TW593438B - Silicone resin compositions having good solution solubility and stability - Google Patents

Abstract

The present invention refers to soluble silicone resin compositions having good solution stability, to a method for their preparation, to nanoporous silicone resins and coatings and to a method of making those. The silicone resins comprise the reaction product of a mixture comprising (A) 15-70 mol% of a tetraalkoxysilane described by formula Si(OR1)4, where each R1 is an independently selected alkyl group comprising 1 to 6 carbon atoms, (B) 12 to 60 mol% of a hydrosilane described by formula HSiX3, where each X is an independently selected hydrolyzable substituent, (C) 15 to 70 mole percent of an organotrialkoxysilane described by formula R2Si(OR3)3, where R2 is a hydrocarbon group comprising 8 to 24 carbon atoms or a substituted hydrocarbon group comprising a hydrocarbon chain having 8 to 24 carbon atoms and each R3 is an independently selected alkyl group comprising 1 to 6 carbon atoms; in the presence of (D) water, (E) hydrolysis catalyst, and (F) organic solvent for the reaction product.

Description

593438 V. Description of the invention (l): About the soluble silicone resin combination glaze method with good solution solubility. The Shi Xi_resin is used to form a microporous rhenium film with a low dielectric constant. It usually has one or more sets of modeled mutual edge plane layers, which are: individual circuit elements that form an integrated circuit (ic) from electrical connections. lif in: Generally separated by an insulating film or a dielectric film. Previously, the most commonly used materials for the formation of dioxide: m electro-composite films using chemical = lice phase deposition (jVD) or plasma toughening (pECVD) techniques. However, due to the reduced space between circuit elements, the relatively high dielectric constant of this type of silicon oxide is insufficient to provide sufficient electrical insulation. 〇 In order to provide lower than the oxidation; ε 夕 介 雷 舍 * based resin to form a dielectric ;: number ;! An example of a thin film that is found to be completely formed is described in Self-polymerizing (hydrogen) times 4,756,977. Although this result is excellent / Patent No. 3,6 1 5,272 and No. provide a lower dielectric constant. In addition, this film is also used to enhance the surface planarization, but this type, such as enhanced gap filling, is larger. , The thickness of the dielectric constant is limited to about 3 or we know that I # 1 i

At the same time, the above discussion must be absent; for thin = and signal delay ICs, S is constantly shrinking in size, and the constant is an important factor. Since it is necessary to be able to raise the value below 3/8, the IΛ constant is an important boost. Therefore, the method of manufacturing this material is very expected; the V number is based on Shi Xi, and the resin material with low dielectric constant is Shi Xi oxygen. It looks like: Xi Bu is very in need of providing high crack resistance and method. Moreover, this kind of "ί; ΓΓ manufacturing lb" fat cube / leane-based resin is processed by standard technology

Page 6 593438 Description of the invention (2) It is highly desirable to provide a film with a low dielectric constant. We know that the dielectric constant of a solid-state thin film decreases with the density of the thin-film material. ^ The development of micropores for semiconductor devices has significantly reduced work. Cong Mian Yao, National Patent No. 5, 49 4, 85 9 describes a two-constant dielectric film for integrated circuit structures and a method for manufacturing the same. The porous layer is formed by depositing a composite layer on a ^ = structure, and the composite layer includes a substance that is converted into a gas when the insulating matrix material undergoes a conversion treatment. The released gas leaves a porous matrix of insulating material with a dielectric constant of two layers. Matrix forming materials & horse lice silicon, and plutonium, such as carbon, which can be converted into gas when subjected to a conversion treatment. ^ Da, Guo, Li No. 5, 77 6, 990 reveals a solution with a pore size less than 00 nanometers (nm) ^ ^ insulating foam polymer, the foam polymer is decomposed by higher than separable = 2 ^ Temperature-coated manufacturing of a copolymer comprising a di-permanent sigma and a pyrolysable polymer. The copolymer is an organic polymer containing no silicon atoms. , World Intellectual Property Organization Patent No. 98/4 972 No. 1 describes a method of forming pores and holes on the substrate, and a method of electrocoating. The method includes the following steps: Agent composition and selected water, so that the mixture is deposited on the base A while evaporating at least a part of the solvent; the substrate is placed in a closed chamber, the chamber%; u I is lower than atmospheric pressure, so that the substrate is low Burst at 7jC *, milk 'at atmospheric pressure and then expose to alkali vapor. 5 patents (HEI) No. 10-287746 teaches to prepare a porous film from a siloxane-based resin having an organic Γ group, and the organic

