TW591057B - Siloxane resins - Google Patents

Abstract

This invention pertains to a siloxane resin composition comprising R1SiO3/2 siloxane units, R2SiO3/2 siloxane units and (R3O)bSiO(4-b)/2 siloxane units wherein R1 is an alkyl group having 1 to 5 carbons, hydrogen, or mixtures thereof; R2 is a monovalent organic group having 6 to 30 carbons; R3 is a branched alkyl group having 3 to 30 carbons, b is from 1 to 3; and the siloxane resin contains from 2.5 to 85 mole percent R1SiO3/2 units, 2.5 to 50 mole percent R2SiO3/2 units and 5 to 95 mole percent (R3O)bSiO(4-b)/2 units. The siloxane resin is useful to make insoluble porous resin and insoluble porous coatings. Heating a substrate coated with the siloxane resin at a sufficient temperature effects removal of the R2 and R3O groups to form an insoluble porous coating having a porosity of 1 to 60 volume percent and a dielectric constant in the range of 1.5 to 3.0.

Description

591057 V. Description of the Invention (Field of the Invention: this month, about the silicone resin including the ruler, the sichuan siloxane unit, r2s, ο% siloxane unit, and (R OhSiO ^ M / 2 siloxane unit) A composition wherein R1 is independently selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, hydrogen or the like, and R is independently selected from the group consisting of a monovalent organic group having 6 to 30 carbon atoms and having 6 A monovalent substituted organic group of 30 to 30 carbon atoms; r3 is independently selected from the group consisting of a branched fluorenyl group having ⑴0 carbon atoms and a substituted branched chain alkyl group having 3 to 3 g carbon atoms, 13 is 丨 to 3. The invention is also related to insoluble porous resins and insoluble porous coatings prepared from siloxane resin compositions. BACKGROUND OF THE INVENTION Semiconductor devices typically have one or more types of integrated circuit components that can be used to electrically couple separate circuit components. 1C) An array of patterned connection layers. The connection layers are generally separated by an insulating or dielectric coating. Previously, silicon oxide formed using chemical vapor deposition (CVD) or plasma etching technology (PECVD) was the most dielectric coating. Common materials. However, when circuit components and When the space between the elements decreases, the relatively high dielectric constant of the silicon oxide coating (ie, about 4) is not suitable for providing proper electrical insulation. In order to obtain a dielectric constant lower than that of stone oxide, 'it can be used Dielectric coatings based on resins based on oxidant firing. Examples of such coatings are described in US Patent No. 3,615,272 to CoUins et al. And US Patent No. 4,7,56,977 to Haluska et al. ' Formed by hydrogen silsesquioxane resin. Although this coating can provide low dielectric constant of i ^ CVD or PECVD silicon oxide coatings, it can also provide other benefits, such as improved gap filling and surface flatness, but usually the coating The dielectric constant is limited to about 3 or more. -5- Applicable to China National Standard Kit (CNS) A4 specification (210X297 mm) 0751 591057

AT B7 V. Description of the invention (2 The dielectric constant of the insulating coating is known to be an important factor for low power consumption, 1C, and 1C of signal delay. When the size of iC continues to shrink, the importance of this factor increases. Because of A ', it is expected to provide a resin material mainly based on siloxane with a dielectric constant lower than 3 and a method for manufacturing the material. In addition, it is hoped that it can provide high crack resistance to the coating. Oxygen-firing resin and method for manufacturing the same. Moreover, it is hoped that the silicone-based resin can be obtained by standard manufacturing techniques such as spin coating. The dielectric constant of known solid coatings is The density of coating materials decreases and decreases. The density of porous coatings is generally lower than that of corresponding solid coatings.

U.S. Patent No. 5,446,088 to Haluska describes a method for co-hydrolyzing silanes of the formula HSi (OR) 3 and Si (OR) 4 to form a co-hydrolysate used in coating formation. The R group is an organic group containing -20 carbon atoms. When it is bonded to silicon through an oxygen atom, it forms a hydrolyzable substituent. The most hydrolyzable groups are methoxy and ethoxy. Hydrolysis is carried out in a polar solvent containing acidified oxygen. The co-hydrolysate in the solvent is applied to the substrate, the solvent is evaporated and the coating is heated to 50 to 10,000. (:, The coating is converted into silicon oxide. Haiuska & does not disclose stone yaki with branched oxy groups.

Chung et al. U.S. Patent No. 6,231,989 describes a method for forming a porous coating material from a hydrospar resin. The porous network is a method of depositing a coating on a substrate by using a solution including a hydrosilsesquioxane resin and a solvent so that at least ^ vol% of the solvent remains in the coating after deposition. The coating is then exposed to an environment including alkaline catalysts and water; the solvent evaporates from the coating to form a porous network with a dielectric constant between 1.5 and 2.4.

Smith et al. WO 98/4972 No. 1 describes a method for forming nanometers on a substrate. Freshness (CNS) Λ4 size (21 () x 297) 591057

Method of porous dielectric coating. The method includes the steps of blending an alkoxysilane with a solvent composition and optionally water; depositing the mixture on a substrate while evaporating at least a portion of the solvent; placing the substrate in a closed chamber, and opposing the chamber. Vacuum is applied to lower the pressure to atmospheric pressure; the substrate is exposed to water vapor at a pressure lower than atmospheric pressure, and then the substrate is exposed to alkali vapor.

U.S. Patent No. 6,022,814 to Mikoshiba et al. Describes a resin based on hydrogen and methylsiloxane with an organic substituent that can be removed at a temperature between 250 C and the temperature of the Plexiglas transition point, formed on a substrate Method of silicon oxide film. The recorded properties of the silicon oxide film include a density of 0.8 to 14 g / cm3 ', an average pore diameter of 1 to 3 nm, a surface area of 600 to 1500 m2 / g, and a dielectric constant of 2.0 to 3.0. The organic substituents disclosed that can be oxidized at 250 ° C or higher include substituted and unsubstituted alkyl or alkoxy groups. Examples include 3,3,3-trifluoropropyl, o-phenylethyl Group, tert-butyl group, 2 • cyanoethyl group, —yl group, and vinyl group.

Mikoskiba et al. J. Mat. Chem., 1999, 9, 59 1-598 proposed a method for producing angstrom-sized pores in methylsilsesquioxane to reduce the density and dielectric constant of coatings. Spin-coated a copolymer with a methyl (trisiloxysilyl) unit and an alkyl (trisiloxysilyl) unit on a substrate, and heated at 250 ° C to obtain a hard siloxy Alkyl. The coating is then heated at 450 ° C to 500 ° C to remove the thermally unstable substrate and leave a hole the size of the substituent, with a dielectric constant of about 2.3. Trifluoropropyl, cyanoethylphenylethyl and propyl can be used as the thermally unstable substituent.

Japanese Patent Publication No. 5-333553 of Ito et al. Describes that in the presence of a proton acceptor, hydrolyzation of diethylfluorenylbis (third-butoxy) silane produces a volume 0 national standard (CNS > Λ4) Specifications (210 × 297 mm > 591057 A7 B7 V. Description of the invention (4 Preparation of Shixiu oxyfiring resin containing the oxygen and Shixuan alcohol functions. The resin is hardened in the presence of photoacid, and then heat-treated in the future to form It looks like a coating of 〇2 and can be used as a photoresist material manufactured by 1C. It has been found that the organic group with 6 to 30 carbon atoms and the branched stone with 3 to 30 stone antiatoms will have oxygen appearance. Based on the sintered resin, many advantages can be obtained, such as improved storage stability, increased modulus and porosity of the hardened resin. At the same time, the dielectric constant can be maintained between 15 and 30. Therefore, it was invented -The purpose is to provide-a stone m composition having improved storage stability. Another object of the invention is to provide a method for producing a siloxane resin, and to make these tree-cured hardened ia dielectric constants of 15 to 30. , Porosity is ^ to volume =, and modulus is 1.0 to 10 Gpa Method for insoluble porous coatings. The advantage of this special coating is that it can be formed using ordinary thin film processing. SUMMARY OF THE INVENTION The present invention relates to a silicone resin composition, including (A) 2.5 to 85 moles of Si. / 2 Shi Xi oxygen hospital unit, wherein Ri is independently selected from the group consisting of alkyl groups having 5 to 5 carbon atoms, hydrogen and mixtures thereof; line (8) 2.5 to 50 mole ears 1 ^ 3 丨 〇3 / 2 Shi Xi oxygen burning unit, wherein Hua 2 is independently selected from the group consisting of a monovalent organic group having 6 to 30 carbon atoms and a monovalent substituted organic group having 6 to 30 carbon atoms; and (C) 5 to 95 A mole fraction of the siloxane unit, wherein R3 is independently selected from the group consisting of a branched alkyl group having 3 to 30 carbon atoms and a branched substituted alkyl group having 3 to 30 carbon atoms, and b is 1 to 3. Ingredients The total amount of (A), (B), and (C) is 100 mol parts, and the sum of the components (A), (B), and (c) is at least 50% of all the siloxane units in the resin composition -8 National Standards (CNS) A4 specification (210X 297 mm) 591057 5. Description of the invention (5) The present invention also relates to a silane or Silane mixtures, silane or silane mixtures of the formula R2SiX3 'and (R30) eSix (4 e) sintered or silane mixtures, where R1 is independently selected from the group consisting of alkane groups having 1 to 5 carbon atoms, hydrogen and mixtures thereof; Is independently selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and substituted monovalent organic groups having 6 to 30 carbon atoms; R3 is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms And substituted branched alkyl; c is 1 to 3, and X is a hydrolyzable group or a hydroxyl group. The present invention also relates to a method for forming an insoluble porous resin and a method for forming an insoluble porous coating on a substrate. The insoluble porous coating has a dielectric constant of 1.5 to 3.0, a porosity of 1 to 60% by volume, and a modulus between 1.0 and 10 Gpa. Detailed description of the invention The silicone resin composition includes: (8) 2.5 to 85 moles of Han 1§; 丨 〇 / 2/2 Shixi oxygen firing unit, wherein & 1 is independently selected from the group consisting of 5 carbon atoms of alkyl, hydrogen and mixtures thereof; (8) 2.5 to 50 moles of ruler 28 丨 〇3 / 2 Shixoxane unit, where ruler 2 is independent, self-contained 3 has 6 to 30 A monovalent organic group of carbon atoms and a monovalent substituted organic group having 6 to 30 carbon atoms; and / 05 to 95 moles of jealousy 0) Na (") / 2 Shi Xixuan units, which makes R1 Independently selected from the group consisting of branched radicals having 3 to 30 carbon atoms and branched substituted radicals having 3 to 30 carbon atoms, b is 1 to 3. The total of components ⑷, (B) and (C) The amount is 100 mol parts, and the sum of the ingredients (Ab and γ) is at least 50% of the total siloxane units in the resin composition. The preferred silicone resin contains 30 to 60 mol parts on average. Ingredients (eight), 10 to 25 moles: • 9- 591057

