Fast curing oximo-ethoxy functional siloxane sealants

Abstract: A room temperature curing composition which cures fast and has good reversion resistance and good package stability is a mixture of 66.75 to 89.4 weight percent of a hydroxyl endblocked polydiorganosiloxane; 5.5 to 10 weight percent of a tetrafunctional ethoxy-ketoximo silane mixture having 6 to 27 weight percent tetraketoximosilane, 9 to 39 weight percent of monoethoxytriketoximosilane, 38 to 60 weight percent of diethoxydiketoximosilane and 5.5 to 25 weight percent triethoxymonoketoximosilane; 0.1 to 0.25 weight percent of a tin catalyst, 0 to 3 weight percent of an adhesion promoter and 5 to 20 weight percent of reinforcing silica. These compositions cure to elastomeric materials useful as caulking materials, adhesives, coatings and encapsulating materials for construction and automotive industries.

Description: Many kinds of very useful compositions cure at room temperature to elastomeric materials having a broad spectrum of physical and chemical properties. However, with every desirable property, there seems to be undesirable properties and one is continually faced with the problem of choosing the right composition for the specific application. The applications to which room temperature curing compositions can be put keep increasing, and with the increasing variety of applications, the specific kinds of properties required, keep changing. The need for new room temperature curing compositions with new properties is thus in demand. The market is continually looking for the new desirable properties without the same previous undesirable properties. An object of the present invention is to produce a room temperature curing composition which which does not undergo substantial color changes during storage cures faster than other compositions having tetrafunctional ethoxy-ketoximo silane crosslinker while maintaining good reversion resistance and good package stability. Another object is to improve the initial strength and adhesion to substrates, such as polyvinyl chloride, wood, aluminum and glass. Still another object is to produce elastomeric products useful as sealants. This invention relates to a composition which essentially consists of a product which is storage stable in a package when protected from moisture but cures when removed from the package and exposed to moisture and which is obtained by mixing the following ingredients, (A) at least 66.75 weight percent of an OH-terminated polydiorganosiloxane having an average viscosity at 25°C. of from 0.5 to 100 Pa·s and the organic radicals bonded to the silicon atom are selected from the group consisting of monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, (B) from 5.5 to 10 weight percent of a tetrafunctional ethoxyketoximo silane mixture of 6 to 27 weight percent of tetraketoximosilane, 9 to 39 weight percent of monoethoxytriketoximosilane, 38 to 60 weight percent of diethoxydiketoximosilane and 5.5. to 25 weight percent triethoxymonoketoximosilane in which the ketoximo groups have a formula -O-N=CR'R' in which each R' is an alkyl radical having from 1 to 4 carbon atoms, (C) from 0.1 to 0.25 weight percent of a tin catalyst, (D) from 1.5 to 3 weight percent of an adhesion promoter which does not impart color to the composition and which is a purified aminoalkyl functional silane being substantially free of acid chlorides and having the formula in which R' is an alkyl radical having from 1 to 4 carbon atoms; R² is an alkylene radical selected from ethylene, propylene, isopropylene, butylene and isobutylene; R³ is an alkyl radical having from 1 to 5 carbon atoms per radical; R⁴ is a hydrogen atom or R³; a is 0 or 1 and b is 0, 1 or 2, and (E) from 5 to 20 weight percent of reinforcing silica filler. The compositions of the present invention are stable at room temperature when protected from moisture, but cure when exposed to moisture. The composition can be protected from moisture by placing the composition in a package which is sealed and does not allow moisture to enter, including atmospheric moisture. The composition of the present invention should not be made with ingredients which contain quantities of water which will effect the storage stability. The presence of water-containing ingredients in the composition will cause the composition to cure in the storage package and thus the composition will not be a useful material. Compositions which can be stored in a single package and later cured by extruding the composition from the package and allowing moisture to contact it, are known as one package compositions, one component compositions or one-part compositions. The compositions of the present invention contain at least five ingredients, (A) an OH-terminated polydiorganosiloxane, (B) a tetrafunctional ethoxy-ketoximo silane, (C) a tin catalyst, (D) a purified adhesion promoter and (E) a reinforcing silica