Page 7 593438 V. Description of the invention (3) Generation ^ is oxidized at 250 ° C or higher. In this document, the organic groups used which can be oxidized at 25 ° C or higher include substituted and unsubstituted groups. Examples are 3, 3, 3-trifluoropropyl, stone-phenethyl , Second butyl, 2-cyanoethyl, benzyl and vinyl. In order to reduce the film's density and dielectric constant, the journal of Natural Chemistry (J · n Chem ·) Mikoshiba et al. (Mikoshiba) reported a kind of Angstrom size produced in poly (methyl half-stone oxy-fired) film Hole method. Wherein, a copolymer carrying a methyl (X-methysilyloxysilyl) unit and an alkyl (trimethylsiloxysilyl) unit is spin-coated on a substrate, and heated at 250 ° C. To provide rigid siloxane. Then, the film is heated at 45 to 500 t to thermally remove the non-t 'group, leaving a hole corresponding to the size of the substituent. According to investigations, the unstable substituents are trifluoropropyl, cyanoethyl, phenethyl and propyl. World Intellectual Property Organization Patent No. 98/4 794 5 discloses a method for reacting trichlorosilane and organic dichlorosilane to form an organohydrosiloxane polymer. The polymer has a cage configuration and about 0.1 to 4. Mol% carbon-containing substituents are reported to have a dielectric constant of less than 3 for resins generated from the polymer. The + object of the invention includes the provision of a silicone resin which is soluble in organic solvents (such as toluene), has a usable solution storage period, and is suitable for crack-free, electrically insulating thin films of electronic elements. Another purpose is to provide a film with a diameter of less than 2 dielectric layers, which is coated on a substrate with a narrow pore size distribution and a low dielectric constant (plus a semiconductor element). , J; 丨 The number of micropores without cracks in the electric suspension number is small. This invention relates to a combination of soluble silicone resins with a good solution such as itching / combination and degree of solution.

Page 8 593438 Five 'invention description (4) Preparation method. The silicone resin is used to generate micro-particles having a low dielectric constant. A specific embodiment of the present invention is a rhenium resin dissolved in a standard solvent and having a dielectric coating applied. Her resin includes a catabolism catalyst and (f) an organic solvent storage product used in the reaction product. The mixture includes (A) 15-70 mole% of tetrakisoxy oxylithium as described by the formula, where (1) each R1 is an independently selected alkyl group of 2 ^ to ^ carbon atoms; (B) 12-60 mole% by formula (2) HsiX3 η: Shixane 'wherein each 其中 is an independently selected hydrolyzable substituent; 7 〇mole% organic di-smoke as described by the formula (3) R2Si (OR3) = wherein ... a substituted hydrocarbon group of a nicotinyl or stone antiatomic hydrocarbon chain containing 8 to 24 carbon atoms, each of which is independently selected A 6 atom alkyl group, where the mole percentage is based on the total moles of the component. The component (A) is a tetraalkoxysilane described by the formula (1). I was unexpected. The existence of component A, which accounts for the total moles of component (A) + (B) + (C), is between 15 mol% and 70 mol%. The solubility and stability of silicone resin in organic solvents are critical. important. If the mole% of component (A) is outside the range, the silicone resin will be at least partially insoluble in the organic solvent forming the resin solution coating. The mole% of component (a) is preferably in the range of 25 mole% to 50 mole%. In formula (1), each R1 is an independently selected alkyl group containing i to 6 carbon atoms. For example, ^ is methyl, ethylbutyl, second butyl, and hexyl. Component A is preferably tetramethoxysilane or tetraethoxysilane because it is easily available. Component (B) is a hydrosilane described by formula (2). The component (β) is

111 593438

V. Description of the invention (5)

(α) + (Β) + (〇Total moles from 12 mole% to 60 mole% is added to the mixture a. Adding component (B) beyond the stated range can limit the obtained silicone resin to Solubility in organic solvents. Component (B) is preferably added to the mixture in an amount of 15 to 40 mole%. In formula (2), χ is a hydrolyzable substituent. X is any water-soluble substituent. Substituents that are hydrolyzed from the silicon atom under the conditions of the method and that do not adversely affect the solubility of the silicon resin when hydrolyzed. Examples of hydrolyzable substituents include hydrogen and alkoxy. X preferably contains i to 6 carbons Atomic alkoxy groups. Groups of tri-gas residues, trimethoxy ^ or triethoxy groups, and base groups.

