Method for producing silicone polymer and method for producing membrane

Abstract

To provide a production method which facilitates automation, and can continuously obtain a silicone polymer having low dispersibility with a high yield.SOLUTION: A method for producing a silicone polymer includes a step of continuously supplying a solution A containing at least one kind of silane compound selected from a compound represented by general formula (1) and a compound represented by general formula (2), and a solution B containing a catalyst to a mixer, and mixing the solutions and obtaining a mixture, a step of supplying the mixture to a tubular reactor having an inner diameter of 1 to 20 mm, reacting the mixture, and obtaining a reaction liquid, and a step of continuously supplying the reaction liquid to a column filled with an ion exchange resin, and bringing the reaction liquid into contact with the ion exchange resin, in this order, wherein the solution A or the solution B contains water, and the ion exchange resin is a gel type. Formula (1): RaSi(OR1)4-a. Formula (2): Si(OR2)4. In the formulae, R represents a hydrogen atom or a monovalent organic group, R1 represents a monovalent organic group, a represents an integer of 1 to 2, and R2 represents a monovalent organic group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a process for producing a silicone polymer. [Background technology]

[0002] Silicone polymers are organic-inorganic hybrid materials in which organic and inorganic compounds are combined at the molecular level. They have been the subject of intensive research in recent years because they combine the properties of organic materials, such as flexibility and processability, with the properties of inorganic materials, such as heat resistance, weather resistance, and chemical resistance.

[0003] In particular, in pattern molding for manufacturing semiconductor elements, etc., it has been proposed to use a silicone polymer as a resist underlayer film when forming a reverse pattern using lithography technology, etching technology, etc. Silicone polymers that contain a large amount of structures derived from tetramethoxysilane or tetraethoxysilane in particular have been known to have excellent embedding properties in fine resist underlayer film patterns and excellent etching resistance when the resist underlayer film pattern is removed by oxygen-based gas etching, etc.

[0004] On the other hand, the practical application of flow micro synthesis is being promoted. In the flow micro synthesis method, raw materials are generally continuously supplied by pumps or the like and reacted in a tubular reactor or a continuous stirring tank type reactor. In particular, when the inner diameter of the tubular reactor is made extremely small, such as several hundred μm, the diffusion distance becomes short, and the apparent reaction rate may be faster than when the reaction is carried out in a conventional batch type reactor (for example, see Non-Patent Document 1). The flow micro synthesis method is expected to be a next-generation manufacturing method because it is easy to automate, can carry out reactions continuously, consumes less energy because the equipment is small, and reduces waste.

[0005] Attempts have been made to obtain silicone polymers using such flow microsynthesis methods (see, for example, Non-Patent Document 2).

[0006] The inventors also discovered that a silicone polymer can be continuously produced by supplying a solution of alkoxysilane and alcohol, and a solution of water and a quaternary ammonium compound to a micromixer using a pump, reacting them in a tubular reactor having an inner diameter of 1 to 3 mm, and removing the catalyst by contacting the mixture with an ion exchange resin packed in a column (see Patent Document 1).

[0007] However, when the catalyst is removed with an ion exchange resin, the silicone polymer is adsorbed by the ion exchange resin, which can reduce the yield. In addition, since a part of the silicone polymer is adsorbed when it comes into contact with the ion exchange resin, the polydispersity (Mw / Mn) of the produced silicone polymer tends to be high, and when the silicone polymer is produced over a long period of time, this can have an undesirable effect on the functionality of the silicone polymer produced later. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Osamu Kobayashi and Toshiya Onozawa, editors and translators, Flow Chemistry for Organic Synthesis, 266p, Tokyo Kagaku Dojin (2020) [Non-Patent Document 2] D. Kessler, et. al., Macromol. Chem. Phys. 210, p807-813, 2009 [Patent documents]

[0009] [Patent Document 1] International Publication No. 2022 / 270336 Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a method for producing a silicone polymer having a low polydispersity, which can be easily automated, continuously, and in a high yield. [Means for solving the problem]

[0011] The method for producing a silicone polymer of the present invention comprises the steps of: continuously supplying and mixing solution A containing at least one silane compound selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and solution B containing a catalyst, to a mixer to obtain a mixture; supplying the mixture to a tubular reactor having an inner diameter of 1 to 20 mm and reacting it to obtain a reaction liquid; and continuously supplying the reaction liquid to a column packed with an ion exchange resin to contact it with the ion exchange resin, in this order; wherein solution A or solution B contains water, and the ion exchange resin is in a gel form. R a Si(OR 1 ) 4-a ...(1) In the formula, R is a hydrogen atom or a monovalent organic group, R 1 represents a monovalent organic group, and a represents an integer of 1 or 2. Si(OR 2 )4...(2) In the formula, R 2 represents a monovalent organic group. The present invention also relates to a method for producing a film, which comprises the steps of applying the silicone polymer obtained by the production method of the present invention to a substrate and heating the applied coating. Effect of the Invention

[0012] According to the present invention, silicone polymers having low polydispersity can be produced in a continuous manner that is easily automated and with high yields. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a flow diagram illustrating an example of the configuration of a production apparatus used in the method for producing a silicone polymer of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The method for producing a silicone polymer of the present invention comprises, in this order, a step of continuously supplying and mixing a silane compound-containing solution A and a catalyst-containing solution B to a mixer to obtain a mixture, a step of supplying the mixture to a tubular reactor having an inner diameter of 1 to 20 mm and reacting to obtain a reaction liquid, and a step of continuously supplying the reaction liquid to a column packed with an ion exchange resin to bring it into contact with the ion exchange resin.

[0015] The silane compound is at least one selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2). R a Si(OR 1 ) 4-a ...(1) In the formula, R is a hydrogen atom or a monovalent organic group, R 1 represents a monovalent organic group, and a represents an integer of 1 or 2. and a compound represented by the following general formula (2): Si(OR 2 )4...(2) In the formula, R 2 represents a monovalent organic group.