filler. The compositions contain a fifth ingredient, which is an adhesion promoter which does not impart color to the composition or the cured product. Compositions containing these ingredients will cure rapidly at room temperature. These compositions cure to tack free surfaces in 1 to 12 minutes and cure in deep section at the rate of 1.7 to 3.0 mm per day. The compositions described by Klosowski et al. in U.S. Patent No. 4,657,967, issued April 14, 1987, without a catalyst cured to provide a skinned over surface in less than 30 minutes when exposed to atmospheric moisture and became tack-free in as little time as one hour. With catalyst, these compositions had tack free times of 22 to 25 minutes. The OH-terminated polydiorganosiloxanes of (A) can be those having an average viscosity at 25°C. of 0.5 to 100 Pa·s, preferably from 1 to 50 Pa·s. The organic radical of the polydiorganosiloxane can be monovalent hydrocarbon radicals or monovalent halogenated hydrocarbon radicals. Examples of the monovalent hydrocarbon radicals are methyl, ethyl, propyl, butyl, phenyl, vinyl, allyl, cyclohexyl, tolyl and isopropyl. Examples of monovalent halogenated hydrocarbon radicals are chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, beta-(perfluorobutyl)ethyl and chlorocyclohexyl. Preferably, the organic radicals are methyl, vinyl, ethyl, phenyl and 3,3,3-trifluoropropyl. The polydiorganosiloxane can have in addition to the diorganosiloxane units, monoorganosilsesquioxane units, triorganosiloxy units and SiO₂ units. A preferred class of the polydiorganosiloxanes are those which have triorganosiloxy units partially endblocking the polymers such that some of the endblocking groups are triorganosiloxy units and some are hydroxyl groups. For example, these polydiorganosiloxanes which have both hydroxyl endblocking and triorganosiloxy endblocking are known in the art from U.S. Patent No. 3,274,145, by Dupree, issued September 20, 1966. The units other than the diorganosiloxane units are preferably present in small amounts, such as less than 5 mol percent of the total units present. (A) can be a mixture of two or more polydiorganosiloxanes, as long as, the average viscosity of the mixture falls within the range of viscosities stated above. For example, (A) can consist of a mixture of two polydimethylsiloxanes of different viscosities or (A) can consist of polydimethylsiloxane, polymethylphenylsiloxane and polymethylvinylsiloxane all being OH-terminated. The viscosity of (A) can result from a mixture of two or more OH-terminated polydiorganosiloxanes wherein some of the polymers can have a viscosity less than 0.5 Pa·s, such as 0.08 Pa·s or greater than 100 Pa·s, such as gum viscosities (>1,000 Pa·s), as long as the average viscosity at 25°C. of (A) is in the range of from 0.5 Pa·s to 100 Pa·s. The mixtures of polydiorganosiloxanes in (A) can provide properties to the uncured composition, as well as, to the cured product. Such properties can be flow characteristics of the uncured composition where low viscosities can provide plasticising properties and high viscosities can provide thixotropic properties. The cured products can have improved reversion properties and the modulus can be controlled by using mixtures of polydiorganosiloxanes for (A). The tetrafunctional ethoxy-ketoximo silane, (B), is a mixture of silane species of 6 to 27 weight percent tetraketoximosilane, 9 to 39 weight percent monoethoxytriketoximosilane, 38 to 60 weight percent diethoxydiketoximosilane, and 5.5 to 25 weight percent triethoxymonoketoximosilane. The ketoximo group has the formula -O-N=CR'R' where each R' is methyl, ethyl, propyl, isopropyl or butyl and can be any of those ordinarily used in making ketoximosilanes, such as methylethylketoximo, dimethylketoximo and diethylketoximo. The preferred ketoximo group is the methylethylketoximo group. The tetrafunctional ethoxyketoximo silanes can be made by heating a mixture of ethylorthosilicate and ketoxime in an azeotroping solvent, such as toluene, to reflux which removes the ethanol as it is formed. This reflux is necessary because the reaction equilibrium lies far to the left of the reaction equation and the ethanol must be removed as it is formed to drive the reaction to the tetrafunctional ethoxyketoximo silanes used in this invention. The reflux temperature at the head is preferably held below 100°C. to prevent the product from decomposing. This reaction will usually provide the tetrafunctional ethoxy-ketoximo silanes used in the compositions of this invention in less than 12 hours. The reaction equation in a simple form is as follows: Si(OCH₂CH₃)₄ + HON=CRR′ -> Si(OCH₂CH₃) x (ON=CRR′) y + HOCH₂CH₃ The ketoxime is used in an excess amount to force the reaction to the right. The values of the subscripts x and y are such as to provide the mixtures as claimed herein, that is x can be 0, 1, 2 or 3 and y can be 1, 2, 3 or 4 in each