Method for producing branched organopolysiloxane containing phenolic hydroxyl group

Abstract

Provided is a method for producing a curing-reactive organopolysiloxane having good alkali solubility and curability (particularly high-energy ray curability). A method for producing a branched organopolysiloxane containing a phenolic hydroxyl group, said branched organopolysiloxane having at least an average unit represented by the following average unit formula (1 '): (D3SiO1 / 2) a (D2SiO2 / 2) b (RSiO3 / 2) c (SiO4 / 2) d (1') (in the formula, R is a monovalent hydrocarbon group or the like, D is each independently the same group as R, at least one of all D is a hydrogen atom, and a, b, c, and d are numbers satisfying the following conditions: 0 < = a, 0 < = b, 0lt; (a + b) and 0 lt; (c + d). And a step in which the branched organopolysiloxane represented by the formula (1) is subjected to a hydrosilylation reaction. The production method may also comprise a step for further introducing the carboxylic acid-containing organic group into the molecule by reacting the phenolic hydroxyl group-containing organic group with an acid anhydride.

Description

Technical Field

[0001] The present invention relates to a method for producing an alkali-soluble branched organopolysiloxane containing a phenolic hydroxyl group that can be cured by actinic rays, such as high-energy rays or electron beams. The branched organopolysiloxane containing a phenolic hydroxyl group produced by the present invention has high solubility in alkaline aqueous solutions and good high-energy ray curability, and therefore exhibits excellent photolithographic performance, and is suitable for use as a resist material or an insulating material for electronic devices and electrical equipment that require patterning, and is particularly suitable for use as a coating agent material. Background Art

[0002] Silicone resins have been used as coating agents, potting agents, insulating materials, etc. for electronic devices and electrical equipment due to their high heat resistance and excellent chemical stability. Among silicone resins, high-energy ray-curable silicone compositions have been reported.

[0003] Touch panels are used in various display devices such as mobile devices, industrial equipment, and car navigation. In order to improve its sensing sensitivity, it is necessary to suppress the film response from the light-emitting parts such as light-emitting diodes (LEDs) and organic EL devices (OLEDs), and an insulating layer is usually arranged between the light-emitting part and the touch screen. On the other hand, thin display devices such as OLEDs have a structure in which multiple functional thin layers are stacked. In recent years, the following research has been conducted: by stacking an insulating layer formed by a high-refractive-index acrylate polymer and a multifunctional polymerizable monomer on the touch screen layer to improve the visibility of the display device. (For example, Patent Documents 1 and 2)

[0004] With the progress of photolithography, the miniaturization of patterns can be achieved in the manufacture of semiconductor elements, and its progress has been remarkable in recent years. As a method for its miniaturization, the short wavelength of the light source used is generally adopted, and in the region where the resolution is below 20nm, the resist material using electron beam and extreme ultraviolet (EUV) has been studied. In the EUV use technology, it is important to utilize the excitation of the irradiated resist material itself, and the polymer with phenol group has been studied in depth as the EUV resist material. Patent document 3 discloses a resist composition with good stability over time containing an acrylic polymer with phenol group and a specific acid generator.

[0005] Similarly, using the characteristics of excellent etching resistance, organosilicon-based resist materials have also been studied. Patent Document 4 discloses a resist composition composed of a phenol-functional polysiloxane as a reaction product of a hydrogen-functional polysiloxane, an alkenyl-functional polysiloxane, and a specific diallyl compound. However, since there are many linear polysiloxane components, the product does not show alkali solubility. In addition, patent documents 5 and 6 disclose phenol-functional polysilsesquioxanes and resist compositions with specific structures. These are alkali-soluble, but there are problems with their solubility. Further, patent document 7 discloses a photosensitive resin composition composed of a mixture of a polysiloxane with a phenolic hydroxyl group protected by acetal and a polysiloxane with a cationic curable group and a phenolic hydroxyl group. The composition here is also alkali-soluble, but polysiloxanes that do not contain a cationic curable group and only contain a phenolic hydroxyl group have not yet been studied.

[0006] That is, although phenol functional polysiloxane and high energy ray curable composition containing the same are disclosed, it is difficult to say that a curable organopolysiloxane and a method for producing the same, which polysiloxane itself has high solubility in alkaline aqueous solution and exhibits excellent high energy ray curability, are fully disclosed.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2013-140229

[0010] Patent Document 2: Japanese Patent Application Publication No. 2021-61056

[0011] Patent Document 3: Japanese Patent Application Publication No. 2017-227733

[0012] Patent Document 4: Japanese Patent Application Publication No. 2004-262952

[0013] Patent Document 5: Japanese Patent Application Publication No. 2016-212350

[0014] Patent Document 6: Japanese Patent Application Publication No. 2005-283991

[0015] Patent Document 7: WO2016-52391 Summary of the invention

[0016] Problems to be solved by the invention

[0017] As described above, there is still a need for a method for producing a curable organopolysiloxane having good alkali solubility and curability (particularly high energy ray curability).

[0018] Solutions for solving problems

[0019] The present invention has been made in order to solve the above-mentioned problems. The present invention has been made by finding that an organopolysiloxane having a phenolic hydroxyl group-containing organic group on a silicon atom and optionally further having a carboxylic acid-containing organic group and having a specific branched structure can be simply produced by a process including a hydrosilylation reaction using an organopolysiloxane having a specific branched structure as a starting material, thereby making it possible to complete the present invention.