AT _______ B7__ 5. Description of the invention (6) Sub-component (B) and 20 to 50 mol parts (c), wherein the total amount of components (A), (B) and (C) is 100 mol parts, and The sum of the components (A), (8), and (C) is at least 700/0 of all the sintering units in the resin composition. There is no particular limitation on the structure of the oxane resin. The silicone resin may be substantially fully condensed, or may be only partially reacted (also containing Si-OR of less than 10 mole% and / or Si-OH of less than 30 mole%). Partially reactive siloxane resins are listed (but not limited) such as —), R2Si (X) dO (3_d / 2) and

Si (X) d (〇RJ) f〇 (4-cUf / 2); wherein R2 & R3 is as defined above; each X is independently a hydrolyzable group or a hydroxyl group; and d and f are 1 To 2. A hydrolyzable group is an organic group attached to a silicon atom (Si-OR) via an oxygen atom to form a silicon-bonded alkoxy group or a silicon-bonded fluorenyloxy group. R is listed as (but not limited to) a linear alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, and a group having 1 to 6 carbon atoms. Fluorenyl, such as formamyl, ethynyl, propionyl, butylamyl, pentamyl, or hexamethylene. The siloxane resin may also contain less than about 10 mole% Si04 / 2 units. The weight-average molecular weight of the oxane resin is between 4,000 and 16,000, and preferably between 5,000 and 100,000. R1 may be a linear alkyl group having 1 to 5 carbon atoms, hydrogen, and a mixture thereof. Examples of the alkyl group are, but are not limited to, methyl, ethyl, propyl, butyl, and pentyl. Preferably, R1 is methyl, hydrogen or a mixture thereof. R may be a substituted or unsubstituted straight chain, chain or cyclic monovalent organic group having from 6 to 30 carbon atoms. The substituted organic group may be substituted with a hydrogen atom (C-H) which hinders bonding. The substituted r2 group is listed as (but not limited to) _ such as gas or fluorine, diethyl ether, formula CH30 (CH2) m0) p (CH2) q_ (of which m -10- this paper, National Standard (CNS) ) Λ4 specification (210 > < 297 male I) 591057 A7 B7 V. Description of the invention (7), p and q are positive integers, and preferably a positive integer of 1 to 9) poly (oxyethylene) , Alkoxy, fluorenyl, fluorenyl, alkoxycarbonyl, and trialkylsiloxy. Examples of R2 include (but are not limited to) hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, triisobutyl, tetraisobutyl, trimethylsilyl Hexyl, octadecyl, CI ^ CHOhOCI ^ CHk, CH30 (CH2CH20) 7.9 (CH2) r, (CH3) 3CCH2 (CH3) 2C (CH3) 3CCH2CHCH2-, cf3 (cf2) 5ch2ch2-, phenylethyl , P-methylphenylethyl, p-methoxyphenylethyl, and p-bromophenylethyl, R2 is preferably a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms. R3 is a substituted or unsubstituted branched alkyl group having 3 to 30 carbon atoms. The substituted branched alkyl group may be substituted with a substituent which replaces a carbon atom-bonded hydrogen atom (C_H). The substituted R2 groups are (but not limited to) halogens such as gas and fluorine, alkoxycarbonyl groups as described in the formula-(CH2) aC (0) 0 (CH2) bCH3, and formulas as-(CH2) aO (CH2 ) bCH3 resin oxy substituent and carbonyl substituent according to formula-(CH2) aC (0) (CH2) bCH3, and b2O. The unsubstituted R3 groups listed are (but not limited to) isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl, 2-methylbutyl , 2-methylpentyl, 2-methylhexyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, and the like. A preferred R / is a tertiary alkyl group having 4 to 18 carbon atoms, and a more preferred R3 is a third butyl group. The method for preparing the siloxane resin includes: combining the following components for a sufficient time and temperature to prepare the siloxane resin: (a) a silane or silane mixture of the formula R ^ SiX], wherein R1 is independently selected from 11-country Standard (CNS) A4 specification (210X297 public love) 591057 A7 B7 V. Description of the invention (8 Contains a cyano group having 1 to 5 carbon atoms, hydrogen or a mixture thereof, X is independently a hydrolyzable group or a hydroxyl group; (b) Silane or silane mixture of the formula R2SiXs, wherein R2 is independently selected from the group consisting of a monovalent organic group having 6 to 30 carbon atoms and a substituted monovalent organic group having 6 to 30 carbon atoms, and X is independently a hydrolyzable group or a hydroxyl group ; (C) Shi Xixuan or Shi Xiyan mixture of formula (R / OhSiX ^ q, wherein r3 is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and branches having 3 to 30 carbon atoms A substituted alkyl group, c is 1 to 3 (inclusive), X is independently a hydrolyzable group or a vial group; and (d) water. Silane (a) is a silane or a mixture of silanes of the formula R ^ SiXs, where Ri is independently selected Self-contained alkyl, hydrogen or mixtures thereof having 1 to 5 carbon atoms as described above. Preferred is R1. Methyl, hydrogen, or a mixture thereof. X is a hydrolyzable group or a hydroxyl group. Π hydrolyzable group means that more than 80 mole% of X reacts with water under the reaction conditions to form a siloxane resin (hydrolysis). Hydroxyl Is a condensable group, of which at least 70 mol% reacts with another X group bonded to a different silicon atom to condense and form a siloxane bond (Si-0-Si). The hydrolyzable group is a! | Chloride, amine, or an organic group attached to a silicon atom (Si-OR) via an oxygen atom to form a silicon-bonded alkoxy group or a silicon-bonded fluorenyl group. When X is an amine group It is generally limited to compositions in which R1 is an alkyl group or contains less than 10 moles of hydrogen because amine groups are not good for hydrogen-containing siloxane resins. Moreover, when X is an amine group, It is generally used in an amount of less than about 30 mole% because the resulting siloxane resin may contain more than 30 mole% of SiOH. R is listed as (but not limited to) a linear alkyl group having 1 to 6 carbon atoms' Such as methyl, ethyl, propyl, butyl, pentyl or

____- 12-

Home Standard (CNS) A4 Specification (210X297 mm I 591057

AT B7 V. Description of the Invention (9) Hexyl, and fluorenyl having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl or hexamyl. The preferred stone yaki (a) is trigas silane, methyltrigas silane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, or methyltriethoxysilane, because of these Both are easily available. Generally, the content of silane (a) is 2.5 to 85 mol parts per 100 mol parts of combined silane (heart, silane (b) and silane (c), and preferably 30 to 60 mol parts (same Basic). Shibuki-yaki (b) is a mixture of Shiyaki-yaki or Shiyaki-yaki of RS iX3, where r2 is independently selected from the group consisting of a monovalent organic group having 6 to 30 carbon atoms as described above, and having 6 Substituted monovalent organic groups of 30 carbon atoms. X is independently a hydrolyzable group or a hydroxyl group as described above. Preferred silanes (b) are R2SiCl3, R2Si (OMe) 3, and R2Si (OEt) 3, where Me represents a methyl group. And Et represents ethyl 'because they are easily available. Generally, the content of silane (b) is 2.5 times the total amount of combined silane (a), silane (b), and silane (c) per 100 mol parts. To 50 mol parts' and preferably 10 to 25 mol parts (on the same basis). Ishigaki (c) is a silane or silane mixture of formula (R3〇) eSiX (4-c), where R3 is as described above Is generally independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and substituted branched alkyl groups having 3 to 30 carbon atoms, c is 1 to 3, and X is independently hydrolyzable as described above Or hydroxy. The preferred silanes are the second and third butoxydioxysilanes, the second and third butoxydihydroxysilanes, the second and third butoxydioxysilanes, and the second and third butoxydiethoxylates. Silane, and second and third butoxydiethyloxysilane, because they are easily available. Generally, the content of silane (c) is 100 mol parts combined of silane, silane (b) and silane (c). Amount) to 95 mol parts, and preferably 20 to 50 mol parts (on the same basis). The size of this paper is applicable to the National Ginseng Standard (CNS) A4 specification (210X297 public goods) 591057 A7 B7 V. Description of the invention (The content of water is the amount that can hydrolyze the hydrolyzable group X. Usually the content of water is silane (a ), (B) and (C) are 0.5 to 2.0 moles per mole of water, and more preferably 0.8 to 1.2 moles (same basis). The reaction to form the siloxane resin can be in a liquid state, It is carried out with or without a solvent. If a solvent is used, it may include a suitable organic solvent that is a solvent containing functional groups participating in the reaction and is a silane (a), (b), and (c). The solvents listed are ( (But not limited to) saturated fats such as n-pentane, hexane, n-heptane, isooctane and dodecane; cyclolipids such as cyclopentane and cyclohexane; aromatics such as benzene and toluene; Dimethyl form, such as tetrachlorobenzene (THF) and No. 17 burn; _ such as methyl isobutyl ketone (MIBK); halogen-substituted alkane such as trigas ethane '_ chemical formula such as > Odor and gas, and alcohols such as methanol, ethanol, propanol, butanol. In addition, the above solvents can be used as a co-solvent in combination of two or more. Are aromatic compounds and cyclic ethers, and the best are toluene, 1,3,5-xylene and tetrahydrofuran. When using a solvent, the total weight of the solvent and silanes (a), (b), and (c) As the standard, the amount of the solvent is generally 40 to 95% by weight. Preferably, the solvent is 70 to 90% by weight (the same basis). The components (a), (b), (c), (d) and selected Solvents (if used) can be combined in any order, as long as there is contact between any hydrolyzable group (χ) and water. Usually, the silane is dissolved in the solvent, and then water is added to the solution. Part of the reaction is usually based on the above Occurs when the ingredients are combined. However, to increase the rate and extent of the reaction, various auxiliary measurements such as temperature control and / or stirring can be used. The temperature at which the reaction proceeds is not limited as long as it does not cause significant gelation or harden the silicone resin product That is, usually the temperature may be between 20t and i 50t, and the preferred temperature is 20 ° C to 100 ° C. When X is an ethoxy group such as ethoxy group