molecule of the mixture. The amount of crosslinker in the compositions of this invention is from 5.5 to 10 weight percent based on the total weight of the composition, ingredients (A)-(E). Preferably, the amount of crosslinker (B) is from 6 to 8 weight percent. The compositions of this invention contain a tin catalyst (C). This tin catalyst is required with the crosslinkers described in (B) to provide the faster curing properties of these compositions which are characterized by a surface which becomes tack free in a short time (dry surface, not sticky), such as in less than 15 minutes after the composition is exposed to atmospheric moisture (about 50 % relative humidity) at room temperature. These compositions cure fast to tack free surfaces, have resistance to reversion in confined areas especially under high temperature conditions, have improved heat stability, and develop sufficient strength and adhesion to be useful for adhering two substrates together in a short period of time so that they may be handled without separation before the composition is fully cured. The tin curing catalysts can include tin carboxylates, dibutyltindiacetate, dibutyltindilaurate and stannous octoate, preferably the tin catalyst is dibutyltindilaurate. The amount of tin catalyst in the compositions of this invention is from 0.1 to 0.25 weight percent based on the total weight of the composition, ingredients (A)-(E). Preferably, the tin catalyst is present in an amount of from 0.15 to 0.2 weight percent. If the amount of the tin catalyst is less than 0.1 weight percent, the composition when exposed to atmospheric moisture does not cure completely through. The composition next to a substrate remains uncured and when elongated it cracks. If the amount of the tin catalyst is greater than 0.25 weight percent, the cured product may revert when confined, especially if the temperature increases much above room temperature. Compositions which contain organotitanate catalyst, such as those described by Klosowski et al yellow upon storage and the rate of cure slows substantially at an organotitanate concentration of 0.4 weight percent. A combination of both organotitanate catalyst and aminoalkyl functional silane causes substantial coloring of the composition upon storage, where the color changes from nearly white to yellow or orange. The use of the tin catalyst and the purified aminoalkyl functional silane has overcome this yellowing problem upon storage as well as improved the adhesion and the cure rate. The compositions of the present invention also contain a reinforcing silica filler, (E). Examples of reinforcing silica fillers are fumed silica and precipitated silica. The reinforcing silicas can be treated to provide a hydrophobic filler surface. The amounts of the reinforcing silica filler can be from 5 to 20 weight percent based on the total weight of the composition, ingredients (A)-(E), preferably the reinforcing silica filler is present in an amount of from 9 to 14 weight percent. These reinforcing silica fillers provide a thixotropic characteristic to the uncured composition and provide increased tensile strengths to the cured products as compared to compositions prepared without reinforcing silica filler. The compositions of the present invention also contain an adhesion promoter (D) with reduced tendency to yellow upon storage. These adhesion promoters are aminoalkyl functional silanes in the purified form. These aminoalkyl functional silanes have the formula in which R' is an alkyl radical having from 1 to 4 carbon atoms, such as, methyl, ethyl, propyl and butyl., R² is an alkylene radical, such as ethylene, propylene, isopropylene, butylene and isobutylene; R³ is an alkyl radical of from 1 to 5 carbon atoms per radical, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl and amyl; R⁴ is hydrogen atom or R³; a is 0 or 1 and b is 0, 1 or 2. The aminoalkyl functional silanes can be purified by a number of different methods. It is believed that the presence of acid chlorides as impurities is a major cause of the yellowing occurring upon storage. Therefore, the use of purified aminoalkyl functional silanes reduces the tendency of the composition to yellow upon storage. One method of purification is to distill the aminoalkyl functional silane after it has been prepared or received from a supplier. Another method of purification is to wash the aminoalkyl functional silane with a base to remove acidic impurities which may be present from the preparation. The base wash is useful with either the prepared aminoalkyl functional silane or the aminoalkyl functional silane received from a supplier. It may be possible to obtain a purified aminoalkyl functional silane from a supplier, but it should be tested to determine whether it will induce yellowing to the composition upon storage. The difference between a purified aminoalkyl functional silane and a non-purified