[0020] In particular, the present invention relates to a method for producing a phenolic hydroxyl group-containing branched organopolysiloxane having high solubility in an alkaline aqueous solution and good curability. It should be noted that the curing method of the branched organopolysiloxane produced by the present invention is not limited to high-energy ray irradiation, and an optional method in which the high-energy ray-curable functional group can induce a curing reaction can be used, for example, electron beam irradiation can also be used to cure it.

[0021] Specifically, the production method according to the present invention is a method for producing a phenolic hydroxyl group-containing branched organopolysiloxane represented by the following average unit formula (1), comprising the step of subjecting a branched organopolysiloxane represented by the following average unit formula (1′) to a hydrosilylation reaction.

[0022] The following average unit formula (1'):

[0023] (D3SiO 1 / 2 ) a (D2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1')

[0024] (In the formula, R is a group selected from a hydrogen atom, a non-substituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group, D is a group that is independently the same as R, at least one of all D is a hydrogen atom, and a, b, c, and d are numbers that satisfy the following conditions: 0≤a, 0≤b, 0<(a+b), and 0<(c+d).)

[0025] Average unit formula (1):

[0026] (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1)

[0027] {wherein, R is the same group as described above, A is each independently the same group as R,

[0028] is selected from the following formula (21):

[0029] [Chemical formula 1]

[0030]

[0031]

[0032] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), m1 is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site to the silicon atom on the organopolysiloxane)

[0033] The group M shown 1 ,

[0034] From the following formula (22):

[0035] [Chemical formula 2]

[0036]

[0037] (Where R 1 , X and Z are the same groups as described above,

[0038] Y is composed of -Wp-R 2 q-CO2H (wherein W is selected from O (C = O) group, NR 5 (C=O) group, S(C=O) group, p is 0 or 1, q is 0 or 1, R 2 It may also be a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain an oxygen atom or a sulfur atom. 5 is a monovalent hydrophilic group represented by a hydrogen atom or a methyl group,

[0039] m2 is 0 or 1, n is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site with a silicon atom on the organopolysiloxane)

[0040] The group M shown 2 ,

[0041] From the following formula (3):

[0042] [Chemical formula 3]

[0043] *-R 4 -X

[0044] (Where R 4is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is the same group as described above)

[0045] The group J shown, and

[0046] From the following formula (4):

[0047] [Chemical formula 4]

[0048] *-R 4 -Z

[0049] (Where R 4 and Z is the same group as described above)

[0050] The group L shown

[0051] More than one group in which at least one of all A is M 1 , a, b, c, and d are numbers that satisfy the conditions.}

[0052] The production method of the present invention may also include at least the following step (I): mixing a branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') with

[0053] From the following formula (33):

[0054] [Chemical formula 5]

[0055]

[0056] (Where R 6 is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Z is the same group as described above, and k2 is a number in the range of 1 to 3)

[0057] The unsaturated hydrocarbon group-containing compound shown is subjected to a hydrosilylation reaction.

[0058] The production method of the present invention may further include the following step (II): after the step (I), the molecule obtained in the step (I) is made to have the following formula (34):

[0059] [Chemical formula 6]

[0060]

[0061] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, Z is the same group as above, k2 is the same number as above, and * is the bonding site with the silicon atom on the organopolysiloxane)

[0062] The branched organopolysiloxane having the functional group represented by formula (34) is reacted with one or more acidic substances to convert at least a part of the group Z into a hydroxyl group (X), thereby converting the functional group represented by formula (34) into the group M represented by formula (21) 1 .

[0063] The production method of the present invention may further comprise the following step (III): after the step (II), the molecule obtained in the step (II) is provided with a group M represented by the formula (21) 1 The branched organopolysiloxane is reacted with one or more acid anhydrides and the group M 1 A portion of is converted into a group M represented by the formula (22) 2 .

[0064] In the production method of the present invention, the number of silicon atoms in the molecule of the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') may be 50 or less, or may be in the range of 5 to 20.

[0065] In the production method of the present invention, in the average unit formula (1'), a may be a number greater than or equal to 1, and further, a, b, c, and d may be numbers that further satisfy the following condition: 0.5≤a / (b+c+d)≤2.0.

[0066] In the production method of the present invention, the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') may also be composed of

[0067] Average unit formula (1-1'): (D3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1') or

[0068] Average unit formula (1-2'): (D3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2')

[0069] (In these formulae, R and D are the same groups as described above, and a, c, and d are numbers that satisfy the above conditions.)

[0070] The organopolysiloxane shown.

[0071] Effects of the Invention

[0072] The present invention provides a method for efficiently manufacturing a branched organic polysiloxane containing a phenolic hydroxyl group: it has good coating properties on a substrate and is used to form a pattern of a desired shape. In the development process, it shows high solubility in a commonly used alkaline aqueous solution, so in the development process accompanied by selective high-energy ray irradiation, the unreacted / uncured organic polysiloxane and the curable composition containing it can be easily removed by a washing operation using an alkaline aqueous solution, and has the excellent feature of being able to achieve high-precision patterning through a simple process. In particular, the cured product formed by the branched organic polysiloxane containing a phenolic hydroxyl group obtained by the manufacturing method of the present invention is optically transparent and has the advantage of being able to design hardness in a wide range, so it is useful as a resist material using a short-wavelength light source, especially EUV. In addition, it is useful as a material for an insulating layer for electronic devices, especially for thin display devices such as OLED, especially a patterning material, and a coating material. DETAILED DESCRIPTION

[0073] Hereinafter, the production method of the present invention will be described in further detail.