591057 Λ 7 Β7

The reaction was carried out at 5m. The time for the shape cut depends on the number of factors, such as (but not limited to) the special siloxane used, the temperature, and the Rl, r2ar3 molar ratios required in the reaction product. Usually, the reaction time is from minutes to hours. In order to increase the molecular weight of the prepared oxox resin and improve the storage stability of the siloxane resin, it is preferable to perform the main step, followed by the above reaction or a part thereof. " Main body 'means that the reaction is carried out at 40t to the reflux temperature of the solvent for several hours to increase the weight. It is better to use the knife. The reaction compound is heated to make the weight average molecular weight of the heated resin in the Shixi Oxygen Institute between Between about 5,000 and 500,000. When X is a fluorenyloxy group such as ethenyloxy group, a considerable acid such as acetic acid is produced as a by-product of the reaction. Since the presence of acetic acid can adversely affect the stability of the siloxane resin product, any acetic acid needs to be neutralized. Neutralization of the by-product acetic acid can be carried out by contacting the reaction mixture with a neutralizing agent or by removal by distillation. Distillation usually removes acetic acid by adding a solvent such as toluene (if not already present), and azeotroping with the solvent under reduced pressure and heating (such as up to 50 ° C). If a neutralizing agent is used, sufficient tests are required to neutralize the remaining acetic acid and insufficient tests, so that the silicone resin product will not be catalytically rearranged. Examples of suitable bases include calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonia, calcium oxide or hydroxide. Neutralization can be achieved by any suitable fraction, such as stirring in a powdered neutralizer, followed by filtration or passing the reaction mixture and any additional solvents through or through a granular neutralizer bed that does not affect flow . The above main steps are generally performed after neutralization, and / or after removing by-product acetic acid. When X · is an oxide group, H 'reaction by-product is formed. Because of the existence of Ηχ _-15- 本 纸 # National Standard (CNS) A4 specification (210M97 male stone 12 V. Description of the invention (It will have a negative impact on the stability of the siloxane product, so it needs to be neutralized or removed.) Known methods to neutralize or remove Ηχ. For example, when HC1 by-products are generated, the reaction tank can be provided with gas removal and removal. Or HQ can be neutralized using the above process. Or the siloxane resin solution can be washed with water until Neutralize and remove HC1. When a sufficient amount of HX is formed (ie, silane (a), (b) & (c), all of which contain χ, where X is a dentate group), it is possible that silane (c) All OR groups in the resin are removed during the formation of the siloxane resin, so that the siloxane resin composition includes (A) and (B) siloxane units, and additional Si04 / 2 units. Alkane resin can be collected in a solid state by removing the solvent (if a solvent is used). The method of removing the solvent is not limited, and many methods are known in the art. For example, it can be used under vacuum and heating (50. (: To 120. (:), remove the solvent by distillation. In addition, if the siloxane resin In special solvents, the solvent can be exchanged by adding the second solvent and distilling off the first solvent. Siloxane resins containing more than 10% by weight of silicon-bonded hydrogen (Si-H) are used in solution The state is maintained, and those with less Si-H can be stored in a solid state. The insoluble porous resin can be heated by the silicone resin at a sufficient time and temperature to harden the silicone resin and remove R2 & R3. The term "removed" means that more than 80 mole% of the R2 and R30 groups bonded to the silicon atom have been used to generate volatile fumes and fumes in the coating. Partially removed, thus forming an insoluble porous resin. This heating can be performed in a single-step process or ordered in a two-step process. According to the two-step heating process, the siloxane resin is first heated at a sufficient temperature for a sufficient time , Hardening without obvious removal of R2 and R30 groups. Generally, the temperature -16- 591057 13 V. Description of the invention (degrees can be more than 20 C to 3 50 0 minutes to hours. Then harden it Silicone fired resin at more than 3 50. (: to ratio The main chain of the silicone resin or the R group bonded to the silicon atom (as described above) is further heated at a low temperature to remove the R- and R / 0 groups from the silicon atom. Generally, the removal step is performed at a temperature exceeding It is carried out at 35.0 to 600 ° C, and the preferred temperature is 400 ° C to 5 50 ° C. During the hardening and heating steps, more than 90 mol% of the Ri group-containing alkyl group is left in the silicon In the siloxane resin, more than 70 mol% of hydrogen-containing hydrogen groups remain in the siloxane resin. The final porosity control of the insoluble porous resin can be controlled by the R2 and R / 0 groups in the siloxane resin and The heating method of the siloxane resin is controlled. The insoluble porous resin formed by the siloxane resin containing both R2 group and R30 group is added to the siloxane resin and the same is contained in the same composition (that is, R2 or R30). 20 mol% of deradicalized is about the same). Siloxane resin added with only or r30 group, and hardened under the same conditions, will generally increase the porosity, and usually increase about 丨〇Volume 0 / 〇. In a single step process, the hardening of the siloxane resin and the removal of R2 and r30 groups are caused by the decomposition of the siloxane group that is more than 201 to less than the siloxane resin main chain or the silicon atom-bound Ri group described herein. Heating at a low temperature is performed simultaneously to remove the R2 and R30 groups from the hardened siloxane resin. Generally, the better hardening / removal step is performed at a temperature exceeding 35 ° C. to 600 ° C., and the optimal temperature range is 400 ° C. to 550 ° C. The better heating is performed in an inert gas. However, other gases can also be used. The inert gas used in this article includes (but is not limited to) nitrogen, helium, and argon with an oxygen content of less than 50 ppm, and preferably less than 15 ppm. Heating can also be performed under vacuum To the effective atmospheric pressure of the above gases, and at any effective oxidation or non-17, this paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 591057 A 7 ______B7 V. Description of the invention (14) Oxidation gaseous state Environment, such as air, 02, oxygen plasma, ozone, ammonia, amines, water vapor, Nβ and hydrogen, etc. Insoluble porous resin can be used to have controllable porosity and up to 600. South Wen's stable porous materials, such as formed selective gas or liquid permeable membranes, catalyst support materials, energy storage systems such as battery and molecular separation and isolation. The term "porosity" means that the porosity is within 1 to 60% by volume of insoluble porous tree . The preferred porosity is 10 to 60% by volume. The modulus of the insoluble porous resin is between 1.0 and 10 Gpa. The sintered resin can prepare a porous coating on the substrate as follows: ( A) The substrate is coated with a coating composition including a silicone resin composition containing the following components: (Strong) 11% of 2.5 to 85 mol parts of a 3/2 siloxane unit, wherein the ruler 1 is independent Selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, hydrogen and mixtures thereof; (b) 2.5 to 50 mol parts of R2Si03 / 2 siloxane units, wherein r2 is independently selected from the group consisting of Monovalent organic groups having 6 to 30 carbon atoms and monovalent substituted organic groups having 6 to 30 carbon atoms; and (c) 5 to 95 mol parts (RJ〇) bsi〇 (4 b) / 2 Siloxane units, wherein RM is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and branched substituted alkyl groups having 3 to 30 carbon atoms, and b is 1 to 3. Ingredient (a) The total amount of (b) and (c) is 100 mol parts, and the sum of the components ⑷ and ⑷ is at least 50,000 / 〇 of all the siloxane units in the resin composition; (B) the coated The substrate is heated to Temperature sufficient to harden the coating composition, and _____ 18 national standards 113 ijl (CNS) A4 specifications (21 () x 297)

AT

(C) The coated substrate is further heated to a temperature sufficient to remove the R2 and r30 groups from the hardened coating composition, thereby forming an insoluble polytropic coating on the substrate. (A), (b), and (c) of each 100 mol parts of the preferred siloxane resin are averaged at 30 to 60 mol parts, 10 to 25 mol parts, and (C) 20 to 50 moles, and all and at least 70% of the total siloxane units in the resin composition. The epoxy resin is generally added to a substrate as a solvent dispersion. The available solvent d I 3 can dissolve or disperse the siloxane resin to form a homogeneous liquid mixture 'without affecting the coatings or substrates or the mixture of agents. The solvent may generally be free of functional groups that can participate in the reaction of the siloxane resin, such as any of the hydroxyl groups; The amount of t / cereal that is used to dissolve the oxidized sintered resin to the concentration required for special applications. The content of the general solvent is 40 to 95% by weight, preferably 7G to 70% by weight based on the weight of the siloxane resin and the solvent. If Qian Zhizhi has been left in the solvents mentioned above, a solvent can be used in the coating of the substrate, or if necessary, a simple solvent exchange can be performed by adding the second solvent and distilling off the first solvent. Special methods for applying a siloxane resin to a substrate include, but are not limited to, spin coating, dip coating, spray coating, dynamic coating, screen printing, or other. The preferred coating method is spin coating. When a solvent is used, the solvent is evaporated from the coated substrate to deposit a siloxane resin coating on the substrate. Evaporation ^ Any suitable device can be used, such as simple air drying caused by exposure to the surrounding environment, vacuum or medium temperature heating (up to 50ΐ) or early in the hardening process