[0016] In the above general formula (1), when R is a monovalent organic group, R and R 1 are independent of each other and may be the same or different organic groups. When a is 2, R are independent of each other and may be one type of monovalent organic group or two types of monovalent organic groups. Furthermore, when two or more R 1 are each independently one type of monovalent organic group or two or more types of monovalent organic groups. 1 Examples of the monovalent organic group include an alkyl group, an aryl group, a vinyl group, an allyl group, a glycidyl group, etc. In addition, in the general formula (1), R is preferably a monovalent organic group, particularly an alkyl group, an aryl group, or a vinyl group.

[0017] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. These alkyl groups may be linear or branched, and further, a hydrogen atom of the alkyl group may be substituted with a functional group containing a fluorine atom or a hetero atom.

[0018] Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

[0019] Specific examples of the compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, and ethyltri-sec-butoxysilane. silane, ethyl tri-tert-butoxysilane, ethyl triphenoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri-n-propoxysilane, vinyl tri-iso-propoxysilane, vinyl tri-n-butoxysilane, vinyl tri-sec-butoxysilane, vinyl tri-tert-butoxysilane, vinyl triphenoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, n-propyl tri-n-propoxysilane, n-propyl tri-iso-propoxysilane, n-propyl Tri-n-butoxysilane, n-propyl tri-sec-butoxysilane, n-propyl tri-tert-butoxysilane, n-propyl triphenoxysilane, i-propyl trimethoxysilane, i-propyl triethoxysilane, i-propyl tri-n-propoxysilane, i-propyl tri-iso-propoxysilane, i-propyl tri-n-butoxysilane, i-propyl tri-sec-butoxysilane, i-propyl tri-tert-butoxysilane, i-propyl triphenoxysilane, n-butyl trimethoxysilane, n-butyl n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltri-iso-propoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane,sec-Butyltri-tert-butoxysilane, sec-Butyltriphenoxysilane, t-Butyltrimethoxysilane, t-Butyltriethoxysilane, t-Butyltri-n-propoxysilane, t-Butyltri-iso-propoxysilane, t-Butyltri-n-butoxysilane, t-Butyltri-sec-butoxysilane, t-Butyltri-tert-butoxysilane, t-Butyltriphenoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltri-n-propoxysilane, Phenyltri-iso-propoxy Silane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-trifluoropropyltrimethoxysilane, gamma-trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-is o-Propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldi-iso-propoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi -n-propoxysilane, di-n-propyl di-iso-propoxysilane, di-n-propyl di-n-butoxysilane, di-n-propyl di-sec-butoxysilane, di-n-propyl di-tert-butoxysilane, di-n-propyl diphenoxysilane, di-iso-propyl dimethoxysilane, di-iso-propyl diethoxysilane, di-iso-propyl di-n-propoxysilane, di-iso-propyl di-iso-propoxysilane, di-iso-propyl di-n-butoxysilane, di-iso-propyl di-sec-butoxysilane,Di-isopropyl di-tert-butoxysilane, di-isopropyl diphenoxysilane, di-n-butyl dimethoxysilane, di-n-butyl diethoxysilane, di-n-butyl di-n-propoxysilane, di-n-butyl di-iso-propoxysilane, di-n-butyl di-n-butoxysilane, di-n-butyl di-sec-butoxysilane, di-n-butyl di-tert-butoxysilane, di-n-butyl diphenoxysilane, di-sec-butyl dimethoxysilane, di-sec-butyl diethoxysilane, di-sec-butyl di-n-propoxysilane, di-sec-butyl di-iso-propoxysilane, di-sec-butyl di-n-butoxysilane, di-sec-butyl di-sec-butoxysilane, di-sec-butyl di-tert-butoxysilane, di-sec- Examples of the silane include butyldiphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldi-iso-propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldiphenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, and divinyldimethoxysilane.

[0020] Among the compounds represented by the general formula (1), methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. are easily available industrially and are therefore preferred. These may be used alone or in combination of two or more.

[0021] In the general formula (2), R 2 As the monovalent organic group represented by the formula (1), R 1 In addition, the four R 2 may be, independently of each other, one type of monovalent organic group, or two or more types of monovalent organic groups.

[0022] Specific examples of the compound represented by general formula (2) include tetramethoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc. Among these, tetramethoxysilane and tetraethoxysilane are preferred because they are easily available industrially.

[0023] Solution A is a solution in which the silane compound is dissolved in a solvent. Examples of the solvent that can be used for solution A include water; alcohols such as methanol, ethanol, n-propanol, and isopropanol; aprotic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether-based solvents such as diethyl ether and tetrahydrofuran; and high-boiling point solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Two or more types of solvents may be used.

[0024] In the method for producing a silicone polymer of the present invention, in order to promote the hydrolysis and condensation of the silane compound, a catalyst-containing solution B is used. Solution B is a solution in which a catalyst is dissolved in a solvent.

[0025] As the catalyst, either an acid catalyst or a base catalyst can be used. The acid catalyst is preferably an acid catalyst other than hydrochloric acid, and both inorganic and organic acids can be used. Examples of inorganic acids include nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Among them, organic acids are preferred because they have high compatibility with organic solvents. Preferred organic acids are oxalic acid, maleic acid, and methanesulfonic acid. Two or more types of acid catalysts may be used.

[0026] As the base catalyst, either an inorganic base or an organic base can be used. Specific examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, calcium carbonate, and sodium hydrogen carbonate. Specific examples of the organic base include quaternary ammonium compounds, which do not contain metals and are therefore suitable for use in electronic information materials. Among these, quaternary ammonium compounds containing a hydroxyl group are preferred.