[0074] The branched organopolysiloxane obtained by the production method of the present invention may have at least one phenolic hydroxyl group and optionally a carboxyl group. Due to this property, it has high solubility in alkaline aqueous solutions generally used as photolithography developers in the semiconductor industry.

[0075] Among them, alkali solubility means that in the development process for forming a pattern of a desired shape, the formed coating film is soluble in a commonly used alkaline aqueous solution. As alkaline aqueous solutions, well-known alkaline aqueous solutions such as sodium hydroxide (NaOH), potassium hydroxide (KOH), and quaternary ammonium salts are used, but standardly, aqueous solutions of KOH and tetramethylammonium hydroxide (TMAH) are used, and TMAH aqueous solutions are particularly commonly used. In the present invention, it means that it is soluble in the alkaline aqueous solution.

[0076] More specifically, "soluble in alkaline aqueous solution" means that after the branched organopolysiloxane involved in the present invention is coated on a glass plate in a thickness of 0.5 μm, the coating film is immersed in a 2.38% aqueous solution of TMAH for 1 minute and then washed with water, the mass reduction rate of the coating film composed of the organopolysiloxane is 90% by mass or more, especially when the mass reduction rate of the coating film composed of the organopolysiloxane is 95% by mass or more or 98% by mass or more when evaluated by the above method, the solubility in alkaline aqueous solution is particularly excellent. It should be noted that the method of coating the organopolysiloxane on the glass plate is usually spin coating, etc., and when the organic solvent described later is used for coating, the organic solvent needs to be removed in advance by drying, etc. Further, if it is a composition mainly composed of organopolysiloxane, the solubility of the high-energy ray-curable composition containing the organopolysiloxane involved in the present invention in alkaline aqueous solution can be evaluated by the above method. The water washing step is generally performed by immersion in a water bath at room temperature (25° C.) or by running water at a flow rate similar to that of household tap water for about 10 to 15 seconds to avoid adverse effects on the formed pattern and substrate.

[0077] It should be noted that the branched siloxane obtained by the production method of the present invention comprises a repeating unit selected from the above (A3SiO 1 / 2 ) and (A2SiO 2 / 2 ), and therefore, the solubility in alkaline aqueous solution tends to be further improved compared to an organopolysiloxane consisting only of silsesquioxane units. Regarding a branched organopolysiloxane containing these siloxane units, when the solubility in alkaline aqueous solution of a coating film composed of the organopolysiloxane is evaluated by the above-mentioned method, an organopolysiloxane having particularly excellent alkali solubility with a mass reduction rate of 90% by mass or more, preferably 98% by mass or more, can often be obtained.

[0078] The method for producing the branched organopolysiloxane containing phenolic hydroxyl groups of the present invention is as follows:

[0079] At least having the following average unit formula (1'):

[0080] (D3SiO 1 / 2 ) a (D2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1')

[0081] (In the formula, R is a group selected from a hydrogen atom, a non-substituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group, D is a group that is independently the same as R, at least one of all D is a hydrogen atom, and a, b, c, and d are numbers that satisfy the following conditions: 0≤a, 0≤b, 0<(a+b), and 0<(c+d).)

[0082] A step of subjecting a branched organopolysiloxane containing silicon-bonded hydrogen atoms to a hydrosilylation reaction,

[0083] And it is represented by the following average unit formula (1).

[0084] Average unit formula (1):

[0085] (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1)

[0086] {wherein, R is the same group as above, A is each independently the same group as R,

[0087] It is given by the following formula (21):

[0088] [Chemical formula 7]

[0089]

[0090] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), m1 is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site to the silicon atom on the organopolysiloxane)

[0091] The group M shown 1 ,

[0092] From the following formula (22):

[0093] [Chemical formula 8]

[0094]

[0095] (Where R 1 , X and Z are the same groups as above,

[0096] Y is composed of -W p -R 2q -CO2H (wherein W is selected from O (C = O), NR 5 (C=O) group, S(C=O) group, p is 0 or 1, q is 0 or 1, R 2 It may also be a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain an oxygen atom or a sulfur atom. 5 is a monovalent hydrophilic group represented by a hydrogen atom or a methyl group,

[0097] m2 is 0 or 1, n is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site with a silicon atom on the organopolysiloxane)

[0098] In the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1'), R in the formula is a group selected from a hydrogen atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group. The unsubstituted or fluorine-substituted monovalent hydrocarbon group is preferably a group selected from an unsubstituted or fluorine-substituted alkyl group, a cycloalkyl group, an arylalkyl group, and an aryl group having 1 to 20 carbon atoms. Examples of the above-mentioned alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, octyl and the like, but methyl and hexyl are particularly preferred. Examples of the above-mentioned cycloalkyl group include: cyclopentyl, cyclohexyl, etc. Examples of the above-mentioned arylalkyl group include: benzyl, phenethyl, etc. Examples of the above-mentioned aryl group include: phenyl, naphthyl, etc. Examples of the monovalent hydrocarbon group substituted with fluorine include 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and 3,3,3-trifluoropropyl is preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and isopropoxy.

[0099] In the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1'), the functional groups D in the formula may be groups that are independently the same as R, but at least one of all D is a hydrogen atom. By the hydrosilylation reaction described below, a group M is introduced into the group D that is a hydrogen atom. 1 The phenolic hydroxyl-containing organic group shown, its precursor functional group or the phenolic hydroxyl-containing organic group obtained by reacting the phenolic hydroxyl-containing organic group with an acid anhydride 2 That is, the number of each modified group in the finally obtained phenolic hydroxyl group-containing branched organopolysiloxane is determined by the functional group D as a hydrogen atom in the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1').