16W1057 V. Description of the invention (phase). When spin coating is used, the extra drying method is minimal, because the spin will remove the solution. After coating on the substrate, the silicone resin coating is sufficient to make the silicone tree It is hardened and heated at a temperature that removes the R2 and R3o groups bonded to the Shi Xi atom, thereby forming an insoluble porous coating. "The hard coating composition " the word think " the coating is basically Insoluble in the solvent that deposits the siloxane resin on the substrate, or any of the solvents described above for coating the siloxane resin. "Removed, means more than 80 mole% of R2 bonded to the silicon atom And r30 groups have been removed with the volatile hydrocarbons and hydrocarbons produced during coating to form a porous resin. Heating can be performed in a single step process or in a two step process. Heating in two steps In the manufacturing process, the siloxane resin is first heated at a sufficient temperature to be hardened without significantly removing the R2 and R30 groups. Generally, the temperature can be more than 20C to 350C. Then the hardened stone oxy-fired resin is cured at more than 35 〇C to specific silicone resin The main chain or bond is further heated at a temperature where the Rl group of the silicon atom (as described above) decomposes to remove the R2 and R30 groups (leaving groups) from the silicon atom. Generally, the better removal step is at temperature It is carried out at a temperature of more than 350,000 to 600, and the preferred temperature is 400 ° C to 550 ° C. During the hardening and heating steps, more than 90 mol% of the Ri group-containing alkyl group is left in the siloxane resin And more than 70 mol% of hydrogen-containing Ri groups remain in the siloxane resin. In a single step process, the curing of the siloxane resin and the removal of the R2 and R30 groups are carried out at temperatures in excess of 20 ° C to Heating is performed at a temperature lower than the decomposition temperature of the siloxane resin main chain or the Ri group bonded to the silicon atom as described herein to perform the 'removal of the R2 and r30 groups from the hardened coating composition. The hardening / removing step is performed at a temperature exceeding 35 ° C to 600 ° C, and the optimal size of the paper is _-20- "Home Standard (CNS) A4 Specification (210X297mm) 17 V. Invention Note (The temperature range is from 400 ° C to 550. (: Gap control can be controlled by hard-oxygen resin heating method. In the end it is not possible The R and R 0 groups in the pores of the porous resin and the siloxane resin are preferably heated in an inert gas, but other gases can also be used. The inert gas used herein includes (but is not limited to) an oxygen content lower than 5—, and preferably less than 15 ppm of nitrogen, helium and argon. It can also be added directly to the effective atmospheric pressure of the above-mentioned gas II, and in any effective oxidation or emulsification gaseous environment, such as Including air, 02, oxygen plasma, ozone, ammonia, amine, water vapor, N20 and hydrogen, etc. By the above method, thin (less than 5 microns) insoluble can be prepared on the substrate. Porous coating. The thickness of the insoluble porous coating is preferably 3 to 25 microns and the thickness is more preferably 0.5M.2 microns. This coating flattens the surface of various substrates and has excellent adhesion. Any type of heating method, such as the use of a quartz tube furnace, convection furnace, or radon or microwave energy, can provide the functions of this article. Similarly, the rate of heating is generally not an important factor, but the most practical and best way to heat the coated substrate is as fast as possible. The insoluble porous coatings prepared herein can be prepared on any substrate. However, this coating is particularly useful for electronic substrates. "Electronic substrate" means silicon-based devices and gallium-arsenic-based devices used in the manufacture of semiconductor components, including focusing planar arrays, photovoltaic devices, photocurrent cells, optical devices, such as transistors , 3-D devices, silicon-on-insulator devices, supercrystalline silicon devices, etc. On the right, additional coatings can be applied on top of the insulating porous coating. These can include, for example, Si02 coatings, Coating of silicon, coating containing silicon carbon, containing 591057 A? _______B7 V. Description of the invention ^ ~~ '~

Silicon II coatings, siloxane-containing coatings, silicon-nitrogen-carbon-containing coatings, and / or diamond-like coatings prepared from 揲 疋 -type SiC · H, diamond, silicon nitride deposition (ie, CVD, pEcvD, etc.) . The method of applying the coating is known in the art. The method of applying additional coatings is not limited, and the coating is generally applied by chemical vapor deposition techniques, such as thermochemical vapor deposition (TCVD), photochemical vapor deposition, plasma enhanced chemical vapor deposition (pECVD), electronics Cyclotron resonance (ECR) and jet vapor deposition. Additional coatings can also be applied by physical vapor deposition techniques such as sputtering or e-beam evaporation. These processes include adding energy to the evaporated species in the form of heat or plasma to generate the required radiation, or focusing the energy on a solid sample of the material, causing its deposition. The insoluble porous coating formed by this method is particularly useful as a coating on electronic devices such as integrated circuits. The dielectric constant of the insoluble porous coating layer prepared by this method is between 1.5 and 3, and more preferably between 1.5 and 2.5 for the dielectric coating layer. The term "porosity" means an insoluble porous coating having a porosity of 1 to 60% by volume. The preferred porosity is between 0 and 60% by volume. The modulus of the insoluble porous coating is between 10 and 10 Gpa. Examples The following non-limiting examples are provided to make the present invention easier for those skilled in the art. The weights in the examples are expressed in grams (g). The molecular weight is the weight average molecular weight (Mw) series average molecular weight (Mn) measured by gel permeation chromatography. The analysis of the resin composition of Shixi Oxygen Institute was performed using 29Si nuclear magnetic resonance (NMR). However, the measurement of the porosity of the absorption was performed using the QuantaChrome Autosorb 1 MP system. The hardened siloxane resin was ground to a fine powder ' for several hours before being placed in the sample cell, and added to the analysis station. Surface area is based on 1 007nQQ -22- in this paper rule " ^ 标 _NS ^ 4 specifications (2ι〇 χ Norwegian public f

Binding

k 591057 A7 ___ B7 Note 7 19) " " ~~

Br * unauer-Emmett-Teller method. The total pore volume is determined by the amount of vapor absorbed in the pores at a relative pressure close to 1 (P / P0 = 0.995), plus the pores filled with the absorbent. Backbone density is measured using a helium pycnometer. Backbone density represents the actual density of the siloxane resin solid structure without any internal voids, cracks or pores in the measurement. Percent porosity is calculated from backbone density and total pore volume. The refractive index (RI) and coating thickness were measured using a Wo oil am M-88 spectroscopic ellipsometer. In the following examples, Me represents methyl, tBu represents third butyl, and AcO represents acetoxyoxy 'Et represents ethyl. In the table below, n.m • stands for special properties that have not been measured. Example 1 This example illustrates the formation of a sintered oxygen fired resin composition in which R 1 is hydrogen, R 2 is an organic group having 8 to 22 carbon atoms, and R 3 is a third butyl group. Add HSi (OEt) 3 (A), (AcO) 2Si (OtBu) 2 (B), and R2Si (〇Me) 3 (C) in the amounts described in Table 1 to 75 g under argon in a bottle Tetrahydropyran (thf). Deionized water (D) was added to the bottle, and the mixture was stirred at room temperature for 1 hour. 75 grams of toluene was then added to the mixture. The solvent was removed using a rotary evaporator to obtain a viscous oily sintered resin, which was then immediately dissolved in 150 g of toluene. The by-product acetic acid was removed by heating to 38t ' with azeotrope under reduced pressure. The resin was dissolved in toluene and azeotropically dried and heated in refluxing toluene for 1 hour. The solution was filtered and the solvent was removed by evaporation to obtain a siloxane resin product. The summary of M lipid synthesis is listed in Table 1 and R2 in r 2 S i (0 M e) 3 (C) is listed in Table 2. The analysis of the resin structure and molecular weight is shown in Table 3.

This paper> 〇 Set the appropriate angle ψ -23- Γ family standard (CNS) A4 specifications (210X297) 591057 AT B7 V. Description of the invention (20 Table 1 Resin synthesis example edited (A) (g) ( B) (g) (C) (g) (D) (g) Toluene (g) in the reflux step Yield (g) Appearance M 25.3 40.0 19.3 14.4 250 43.6 Oil 1-2 22.5 40.0 25.7 14.4 250 46.7 Oil 1 -3 36.5 20.0 25.6 16.4 250 44.4 Oil 1-4 12.4 10.0 10.3 6.7 110 19.6 Wax 1-5 29.0 40.8 10.3 14.0 120 37.0 Wax 1-6 40.0 25.0 11.8 13.2 250 41.0 Oil 1-7 40.0 25.0 25.5 15.1 250 47.4 Oil 1 -8 40.0 25.0 21.3 14.8 250 49.2 Oil 1-9 40.0 25.0 16.0 13.1 250 42.9 Oil Table 2 Example number R- group in (C) 1-1 CH3 (CH2) i7- 1-2 CH3 (CH2) i7- 1- 3 ch3 (ch2) 17- 1-4 CH3 (CH2) i7- i 1! 1-5 ch3 (ch2) 17--!! 1 1-0! CH3〇 (CH2CH2〇) 7_9 (CH2) 3- 丨 C 'f. 丨; (VH 2)} 丨 (X' H, CH,-1 ί-Ν (CM3) 3CCH2 (^. 'M3 C'ihCi-iCH2- 1 (: 卜' 丨 CF'sCT 卜 CTi, -ΙΠ7 ^ α.ο_1 —--- ί Standard (CNS) A4 specification (210X297 mm) 591057 A7B7 V. Description of the invention (21 Table 3 (then 丨 03/2) 〖, (1123 丨 〇3 / 2 to 1111) 1) 8 丨 044/2) Resin analysis example based on reactant Molar ratio of f / g / h Molar ratio of Pg / h (29SiNMR ) Μη Mvv ij 1 1 1! 1-1 0.45 / 0.15 / 0.40 0.46 / 0.13 / 0.41 9360 72.100 1-2 0.40 / 0.20 / 0.40 0.41 / 0.19 / 0.40 5660 80,200 1-3 0.65 / 0.20 / 0.15 nmnm > 100 , 00 1-4 0.55 / 0.20 / 0.25 0.54 / 0.18 / 0.24 8270 35,900 1-5 0.50 / 0.10 / 0.40 nmnmnm 1-6 0.48 / 0.09 / 0.43 0.42 / 0.04 / 0.54 nmnm 1-7 0.43 / 0.18 / 0.39 0.43 / 0.14 / 0.43 2880 72,200 1-8 0.43 / 0.18 / 0.39 0.55 / 0.23 / 0.22 1450 19,700 1-9 0.48 / 0.083 / 0.44 0.47 / 0.05 / 0.48 9040 158,100 Example 2a This example illustrates the description of a silicone resin composition, where Wherein R 1 is hydrogen, R 2 is octadecyl and R 3 is third butyl. (MeO) 2SiCM $ By making 256.0 grams (1.51 moles) of SiCl4, 228.0 grams (1.46 moles) of Si (OMe) 4 and 13.5 grams (10 1.3 millimoles) of A1C13 in nitrogen, in a bottle covered with aluminum foil Medium-mixed to protect the reaction from UV light. The mixture was stirred at room temperature under nitrogen for 17 days while continuously protected from UV light. The reaction mixture was evacuated and the unreacted gas stone burned in Luoguan 'was left in a Schlenk tube immersed in liquid gas. The remaining product was distilled at 760 mmHg to obtain a number of characteristics of 29Si NMR and a fraction rich in Cl2Si (OMe) 2: Fraction 1 (bp · 95 ° C, 70 mmHg) 87.0 g '44 .0% by weight Cl3Si (OMe) -25- (CNS) A4 size (210X297 mm) 591057