aminoalkyl functional silane is remarkable. Compositions were compared which were prepared using either purified or non-purified aminoalkyl functional silanes and which were stored for six weeks at 50°C. and then cured. Different colorimeter readings were obtained. For example the purified aminoalkyl functional silane gave a colorimeter reading of 3 and the non-purified aminoalkyl functional silane gave a colorimeter reading of between 40 and 50. The preferred aminoalkyl functional silane is distilled N-(2-animoethyl)-3-aminopropyl-triethoxysilane. The amount of adhesion promoter in the composition of this invention is from 1.5 to 3 weight percent based on the total weight of the composition. Other ingredients can also be used in the compositions of the present invention, such as heat stability additives, extending fillers, plasticizers, pigments and other colorants, other adhesion promoters, solvents and flame retardant additives. These other ingredients should be thoroughly tested before a composition is put into commercial practice because they may have a detrimental effect on the curing properties, the storage stability or the color formation on storage. Extending fillers can be calcium carbonate, diatomaceous earth, titanium dioxide, alumina, crushed quartz and iron oxide. Another material which might be useful either as a filler or as a coloring agent is carbon black. The extending fillers may be used in larger quantities than the reinforcing fillers. The amounts of the fillers used will depend upon the particular properties wanted in the final cured product. Mixtures of fillers can be used such as a mixture of reinforcing silica and calcium carbonate. These ingredients should not be used if they cause the uncured composition to cure in the package, not to cure when exposed to moisture or to cure to a product which has inferior properties for the intended utility. The compositions of this invention are made by mixing ingredients (A) through (E) in amounts as specified, to provide a one package composition which is stable in the absence of moisture and which cures to an elastomeric material when exposed to moisture. For purposes of this application, ingredients (A)-(E) should add up to 100 weight percent. The compositions of the present invention are preferably prepared by mixing (A)-(E) under anhydrous conditions, i.e., the ingredients used should not contain amounts of moisture or water which will cause the composition to cure in the storage package. The compositions should also he mixed under conditions which do not allow the entrance of moisture into the system in an amount sufficient to cause the mixture to have deleterious storage properties, curing properties or cured properties. After the compositions are made, they are stored in packages which keep moisture out. The longest storage stability times can be obtained by making and storing the compositions under conditions which are free from moisture and water. The more the composition is maintained under anhydrous conditions, the longer the time the composition will remain uncured in the storage package. The compositions can also be protected from moisture entering the composition incidentally and accidentally by using an excess of ingredient (B). The compositions of this invention should have at least one mole of tetrafunctional ethoxyketoximo silane present per mole of hydroxyl group in (A). Because small amounts of water entering the composition either during preparation or during storage can result in a cured product, it is advisable to use a mole ratio of silane (B) to hydroxyl group of (A) of greater than one to one. However, if careful attention is given to the preparation and the storage package, compositions can be made with a ratio of about one mole of silane (B) per mole of hydroxyl group of (A). Because the molecular weight of the polydiorganosiloxane can vary, the higher the molecular weight used in preparing a composition, the lower the hydroxyl group content of a given weight of polydiorganosiloxane will be. Therefore, it is recommended that in the preparation of the compositions, the ratio of the moles of silane in (B) to the moles of hydroxyl group in (A) be observed and controlled to provide a stable product. Preferably, the compositions of this invention are those which contain from 4 to 7 moles of silane (B) per mole of hydroxyl group of (A). Compositions which have these higher mole ratios of silane (B) to hydroxyl group of (A) are not as sensitive to the entrance of moisture as compositions having smaller amounts of silane (B) per hydroxy group of (A). The compositions of this invention cure to elastomeric material, such as rubbery sealants, caulking materials, adhesives, coatings and encapsulating materials. An advantage of the compositions of this invention is that they cure rapidly, developing enough adhesive strength when used between two substrates to