[0100] As the group D other than hydrogen atoms and hydroxyl groups, it is preferred to be selected from non-substituted or fluorine-substituted alkyl, cycloalkyl, arylalkyl, aryl and alkoxy groups having 1 to 20 carbon atoms. As the above-mentioned alkyl group, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, and octyl can be listed, but methyl and hexyl are particularly preferred. As the above-mentioned cycloalkyl group, cyclopentyl and cyclohexyl can be listed. As the above-mentioned arylalkyl group, benzyl and phenethyl can be listed. As the above-mentioned aryl group, phenyl and naphthyl can be listed. As examples of monovalent hydrocarbon groups substituted with fluorine, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl can be listed, but 3,3,3-trifluoropropyl is preferred. As alkoxy groups, methoxy, ethoxy, propoxy and isopropoxy can be listed.

[0101] The number of silicon atoms in the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') is preferably 50 or less, more preferably 20 or less, particularly preferably in the range of 3 to 50 and 5 to 20. This is because the smaller the number of silicon atoms, the smaller the composition distribution and molecular weight distribution of the branched organopolysiloxane can be. Therefore, as long as the number of silicon atoms is within this range, the phenolic hydroxyl group-containing branched organopolysiloxane obtained by the production method of the present invention using the branched organopolysiloxane as a starting material can suppress the overall viscosity of the curable composition and improve the coating property and photolithography characteristics.

[0102] In the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the above average unit formula (1'), the ratio of each structural unit is not particularly limited, but at least one of a and b is not 0. Similarly, at least one of c and d is not 0. Therefore, a, b, c and d are numbers that satisfy the following conditions: 0≤a, 0≤b, 0<(a+b) and 0<(c+d).

[0103] As described above, since the functional group D, which is a hydrogen atom on the branched organopolysiloxane containing a silicon-bonded hydrogen atom, is introduced with a group M 1 The phenolic hydroxyl-containing organic group shown, its precursor functional group or the phenolic hydroxyl-containing organic group obtained by reacting the phenolic hydroxyl-containing organic group with an acid anhydride 2 Therefore, by setting the values ​​of a, b, c and d of the branched organopolysiloxane containing silicon-bonded hydrogen atoms as a raw material within appropriate ranges, the high-energy-ray curing property, alkali solubility and surface viscosity of the branched organopolysiloxane containing phenolic hydroxyl groups after coating on a substrate can be appropriately controlled. In order to maintain these properties in a good balance, it is preferred that the values ​​of a, b, c and d be set to satisfy the following formula.

[0104] 0.5≤a / (b+c+d)≤2.0

[0105] Where b is (D2SiO 2 / 2 ) units, but b=0 is also possible. In this case, (D3SiO 1 / 2 ) unit is a hydrogen atom.

[0106] Furthermore, the above-mentioned relationship 0.5≤a / (b+c+d)≤2.0 can be applied to the preferred range of the ratio a / c and a / d of the siloxane units constituting the branched organopolysiloxane containing silicon-bonded hydrogen atoms. That is, 0.5≤a / c≤2.0 and 0.5≤a / d≤2.0. Within these ranges, it is easy to appropriately control the above-mentioned properties of the finally obtained branched organopolysiloxane containing phenolic hydroxyl groups, i.e., high-energy ray curability, alkali solubility, and surface adhesion after coating on a substrate.

[0107] As specific examples of the branched organopolysiloxane containing silicon-bonded hydrogen atoms preferably used in the present invention, it is preferred to contain a monoorganosiloxy unit (D3SiO 1 / 2 In particular, substances having one or more structures selected from the following average unit formulas (1-1') and (1-2') can be cited. That is, b in the above average unit formula (1') is preferably 0.

[0108] Average unit formula (1-1'): (D3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1') or

[0109] Average unit formula (1-2'): (D3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2')

[0110] (In these formulae, R and D are the same groups as above, and a, c and d are numbers satisfying the above conditions.)

[0111] As a more specific structure of the branched organic polysiloxane containing a silicon atom-bonded hydrogen atom, a polysiloxane composed of the following structural units can be cited. 1 / 2 ), D represents (Me2SiO 2 / 2 ), T represents (MeSiO 3 / 2 ), Q represents (SiO 4 / 2 ), D Ph represents (MePhSiO 2 / 2 ), D Ph2represents (Ph2SiO 2 / 2 ), T Ph represents (PhSiO 3 / 2 ), M H represents (Me2HSiO 1 / 2 ), D H Represents (MeHSiO 2 / 2 ), T H Represents (HSiO 3 / 2 ), Me represents a methyl group, and Ph represents a phenyl group.

[0112] MM H Q.M H Q.M H DQ, M H TQ, MD H Q. MDD H Q.M H D H Q.MD H TQ, M H T H Q.M H T Ph ,MM H T Ph 、M H DT Ph 、M H D Ph T Ph 、M H D H T Ph 、M H T Ph Q.M H TT Ph 、M H DTT Ph 、M H D Ph2 T.M. H DD Ph2 T

[0113] Among them, MM H Q.M H Q.M H T Ph ,MM H T Ph 、M H DT Ph 、M H T Ph Q is exemplified as a preferred branched organopolysiloxane, M H Q.M H T Ph It is a particularly preferred branched organopolysiloxane.