AT B7 V. Description of the invention (22), 43.2% by weight Cl2Si (OMe) 2 & 12.8% by weight CISi (〇IV [e) 3. Defen 2 (bp 102 ° C, 70mmHg) 119.0 g containing 8.5% by weight Cl3Si (OMe), 58.7% by weight C12Si (OMe) 2 and 32.8% by weight ClSi (OMe) 3 〇Example 2b by nitrogen and 0 At a temperature of 9 ° C, Π9 · 0 g of the above-mentioned fraction 2 was added to 1.5 liters (1.5 mol, excess) of a 1M solution of potassium third butoxide / THF to prepare (MeO) 2Si (OtBu) 2. Then, 500 ml of anhydrous THF was added to the reaction mixture while stirring at reflux (65 ° C) for 4 hours. The solvent was evaporated in a vacuum of 100 mmHg at 20 ° C. The reaction product was washed with a pentane / ether mixture several times, filtered, and evaporated (92 ° C, 75 mmHg) to obtain 79.5 g of a colorless liquid characterized by 29Si NMR, 13C NMR, GC, and GC-MS, containing go "% By weight (MeO) 2Si (OtBu) 2, 3.8% by weight (MeO) 3Si (OtBu), and 5.9% by weight (MeO) Si (OtBu) 3. Example 2c A mixture of 5.48 g of the reaction product of Example 2b, 8.70 g of CH3 (CH2) 17Si (〇Me) 3, and 7.62 g of HSi (OEt) 3 was added to 40 ml of MIBK, followed by dropwise addition under nitrogen. In a mixture comprising 80 ml of MIBK, 40 ml of toluene and 60 ml of deionized water. The reaction mixture was refluxed overnight at 120 ° C. After cooling, the reaction mixture was separated into two phases, water / insoluble matter and organic phase. The organic phase was separated from the water / insoluble material phase and dried using a dean stark tray. The solvent was evaporated using a rotary evaporator to obtain 7.2 g of a waxy solid, which was identified as CH3SiO3 / 2) 0.55 (CH3 (CH2) 17SiO3 / 2) 0.24 ((tBnO) bSi〇4.b / 2) () " , Mη is 3030 and Mw is 4410. 26- This paper S [National National Standard (CNS) A4 specification (210X297 mm) 591057 23 V. Description of the invention (Example 3 This example illustrates the preparation of silicon oxide under similar conditions to Example 丨Alkane resin composition, wherein Ri is hydrogen, R2 is a substituted phenylethyl group, and r3 is a second butyl group. HS1 (〇Et) 3 (A), (Ac〇) 2Si (〇tBu) 2 ( B) and p-ZC ^ hCt ^ CHeKOEtWC) were added to 37 g of tetrahydrofuran (thf) in a bottle under argon in the amounts described in Table 4. Next, deionized water (D) was added to the solution. And the mixture was stirred at room temperature overnight. 50 grams of methylbenzyl was added to the reaction mixture. Using a rotary evaporator, the solvent was removed at 35 to 4 (rc) to obtain a viscous liquid, and it was immediately dissolved in 80 G of toluene. Residual acetic acid (azeotropic boiling point: 3 8 ° C) was removed with cobenfos. The viscous liquid was added to 120 g of toluene to obtain 10 weight 0 / 〇 viscous liquid (with methylbenzyl and viscous The total weight of the liquid is based), it is heated under reflux for 30 minutes, and azeotropically dried and refluxed for 1 hour. The solution is filtered and the solvent is removed by evaporation to obtain the final resin product. The summary of the resin synthesis is shown in Table 4. Resin The analysis is shown in Table 5. Table 4 Resin Synthesis Example No. ㈧ (g) (B) (g) (C) Pair-zc6h, ch2ch2- Si (OEt) 3 ——-. (D) (g) —---- Yield (g) 3-1 5.6 5 9.6 (Z = Me)! 3.1 ^^ Ύο 3-2 5.6 5 10.2 (Z = MeO) 3.1 ~ 9.6 Λ, 5.6 5 11.8 (Z = Br) TP ^ 1〇8 3-4 5.6 5 9.2 (Z = H) Ί 6.7 u— National standard for each paper section 27- (CNS) A4 specification (210X297 mm) 591057 Λ7 B7 V. Description of the invention (24 Table 5 (HSi03 / 2) f (ZC6H4CH2CH2) Si03 / 2) g ((tBu0) bSi04.b / 2) h Resin analysis example Based on the reactant% 1 Molar ratio fg / h Molar ratio (29Si NMR) Μη Mw 3-1 0.25 / 0.5 / 0.25 0.27 / 0.5 / 0.23 580 1.400 3-2 0.25 / 0.5 / 0.25 0.21 / 0.51 / 0.28 480 930 jj 0.25 / 0.5 / 0.25 0.25 / 0.47 / 0.28 nm 460 — 3-4 0.25 / 0.5 / 0.25 0.24 / 0.53 / 0.23 nm 600 — Example 4 This example illustrates the preparation of an insoluble porous resin Wherein Ri is hydrogen, R2 is an organic group having 8-2 carbon atoms 2, and R3 is tert-butyl. The resins (2 to 3 g) prepared in Examples 1 and 2 were weighed into an alumina crucible and transferred to a quartz tube furnace. The furnace was evacuated to < 20 mmHg (< 2666 Pa) and backfilled with argon. The sample was heated to a temperature shown in Table 6 at a rate of 50 to 60 ° C / min, and maintained at that temperature for 2 hours while cooling to room temperature while flushing argon. The obtained hardened substance is a transparent or slightly opaque film. The pyrolysis conditions, coke yield, TGA (thermal specific gravity analysis) yield and porosity data for nitrogen absorption measurements are listed in Tables 6 and 7. Coke yield and TGA yield are expressed as weight percent remaining after analysis at a specific temperature. _ -28- One specimen (CNS) A4 size (210 X 297 mm) 591057 Λ7 B7 V. Description of the invention (25 Table 6 Analysis example of hardened resin No. Resin sample No. Coke yield '450 ° C (wt%) TGA yield 450 ° C (wt%) TGA yield 500 ° C 1 (wt%) Pore 1 volume cm " gram surface area BET, m2 / g 4-1 1-1 51.9 73.8 56.4 0.701 1213 4-2 1-2 53.0 75.2 53.2 0.678 1123 4-3 1-3 53.9 77.5 57.9 0.623 1007 4-4 1-4 61.8 80.2 58.2 0.349 534 4-5 1-5 60.8 70.8 62.6 0.515 882 4-6 1-6 48.5 49.8 483 0.297 528 4 -7 1-7 52.1 52.5 46.4 0.430 723 4-8 1-8 40.1 38.8 36.2 0.452 770 4-9 1-9 60.6 54.3 52.7 0.246 417 4-10 2c nmnmnm 0.457 752 Table 7 Analysis example of hardened resin No. 1 Resin sample No. Skeletal density g / cm3 pore volume cm3 / g porosity 丨 weight%! | I surface area j 丨 BET,! M2 / g!! 4-1 Μ: 1.669! 0.701 1 53.9 " 213: 4-2 1.638: 0.678 52.0 1123 4-3: -3 1.337: 0.623, 45.4: 1007 4-4 1.346 0.349: 32.U ^ 34: 4-5] -5 1.751 0.515 47.4 | S8: Example 5 This example illustrates the formation of an insoluble porous coating on a substrate, of which R1 007 ?; 〇7 ____ This paper size applies to the China National Standard (CNS) A4 specification (210X297 mm) 591057