allow the bonded assembly to be handled within one or two hours compared to several hours or days. The compositions of the present invention are useful in the construction industry for adhering substrates such as polyvinyl chloride, wood, metals such as aluminum or steel, and glass. The compositions of the present invention do not bubble when cured under hot conditions as do the methoxy-ketoximo silanes where the hot conditions are temperatures such as above 100°C. The compositions of the present invention can have a modulus determined by selecting the kind of polydiorganosiloxane (A) and the amount of crosslinker (B). The cured products of the compositions of this invention also exhibit resistance to oils and other solvents such as glycol and water mixtures, such properties would make the compositions of this invention useful as formed-in-place gaskets for use in automobiles and other machinery which need gaskets with solvent and oil resistance. The following examples are presented for illustrative purposes and should not be construed as limiting the present invention which is properly delineated in the claims. In the examples, "parts" refers to parts by weight and the viscosities are measured at 25°C. Example 1 Compositions were prepared by adding 100 parts of polydimethylsiloxane having 85 percent of the end groups as hydroxyl and 15 percent of the end groups as trimethylsiloxy and having a viscosity of 12.5 Pa·s which was mixed in a Ross mixer with 7.4 parts of a tetrafunctional ethoxy-ketoximo silane mixture as the crosslinker, 0.19 part of dibutyltindilaurate and 1.9 parts of distilled N-(2-aminoethyl)-3-aminopropyltri-ethoxysilane. To this mixture, 14 parts of reinforcing silica filler having a surface area of 150 square meters per gram was added and mixed until the filler was wet out. The composition was de-aired and then put into a container which protected it from the entrance of moisture. The tetrafunctional ethoxyketoximo silane mixture contained tetra(methylethylketoximo)silane, monoethoxytri(methylethylketoximo)silane and diethoxydi(methylethylketoximo)silane as described in Table I. The silane mixture was prepared by mixing 19 parts of tetraethoxysilane, 36.4 parts of tetra(methylethylketoximo)silane and 44.6 parts of toluene which had been dried. This mixture was then placed in a reflux pot with a distillation column, heated and distilled until the desired mixture of silanes were obtained. The toluene was then distilled to obtain the final ethoxy-ketoximo tetrafunctional silane. The mixture was identified by gas liquid chromatography. The various silane mixtures were prepared by this same method and the mixtures were as described in Table I. Specimens of the compositions were prepared by making slabs by the draw-down method using a chase having a 1.6mm (1/16 inch) depth which specimens were exposed to moisture and the following properties were measured. The skin over time (SOT) was measured by observing the time from exposure of the composition to moisture until a finger lightly touched to the surface of the curing composition was withdrawn without transfer of composition to the finger. The tack free time (TFT) was the time measured from the exposure of the composition until a dry surface, free from tack was obtained. The curing composition was observed to see if any cracking occurred during the curing process. Other specimens were obtained as described above and were allowed to cure at 77°C. and 50% relative humidity for 7 days and then the following properties were measured. The durometer on the Shore A scale was determined according to ASTM Standard D-2240, the tensile strength at break and the elongation at break were determined according to ASTM Standard D-412. The modulus was determined at 100% elongation according to ASTM Standard D-412. The results for each composition were as shown in Table II. Example 2 A composition was prepared as described in Example 1 using the tetrafunctional ethoxy-ketoximo silane mixture A, except that an OH-terminated polydimethylsiloxane having a viscosity of 12.5 Pa·s was used in place of the polydimethylsiloxane having 85 percent of the end groups as hydroxyl and 15 percent of the end groups as trimethylsiloxy groups. The composition was cured and tested as described in Example 1. The composition had a skin-over-time of 3.25 seconds and a tack-free-time of 3.25 seconds. After curing at room temperature for 7 days, the durometer on the Shore A scale was 46, the tensile strength at break was 2.52 MPa, the elongation at break was 278 % and the 100 % modulus was 1.03 MPa. This example shows that similar results were obtained from compositions made with hydroxyl endblocked polydimethylsiloxane and from compositions made with polydimethylsiloxane which was partially endblocked with trimethylsiloxy groups except that the partially endblocked polydimethylsiloxane had lower modulus. Example 3 