[0114] There is no particular limitation on the molecular weight of the branched organopolysiloxane containing silicon-bonded hydrogen atoms. However, considering the properties and molecular weight of the finally obtained branched organopolysiloxane containing phenolic hydroxyl groups, the weight average molecular weight measured by gel permeation chromatography and converted to standard polystyrene is preferably in the range of 500 to 2,000, and more preferably in the range of 800 to 1,500.

[0115] [Step (I)]

[0116] Preferably, the production method of the present invention comprises the following steps: subjecting the branched organopolysiloxane containing silicon-bonded hydrogen atoms to a hydrosilylation reaction with a phenol derivative having a monovalent unsaturated hydrocarbon group, wherein the monovalent unsaturated hydrocarbon group is used to provide a 1 The phenolic hydroxyl-containing organic group or its precursor functional group is shown.

[0117] In this step (I), the compound that undergoes hydrosilylation reaction with the above-mentioned branched organopolysiloxane containing silicon-bonded hydrogen atoms is preferably a phenol derivative having a monovalent unsaturated hydrocarbon group. Among them, the compound can be directly provided for the hydrosilylation reaction, and the phenol group can also be protected and used with an acid dissociable group. In the present invention, from the viewpoint of suppressing side reactions, the phenol group protected with an acid dissociable group is preferably provided for the hydrosilylation reaction. Specifically, it is preferred to use a compound containing an unsaturated hydrocarbon group shown in the following formula (33).

[0118] [Chemical formula 9]

[0119]

[0120] (Where R 6 is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), and k2 is a number in the range of 1 to 3)

[0121] Examples of the monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms include vinyl, allyl, 1-butenyl, 1-pentenyl, and 1-hexenyl, and vinyl and allyl groups are preferably used. 3 It refers to a group that is easily decomposed in the presence of a dilute acid such as acetic acid and formic acid to generate a hydroxyl group. A straight-chain or branched hydrocarbon group, -(C=O)-R 7 (R 7 is a linear monovalent hydrocarbon group) group, -R 8 OR 9 Base (R 8 It is a straight-chain or branched divalent hydrocarbon group. 9It is a linear monovalent hydrocarbon group) and a trialkylsilyl group are well known, and specific examples thereof include a tert-butyl group, an acetyl group, a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, and a trimethylsilyl group. Among them, a tert-butyl group and a trimethylsilyl group are recommended.

[0122] There is no particular restriction on the conditions of the hydrosilylation reaction, but generally, the reaction is stirred for 0.5 to 10 hours at a reaction temperature of about room temperature to about 150° C. in the presence or absence of an organic solvent as a diluent. At this time, it is recommended to use a catalyst for accelerating the reaction, which may include: a platinum catalyst, a rhodium catalyst, a palladium catalyst, a nickel catalyst, an iridium catalyst, a ruthenium catalyst, and an iron catalyst, preferably a platinum catalyst. As a platinum catalyst, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a platinum alkenylsiloxane complex, and other platinum compounds, particularly preferably a platinum alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because a platinum-alkenylsiloxane complex containing the same has good stability. Furthermore, from the viewpoint of improving the stability of the platinum-alkenylsiloxane complex, it is preferred to add to the complex a compound selected from the group consisting of alkenylsiloxanes such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and organosiloxane oligomers such as dimethylsiloxane oligomers. It is particularly preferred to add alkenylsiloxane to the platinum complex.

[0123] The content of the catalyst varies depending on the structure of the catalyst and the alkenyl compound or organopolysiloxane containing silicon-bonded hydrogen atoms to be reacted, but generally, the metal atoms in the catalyst are in an amount in the range of 0.01 to 100 ppm by mass relative to the total amount of the reaction substrate after the solvent is removed. In particular, when a platinum alkenylsiloxane complex is used, it is particularly preferred that the platinum content is in the range of 1.0 to 20 ppm from the viewpoint of good reaction speed and suppression of coloration. If the amount of the catalyst added is too small, the hydrosilylation reaction speed slows down, while if the amount of the catalyst added is too large, it causes coloration and is uneconomical.

[0124] After the hydrosilylation reaction is completed, the product can be filtered as needed and the organic solvent used can be distilled off as needed to separate the branched organopolysiloxane as the target product. In order to disperse it in an organic solvent different from the organic solvent used, a solvent replacement process can also be used.

[0125] [Step (II)]

[0126] The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group of the present invention preferably comprises the following step (step (II)): reacting the branched organopolysiloxane having a functional group represented by the following formula (34) in the molecule obtained in the above step (I) with an acid compound. By the reaction in the step (II), at least a part of the group Z on the aromatic ring is converted to a hydroxyl group (X), and the functional group represented by the formula (34) is converted to the group M represented by the above formula (21). 1 .

[0127] [Chemical formula 10]

[0128]

[0129] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, Z is the above group, k2 is a number in the range of 1 to 3, and * is a bonding site with a silicon atom on the organopolysiloxane)

[0130] Examples of the acid compound that can be used here include organic acids such as acetic acid, formic acid, citric acid, and p-toluenesulfonic acid, and inorganic acids such as dilute hydrochloric acid and dilute nitric acid. In any case, it is preferred to use water in a stoichiometric amount or more.

[0131] The reaction conditions are not particularly limited, but can be adjusted according to the structures of the branched organopolysiloxane and the acid compound used. Specifically, the reaction is generally stirred for 1 to 10 hours at a reaction temperature of about room temperature to 100°C in the presence or absence of an organic solvent that can mix these reaction substrates with water.