Is hydrogen, R2 is an organic group having 8 to 22 carbon atoms, and R3 is a third butyl group. The resin prepared according to Examples 2 and 3 (2 to 3 g) is dissolved in Mΐβκ, containing 25% by weight. Transparent resin solution. The solution was filtered through a 10 micron syringe membrane filter and then through a 0.2 micron syringe membrane filter to remove any large particles. The solution was applied on a silicon wafer by spin coating at 2000 rpm for 20 seconds. The coated silicon wafer was placed in a quartz tube furnace, and the furnace was flushed with nitrogen. The furnace was rapidly heated to 4500c (50 £> c to 60 ° C / min dream) maintained at 450t for 2 hours, and then cooled to room temperature while maintaining nitrogen. The coated wafers were measured for properties Before being stored in nitrogen. Thinness Table 8 Properties of thin films on silicon wafers, 450. Example number Resin sample number Dk "Modulus, GPa ί hardness, GPa 丨 thickness, Angstrom ~ RI 5-1 1-1 2.30 3.4 0.53 9396 1.186 ^^ 1-2 1.97 2.1 0.36 ll 795 T3 1.70 Τδ ΎΤ \ '15020 ~ 一 ^ TTl78 ^^ 5-4 1-4 2.55 4.7 0.80 4921 5-5 1-5 2.25 4.4 0.36 14,532 ΎΤβΓ' ^ 5-6 1-6 2.67 f 6.9 0.63 7478 Τ233 ^ ~ 5-7 ί!: 1-7! 2.58 6.3 0.56 | _ _ ~ L 5737 j Τ23Ϊ—! 5-8: 1-8 ~ | 2.72! 8.0 0.66 4048 1 Τ23ΤΠ! 5-Q; 1-9; 2.8 :: 100.5 0.94! 4244; 5-; 0 2c: .i8: 2.0: 0.39 3295 Τ3ΊΤ—!! 5-i 1: 3-1 2.56: 3.7 丨 0.5: ί 7697 5- ;:-: .89 () · η ΟΛΜ 7355 ΐ-4ΰ (Γ ^; 5- i > 丨 nm 5 Λ.) O.cSM 6〇74 7.433 1 '--L Λ 1 — 5.1 (i.SO '/ ,; 007598 _ Rare book paper standards apply Chinese national standards (CNS) Λ4 specification (210X297 mm) B7 27 V. Description of the invention (Example 6) This example illustrates the formation of three layers of insoluble porous coating on the substrate at various temperatures, where R1 is hydrogen and R2 is An organic group of 8 to 22 carbon atoms, V is a third butyl. The resin (2 to 3 g) prepared according to Example 1 was dissolved in MIBK: One Kelvin> to form a transparent solution containing 25% by weight of resin.丨 0 micron syringe membrane filter, then filtered through a 0.2 micron syringe membrane filter to remove any large particles. The solution was coated on a silicon wafer by spin coating at 2000 for 20 seconds Bell. Place the coated silicon wafer in a quartz tube furnace and flush the furnace with nitrogen. The furnace is heated to 250, 390, and 450 ° C, and the knife is maintained at each temperature for 丨 hours, and then cooled to At room temperature while maintaining a flush of nitrogen. The coated wafers were stored under nitrogen before the properties were measured. The film properties are listed in Table 9. Table 9 Film properties on silicon wafers. Resin sample number r " 1 · ι Dk — modulus, ~~ GPa GPa thickness, RI Tyger 6-1 r λ " 1-1 ^ 17 2.3 0.24 11.580 1.215 6- 2 1-3 1.80 1.2 0.14 11.749 i 1.206 Example 7 This example illustrates the preparation of a siloxane resin composition in which R1 is a methyl group, R2 is an octadecyl group, and R3 is a third butyl group. MeSi (0Me) 3 (A), (AcO) 2Si (〇tBu) 2 (B) and CH3 (CH2) 17Si (〇Me) 3 (C) were added in the amount described in Table 9 'under argon In 75 g of THF in a bottle. Then leave -31-This paper ruler, 39 standard (CNS) A4 size (210X297 mm) 591057

AT B7 V. Description of the invention (28) Water (D) is added to the solution, and the mixture is stirred at room temperature for 1 hour. 75 grams of methylbenzyl were added to the reaction mixture. The solvent was removed using a rotary evaporator to obtain a viscous product, and it was immediately dissolved in 150 g of methylben. It was heated to 38 ° C under reduced pressure, and the residual acetic acid solution resin was azeotropically removed with methylbenzyl, and then dissolved in 250 g of toluene, and dehydrated and refluxed for 1 hour. The solution was filtered and evaporated to remove the solvent to obtain the final resin product. A summary of the resin synthesis is shown in Table i 〇. The molecular weight information of the resin is shown in Table 11. Table 10 Aggregated Examples of Resin Synthesis (Α) (Β) (C) (D) Yield Appearance Coding (g) (g) (g) (g) (g) (g) 7-1 9.3 10.2 12.8 6.1 12.4 Wax 7- 2 14.9 40 10.28 11.2 34.4 Oil 7-3 23.4 40.1 ΓΪ2.8 14.4 Uo.i roll 7-4 21.0 40.0 19.3 14.4 45.4 Wax 7〇27.8 29.9 12.8 15.0 40.0 Oil Table 11 (MeSi03 / 2) f (CH3 (CH2) 17Si03 / 2) g ((tBu0) bSi04.b / 2) h Analysis of Resin 1--32-7 7 Paper Red Transfer Office A4 Specification (2297297 mm) Mole ratio Mη Mw 7-1 0.55 / 0.20 / 0.25 6730 22.600 7 «2 0.40 / 0.10 / 0.50 2790 18,300 7-3 0.50 / 0.10 / 0.40 1560 9800 7-4 0.45 / 0 · 15 / 0.40 1830 10.100 7,5 0.60 / Ό. 10 / 0.30 2470 8320 591057

Example 8. This example illustrates the preparation of an insoluble porous resin, where R1 is methamyl, R2 is octadecyl, and R3 is third butyl. The grease (2 to 3 g) prepared in Example 7 was weighed into an alumina crucible and transferred to a quartz tube furnace. The vacuum was evacuated to < 20 mmHg (< 2666 Pa) and backfilled with argon. The sample was heated to a temperature shown in Table 12 at a rate of 50 to 60 ° C / minute, and maintained at that temperature for 2 hours before cooling to room temperature while flushing nitrogen. The obtained hardened substance is a transparent or slightly opaque film. Pyrolysis conditions, coke yield, TG A yield and porosity data for nitrogen absorption measurements are listed in Tables 2 and 13. Table 12 Porosity and Coke Yield of Hardened Resin • 33- National Standard for Wood and Paper (CNS) Λ4 Specification (210 X 297 Poor 7) Example No. Resin Sample No. Coke Yield 450 ° C (wt%) TGA Yield 450 ° C (wt%) TGA yield 500 ° C (wt%) Pore volume cm3 / g Surface area BET, m2 / g 8-1 7-1 47.0 78.7 49.2 ~ 〇315 ~ 719 8-2 7-2 55.1 59.5 51.4 731 8-3 7-3 52.7 60.7 52.5 " ^ 523 ~ 874 8-4 7-4 51.9 ί 60.8 48.5 0.464 749 8-5 7-5 58.1 64.9 55.8 0.436 711 591057 B7 V. Description of the invention (Table 30) 1 3 Analysis example of hardened resin No. 0 1 Resin sample No. Skeletal Density g / cm3 Pore volume cm3 / g Porosity 1% by weight Surface area j BET, m2 / g --- ^ 7-1 ____] 1.380 0.515 41.5 719 8- 2 73 1 --- 1.591 ---------0.451 ------- 41.8 731 8-j Λ 7-3 1.429 — 0.523 42.8 874 8-4 QC 7-4 1.508 " 0.464 ~ 41.2 749 80 1 7〇 —----- 1.447 " α436 _ — 38.7 711 Example 9 This example illustrates the formation of an insoluble porous coating on a substrate at various temperatures, where R1 is methyl and R 2 is octadecyl and R3 is third butyl. The resin (2 to 3 g) prepared according to Example 7 was dissolved in MIBK to form a transparent solution containing 25% by weight of the resin. The solution was passed through a micrometer syringe Filter through a membrane filter and then filter through a 0.2 micron syringe membrane filter to remove any large particles. The solution was coated on a silicon wafer by spin coating at 2000 rpm for 20 seconds. The silicon wafer was placed in a quartz tube furnace, and the furnace was flushed with nitrogen. The furnace was quickly heated to 45 °. (: (50t: s60t / min), and maintained at 450 ° C for 2 hours, and then cooled to the chamber Temperature while maintaining nitrogen flushing. The coated wafers were stored in nitrogen before measuring properties. The modulus and dielectric constant of the film are listed in Table 14. Paper -34 591057 A7

Hold

Order

591057 A? B7 V. Description of the invention (32 Q & qq (〇5— Κ) p Η— ^ Η 〇 — 〇〇L) UJ ^ Η ON ρ ▲ T] os; Life 5 ί ^ 〇bv〇b D : 00 ^ 3 m 〇L) o to- GO — · c ^ OB On iT 3 〇 | 5 I- ο O 2 b E 〇 〇〇--J u > nm K t · u > 00 > 〇 U) S 〇〇g I obt? -A η h— ^ * 4 ^ go a-a H— ^ 〇E o X-^ r > 15 萆 藏 命 绛 Λ 皭 皭 本 ^ paper China National Standards (CNS) a4 specifications (2i〇x 297) 591057 A7

Table 1 6 Material properties Sample theoretical composition M \ v Mn 10-1 T 0.36〇0.46 D, 0 丨 8 — 10-2 TH 0.55QQ ^ TT 4,790 ~ 188,800 Example 11 According to the general procedure, Cl2Si ( 〇tBu) 2, RSicl3 & HSicl3 was dissolved in 40 liters of MIBK, and added dropwise to 80 ml of MIBK and 60 ml of 0.5 M HC1 solution in a 500 liter bottle under nitrogen at 0 c. The reaction mixture was then mixed at 25 ° C overnight. Remove water and insoluble material and dry the organic phase using a dean stark tray. The solvent was evaporated using a rotary evaporator to obtain 4.0 g of a white solid. The summary of resin synthesis is listed in Table 丨 7. The molecular weight data and composition are listed in Table 18. Table 17 Summary of resin synthesis