[0027] Examples of the quaternary ammonium compound include hydroxymethyltrimethylammonium hydroxide, 1-hydroxyethyltrimethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, 1-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 3-hydroxypropyltrimethylammonium hydroxide, hydroxymethyltriethylammonium hydroxide, 1-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltriethylammonium hydroxide, 1-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 3-hydroxypropyltriethylammonium hydroxide, hydroxymethyltripropylammonium hydroxide, 1-hydroxyethyltripropylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 1-hydroxypropyltripropylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, hydroxide, 3-hydroxypropyltripropylammonium hydroxide, hydroxymethyltributylammonium hydroxide, 1-hydroxyethyltributylammonium hydroxide, 2-hydroxyethyltributylammonium hydroxide, 1-hydroxypropyltributylammonium hydroxide, 2-hydroxypropyltributylammonium hydroxide, 3-hydroxypropyltributylammonium hydroxide, bis(hydroxymethyl)dimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tetrabutylammonium fluoride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetra-n-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, benzyltrin-butylammonium bromide, benzyltriethylammonium bromide, benzyltrimethylammonium bromide,n-Octyltrimethylammonium bromide, hexyltrimethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetradecyltrimethylammonium bromide, tetramethylammonium bromide, tetra-n-propylammonium bromide, tetrabutylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetra-n-propylammonium iodide, trimethylphenylammonium iodide, benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium thiocyanate, tetramethylammonium p-toluenesulfonate, etc.,

[0028] Among these, 2-hydroxyethyltrimethylammonium hydroxide, 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxyethyltributylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, benzyltributylammonium chloride, benzyltrimethylammonium chloride, tetra-n-butylammonium chloride, tetramethylammonium chloride, benzyltri-n-butylammonium bromide, benzyltrimethylammonium bromide, hexyltrimethylammonium bromide, tetrabutylammonium bromide, tetradecyltrimethylammonium bromide, Preferred are tetramethylammonium bromide, tetramethylammonium bromide, benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium thiocyanate, and tetramethylammonium p-toluenesulfonate, and more preferred are tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide.Tetramethylammonium hydroxide is inexpensive and the reaction can be easily controlled, and 2-hydroxyethyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide are generally obtained by the addition reaction of trimethylamine, dimethylamine, and methylamine with ethylene oxide. Since no metals are used as raw materials, 2-hydroxyethyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide, which have low metal contents, are easily available in industrial grade and are preferred.

[0029] The amount of the catalyst used is preferably 0.002 to 2.0 mol, and more preferably 0.005 to 1.0 mol, per mol of the total amount of alkoxyl groups in the silane compound.

[0030] Examples of the solvent that can be used for solution B include water, alcohols such as methanol, ethanol, n-propanol, and isopropanol, aprotic solvents such as toluene and xylene, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, ether-based solvents such as diethyl ether and tetrahydrofuran, and high-boiling point solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Two or more types of solvents may be used.

[0031] Solution A or solution B contains water. The water is used to hydrolyze and polycondense the silane compound. The type of water is not particularly limited, and industrial water, city water, well water, distilled water, ion-exchanged water, ultrapure water, etc. may be used. One type of water may be used, or two or more types may be used. Among them, ion-exchanged water and ultrapure water, which have high electrical resistivity, are preferred, and ultrapure water, which has an electrical resistivity of 15 MΩ·cm or more, is preferred because of its low metal content.

[0032] Water may be added to solution A or solution B. When water is added to solution B, unintended hydrolysis of the silane compound does not occur, which is preferable.

[0033] The amount of water used is preferably 1.0 to 15.0 equivalents, more preferably 1.0 to 10.0 equivalents, relative to 1 equivalent of the total amount of alkoxyl groups of the silane compound. It is even more preferably 1.0 to 5.0 equivalents. When the amount of water is 1.0 equivalent or more, the hydrolysis and polycondensation reaction of the silane compound proceeds quickly, and when the amount is 15.0 equivalents or less, the reaction of the silane compound is controlled and gelation does not occur, which is preferable.

[0034] The method for producing a silicone polymer of the present invention includes a step of mixing solution A and solution B in a mixer to obtain a mixture. When using a mixed solution mixed in a mixer, solution A and solution B can be stored separately, which is preferable as there is no need to consider the pot life.

[0035] The mixer may be a driven mixer such as a centrifugal pump, a volute pump, or an in-line mixer with a stirring blade, or a stationary mixer such as a static mixer, a nozzle, an orifice, or a T-shaped reactor. Among them, a stationary mixer without a driving part or a sliding part, so-called a static mixer, has no driving part, so there is no risk of dust generation from sliding parts or oil contamination, and is suitable for the production of materials for pharmaceuticals and electronic information materials, which require strict management. Static mixers have a larger specific surface area than general reaction vessels, making it easier to manage the temperature.

[0036] The inner diameter of the pipe used in the static mixer is preferably 1 to 20 mm, and more preferably 1 to 10 mm. If the inner diameter is 1 mm or more, the pressure loss is small and the risk of clogging is low. If the inner diameter is 20 mm or less, mixing proceeds quickly, which is preferable. Furthermore, in the case of a micromixer in which the inner diameter of the flow path made of the pipe or block of the static mixer is about 1 mm, the diffusion distance of the substance is limited when the mixing is accompanied by a reaction, so the reaction proceeds quickly, which is preferable. If the inner diameter of the static mixer is small, the specific surface area becomes even larger, which is preferable.

[0037] In static mixers and micro mixers, elements consisting of rectangular plates twisted 180 degrees in opposite directions are arranged alternately inside a tube. The number of elements is preferably 12 or more, and more preferably 18 or more. If the number of elements is 12 or more, sufficient mixing is achieved regardless of the feed rate of the raw materials, which is preferable.

[0038] The material of the mixer may be stainless steel such as SUS304 or SUS316, carbon steel such as SS41, SC, or SCM, metal such as Hastelloy, titanium, Monel, nickel, Carpenter, or tantalum, resin such as Teflon (registered trademark), PFA, PVC, FRP, or CFRP, or ceramic, rubber-lined, Teflon-lined, or glass-lined metal. Teflon or Teflon-lined materials are preferred because they do not dissolve metals into the mixed liquid. Specific examples of static mixers include Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Toray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, Bran&Lube mixer type, YMC Deneb type, YMC Spica type, YMC Hadar type, IMM CPMM-R300 type, and Noritake K1-24-P.