[0132] After confirming the desired product after the reaction is completed, after removing the volatile components, it is usually neutralized and washed with an alkaline compound to produce the target branched organopolysiloxane containing phenolic hydroxyl groups. As the alkaline compound used here, inorganic bases such as sodium bicarbonate, organic bases such as ammonia, or alkaline solid neutralizers can be used. When using a solid neutralizer, a filtering step is necessary.

[0133] Through this step (II), the following formula (21) is introduced into the molecule:

[0134] [Chemical formula 11]

[0135]

[0136] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), m1 is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site to the silicon atom on the organopolysiloxane)

[0137] The group M shown 1 .

[0138] R 1 is a linear or branched divalent hydrocarbon group having 2 to 6 carbon atoms, and is a functional group M represented by the formula (21): 1 and the functional group M represented by formula (22) 2 Specifically, as R 1 , Examples thereof include a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, a butylene group, and a hexylene group, among which an ethylene group, a methylmethylene group, and a propylene group are preferred.

[0139] The functional group M represented by formula (21) 1 and the functional group M represented by formula (22) 2 The substituent Z on the aromatic ring in or the functional group Z in formula (4) is -OR 3 (Where R 3 In other words, Z is a monovalent group represented by an acid dissociable group R 3 Protected hydroxyl groups.

[0140] Among them, R 3 is an acid-dissociable group, which is a group that is easily decomposed in the presence of a dilute acid such as acetic acid and formic acid to generate a hydroxyl group from the functional group Z. Specifically, R 3 It may be a straight chain or branched hydrocarbon group, -(C=O)-R 31 (R31 is a linear monovalent hydrocarbon group) group, -R 32 OR 33 Base (R 32 It is a straight-chain or branched divalent hydrocarbon group. 33 is a linear monovalent hydrocarbon group) and a trialkylsilyl group, and more specifically, tert-butyl, acetyl, methoxymethyl, ethoxymethyl, ethoxyethyl, trimethylsilyl and the like are mentioned, and tert-butyl and trimethylsilyl groups are preferably used.

[0141] m1 represents a functional group M represented by formula (21) 1 The number of hydroxyl groups (—X) on the aromatic ring in the is in the range of 1 to 3, and preferably 1 or 2.

[0142] k represents a functional group M represented by formula (21) 1 and the functional group M represented by formula (22) 2 The acid dissociable group R 3 The number of protected hydroxyl groups (-Z) is a number in the range of 0 to 3, preferably 0 or 1, and more preferably 0. That is, the functional group Z is an optional functional group in the branched organopolysiloxane involved in the present invention, and is preferably not included in the molecule. This is achieved by converting all functional groups Z on the functional group represented by formula (34) into hydroxyl groups (X) by reacting with an acidic substance in step (II).

[0143] [Step (III)]

[0144] The phenolic hydroxyl group-containing branched organopolysiloxane of the present invention may further optionally have a group M 2 The carboxylic acid-containing organic group is preferably obtained by step (III), which is performed after step (II) to make the molecule obtained by step (II) have a group M represented by the above formula (21): 1 The branched organopolysiloxane is reacted with one or more acid anhydrides and the group M 1 A portion of is converted into a group M represented by the above formula (22) 2 .

[0145] As the acid anhydride in step (III), an anhydride of a dicarboxylic acid is recommended. Specifically, succinic anhydride, butylsuccinic anhydride, nonylsuccinic anhydride, glutaric anhydride, 3,3-dimethylglutaric anhydride, adipic anhydride, phthalic anhydride, homophthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, tetrachlorophthalic anhydride, 3-nitrophthalic anhydride, 4-methylphthalic anhydride, 4-bromophthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, 4,4'-diphthalic anhydride, etc. can be mentioned, but succinic anhydride, glutaric anhydride, phthalic anhydride, and homophthalic anhydride can be preferably used.

[0146] The reaction conditions are not particularly limited, but can be based on the 1 The structure of the branched organic polysiloxane and the acid anhydride is adjusted. Specifically, it is generally stirred for 0.5 to 10 hours at a reaction temperature of about room temperature to 100°C in the presence or absence of an organic solvent that has the function of mixing these reaction substrates. The reaction is carried out by heating the substrate mixture, but a catalyst can also be used to accelerate the reaction. As effective catalysts, basic compounds can be listed, and examples include: triethylamine, pyridine, N,N-dimethylaniline, tetramethylguanidine, 1,8-diazabicycloundecene, 1,5-diazabicyclononene, etc. Relative to the total amount of the substrate mixture, 0.1 to 3.0% by mass of the catalyst can be appropriately used.

[0147] After confirming the desired product after the reaction is completed, it is usually neutralized and washed with an alkaline compound to obtain the target curable branched organopolysiloxane containing phenolic hydroxyl groups and carboxyl groups. As the alkaline compound used here, inorganic bases such as sodium bicarbonate, organic bases such as ammonia, or alkaline solid neutralizers can be used as described above. When a solid neutralizer is used, a filtering step is necessary.

[0148] The functional group M represented by formula (22) introduced in step (III) is 2 The substituent Y on the aromatic ring is -W p -R 2 q -CO2H-containing carboxylic acid organic group. W on the group Y in the formula is a divalent linking group containing a heteroatom, selected from ester group: O(C=O), amide group: NR 5 (C=O)(wherein, R 5 is a hydrogen atom or a methyl group), a thioester group: S(C=O). In the phenolic hydroxyl group-containing branched organopolysiloxane of the present invention, an ester group can be preferably used.