Sample 11 1 I Theoretical composition -T ′ ι * j —y-, W i HsiCl3 g / Cl2Si (OtBu) 2 g RSiCl3 g 'Appearance 11-1! 1; ί!! J ^ 0.5 0.5 (125 0.25 7.8 7.0 CH3 (CH2) i7SiCl; 11.2 4. solid 1 I;-: 1 j:! 6.2 | 10.6 CH3 (CH:) rSiCh 10.0 i g- ~~; 1 i-3 ΤΆ. ::: ΊΛ: 5 i I 7 8 i _____ 7.0 Ci ^ Si-triisobutxlene j _ I | 8 · 7 Q Including Q (QtBu) b _-37 · The paper's meaning is applicable to Chinese national standards (CNS > A4 specification (210X297 praise) 591057 Λ 7 Β7 34 V. Description of the invention (Table 1 8 Material characteristics Sample R-based theoretical resin composition nmr Resin composition Mvv Mη 11-2 CH3 (CH2) i7 T, 10.4Q.575TK〇.225 々 \ ^ _ ΤΗα6ΐ 14200 3790 11-3 tri-isobutylene? 〇5Q〇.25T " ~~ ^ " 〇.42Q〇.〇6TH〇.53 1870 1380 Example 12 The mother liquor of the resin sample prepared in Example 11 was weighed to the oxide Mingcai Exhausted, and moved to a tubular furnace. The furnace was evacuated to < 20 torr, and backfilled with gas. Under nitrogen filling, the sample was heated to a predetermined temperature at 10 c / min, and immediately cooled to The temperature is maintained at this temperature for 2 hours Time. Obtain a transparent or slightly opaque film-like final hardened substance. The pyrolysis conditions, coke porosity, and porosity data for nitrogen absorption measurements are listed in Table 19. Table 19 Porosity and temperature of the resin pyrolyzed at 450 ° C The pores of the resin composition of the aggregate sample of the coke yield based on R-NMR cc / g 11-1 ch; (ch2) 17 —T% wQa2: Thl:) 60 0.54 ^ 11-2 CH ;, (CH:) r '满 Άι lU8 ^; 11-3 tri-isobut \ -lene

(01 B u) b

Q contains Q -38 ^ National National Standard Apple (CNS) Λ4 specification (210 X 297) ^ 1057 ^ 1057

A7 B7 V. Description of the invention (35 Example 1 3 The mother liquor prepared in Example 11 was dissolved in methyl isobutyl ketone (MIBK) to form a 25% by weight transparent solution. Then passed κο microns and 0.2 microns Syringe filter filters the solution to remove any larger particles. The solution is applied to a silicon wafer and spin-coated on a silicon wafer using a Karl Suss RC8 or Headway spin coater and spinning at 2000 rpm for 20 seconds The thickness of the rotating film can be controlled by combining the concentration of the solution and the speed of rotation, and the range is between 2000 and 20,000 Angstroms. Add the film to the QTF furnace and quickly heat it under nitrogen. 4 5 0. The film was heated at 450 C for 2 hours, and then cooled to room temperature. All coated wafers were stored in nitrogen before measuring properties. Molds of thin films made of DbRbh resin The numbers and dielectric constants are shown in Table 20. Table 20

Q contains Q (QtB10b Comparative Example 1 This example illustrates the formation of a siloxane resin composition, where R1 is nitrogen, r

___ -39- Use Chinese National Standard Ping (CMS) A4 specification (210X297 mm) ------ 591057 A7 B7 V. Description of the invention (36 does not exist and is the third butyl. HSi (〇Et ) 3 (A), (AcOhSKOtBuMB) were added to 72 g of tetrahydrofuran (THF) in a bottle under argon in the amounts described in Table 13. Deionized water (D) was added to the bottle, and The mixture was stirred at room temperature for hr. Then 75 g of toluene was added to the mixture. The solvent was removed by evaporation using a rotary hair dryer to obtain a viscous oily siloxane resin, which was then immediately dissolved in 150 g of toluene. Heat to 38 ° C, remove by-product acetic acid azeotropically with methylbenzyl. Then dissolve the resin in 110 g of methylbenzyl, and azeotropically dry and heat in reflux methylbenzyl for 1 hour. Filter the solution and remove the solvent by evaporation to obtain Siloxane resin products. The aggregates of resin synthesis are listed in Table 2i. The molecular weight information of the resins are listed in Table 22. Table 21 Summary examples of resin synthesis (A) (g) (B) (g) (D) (G) Yield (g) Appearance C1-1 (5.67 40.2 6.1 23.7 ~ Colloidal C1-2 11.23 30.0 6.65 18.7 Colloidal C1-3 26.2 20.0 10.0 19.2 Colloidal Table 22 (HSi03 / 2) f (tBu0) bSi04-b / 2) g resin analysis example | Molar ratio of f / h based on the reactant fg Molar ratio of 29Si NMR Μη Mw 'CM 0.20 / Ό.80 0.21 / 0.79 3,040 6.300 ^ C1-2 0.40 / 0.60 0.43 / 0.57 6,750 25.800' C1-3 0.70 / 0.30 nmnm 1 -------- nm 〇〇1 ^ θ- 40- This paper size applies the CNS standard Λ4 specification (210X297 male I) 591057 Λ7 B7 i. Description of the invention (37) Weigh the resin sample (2 to 3 grams) into the alumina crucible and move it Quartz tube furnace. The furnace was evacuated to < 20 mmHg (< 2666 Pa) and backfilled with gas. The sample was heated to 4501 at a rate of 50 to 60 ° C / minute and cooled to room temperature. It was maintained at 450 ° C and argon for i hours before temperature. A transparent or slightly opaque film-like hardened siloxane resin was obtained. The pyrolysis temperature, coke and carbon yields, and porosity data are listed in Table 23. .Coke yield is expressed as weight% remaining after analysis at a specific temperature. Table 23 Porosity and Coke Yield Pore Product of Hardened Resin ^ _3g C j degree m3 5ke dense: g / c Sample

1.787 65.0 0.224 -¾- A sample of fef resin (2 to 3 g) was dissolved in MIBK to form a transparent solution containing 25% by weight of resin. The solution was then filtered through a 1.0 micron injection membrane filter and a 0.2 micron injection membrane filter to remove any larger particles. The solution was applied on a silicon wafer during spin coating at 2000 rpm for 20 seconds. The coated silicon wafer was placed in a quartz tube furnace, and the furnace was flushed with nitrogen. Quickly heat the furnace to 45 ° C (5 ° C to 6 ° C / min), and maintain it at this temperature for 2 hours: then cool down to chamber S, while maintaining degassing. The coated wafers were tested The properties are stored in nitrogen before. The modulus and dielectric properties (Dk) of the film are listed in Table 24. Ό0761〇 ___- 41- This paper is suitable for your scale "_ House Standard Rate (CNS) μ Regulation (Total X 297 public celebration) ------- 591057 Λ / Β7 38 V. Description of the invention (Table 24 Film properties of resin on silicon wafer Resin sample number Dk 丨 Modulus 1 GPa Hardness! GPa i!! Thickness, Angstrom T ---- -^ RI CM 24.3] 18.6 0.88! 4.180 1.321 C1-2 14.9! J — j 16.1 1 0.77 4.120 1 ~ 35T ^ Cl-3 6.34 | 10.8! 1.06 i J_ [6.590! 1 1 1.290 __ __ R1 is hydrogen, R2 is absent and R3 is a tertiary butyl silica resin. An excellent modulus can be obtained, but high Dk cannot be accepted when compared with Examples 1 and 2. This example also shows that it contains ^ Examples 1 and 2 which are both R3 and R3 groups also exhibit lower porosity when compared. Comparative Example 2 This example illustrates the preparation of a siloxane resin composition where Ri is methyl 'R2 is not present and R3 Is the third butyl. MeSi (〇Me) 3 (A), (AcO) 2Si (〇tBu) 2 (B) and THF were added to the bottle under argon in the amounts shown in Table 17. AcO Represents ethoxyl, Me represents methyl and tBu represents third butyl. Next, deionized water is added to the bottle, and the mixture is allowed to stir at room temperature for 1 hour. 75 grams of toluene is added to the reaction mixture. Use The solvent was removed by evaporation on a rotary evaporator to obtain a viscous oily product, which was immediately dissolved in 150 g of toluene. The residual acetic acid was co-removed with toluene under reduced pressure (azeotropic boiling point 38 ° C). The resin was again It is dissolved in 10 grams of toluene, and azeotropically dried and refluxed for 1 hour. The solution is filtered and evaporated to remove the solvent to obtain the final resin product. The synthesis of the resin is listed in Table 25. The molecular weight information of the resin is listed in Table 2. 6. ύ 07611 -42- This paper size applies to coffee house standard (CNS) Μ specifications (2ΐΰ × 297 male I) 591057 A7 B7 V. Description of the invention (39 Table 25 Summary of resin synthesis 丨 Example number㈧ (g) (B) (G)! THF (g) h2o (g) Yield (g) Appearance ~ C2-1 18.6; 40.0 i 72.0 11.1 23.6 Solid C2-2 27. 9 40.0 80.0 Til 26.0 solid C3-3 43.5 40.3 90.0 20.0 40.0 solid C3-4 92.9 39.9 120.3 IsJ ~~ — 67.3 Wax Table 26 (1 ^ 8 丨 03/2) heart 811〇) | 58 丨 04. ^) / 2) Analytical example of 11 resin Molar ratio based on the reactant 1 Molar ratio Μη Μνν in terms of 29SiNMR ^ ~ C2-1 0.50 / 0.50 0.44Ό.56 2,990 17.700 — C2-2 0.00 / Ό. 40 0.5 > 0.44 2.010 46.000 'C2-3 0.70 / 0.30 0.69.0.31 " nm ί > 100.000 C2-4 0.85 / 0.15 —0.83 / 0.17' 3.400 131100]-^ Weigh the resin sample (2 to 3 g) Heavier than the oxidation chain, and moved into the quartz tube furnace. The furnace was evacuated to < 20 mmHg (< 2666 Pa) and backfilled with argon. The sample was heated to 450 ° C at a rate of 10 ° C / min, and maintained at 450 ° C under argon for 1 hour before cooling to room temperature. A transparent or slightly opaque film-like hardened silicone resin was obtained. Pyrolysis temperature, coke yield, and porosity data are listed in Table 27. Coke yield is expressed as the weight percent remaining after analysis at a specific temperature. ^ 43- 007612 591057