[0039] The pressure when mixing the mixture of solution A and solution B in the mixer is preferably 0 MPa to 5 MPa, more preferably 0 MPa to 2 MPa. The temperature when mixing in the mixer is preferably 0 to 100° C., more preferably 5° C. to 80° C. If the temperature is 0° C. or higher, mixing is sufficient, and if it is 100° C. or lower, the reaction can be easily controlled, which is preferable.

[0040] The time for mixing in the mixer depends on the feed rate of the raw materials and the design of the mixer, but is preferably 0.1 to 600 seconds, more preferably 1 to 300 seconds. If it is 0.1 seconds or more, mixing is sufficient, and if it is 600 seconds or less, it is preferable because it has little effect on the control of the reaction time.

[0041] A pump is used to supply the raw materials to the mixer. It is preferable to use a personal computer (hereinafter sometimes referred to as "PC") to control the pressure and flow rate of the pump, as this leads to automation and labor saving.

[0042] The method for producing a silicone polymer of the present invention includes a step of supplying the mixture to a tubular reactor having an inner diameter of 1 to 20 mm and reacting to obtain a reaction liquid. A tubular reactor is a type of reactor in which a reaction is carried out while a fluid is flowing through a tube. The tubular reactor is not particularly limited as long as it can withstand the temperature and pressure required for the polymerization reaction of a silicone polymer, and examples thereof include a pipe, a tube, a hose, and the like. The inner diameter of the tubular reactor is 1 to 20 mm, and more preferably 1 to 10 mm. If the inner diameter is 1 mm or more, the pressure loss is small and the risk of clogging is low. In addition, even if a long tubular reactor is designed or the supply amount is increased to increase the production amount, excessive pressure is not applied. On the other hand, a tubular reactor having an inner diameter of 20 mm or less is preferable because the diffusion distance of the substance is short compared to a conventional reaction vessel, the apparent reaction rate is high, and the reaction is completed quickly.

[0043] The material of the tube of the tubular reactor is not particularly limited, but examples thereof include stainless steels such as SUS304 and SUS316, carbon steels such as SS41, SC, and SCM, metals such as Hastelloy, titanium, Monel, nickel, Carpenter, and tantalum, resins such as Teflon, PFA, PVC, FRP, and CFRP, and further, ceramics, rubber-lined, Teflon-lined, and glass-lined materials on metals, etc. When Teflon, PFA, or Teflon-lined materials are used, metals are not eluted into the mixed liquid, which is preferable.

[0044] The pressure during the reaction in the tubular reactor is preferably 0 MPa to 5 MPa, more preferably 0 MPa to 2 MPa. A pressure of 0 MPa or more is preferable because the reaction can be carried out at a temperature equal to or higher than the boiling point of the solvent, and a pressure of 5 MPa or less is preferable because the apparatus can be simplified. The temperature during the reaction in the tubular reactor is preferably 0 to 200°C, and more preferably 5 to 150°C.

[0045] The reaction time in the tubular reactor depends on the volume of the tubular reactor and the supply rate of the raw materials, but is preferably 1 to 900 seconds, more preferably 10 to 600 seconds. If it is 1 second or more, polymerization is sufficient, and if it is 900 seconds or less, it is economically preferable.

[0046] When reacting the silane compound, an alcohol may be added. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Among them, methanol is preferred because it is easy to distill off. Two or more types of alcohol may be used.

[0047] The amount of the alcohol used is preferably 0.5 times by mass or more, more preferably 1.0 to 10 times by mass, even more preferably 1.2 to 8 times by mass, and even more preferably 1.5 to 5 times by mass relative to the mass of the silane compound. When the amount of the alcohol is 0.5 times by mass or more of the silane compound, the mass of the silane compound represented by general formula (1) and / or the silane compound represented by general formula (2) is easily mixed with water, and gelation of the silicone polymer is suppressed and stabilized. When the amount is 10 times by mass or less, it is economically preferable.

[0048] When reacting the silane compound, a solvent may be added in addition to the alcohol. As the solvent, aprotic solvents such as toluene and xylene, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, ether-based solvents such as diethyl ether and tetrahydrofuran, and high-boiling solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate may be used. Two or more types of solvents may be used.

[0049] The method for producing a silicone polymer of the present invention includes a step of contacting the reaction liquid with an ion exchange resin. By contacting the reaction liquid with the ion exchange resin, catalysts and ionic impurities such as metals can be continuously removed from the reaction liquid. The ion exchange resin can be regenerated and used repeatedly, which is preferable in terms of resources and economy.

[0050] The ion exchange resin may be either a cation exchange resin or an anion exchange resin, and the reaction solution containing an acid catalyst may be contacted with the anion exchange resin, and the reaction solution containing a base catalyst may be contacted with the cation exchange resin. The cation exchange resin may be either a strongly acidic cation exchange resin or a weakly acidic cation exchange resin. A commonly used one, for example, a commercially available hydrogen type cation exchange resin, specifically, for example, "Amberlyst" (manufactured by Organo Corporation), "Lewatit (registered trademark)" (manufactured by Lanxess KK), "Diaion (registered trademark)" (manufactured by Mitsubishi Chemical Corporation), "Monosphere (registered trademark)" (manufactured by Dow Chemical Co., Ltd.), etc., may be used. As the cation exchange resin, a strongly acidic cation exchange resin is preferred. The anion exchange resin may be either a strongly basic anion exchange resin or a weakly basic anion exchange resin, and preferably a strongly basic anion exchange resin. Examples of anion exchange resins include "Amberlyst" (manufactured by Organo Corporation), "Lewatit (registered trademark)" (manufactured by Lanxess KK), "Diaion (registered trademark)" (manufactured by Mitsubishi Chemical Corporation), and "Monosphere (registered trademark)" (manufactured by The Dow Chemical Company).