[0149] The linker R on the group Y 2 It is a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms which may optionally contain an oxygen atom or a sulfur atom; a sulfur-containing linear, branched or cyclic divalent hydrocarbon group; an oxygen-containing linear, branched or cyclic divalent hydrocarbon group. More specifically, the divalent groups exemplified by the following structural formula (7) can be listed. Among them, the divalent linking groups represented by 6a, 6b, 6c, 6d, 6e, 6i, 6k, 6m, 6p, 6q, 6q, and 6s can be preferably used.

[0150] [Chemical formula 12]

[0151]

[0152] (Wherein, * represents the bonding site)

[0153] In the group Y, the above p is 0 or 1, but preferably 1. Further, q is 0 or 1, but preferably 1

[0154] m2 represents a functional group M represented by formula (22) 2 The number of hydroxyl groups (-X) on the aromatic ring in is 0 or 1, but preferably 0. In addition, n represents the functional group M 2 The number of the carboxylic acid-containing organic group of the substituent Y on the aromatic ring in is in the range of 1 to 3, and is preferably 1. In addition, k is the same as described above.

[0155] The branched organopolysiloxane containing phenolic hydroxyl groups involved in the present invention has a functional group M 2 In the case of, from the viewpoint of achieving good curability to high energy rays, it is preferred that the functional group M in the entire molecule 1 With functional group M 2 The sum of the phenolic hydroxyl groups (X) in the 2 The sum of the carboxylic acid-containing organic groups (Y) in the molecule, i.e., the group M 1 With group M 2 The sum of the amounts of hydroxyl groups (X) in the molecule] / [the sum of the amounts of groups M in the molecule 2 The value of the sum of the amounts of the carboxylic acid-containing hydrophilic groups (Y) in the mixture] is 1 or more.

[0156] [Branched organopolysiloxane containing phenolic hydroxyl groups]

[0157] The phenolic hydroxyl group-containing branched organopolysiloxane produced in the present invention has a structure represented by the following average unit formula (1). 1 , optionally, especially when produced by the above step (III), at least one of all A is M 1 , at least one is M2 , which may be a co-modified branched organopolysiloxane having both a phenolic hydroxyl group-containing organic group and a carboxylic acid-containing organic group, is preferred.

[0158] Average unit formula (1):

[0159] (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1)

[0160] {wherein, R is the same group as above, A is each independently the same group as R,

[0161] is selected from the following formula (21):

[0162] [Chemical formula 13]

[0163]

[0164] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), m1 is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site to the silicon atom on the organopolysiloxane)

[0165] The group M shown 1 ,

[0166] From the following formula (22):

[0167] [Chemical formula 14]

[0168]

[0169]

[0170] (Where R 1 , X and Z are the same groups as above,

[0171] Y is composed of -Wp-R 2 q-CO2H (wherein W is selected from O (C = O) group, NR 5 (C=O) group, S(C=O) group, p is 0 or 1, q is 0 or 1, R 2 It may also be a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain an oxygen atom or a sulfur atom.5 is a monovalent hydrophilic group represented by a hydrogen atom or a methyl group,

[0172] m2 is 0 or 1, n is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site with a silicon atom on the organopolysiloxane)

[0173] The group M shown 2 ,

[0174] From the following formula (3):

[0175] [Chemical formula 15]

[0176] *-R 4 -X

[0177] (Where R 4 is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is the same group as above)

[0178] The group J shown, and

[0179] From the following formula (4):

[0180] [Chemical formula 16]

[0181] *-R 4 -Z

[0182] (Where R 4 and Z is the same group as above)

[0183] The group L shown

[0184] More than one group in which at least one of all A is M 1 , a, b, c, and d are numbers that satisfy the above conditions.}

[0185] The functional group J in the branched organopolysiloxane containing a phenolic hydroxyl group of the present invention is a group containing an alcoholic hydroxyl group represented by the above formula (3). The group X in formula (3) is the same as above and is a hydroxyl group. 4 It is a linear or branched divalent hydrocarbon group having 2 to 6 carbon atoms, and specifically, examples thereof include methylene, ethylene, methylmethylene, propylene, methylethylene, butylene, hexylene, etc., but preferably ethylene, methylmethylene, and propylene. The functional group J is an optional structure of the branched organopolysiloxane containing a phenolic hydroxyl group of the present invention, and may not be included in the molecule.

[0186] The functional group L in the branched organopolysiloxane containing a phenolic hydroxyl group of the present invention is a functional group L represented by the above formula (4) via a linking group R 4 The acid dissociable group R 3 wherein R in formula (4)4 and Z are the same groups as described above. The functional group L is an optional structure of the phenolic hydroxyl group-containing branched organopolysiloxane of the present invention, and may not be contained in the molecule, but is preferably not contained.

[0187] [Optional Steps]

[0188] The functional group J or the functional group L can be introduced into the phenolic hydroxyl group-containing branched organopolysiloxane of the present invention by subjecting the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') described above to a hydrosilylation reaction with a compound containing an unsaturated hydrocarbon group represented by the following structural formula (3') or the following structural formula (4') in step (I) or the like.

[0189] Formula (3'): R 6 -X

[0190] (Where R 6 is the same group as above)

[0191] Formula (4'): R 6 -Z

[0192] (Where R 6 , Z is the same group as above)

[0193] In addition, the molecular weight of the branched organopolysiloxane containing a phenolic hydroxyl group is not particularly limited, but in consideration of coating properties, high energy ray curing properties, alkali solubility, and mechanical strength properties of the coated film, the weight average molecular weight measured by gel permeation chromatography in terms of standard polystyrene is preferably 1,000 to 3,000, more preferably 1,500 to 3,000, and particularly preferably 1,500 to 2,500. In addition, from the viewpoint of maintaining excellent alkali solubility, the molecular weight distribution is preferably 1.5 or less, and particularly preferably 1.4 or less.