/ Component (C) is an organic trialkoxysilane described by formula (3). Component (c) is added to the mixture to account for component (human) + (^ + ((:) total moles 15 to 70 mole%). Component (C) is important to provide Mechanism of forming microporous film from silicon resin. To be precise, component (c) includes non-substituted or substituted hydrocarbon groups. R2 is removed from silicon atoms by pyrolysis in a heatable process, and is used in the resulting silicone resin. Micropores are generated in the mixture. Therefore, the component (C) is added to the mixture to control the porosity of the obtained lithone resin in heating the solid and pyrolyzing the r2 substituent. Generally, the component (C) If the amount is less than 15 mol%, the porosity of the resin coating of Shixi Steel will be too small to give the material the best dielectric properties. Moreover, the solubility in the solvent is poor, and the amount of component (C) above 70 mol% will Causes the resin to have limited solubility in solvents and insufficient physical properties (such as crack resistance when used as a porous coating on a substrate). Component (c) is preferably 5 Mo 0/0 to 40 Mo % Range is added to the mixture. In the formula (3), a hydrocarbon group containing 8 to 24 carbon atoms or containing 8 to 24

Page 10 593438 V. Description of the invention (6): A substituted hydrocarbon group of a carbon atom hydrocarbon chain. R2 can be linear or split. The substituted hydrocarbon group may be substituted with the following substituents. Such as the teeth, the polyoxidized dilute base described by m) soil ('m and the parent are ^ positive integers to the positive integer). Alkoxy, alkoxy, alkoxy, alkane = carbonyl and trialkyl sulfo. R2 preferably contains 8 to " · Xin? Contains? 6 to 2. A straight-bonded alkyl group with more than one carbon atom is equal to a radical, an ethoxyoctyl group, a nonyl dioctyl octadecyl group, an octadecyl undecyl group, a cetyl group, and a trioctyl hexadecyl group. , Octadecyl and behenyl. In ^^ 3,), each R3 is an independently selected alkane containing 1 to 6 carbon atoms. R is, for example, fluorenyl, ethyl, propyl, isobutyl, and hexyl. R3 is preferably methyl or ethyl. Specific examples of the organic trisalkanesene group of butylheptyltrifluorene include octylalkane, dioctyltrimethoxysilane, octadecyltrimethoxysilylorganodimethoxysilane, and dodecyltriethyl Oxysilane. The organic milk base is preferably selected from the group consisting of octyltriethoxy, octadecyldimethoxysilicon, and AW's AW, and alkyl dimethyllactylxane group. Further examples of organic compounds and compounds include compound (CHJCHOn-O-CH2CH2) Si (OMe) 3 described by the following formulas. (ch3 (ch256c (= 〇)-(CH2) (CH2) Si (0Me) 3 〇Product (CH3 (CH2) i7 ~ 〇-C (= 〇) -CH2CH2) Si (OMe) 3 and CKCDfCbO)- 〇-CH2CH2) Si (0Me) 3, where Me is forma

Page 11 593438 V. Description of the invention (7) Into, f, (D) is water. The component (D) is preferably added in a sufficient amount, and the hydrolyzable " kibe group " radicals of the Shixi atom of the linked components 连接, ⑻ and (0) are not excessively large to produce a biphasic phase that slows down the reaction. Mixtures are preferably used per mole of components (A), (B), and (C)]. 4 to 6 moles "is better than the amount of 2.5 to 4.5 moles (on the same basis). Water uses the component (E) as a hydrolysis catalyst, and may be an arbitrary substituent. The technique of the atomic hydrolysis has been: two in existence, the hydrolysis catalyst may be inorganic, such as or, the catalyst may also be Inorganic acids, such as hydrogen chloride, sodium. Early addition of a hydrolysis catalyst to the reaction mixture, or at least partially generated in place when a group of ^ dentable silanes. Preferred hydrolysis catalysis: () is two 'T = (β) is The trichloride side can be generated at least partially in situ from the connecting stones of the components (A), (B) and (C).] =) For any benefit, the optimal amount depends on the catalyst's chemistry. , 0 0 = 5 a: Λ per mole component (Α), ⑻ and ⑹ use the same standard; the amount of catalyst is preferably Gl to " Moore (with 4 ΓΓΛ reaction products should be produced in Λ is used for ㈣, which can make the reaction products form homogeneous squares & grains [such as methylben, xylene, J, 3 卞 isobutyl ester, trifluoroxobenzene, propylmetraz, 'stone' & a Gelben rice, /, butyric acid, trifluorotoluene, and sauté. There are two soluble solvents, butyric acid, butyric acid, and acetic acid. It should be sufficient for reaction mixing.