Compositions were prepared as described in Example 1 using Silane Mixture A but varying the amounts of the silane mixture, the reinforcing silica, dibutyltindiacetate and using 1.6 parts of distilled N-(2-aminoethyl)-3-aminopropyltriethoxysilane instead of the 1.9 parts as used in Example 1. The amounts which were varied were as shown in Table III. The compositions were cured by exposure to the atmosphere at room temperature. The properties of the compositions were measured after initial preparation, after storing the composition in a sealed container for four weeks at 50°C and then curing the composition by exposing it to atmospheric moisture for 7 days. The properties were then measured after storing the composition in a sealed container for four weeks at 70°C and then, after curing the composition by exposing it to atmospheric moisture for 7 days. The properties were as shown in Table IV and were determined as described in Example 1. The rate of cure and extrusion rate were observed and are reported in Table IV. The above results showed that the compositions outside the limits do not provide satisfactory properties. Runs 4 and 6 exceed the limit of dibutyltindilaurate, Runs 8 and 10 have insufficient silane mixture and Run 9 exceeds the limit of dibutyltindilaurate and has insufficient silane mixture. Example 4 A composition was prepared as described in Example 1 using the ingredients described in Example 1 in the amounts of 79.74 parts of the polydimethylsiloxane, 6.5 parts of silane mixture A, 12 parts of reinforcing silica, 1.6 parts of distilled N-(2-aminoethyl)-3-aminopropyltriethoxysilane and 0.16 part of dibutyltindilaurate. This composition is designated Composition A. A similar composition was prepared as described above using the same ingredients but instead of using silane mixture A, a silane mixture of methyltri(methylethylketoximo)silane, methyldi(methylethylketoximo)methoxysilane and methyl(methylethylketoximo)dimethoxysilane was used. This composition is designated Composition B and is presented as a comparative example. Each of the above compositions were used to determine the degree of the development of adhesive strength when used between two substrates. Each composition was deposited between a glass substrate and a polyvinyl chloride substrate and also between a glass substrate and a wood substrate. The adhesive strength was determined one hour after deposition and two hours after deposition. The results obtained were as shown in Table V. The peel strength of Composition A was determined on the substrates shown in Table VI after curing for seven days at room temperature. The results are shown in newtons per meter. SUBSTRATE PEEL ADHESION, N/m Anodized Aluminum 3327 Clear Glass 3152 Polyvinyl chloride 2977

Claims: A composition consisting essentially of a product which is storage stable in a package when protected from moisture but cures when removed from the package and exposed to moisture and which is obtained by mixing the following ingredients, (A) an OH-terminated polydiorganosiloxane having an average viscosity at 25°C of from 0.5 to 100 Pa·s and the organic radicals bonded to the silicon atom are selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, (B) from 5.5 to 10 weight percent of a tetrafunctional ethoxy-ketoximo silane mixture of 6 to 27 weight percent of tetraketoximosilane, 9 to 39 weight percent of monoethoxytri-ketoximosilane, 38 to 60 weight percent of diethoxydiketoximosilane and 5.5 to 25 weight percent triethoxymonoketoximosilane in which the ketoximo groups have a formula -O-N=CH'R' in which each R' is an alkyl radical having from 1 to 4 carbon atoms, (C) from 0.1 to 0.25 weight percent of a tin catalyst, (D) from 1.5 to 3 weight percent of an adhesion promoter which does not impart color to the composition and which is a purified aminoalkyl functional silane being substantially free of acid chlorides and having the formula in which R' is an alkyl radical having from 1 to 4 carbon atoms; R² is an alkylene radical selected from ethylene, propylene, isopropylene, butylene and isobutylene; R³ is an alkyl radical having from 1 to 5 carbon atoms per radical; R⁴ is a hydrogen atom or R³; a is 0 or 1 and b is 0, 1 or 2, and (E) from 5 to 20 weight percent of reinforcing silica filler, wherein the amount of ingredient (A) is at least 66.75 weight percent and the ingredients (A) - (E) add up to 100 weight percent. The composition according to claim 1 in which the adhesion promoter (D) is distilled N-(2-aminoethyl)-3-aminopropyl-triethoxysilane. The composition according to claim 1 in which the OH-terminated polydiorganosiloxane of (A) is partially endblocked with triorganosiloxy groups.

Inventors: HAUGSBY HAWLEY MICHAEL, LOWER LOREN DALE, HAUGSBY, HAWLEY MICHAEL, LOWER, LOREN DALE
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1990
Main classification: C08L83
IPC codes: C08K5, C08L83, C09K3, C08K3