[0051] Ion exchange resins are broadly classified into gel type and macroporous type according to their macroscopic structure. Generally, copolymers of styrene and divinylbenzene are used as the base polymer matrix for ion exchange resins, but gel type ion exchange resins are formed by copolymerizing styrene and divinylbenzene to form a spherical, almost homogeneous, so-called gel phase, and are transparent in appearance. On the other hand, macroporous type ion exchange resins are polymerized by adding a high-boiling organic solvent (e.g., aromatic hydrocarbons, halogenated ethane, etc.) that is insoluble in water, dissolves styrene and divinylbenzene well, and can sufficiently swell the resulting copolymer when copolymerizing styrene and divinylbenzene. After polymerization, the organic solvent is removed to obtain a porous base polymer matrix with large pores (macropores) deep inside the sphere, and is called macroporous type.

[0052] In the present invention, a gel-type ion exchange resin is used as the ion exchange resin, which makes it difficult for the silicone polymer to be adsorbed by the ion exchange resin, and as compared with the case where a macroporous type is used, a silicone polymer can be obtained in a higher yield, with a lower degree of dispersion, and with excellent functionality, particularly oxygen gas etching resistance.

[0053] Examples of gel-type ion exchange resins include "Amberlite (registered trademark)" (Organo Corporation), IR120B, IR124, HPR1200, HPR1024, HPR1006NNC, IRA400J, IRA402BL, HPR4002, HPR4580, IRA410J, HPR4010, HPR4780, and IRA67.

[0054] Examples of the method for contacting the reaction liquid with the ion exchange resin include a method of passing the reaction liquid through a column filled with an ion exchange resin, and a method of adding an ion exchange resin to the reaction liquid and stirring it. In the latter case, the ion exchange resin may be removed by filtration or the like after the treatment. Preferably, the reaction liquid containing the silicone polymer, the quaternary ammonium compound, and water is passed through a tank filled with a cation exchange resin to contact the reaction liquid with the cation exchange resin.

[0055] The amount of the ion exchange resin (preferably the cation exchange resin) is preferably 1.0 to 10.0 equivalents relative to 1 equivalent of the catalyst (preferably the quaternary ammonium compound) used, more preferably 1.1 to 8.0 equivalents, and even more preferably 1.2 to 5.0 equivalents. If the amount of the cation exchange resin is 1.0 equivalent or more, the catalyst in the reaction solution can be removed, and if the amount is 10.0 equivalent or less, the obtained silicone polymer is stable and the amount of the ion exchange resin used is small, which is economically preferable.

[0056] The temperature when the reaction liquid is brought into contact with the ion exchange resin is preferably 0 to 60° C., and more preferably 5 to 50° C. If the temperature is 0° C. or higher, catalysts such as quaternary ammonium compounds are sufficiently removed, and if the temperature is 60° C. or lower, the silicone polymer is stable, which is preferable.

[0057] The time for contacting the reaction liquid with the ion exchange resin is preferably 5 minutes to 6 hours, and more preferably 10 minutes to 3 hours. If the contact time is 5 minutes or more, the catalyst such as the quaternary ammonium compound can be removed, and if it is 6 hours or less, the silicone polymer is stable, which is preferable.

[0058] In the method for producing silicone polymers of the present invention, raw materials consisting of solution A containing a silane compound and solution B containing a catalyst are continuously supplied by pumps or the like to mix and react, and therefore manual operation is less and labor-saving compared to conventional batch reactions. In addition, automatic operation is possible by controlling the operation of pumps and the temperature control of the mixer and tubular reactor by programs using a personal computer or the like. By utilizing an information transmission network, the operation of the equipment can be remotely controlled, and workers are not exposed to dangerous chemicals. Work near risky equipment can also be reduced. Automatic operation eliminates the variation caused by manual operation, allowing for highly reproducible production.

[0059] The weight average molecular weight of the silicone polymer produced by the method for producing a silicone polymer of the present invention is preferably 300 to 100,000, more preferably 500 to 50,000, and even more preferably 1,000 to 20,000. If the weight average molecular weight is 300 or more, the polymer can form a coating film, and if it is 100,000 or less, the polymer is soluble in an organic solvent, which is preferable.

[0060] The silicone polymer preferably has a polydispersity (Mw / Mn) calculated by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) of 1.00 to 1.20, and more preferably 1.00 to 1.16.

[0061] In the present invention, the weight average molecular weight (Mw), number average molecular weight (Mn) and Z average molecular weight (Mz) of the silicone polymer can be measured using gel permeation chromatography (GPC) and calculated relative to standard polystyrene. The silicone polymer may have a cage-type higher-order structure.

[0062] The silicone polymer may be dissolved in a solvent. As the solvent, an alcohol-based solvent or a high-boiling point solvent is used. As the alcohol-based solvent, methanol, ethanol, isopropanol, etc. are listed, and as the high-boiling point solvent, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, ethyl lactate, etc. are listed.

[0063] The silicone polymer and the composition thereof can be formed into a coating film by a general method such as spin coating. As a method for obtaining a coating film using the silicone polymer, for example, a method for forming a film by applying a silicone polymer to a substrate and heating the applied film can be mentioned.

[0064] The coating film is prepared by spin-coating the silicone polymer onto a substrate to form a thin film, which is then heated to obtain a coating film. Examples of the substrate include glass substrates, ceramic substrates, silicon wafers, and substrates made of resins such as polyethylene, polypropylene, and polypropylene terephthalate.

[0065] Next, the thin film formed on the substrate is heated on a hot plate or in an incubator to remove the solvent and to cause hydrolysis and polycondensation reactions of the silicone polymer, thereby producing a coating film. In general, in the preparation of a membrane, the membrane can be prepared by heating at preferably 80° C. or higher, more preferably 100° C. or higher.

[0066] The coating film thus produced is very hard, preferably having a pencil hardness of 4H or more, and has excellent scratch resistance. The pencil hardness can be measured in accordance with JIS K5600-5-4 (1999).

[0067] In addition, when the silicone polymer and the composition thereof are applied to a substrate, a thin film can be formed on the substrate, and a thermosetting film can be formed on the substrate by applying heat. The thermosetting film thus formed has excellent properties such as transparency, heat resistance, and oxygen gas etching resistance, and can be used as a protective film for semiconductors and displays, a resist underlayer film, etc.