$ 12 pages 593438 V. Description of the invention (8) = Liquid storage. The organic solvent generally accounts for 70 to 95% by weight, preferably 85 to 95% by weight, based on the total weight of components VII to (F). In a preferred method for making fat-removing products, the first mixtures (c) and (F) / tc * are first synthesized. Then (in the mixing as: entering the knife), a mixture of the two can be added separately or = two, and the reaction product is formed by one. The reaction product is generated at 15 3 Λ her ambient temperature is good at ambient temperature. In the preferred method, after the reaction product is obtained, the volatiles are separated from the reaction product to remove the resin solution under reduced pressure. Such volatiles include by-product alcohols, water: catalysts, and solvents. It is necessary to 'remove all solvents from the resin solvent' to form solids. When all the solvents are removed to separate the resin solids, the temperature of the resin solution should be kept below 60 ° C, preferably within the range of 30 to 50 ° C. Overheating can cause this Insoluble resin is formed. If necessary, the catalyst and alcohol by-product can be separated from the reaction product by temporary phase separation after one or more water washings, so as to = dissolve in the solvent silicone solution. -OH functionality, and may contain Si -OR3 functionality, where r3 is as previously described, the silicon-tree to 30 mole% SiOH and 0 to 10 mole% Si_0R3. 1 '" 3l ° The present invention A further specific embodiment is to add the above Preparation of molecular compounds containing the reaction product of syringone, and methods for improving storage stability (hereinafter referred to as "weight-increasing method 0." Weight-increasing methods include, (i) making the silicone resin in the presence of the selected condensation catalyst A solution is formed in a solvent at 10 to 60% by weight, and (ii) the solution is heated at a sufficient temperature to condense the resin to a weight-average molecular weight of 10, 0, 0 to 40, 0, 0 0 , And (iU) to neutralize the stone ketone tree

Page 13

593438 V. Description of the invention (9) A lipid solvent solution. In step (丨) of the method, the silicone resin is preferably present in the organic solvent at 20 to 30% by weight. The organic solvent may be any of the above-mentioned organic solvents. The optional condensation catalyst added in step (i) is the acid and base of any of the hydrolysis catalysts used to form the reaction product described above. A preferred condensation catalyst is hydrogen chloride in a concentration of 5 to 200% by weight of the solids of the resin. The condensation catalyst is more preferably hydrogen chloride at a concentration of 10 to 50 ppm by weight of the resin solids. The temperature for heating the silicone resin solution in step (1 1) is from 500 to the reflux temperature of the solution. However, the solution of the silicone resin is added to increase the weight average molecular weight by reflux. In step (i i), the solution is preferably heated so that the silicone resin has an amount of 150,000 to 250,000 after heating! Average molecular weight:? Step (i) of the method is a solvent solution that neutralizes the silicon resin. Towels are made by washing the solution with one or more parts of water, or tincture, and redissolving the silicone resin in one or more parts of the organic solvent. The solvent used in the neutralization step is any of the above-mentioned organic solvents. In order to further improve the stability of the solution of the neutralized silicon resin, the person who dissolves the fat in an organic solvent or an organic solvent sets ^ A < Juice, and adds Zhan Shixi 0¾ tree month, soluble > 彳 and water Total weight 0.05 to 04 weight # yj ^ benchmark. .i 至。 To. .25% by weight of water. =============================================================================== The organic solvent is any of the above organic solvents or three thereof, and the preferred solvent is isobutyl isobutyrate. The silicone resin has a thin film of ^ n constant film, # IT T _ / · Α β (such as integrated solar panels) with a special angle for low dielectric: "Orbital: t is used as a filler. The silicone resin The specific example of the solid step is about the progress of the pores of this hair month /] W Yueyue and pores of the silicone resin film and 593438 V. Description of the invention (ίο) The manufacturing method. Specifically, 'progress of the invention-step The specific embodiment relates to a method for forming a nanoporous silicone resin. &Quot; Nanoporous " refers to a silicone resin having less than 20 nanometer pores. A preferred embodiment of the present invention is a nanoporous coating containing a silicone resin. Electronic crystal; in this specific embodiment, the nanoporous coating has G. 3 nanometers to 2 nanometers direct control. If it is a solid, then the reaction product containing Shi Xiyu resin is dissolved and diluted in the above organic solvent, Isobutyl isobutyrate and chlorotrimethylbenzene are the preferred solvents for forming coating solutions. The concentration of lithone ester in organic solvents is not particularly critical to the present invention, and can be dissolved and used for coating. Provides acceptable concentration of flow properties. The silicone resin in organic solvents The degree is preferably 1. to 25% by weight. The lithone resin is applied to a substrate by a standard method of forming a coating on an electronic component, such as spin coating, flow coating, dip coating, and spray coating. The substrate with a silicon resin coating is heated in an inert atmosphere at a sufficient temperature to cure the silicone resin coating and pyrolyze the R2 groups from the silicon atoms. Heating can be performed as a single step method or a two-step method. In a two-step method In the method, the silicone resin is first cured at a sufficient temperature in an inert atmosphere, but the R2 group is not significantly pyrolyzed from the silicon atom. The temperature is generally from 20 ° C to =. Then, the cured stone resin is further heated. , Whose temperature is greater than C, which is still lower than the temperature at which the silicone resin polymer skeleton is cracked or the radical = the temperature at which the R2 group produces an undesired effect from the pyrolysis of the Shi Xi atom. The pyrolysis step = generally better than 35 (rc to 6G (rc, the best operation to 55 ot.) In the rrt method, the curing of the Shixigang resin and the self-heating group of the Ishido atom is performed simultaneously by: heating the base material of the silicone resin. The temperature is higher than 35 ° C, and the temperature is lower than the temperature at which the silicone polymer framework cracks or The substrate has an adverse effect 593438 V. Explanation of the invention (11) The temperature of the invention. Single-step heating is generally preferred to be performed at a temperature of greater than 350,000 to 60, and the best is at 40 (TC to 550,000). The method of forming a nanoporous coating (single-step or two-step heating method) is performed more in an inert atmosphere. Because the presence of oxygen can oxidize the bond and increase the residual silanol content in the film, the dielectric constant of the silicone resin is caused. Add, so the inert atmosphere is ideal. However, if necessary, a small amount of oxidant (such as oxygen) can be present in ^ to adapt the properties of the resulting nanoporous silicone resin. The inert atmosphere is familiar to the art, such as argon, helium or nitrogen The nanoporous silicone resin formed by the above method is particularly suitable for being used as a low-dielectric-constant film on an electronic component (such as an integrated wafer). The silicone resin coating prepared by this method preferably has a dielectric constant of less than 2. These nanopores can also be manufactured in the form of particles by standard methods, such as mouth mist drying: the above-mentioned heating method to generate nanopores is used for packing in chromatographic columns and other occasions where porous materials are used. Examples are provided to illustrate the method of the invention. In each example, all parts are parts by weight, and mole% is based on the total mole number of component (eight) + (] 6) + ((:). Molecular weight is reported as weight average molecular weight, It was determined by gel permeation chromatography (GPC) with toluene mobile phase and polystyrene standard calibration. * Sample 1 -1 $ 1-izi is a silicone resin prepared in a glass container as shown in Table i. The components (A), (B), (C) and (F): 5 times (A) tetraethoxysilane, (3) triethoxysilane, (C) octadecyltriazine Ethoxysilane and (F) fluorenyl-isobutyl ketone (ΜΙΒΚ)