AT B7 V. Description of the invention (40) Table 2 7 Porosity and coke yield of hardened resin Resin sample number Skeletal density (g / cm3) Coke yield 450 ° C (wt%) Pore volume cm3 / g porosity (%) Surface area bet, m2 / g C2-1 1.693 60.5 0.271 31.4 461 C2-2 1.624 72.5 0.280 31.3 481 C2-3 1.505 78.0 0.249 27.2 425 C2-4 1___ 1.398 76.5 0.125 14.9 168 Resin samples (2 to 3 G) Dissolved in MIBK to form a transparent solution containing 25% by weight of resin. The solution was then filtered through a .0 micron injection membrane filter and a 0.2 micron injection membrane filter to remove any larger particles. The solution was applied to a silicon wafer during spin coating at 2000 rpm for 20 seconds. The coated silicon wafer was placed in a quartz tube furnace, and the furnace was flushed with nitrogen. The furnace was rapidly heated to the temperature shown in Table 21 (other than it / minute), and maintained at this temperature for 2 hours, and then cooled to room temperature while maintaining nitrogen flushing. The coated wafers were stored under nitrogen before the properties were measured. The modulus and dielectric properties (Dk) of the film are listed in Table 28. 7613 __- 44-This paper size applies Chinese national standard (CNsTXTi grid (210X297mm) 591057 A7 B7 V. Description of the invention (41 Table 28. Properties of resin film on silicon wafer)

C C2 -2-2 2-2-c ic C C2 c C -4 2-12 C C

Zhipin number tree

-4 | 22-c C

This example shows that R1 of t is a methyl group, R2 is a hexasiloxane, a siloxane resin and an example containing R1r3 and R is a third butyl group, but the porosity is low. Excellent Dk can be obtained when I Π 仏 Comparative Example 3 This example illustrates the preparation of a sand-fired resin where Ri is hydrogen, R, octadecyl, and V are absent. Prepared by the method of beauty of Collins et al. No. 3,6i 5,272, and the weight of hydrogen silicon in Jiabenzhong is 70,000, and the solution of τ and oxane resin is at 110. 〇Under 10 ° parts by weight with 丨 3_— # 芙 x -ethynyltetramethyldisilaxane M7614 591057 Λ 7 —-___ B7 5. In the presence of platinum in the form of (42), and Octane was reacted for 2 hours. Each sample of the resin solution after the reaction was placed in a ceramic crucible, heated in 35 crc and nitrogen for 0.5 hours, and then heated in nitrogen at 500 ° C for 2 hours. Samples of each resin solution were diluted to 17% by weight with toluene and applied to a silicon wafer by spin coating, hardened as described in Example 5, and the dielectric constant was measured. Table 29 shows the weight of the solution used in the silsesquioxane resin and the weight of the octadecenyl group, and the porosity and dielectric constant of each sample. Sample C3-3 was a toluene solution of hydrogen-containing silsesquioxane resin, which did not react with octadecane. Table 29 Analysis of (HSi03 / 2) fCH3 (CH2) 17Si03 / 2) g resin Comparative Example No. Guang 1 1 parts by weight of toluene, 18 parts by weight of dilute, fg mole ratio porosity based on reactant% Dk C3-1 12.22 1.60 ~ > 0.66 / 0.34 127.1 2.1 Cj-2 2.72 1.10 0.77 / 0.23 ...... 27.9 2.2 C3-3 4.72 0 Τ〇〇〇 " ~ '0 3.0 ~ This example shows that R1 is a When the siloxane resin in which R2 is octadecyl and R3 is absent is compared with Example 1 containing R2 and R / 0, excellent Dk can be obtained, but the porosity is low. -46- National Standards (CNS) Λ ’〖Specifications (210X297 mm)

Claims (1)

591057 i 591057 ABC 8 D, patent application scope. For example, the siloxane resin composition of the first patent application scope, wherein the resin additionally contains at least one selected from Risi (x) d〇 (3d⑺; R2Si (X) dO ( 3-d / 2); si (X) d (〇R3) f〇 (nf / 2), si〇4 / 2 & a mixture of siloxane units and siloxane units, wherein R1, R2 & R3 The definitions are as above 'and each X is independently a hydrolyzable group or a hydroxyl group, and 4 and [is 1 to 2 06. Preparations include RlSi〇3 / 2 Shixi Oxygen Unit, R2Si03 / 2 Shixi Oxygen Unit, and The method of (R3〇) bSl0 (4-b) / 2 siloxane resin siloxane resin, wherein the division method includes: combining the following components for a sufficient time and temperature to prepare the siloxane resin: (a ) 2.5 to 85 mol% of a silane or silane mixture of the formula RiSiX3, wherein R1 is independently selected from the group consisting of alkyl, hydrogen or a mixture thereof having 1 to 5 carbon atoms, and X is independently a hydrolyzable group or a hydroxyl group (B) 2.5 to 50 mol% of a silane or silane mixture of the formula R2SiX3, wherein R is independently selected from monovalent organic groups containing 6 to 30 carbon atoms and having 6 to 30 carbons Substituted monovalent organic groups, χ is independently a hydrolyzable group or a hydroxyl group; (c) 5 to 95 mol% of a stone syringa or stone oxane mixture of the formula (R3〇) cSix (4c), where R3 Is independently selected from the group consisting of a branched alkyl group having 3 to 30 carbon atoms and a branched substituted alkyl group having 3 to 30 carbon atoms, (; is 1 to 3 (inclusive), and X is independently a hydrolyzable group or a hydroxyl group , ㈣⑷, ㈨ and ⑷ total 100 mol parts; and (d) water. -2-This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 public directors) 591057, patent application park: · If you apply The method of the scope of the patent No. 6 includes a solvent. For example, the method of the scope of the patent No. 6 wherein R1 is selected from the group consisting of methyl: hydrogen and mixtures thereof, and R2 is a group of 10 to 20 carbon atoms. After taking two :, "I-substituted alkyl group" and r3 is a tertiary group having 4 to 18 carbon atoms. For example, in the method of applying for the scope of the patent, item 6, wherein r3 is a third butyl group. The method of the sixth item of the patent, wherein the content of water is 0.5 to 2 per mole in Qian Zhi, Shi Xiyao (b) and Shi Xiyao (c) Mol. H. The method according to item 6 of the patent application, wherein the content of water is ⑷, from 18 to 18 mol per mol in ⑷, silane (b) and silane (c). 12. For example, the method in the patent application No. 6 is a chlorine atom. 13 'A method for forming an insoluble porous resin with a dielectric constant between 5 and 3 G, including: (A) using The siloxane resin in the scope of the patent application is heated at a sufficient temperature for a sufficient time to harden the siloxane resin. (B) further heats the siloxane resin at a sufficient temperature for a sufficient time to self-harden. Siloxane resin removes R2 & R30 groups, thus forming an insoluble porous resin. 14. The method according to item 13 of the patent application range, wherein the heating in the step is from more than 20t to 350,000t, and the further heating in the step (B) is from 35 ° C to 600 °. 15. For the method according to item 13 of the scope of patent application, the hardening of the siloxane resin and the removal of the r3o group from the self-hardening siloxane resin are performed in a single step. 0 -3-This paper standard is applicable to Chinese national standards ( CNS) A4 specification (210X297 mm) 6. Application scope of patent 16. If the method of the scope of application for item 13 is applied, the pores of t1, 1 and 2 will be used to make the gap of non-bathable pore resin. % By volume, and the modulus is from 0 to 0 GPa. π ·: Method for forming a porous t layer with a dielectric constant between 15 and 30 on a substrate, including the steps of: ⑷ coating composition including a siloxane resin composition containing the following ingredients Material coating base material ·· 〇) 2.5 to 85 mol% of 〇3 / 2 siloxane unit, wherein R1 is independently selected from the group consisting of a carbon, a carbon and a pot mixture; 2 (b) 2.5 to 50 moles of R2Si〇3 / 2 siloxane units, wherein R2 is independently selected from the group consisting of a monovalent organic group having 6 to 30 carbon atoms and a monovalent group having 6 to 30 carbon atoms Substituted organic groups; and (c) 5 to 95 moles of (R ^ cObSiOH, / 2 siloxane units, wherein R3 is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and having 3 A branched substituted alkyl group of 30 to 30 carbon atoms, 1 ^ is a total of 100 mol parts of components (a), (b), and (c), and components (a), (b), and (C) the sum is at least 50% of the total silica firing units in the resin composition; (B) the coated substrate is heated to a temperature sufficient to harden the coating composition, and (C) further The coated substrate is heated to a temperature sufficient to remove the R2 and R30 groups from the hardened coating composition, thereby forming an insoluble porous coating on the substrate. 18. A method as claimed in item 17 of the scope of patent application , Where the heating system in step (B) is -4-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 591057 The scope of patent application is more than 20C to 350C, and the further heating of step (0 is more than 3500C to 600C) 〇19. The method of item 17 of the patent scope is declared, wherein the hardening and removal of R2 and r30 groups are In a single step, and the temperature exceeds 20 ℃. (: To 600 ℃: below. 20. The method of claim 17 of the scope of the patent application, wherein the removal of r2 and radicals is more than 350 to 600t 2L The method according to item 17 of the scope of patent application, wherein the porosity of the insoluble porous coating is 丨 to 6 (% by volume), the dielectric constant is between 15 to 30, and the modulus Between 1.0 and 10 GPa. 22. The method according to item 17 of the scope of patent application, wherein the substrate is an electronic substrate. 23 · —A dielectric constant of 15 to 3 is formed on the substrate A method of insoluble porous coating between 〇, comprising the steps of: (A) coating the substrate with the product prepared as the towel of the patent application No. 12; (B) making the coated substrate sufficient Heating at a temperature to harden the coating composition, and (C) further heating the coated substrate to a sufficient temperature ， R2 is removed from the hardened coating composition, so a non-porous coating is formed on the substrate. 24. If the method of the scope of patent application No. 23, the hardening and removal steps are more than 2 (TC At a temperature of up to 600t, it is performed in a single step. 25. The method according to item 23 of the patent application, wherein the substrate is an electronic substrate. -5-