[0068] An example of an apparatus suitable for use in the method for producing a silicone polymer of the present invention is shown in Figure 1. The apparatus shown in Figure 1 generally comprises a monomer tank 1 for preparing solution A, a catalyst tank 2 for preparing solution B, a mixer 4 for mixing solutions A and B, a tubular reactor 5 for reacting the resulting mixture of solutions A and B, and a column 6 packed with an ion exchange resin with which the resulting reaction liquid is contacted.

[0069] The monomer tank 1 is an apparatus for preparing a monomer solution (solution A) by weighing, charging, mixing, and removing the silane compound and the solvent, and has means for each of the operations described above. The monomer tank 1 may be of either a batch type or a continuous type, or a combination of these. The solution A prepared in the monomer tank 1 is supplied to a mixer 4 via a pump 3 such as a dual plunger pump and a flow control means.

[0070] The catalyst tank 2 is an apparatus for preparing a catalyst solution (solution B) by weighing, charging, mixing, and removing the catalyst and its solvent, and has means for each of the operations described above. The catalyst tank 2 may be of either a batch type or a continuous type, or a combination of these. Solution B prepared in the catalyst tank 2 is supplied to a mixer 4 via a pump 3 such as a dual plunger pump and a flow control means.

[0071] As described above, the mixer 4 is preferably a static mixer such as a static mixer or a micro mixer. The mixer 4 mixes the supplied solutions A and B to prepare a mixture (raw material solution). The obtained raw material solution is supplied to the tubular reactor 5 as is.

[0072] As described above, the tubular reactor 5 is a reactor having an inner diameter of 1 to 20 mm. The material of the tubular reactor 5 is not particularly limited, and may be a rigid material such as metal or a relatively flexible material such as resin. In the tubular reactor 5, the silane compound, catalyst, and water contained in the supplied raw material solution react with each other to polymerize a silicone polymer. The tubular reactor 5 has a means for appropriately adjusting the polymerization conditions such as temperature, pressure, and residence time. The reaction liquid containing the obtained silicone polymer, catalyst, etc. is discharged.

[0073] The reaction liquid discharged from the tubular reactor 5 is supplied to a column 6 filled with an ion exchange resin, where the catalyst that has come into contact with the ion exchange resin is removed. The column 6 has a means for appropriately adjusting the contact conditions with the ion exchange resin, such as temperature, pressure, and residence time. The reaction liquid containing the silicone polymer and from which the catalyst has been removed is discharged from the column 6 and collected in a product container or the like.

[0074] The silicone polymer produced by the present invention does not contain metal as a raw material and can therefore be suitably used in electronic information materials such as displays and semiconductors. Furthermore, it can be used in a wide range of fields, including paints, adhesives, etc., in addition to the electronic information materials field. EXAMPLES

[0075] The present invention will be described in detail below with reference to examples and comparative examples. In the following examples, the following apparatuses were used for analysis, and general reagents purchased from reagent manufacturers were used as raw materials unless otherwise specified. The following methods were used for analysis.

[0076] ·Molecular weight measurement Analysis was performed using a Tosoh HLC-8420 GPC system with Tosoh TSKgel SuperHZ3000, TSKgel SuperHZ2000, and TSKgel SuperHZ1000 connected in series. Detection was performed with an RI (refractometer), and one TSKgel SuperH-RC was used as the reference column. Wako Pure Chemical Industries used tetrahydrofuran as the developing solvent, and the flow rate of the column and reference column was 0.35 mL / min. The measurement temperature was 40°C for both the plunger pump and the column. Sample preparation was performed by diluting approximately 0.025 g of silicone polymer with 10 mL of tetrahydrofuran, and injecting 25 μL of the diluted solution. For molecular weight distribution calculations, TSK standard polystyrenes (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, F-80) manufactured by Tosoh Corporation were used as standards.

[0077] Solid concentration measurement and yield measurement Approximately 1.0 g of the solution containing the silicone polymer was precisely weighed in an aluminum cup, and the mass was measured after baking at 175° C. for 1 hour using a hot plate to determine the mass of the solid content relative to approximately 1.0 g of the solution containing the silicone polymer, and the solid content concentration (mass%) of the solution containing the silicone polymer was calculated. Furthermore, the solid content of the entire silicone polymer was calculated from the obtained solid content concentration, and the ratio to the theoretical yield was taken as the yield.

[0078] -Oxygen gas etching resistance The silicone polymer was applied onto a silicon wafer (substrate) by spin coating using a spin coater (MS-100, manufactured by Mikasa Co., Ltd.). The silicon wafer was then heated (baked) on a hot plate at 215°C for 1 minute. The thickness of the resulting film was measured using an optical interference film thickness measuring device (Lambda Ace VM-1210, manufactured by SCREEN Semiconductor Solutions Co., Ltd.) and found to be 130 nm on average. The substrate with the resulting coating film was treated using an etching device (parallel plate type RIE device) under conditions of 200 W, 5 Pa, oxygen gas flow rate of 50 sccm, and 10 min, and the etching rate (nm / min) was calculated from the average film thickness before and after treatment.

[0079] Example 1 As a flow reactor, KeyChem Integral (manufactured by YMC Corporation), consisting of two dual plunger pumps, a micromixer, a controller, and a control PC, was used. Each of the dual plunger pumps was connected to a micromixer. Furthermore, the micromixer was connected to a 250 ml column through a tube (tubular reactor) with an inner diameter of 2.4 mm and a length of 138 mm, and the 250 ml column was filled with 200 ml of pretreated ion exchange resin ("Amberlite (registered trademark)" IR124(H)-HG, a gel-type cation exchange resin manufactured by Organo Corporation). The reaction liquid that passed through the 250 ml column was collected in an eggplant flask.