Page 16 593438 5. Description of the invention (12) and toluene (weight ratio of 8 5: i 5). A mixture of (D) water and (E) hydrogen chloride was added to the mixture in an amount shown in Table 1 'In Sample 1-; [To, the component (c) was 1 part by weight. The resulting reaction product was removed under reduced pressure at 60 ° C. After complete absorption, 8.3 g of methyl was added to 1.7 g of the solid silicone resin, and the solubility of the obtained solid silicone resin in toluene was measured over 24 hours. If a clear solution is formed, or no particles or gels are visually observed, the solid is considered to be soluble in toluene. Methabenz solubility is also reported in Table 1. The data in Table 1 demonstrate the importance of the mole% of components (A) and (B) to the dissolution of the syringone resin. Table 1 Effect of mole% of components (A) and (B) on the solubility of silicone resin in toluene

Sample weight parts Mol toluene one-to-one number (A) (B) (D) — (E) (F) (A) (B) dissolved ΓΤ-1 0.56 1.32 0.84 0.078 12.0 20 60 is 1-2 0.70 1.21 0.86 0.079 12.1 25 55 1-3 0.84 1.10 0.87 0.080 12.2 30 50 Yes 1_4 0.97 0.98 0.88 0.081 12.2 35 45 Yes 1 -5 1.11 0.88 0.90 0.082 12.3 40 40 --- ~ T6l 1.25 0.77 0.91 0.084 12.4 ~ 45 > 35-Yes 1 1 -7 1.39 0.66 0.92 0.085 12.5 50 30 Yes 1-8 1.67 0.44 0.95 0.087 12.6 60 20 Yes 1-9 1.81 0.33 0.96 0.088 12.7 65 15 --- Yes 1_10 * 0.00 1.75 0.79 0.073 11.7 0 80 _-- No Ml * 0.28 1.53 0.82 0.075 11.9 10 70 M2 * 0.42 1.42 0.83 0.076 12.0 15 65 No 1-13 * 1.95 0.22 0.98 0.090 12.8 70 Ροο / 1-14 * 2.22 0.00 1.00 0.092 12.9 80 0 No HI is not an example of the present invention

