (en) | 1981-09-21 | 1982-08-12 | Coating composition and primer |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1187239A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138013A (en) * | 1990-12-17 | 1992-08-11 | Ford Motor Company | Epoxy curable ion-conducting electrolyte useful in electrochromic devices |
| US5225582A (en) * | 1990-12-17 | 1993-07-06 | Ford Motor Company | Epoxy curable ion-conducting electrolyte useful in electrochromic devices |
| CN113930147A (en) * | 2021-11-12 | 2022-01-14 | 上海三棵树防水技术有限公司 | Silane modified aliphatic epoxy resin waterproof coating and preparation method thereof |
| CN115124694A (en) * | 2021-03-24 | 2022-09-30 | 中国科学院海洋研究所 | Hydroxyl organic silicon modified epoxy resin and magnesium-rich primer prepared from same |
-
1982
- 1982-08-12 CA CA000409330A patent/CA1187239A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138013A (en) * | 1990-12-17 | 1992-08-11 | Ford Motor Company | Epoxy curable ion-conducting electrolyte useful in electrochromic devices |
| US5225582A (en) * | 1990-12-17 | 1993-07-06 | Ford Motor Company | Epoxy curable ion-conducting electrolyte useful in electrochromic devices |
| CN115124694A (en) * | 2021-03-24 | 2022-09-30 | 中国科学院海洋研究所 | Hydroxyl organic silicon modified epoxy resin and magnesium-rich primer prepared from same |
| CN115124694B (en) * | 2021-03-24 | 2023-09-19 | 中国科学院海洋研究所 | Hydroxyl organic silicon modified epoxy resin and magnesium-rich primer prepared from same |
| CN113930147A (en) * | 2021-11-12 | 2022-01-14 | 上海三棵树防水技术有限公司 | Silane modified aliphatic epoxy resin waterproof coating and preparation method thereof |
| CN113930147B (en) * | 2021-11-12 | 2023-03-28 | 上海三棵树防水技术有限公司 | Silane modified aliphatic epoxy resin waterproof coating and preparation method thereof |
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