[0080] 9.28g (0.061mol) of tetramethoxysilane, 24.91g (0.183mol) of methyltrimethoxysilane, and 102.58g of methanol were weighed in a 500ml poly container and stirred with a magnetic stirrer to obtain a monomer solution (solution A). Also, 38.61g of a 50% aqueous solution of choline (2-hydroxyethyltrimethylammonium hydroxide) and 85.48g of methanol were weighed in a 500ml poly container and stirred with a magnetic stirrer to obtain a catalyst solution (solution B).

[0081] A plastic container containing solution A and a plastic container containing solution B were connected to dual plunger pumps (hereinafter sometimes referred to as "Pump A" and "Pump B"), respectively, and the solutions were sent to the micromixer. The sending rate of Pump A, which supplied solution A, was 0.90 ml / min, and the sending rate of Pump B, which supplied solution B, was 0.77 ml / min, and the temperature of the micromixer was 25°C. The mixture of solutions A and B mixed in the micromixer was reacted in a tube (tubular reactor) with an inner diameter of 2.4 mm and a length of 138 m. The reaction solution remained in the tube for 225 seconds.

[0082] The reaction solution discharged from the tubular reactor was brought into contact with an ion exchange resin packed in a column to remove the catalyst. Meanwhile, while the reaction solution was being collected in a recovery flask, 239.33 g of propylene glycol monoethyl ether was added to the recovery flask using a plunger pump. The resulting reaction solution was concentrated under reduced pressure to obtain 159.4 g of a colorless, transparent silicone polymer solution.

[0083] The number average molecular weight (Mn) of the obtained silicone polymer was 1,410, the weight average molecular weight (Mw) was 1,590, the polydispersity (Mw / Mn) was 1.13, and the solid content was 10.1% by mass. The yield of the silicone polymer calculated from the solid content was 100%. In addition, except for the operation of feeding the raw materials, the operation of concentrating the reaction liquid under reduced pressure was performed automatically using a control PC.

[0084] Comparative Example 1 The procedure of Example 1 was repeated, except that the ion exchange resin was changed from "Amberlite (registered trademark)" IR124(H)-HG (a gel-type cation exchange resin manufactured by Organo Corporation) to "Amberlyst (registered trademark)" 15JWET (a macroporous cation exchange resin manufactured by Organo Corporation), to obtain 156.2 g of a colorless, transparent silicone polymer solution.

[0085] The silicone polymer obtained had a number average molecular weight (Mn) of 1,500, a weight average molecular weight (Mw) of 1,920, a degree of dispersion (Mw / Mn) of 1.28, and a solid content of 10.0 mass%. The yield of the silicone polymer calculated from the solid content was 98%. Compared to Example 1, the degree of dispersion was high and the yield was low.

[0086] Example 2 9.28g (0.061mol) of tetramethoxysilane, 24.91g (0.183mol) of methyltrimethoxysilane, and 102.58g of methanol were weighed in a 500ml poly container and stirred with a magnetic stirrer to obtain a monomer solution (solution A). Also, 38.61g of a 50% aqueous solution of choline (2-hydroxyethyltrimethylammonium hydroxide) and 85.48g of methanol were weighed in a 500ml poly container and stirred with a magnetic stirrer to obtain a catalyst solution (solution B).

[0087] A plastic container containing solution A and a plastic container containing solution B were each connected to a dual plunger pump, and the solutions were fed into the micromixer. The feed rate of pump A, which supplied solution A, was 1.01 ml / min, and the feed rate of pump B, which supplied solution B, was 0.87 ml / min, and the temperature of the micromixer was 25°C. The mixture of solutions A and B mixed in the micromixer was reacted in a tube (tubular reactor) with an inner diameter of 2.4 mm and a length of 138 m. The reaction solution remained in the tube for 200 seconds.

[0088] The catalyst was removed by contacting the reaction liquid discharged from the tubular reactor with an ion exchange resin packed in a column. The 250 ml column was packed with 150 ml of pretreated ion exchange resin ("Amberlite (registered trademark)" IR124(H)-HG, a gel-type cation exchange resin manufactured by Organo Corporation). Meanwhile, while the reaction liquid was being collected in an eggplant flask, 239.33 g of propylene glycol monoethyl ether was added to the eggplant flask using a plunger pump. The resulting reaction liquid was concentrated under reduced pressure to obtain 159.4 g of a colorless, transparent silicone polymer solution.

[0089] The number average molecular weight (Mn) of the obtained silicone polymer was 1,450, the weight average molecular weight (Mw) was 1,680, the polydispersity (Mw / Mn) was 1.16, and the solid content was 10.2% by mass. The yield of the silicone polymer calculated from the solid content was 100%. In addition, except for the operation of feeding the raw materials, the operation of concentrating the reaction liquid under reduced pressure was performed automatically using a control PC.

[0090] Example 3 The ion exchange resin used in Example 2 was washed with methanol. About 1500 g of 3.5% hydrochloric acid was prepared in a 2 L plastic container, and supplied to the micromixer with a dual plunger pump at a supply rate of about 10 ml / min. The ion exchange resin was regenerated by contacting it with the ion exchange resin. After regeneration, the resin was pretreated with methanol and used again in the same manner as in Example 2 to obtain 156.2 g of a colorless and transparent silicone polymer.

[0091] The resulting silicone polymer had a number average molecular weight (Mn) of 1,460, a weight average molecular weight (Mw) of 1,690, a polydispersity (Mw / Mn) of 1.16, and a solid content of 10.1 mass%. The yield of the silicone polymer calculated from the solid content was 98%. Even when the gel-type ion exchange resin was regenerated and reused, a silicone polymer with a low polydispersity was obtained, although the yield decreased.

[0092] Comparative Example 2 The procedure was repeated in the same manner as in Example 2, except that the ion exchange resin was changed from "Amberlite (registered trademark)" IR124(H)-HG (a gel-type cation exchange resin manufactured by Organo Corporation) to "Amberlyst (registered trademark)" 15JWET (a macroporous cation exchange resin manufactured by Organo Corporation), and 149.6 g of a colorless, transparent liquid was obtained.