Page 17

593438 V. Description of the invention (13) ---- The sample αu is further detected by Si29 and C13 NMR analysis, then the resin described in samples 1 to 3, which has 25 mole% SiOH and SiOR3, among which R3 Bucket, ^, two T group or ethyl. iiM2 Samples 2-1 to 2-6 similar to those described in Example 1 were prepared, with the following exceptions, and the mole% of component (A) was kept constant at 30 moles (1 part by weight). The respective concentrations of the other components as described in Example 1 and the toluene solubility of the obtained silicone resin are shown in Table 2. Components ((: Moore% on Silicone Tree: Stupid Dissolving Tang Effect of Sample Weight Parts Moore Toluene Number (B) (C) (D) (E) (F) (B) (C)- --- Dissolve 2-1 1.05 1.80 1.047 0.0960 18.8 40 30 Yes 2-2 1.16 1.56 1.045 0.0959 17.1 44 26 Yes 2-3 1.29 1.26 1.046 0.0959 15.0 49 21 ------- 2-4 1.42 0.96 1.046 0.0959 13.0 54 16 Yes 2-5 * 1.50 0.78 1.045 0.0958 11.7 57 13 -----. No 2-6 * 1.58 0.60 1.046 0.0959 10.5 60 10 No ---------- * Not an example of the invention iJ13 Samples 3_1 to 3-3 were prepared according to the method described in Example 1, but component (C) was (C-1) hexadecyltrimethoxysilane or (〇2) octyltriethoxylxane, as shown in Table As shown in Table 3. The amount of each component (parts by weight of (a)) and the solubility of the obtained resin in methylbenzyl are provided in Table 3.

Page 18 593438 V. Description of the invention (14) Table 3 Sample weight parts Mol toluene Number (C) Type (B) (C) (D) (E) (F) ㈧ ⑼ (C) Dissolved 3-1 C -1 0.99 1.80 1.05 0.096 20.13 30 37.5 32.5 Yes 3-2 C-2 0.92 1.55 1.05 0.10 13.73 30 35 35 3-3 C-2 0.63 2.92 1.24 0.11 21.88 25 20 55 Yes Example 4 Hydrogen chloride hydrolysis catalyst generated in situ Preparation of silicone resin. (A) 1 part of tetraethoxysilane, (B) 1.08 parts of trichlorosilane, (C) 1.19 parts of decyl octadecyltrimethoxysilane, (D) 1.03 parts of water and (F ) 14.87 parts of a mixture of MIBK and toluene (weight ratio 8 5: 1 5). A silicone resin was produced in a similar manner as described in Example 1. The mixture was refluxed for 5 minutes and the volatiles were removed under vacuum at 40 ° C. According to the method described in Example 1, the silicone resin was dissolved in toluene. Example 5 Effects of heating and hydrocarbon substitution on the weight average molecular weight of silicone resins. Samples 5-1 to 5-6 were prepared in a manner similar to that described in Example 1. Component (C) is (C-1) octadecyltrimethoxysilane or (C-2) octyltriethoxysilane as shown in Table 4. Table 4 also provides mole% of component (C) and components (A) and (B) as described in Example 1. The amount of the tasks (D) and (E) is the same as that described in Example 1. The volatiles were removed under vacuum at 30 ° C and the solid silicone resin was recovered. The solid silicone resin was dissolved in toluene to 30% by weight, and heated under reflux for the time described in Table 4 to continuously remove the released water. Determination of the silicone resin by GPC method before and after heating

Page 19 593438 5. The weight average molecular weight of the description of the invention (15). The results are reported in Table 4. The toluene solubility of the silicone resin was measured as described in Example 1. All resins were soluble in toluene before and after heat treatment. Table 4 Mw samples of silicone resin before and after heat treatment Molar% Time Mw Number type (C) ㈧ (B) (C) (hours) Before heating After heating 5-1 C-1 30 47 23 1 12,700 55,000 5-2 C-1 30 47 23 2 12,700 91,500 5-3 C-1 30 47 23 3 12,700 139,400 5-4 C-1 30 49 21 1 11,600 81,500 5-5 C-2 30 30 40 1 5,240 23,800 5-6 C- 2 30 25 45 1 7,540 16,300. Example 6 A soluble silicone resin was prepared by the method of Example 1. The sample was heated to generate pores and measure porosity. The sample was coated on a substrate and measured on the substrate. Physical properties of the sample. The soluble silicone resin was produced by adding the components described in Table 5. Table 5 Component description Molar% by weight (A) Tetraethoxysilane 1 30 (B) Triethoxysilane 1.31 ^ 50 (C) Octadecyltrimethoxysilane 1.20 20 (D) Water 0.57 -(E) Hydrogen chloride 0.096-(F) Mixture of MIBK and toluene (85:15 weight ratio) 15.8-

Page 20 593438 V. Description of the invention (16) ^ Put the solid resin sample into the crucible (or crucible) and heat it under nitrogen at 500 for 0.5 hour. Using micrometer (% 1 (:): 〇11161: 1 ^ 〇3) person 38? 2 0 0 0 accelerating surface area and porometer system [Georgia, Norcross, Microcross Instrument Company (Micrometries Instrument Corporation, Norcross, GA)] The nitrogen absorption of the obtained solid was measured at 770k. The specific surface area of BEt was determined to be 913 in2 / g. HK analysis [Hovaz (Horvath). J. Chera.

Eng. Jpn., 1 98 3, Issue 16, p. 476] Absorption data show. The solid had a pore volume of 0.41 cubic centimeters / gram, a narrow pore size distribution and a mesopore size of 0.83 nm. A solid silicone resin sample was also dissolved in xylene at 17% by weight for spin-coating 4 stone = wafer. The coated silicon wafer was placed in a nitrogen atmosphere at 45 °. 〇Heating for 1 hour ^ Soot > The special film has a thickness of 1.2 micrometers, and the thickness varies by 0.9%. The dielectric constant is 1.8.

Example J is the preparation of samples 7-1 to 7-4. The following components (A), (B), (C), and (F), (A) tetraethoxy are mixed in a glass container in the amounts described in Table 6. Silane. (B) As shown in Table 6. (C) octadecyltrimethoxysilane, and (F) a mixture of methyl, isobutyl ketone (MIBK) and toluene (85:15 weight ^ love ratio). In the stomach, a mixture of (0) water and (E) hydrogen chloride was added to the above mixture in the amount shown in Table 6. The weight part of component (C) is 丨. Molar% of (A), (B), and (c) in each sample was 30%, 50%, and 20%. The obtained reaction product is under reduced pressure

Page 21 593438 V. Description of the invention (17) ---- Absorb volatile matter at 60 ° C. After entering the risk 6 ^ ▽ Shi Fanquan, add 8.3 grams of MIBK to 1.7 grams f sad evening tree said, after 24 hours inspection, the obtained solid silicone resin has a clear solution to the ridges of MIBK and produces a clear solution and Visually, if there are no particles or coagulation, the solid is considered to be soluble. Sample characteristics—— ________ r—_ parts by weight MIBK number (B) ⑷ (B) (D) (E) (F) Dissolve 7-1 MeSi (OMe) 3 0.83 _0.91 0.87 0.081 14.4 is 7 -2 MeSiCl3 0.83 1.00 0.87 0 13.5 Yes 7-3 PrSiCl3 0.83 1.18 0.87 0 15.3 Yes 7-4 PhSiCl3 0.83 [Τ4Γ ~ 0.87 0 17.6 Yes Heat samples 7 -1, 7-3 and 7-4 to generate holes and measure Porosity. The solid resin sample was placed in a melting pot and heated under nitrogen at 500 for 5 hours. The nitrogen absorption of the obtained solid at 77 ° K was measured using a micrometer ASAP 2000 accelerated surface area and porometer system (Georgia, Norcross, Micrometer Corporation). The size of mesopores (mean pore size) and micropore volume were measured using Η-K analysis (Hertz ‘J \ Chem, Eng. Jpn ·, 1983, Issue 16’ p. 476) data. The results are shown in Table 7. Table 7: Nitrogen absorption data of nanoporous resin M compounds. Soluble Λ lipid sample. "5 Tiger BET specific surface area m2 / g micropore volume ^ cm / g average pore diameter nano 7-1 386 0.180 0.62 7-3 437 .0.203 0.60 7-4 564 0.263 0.57

Page 22 593438 V. Description of the invention (18) Samples 7-1, 7-2 and 7-4 were coated on the substrate, and the physical properties of the coating on the substrate were measured. A solid silicone resin sample was dissolved in MI BK at 17.7% by weight for spin-coated silicon wafers. The coated silicon wafer was heated at 450 ° C for one hour in a nitrogen atmosphere. The film data is shown in Table 8. Table 8 Film data Soluble resin (sample number) Film thickness (nm) Dielectric constant 7-1 887 1.87 7-2 698 L97 7-4 693 2.60

Page 23 593438

Page 24

Claims (1)