[0093] The silicone polymer obtained had a number average molecular weight (Mn) of 1,460, a weight average molecular weight (Mw) of 1,790, a degree of dispersion (Mw / Mn) of 1.22, and a solid content of 10.0 mass%. The yield of the silicone polymer calculated from the solid content was 94%. Compared to Example 2, the degree of dispersion was high and the yield was low.

[0094] Example 4 As a flow reactor, KeyChem Integral (manufactured by YMC Co., Ltd.), consisting of two dual plunger pumps, a static mixer (K1-24-P, manufactured by Noritake Co., Ltd.), a controller and a control PC, was used. Each of the dual plunger pumps was connected to a static mixer. Furthermore, the static mixer was connected to a 5L column with a tube (tubular reactor) having an inner diameter of 2.4 mm and a length of 15.3 m, and the 5L column was filled with 3.75 ml of pretreated ion exchange resin ("Amberlite (registered trademark)" IR124(H)-HG, gel-type cation exchange resin manufactured by Organo Co., Ltd.). The static mixer and the tube were kept at 25°C in an incubator. The reaction liquid that passed through the 5L column was collected in an eggplant flask.

[0095] In a 10L clean bottle, 234.88g (1.543mol) of tetramethoxysilane, 630.57g (4.629mol) of methyltrimethoxysilane, and 4759.98g of methanol were weighed and stirred to obtain a monomer solution (solution A). Furthermore, 996.32g of 25% tetramethylammonium hydroxide aqueous solution was weighed in a 4L clean bottle to obtain a catalyst solution (solution B). The clean bottles containing the monomer solution, catalyst solution, and dilution solution were each connected to a dual plunger pump. The liquid delivery rate of pump A supplying solution A was 35.6ml / min, and the liquid delivery rate of pump B supplying solution B was 5.0ml / min, and the monomer solution and catalyst solution were supplied to the static mixer and mixed. The mixture consisting of the monomer solution and catalyst solution mixed in the static mixer reacted in a tube with an inner diameter of 2.4mm and a length of 15.3m. The time the reaction liquid remained in the tube was 103 seconds. The reaction solution discharged from the tube was brought into contact with an ion exchange resin packed in a column to remove the catalyst. Meanwhile, while the reaction solution was collected in a 20 L round flask, 5426 g of propylene glycol monoethyl ether was added to the 20 L round flask using a plunger pump. The reaction solution obtained was concentrated under reduced pressure to obtain 4.015 kg of a colorless, transparent silicone polymer solution. The number average molecular weight (Mn) of the obtained silicone polymer was 1,370, the weight average molecular weight (Mw) was 1,440, the degree of dispersion (Mw / Mn) was 1.30, and the solid content was 10.1 mass%. The yield of the silicone polymer calculated from the solid content was about 100%. The oxygen gas etching resistance of the obtained silicone polymer was evaluated to be 5.0 nm / min.

[0096] Comparative Example 3 The procedure of Example 4 was repeated, except that the ion exchange resin was changed from "Amberlite (registered trademark)" IR124(H)-HG (a gel-type cation exchange resin manufactured by Organo Corporation) to "Amberlyst (registered trademark)" 15JWET (a macroporous cation exchange resin manufactured by Organo Corporation), to obtain 3.905 g of a colorless, transparent silicone polymer solution.

[0097] The number average molecular weight (Mn) of the obtained silicone polymer was 1,530, the weight average molecular weight (Mw) was 2,040, the degree of dispersion (Mw / Mn) was 1.33, and the solid content was 10.1 mass%. The yield of the silicone polymer calculated from the solid content was about 100%. The oxygen gas etching resistance of the obtained silicone polymer was evaluated and found to be 6.0 nm / min. Compared to Example 4, the degree of dispersion was increased and the etching resistance was decreased.

[0098] [Table 1] [Explanation of symbols]

[0099] 1 Monomer tank 2 Catalyst tank 3. Pump 4. Mixer 5 Tubular reactor 6 Columns

Claims

1. A method for producing a silicone polymer, comprising the steps of: continuously supplying and mixing a solution A containing at least one silane compound selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and a solution B containing a catalyst, to a mixer to obtain a mixture; supplying the mixture to a tubular reactor having an inner diameter of 1 to 20 mm and reacting it to obtain a reaction liquid; and continuously supplying the reaction liquid to a column packed with an ion exchange resin to contact the ion exchange resin, in this order; wherein solution A or solution B contains water, and the ion exchange resin is in a gel form. R ａ Si(OR １ ) ４－ａ ・・・・・(1) In the formula, R is a hydrogen atom or a monovalent organic group, R １ represents a monovalent organic group, and a represents an integer of 1 or 2. Si(OR ２ ) ４ ・・・・・(2) In the formula, R ２ represents a monovalent organic group.

2. The method for producing a silicone polymer according to claim 1 , wherein solution B contains water.

3. The method for producing a silicone polymer according to claim 1 or 2, wherein the catalyst is an acid catalyst other than hydrochloric acid or a base catalyst.

4. 4. The method for producing a silicone polymer according to claim 3, wherein the acid catalyst is at least one selected from the group consisting of oxalic acid, maleic acid, phosphoric acid, and methanesulfonic acid.

5. The method for producing a silicone polymer according to claim 3, wherein the base catalyst is a quaternary ammonium compound.

6. The method for producing a silicone polymer according to claim 5, wherein the quaternary ammonium compound is a quaternary ammonium compound containing a hydroxyl group.

7. 7. The method for producing a silicone polymer according to claim 6, wherein the quaternary ammonium compound containing a hydroxyl group is at least one selected from the group consisting of 2-hydroxyethyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide.

8. The method for producing a silicone polymer according to claim 1 or 2, wherein solution A and / or solution B contains an alcohol.

9. The method for producing a silicone polymer according to claim 8, wherein the alcohol is used in an amount 1.0 to 10 times by mass relative to the silane compound.

10. 3. A method for producing a film, comprising the steps of applying the silicone polymer obtained by the method according to claim 1 or 2 to a substrate and heating the applied silicone polymer.

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