Amend its leeches ~ &...; you v with water, (E) hydrolysis catalyst I No. 891224 dip 6. Patent application scope 1 · a silicone resin ^ CF) ^ a ^ ^ ^ ^ ^ # Γ # " & Τ ί T 'b reaction products: (A) 15_70 mole% by formula S1 (0R1) VH: S, the reverse alkyl, where each R1 is independently selected containing =: mentioned alkyl alkoxysilane 12-60 Moore% is described by the formula _3 = ^ = selected hydrolyzable group of atom; (c) each X in 1 5 s 7 η seedling ^ is independent ^ ^ ^ a ^ t Rf: 0 ^% ^ (0R3 ) „基: radical or hydrocarbon chain containing 8 to 24 carbon atoms: original ;: dichotomous (A), (m ί mxi loss / pit base 'each mole percentage is based on group knife u), (B) Based on the total mole number of (c). 2. According to the silicone resin in item i of the patent application scope, the bean substance has a weight average molecular weight of 1 0,0 0 0 to 4 0,0 0 0, The middle D reaction yields 3 times; Ϊ Ϊ: a method of oxidizing lipids, including the formation of a mixture, using ί ⑴ / ⑴ ⑴ hydrolysis catalyst and 之 reaction products in the presence of the stack Luo Jian reaction, the mixture Including (A) 丨 5 _ 7 〇 Mo 21 (〇R1) 4 tetraalkoxy described in Silane, where each R1 is an independently selected alkyl group of up to 6 carbon atoms, (B) 12-60 mol% is described by the formula HSiX3. Burning, where each X is an independently selected hydrolyzable group, ( C) 15 to 45% organic trialkoxysilane described by the formula R2Si (OR3) 3, where r2 is a hydrocarbyl group having 8 to 24 carbon atoms or a substituted fe group having a hydrocarbon chain of 8 to 24 carbon atoms Each R3 is an independently selected alkane containing from 6 to 6 carbon atoms. 4. The method according to item 3 of the scope of the patent application, wherein the compound contains (A) + (B) + (C) ) Contains ι · 4 to 6 moles of water. 5,5 The method according to item 3 of the scope of patent application, wherein the mixture per mole 593438 _ Case No. 89122439_ 年月 日 _ί ± ^ __ VI. Patent application scope Ear component (A) + (B) + (C) contains 0.02 to 0.5 Molar hydrolysis catalyst, according to 6. The method of claim 3, wherein the hydrolysis catalyst is nitrogen chloride. 7. The method according to claim 3, wherein the mixture contains 70 to 95% by weight of an organic solvent used in the reaction product. 8. The method according to item 3 of the scope of patent application, wherein the reaction product containing the silicone resin is neutralized, the silicone resin is dissolved in an organic solvent, and 0.05 to 0.4% by weight of water is added. 9. The method according to item 3 of the scope of patent application, wherein the reaction product containing a silicone resin dissolved in an organic solvent is heated at a sufficient temperature in the presence of a selected condensation catalyst to condense the silicone to 100, 0 0 0 to 4 0 0, 0 0 0 weight average molecular weight. 1 0. A method for manufacturing a nanoporous silicone resin coating on a substrate, comprising the step (a) applying a silicone composition including a silicone resin having a patent scope of item 1 or 2 to the substrate, And (b) heating the coated substrate at a temperature of 350 ° C. to 600 ° C. to cure the stone resin and pyrolyze the R2 group from the silicon atom, thereby forming nanopores on the substrate Resin coating. 1 1. The method according to item 10 of the scope of patent application, wherein the heating step (b) is performed as a two-step method, and in the first step, the coated substrate is heated at 20 ° C to 350 ° C. Heating, in the second step it is heated at a temperature greater than 3 50 t to 6 0 ° C. 12. The method according to item 10 of the scope of patent application, wherein the coated substrate is heated in an inert atmosphere. 1 3 · The method according to item 11 of the scope of patent application, which should be in the first step O: \ 66 \ 66886-930506.ptc Page 26 593438 _Case No. 89122439_Year Month _ ^ _, one, six, the scope of the patent application The heating of the step and the second step is performed under an inert atmosphere. 1 4. A method for manufacturing a nanoporous silicone resin, comprising heating a silicone resin composition containing a silicone resin in the scope of claims 1 or 2 at a temperature of 20 ° C to 350 ° C, and The silicone resin is cured and heated at a temperature of 350 ° C to 600 ° C to cause the pyrolysis of the R2 group, thereby forming a nanoporous silicone resin. 15 5. A nanoporous silicone resin coating obtained by a method according to any one of claims 10 to 13. 16. The nanoporous silicone resin coating according to item 15 of the patent application scope, which has a pore diameter of less than 20 nanometers. 17. The nanoporous silicone resin coating according to item 15 or 16 of the scope of patent application, which has a dielectric constant of less than 2. 18. — A nanoporous silicone resin obtained by the method of claim 14 in the scope of patent application. 19. The nanoporous silicone resin according to item 18 of the scope of patent application, which has a pore diameter of less than 20 nanometers. O: \ 66 \ 66886-930506.ptc Page 27