[0194] [Use of organic solvents]

[0195] In the method for producing a phenolic hydroxyl group-containing branched organopolysiloxane of the present invention, the use of an organic solvent is optional, but in consideration of the miscibility of the reaction substrates and the dispersibility of the catalyst compound used optionally, it is preferred to use a suitable amount of an appropriate organic solvent.

[0196] Preferred examples of the organic solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone; methyl 2-hydroxypropionate, 2-hydroxy Lactic acid alkyl esters such as ethyl propionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; toluene, xylene, mesitylene, isopropylbenzene, propylbenzene, diethylbenzene, 1,3-diisopropylbenzene and other aromatic hydrocarbons; anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 3,4-dimethoxytoluene, 1,4-bis(methoxymethyl)benzene and other aromatic ethers. These solvents can be used alone or as a mixed solvent consisting of two or more.

[0197] The amount of the organic solvent used is not limited, but it is recommended to use an amount in a range of 5 to 90% by mass, preferably 10 to 80% by mass, with respect to the base concentration.

[0198] [Method for producing curable composition]

[0199] The phenolic hydroxyl group-containing branched organopolysiloxane obtained by the production method of the present invention contains at least one M 1The organic group containing phenolic hydroxyl group shown in the figure has curing reactivity. The curing reaction mechanism is not particularly limited as long as it is a curing reaction involving phenolic hydroxyl group, but one or more reactions selected from condensation reaction, free radical polymerization reaction, peroxide curing reaction and high energy ray curing reaction such as ultraviolet light can be exemplified, and a curable composition containing the branched organopolysiloxane containing phenolic hydroxyl group of the present invention can be designed. That is, a method for producing a curable composition containing the manufacturing method of the present invention (such as the above-mentioned steps (I), (II) and optional step (III) etc.) can be provided.

[0200] [Method for producing high energy ray curable composition]

[0201] The phenolic hydroxyl-containing branched organopolysiloxane of the present invention has excellent alkali solubility and high-energy ray curability, and can therefore be particularly suitable for use in a high-energy ray curable composition, and a method for producing a high-energy ray curable composition comprising the production method of the present invention can be provided. More specifically, the high-energy ray curable composition of the present invention contains at least the phenolic hydroxyl-containing branched organopolysiloxane of the present invention and a photoacid generator required for curing, and may optionally contain other components.

[0202] More specifically, the high energy radiation curable composition of the present invention contains the following four components. Component (A) is the main component of the present invention described in detail. It should be noted that, when component (A) does not have an organic group containing a carboxylic acid, the crosslinking agent (C) can be added as needed and is an optional structure. In addition, the amount of the organic solvent used can also be appropriately selected for the purpose of adjusting the coating properties of the composition.

[0203] (A) the above-mentioned branched organopolysiloxane containing phenolic hydroxyl groups

[0204] (B) 0.1 to 20 parts by mass based on 100 parts by mass of the photoacid generator (A) component

[0205] (C) 0 to 30 parts by mass relative to 100 parts by mass of the crosslinking agent (A) component

[0206] as well as

[0207] (D) Organic solvents

[0208] As components (B) and (C), well-known photoacid generators, crosslinking agents, etc. can be used without particular limitation, and as component (D), well-known organic solvents other than the above-mentioned organic solvents can be used without particular limitation. The curable composition (especially high-energy ray curable composition) of the present invention can be obtained by mixing component (A) obtained by the production method of the present invention with other components using mechanical force.

[0209] Hereinafter, the present invention will be further described based on examples, but the present invention is not limited to the following examples.

[0210] Example

[0211] The method for producing the curable branched organopolysiloxane of the present invention will be described in detail with reference to Examples.

[0212] [Appearance of Curable Composition and Cured Product]

[0213] The curable composition and the cured product were visually observed to determine their appearance.

[0214] [Alkali solubility of curable branched organopolysiloxane]

[0215] A 20% by mass PGMEA solution of each curable branched organic polysiloxane was spin-coated on an optical glass substrate in a film thickness of 0.3 to 0.5 μm, and heated (pre-baked) at 90°C for 1.5 minutes using a hot plate to form a coating. Then, at 25°C, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for development for 1 minute, and the film was immersed in a water bath at room temperature (25°C) and washed. The washing time was 15 seconds. After washing, the water was removed by drying, and the glass substrate was visually observed to determine the solubility (developability) in alkaline solution according to the following criteria.

[0216] A: Completely dissolved: The coating is completely removed

[0217] B: Almost dissolved: Some coating film remains (scum) observed

[0218] C: Partial dissolution: A large amount of scum (more than 20% of the coating area) was observed

[0219] D: Insoluble

[0220] [High Energy Ray Curability of Curable Composition]

[0221] Using the PGMEA solution of each curable composition (concentration of curable branched organopolysiloxane: 20 mass%), a coating film of the curable composition was formed by the same method as above. The coating film was irradiated with high-energy rays (light amount at 254nm: 2000mJ / cm2) using a high-pressure mercury lamp to obtain a cured coating film. The high-energy ray curability was determined according to the following criteria.

[0222] A: The cured coating is insoluble in the above TMAH dissolution test.

[0223] B: Only the edge portion of the cured coating (less than 5% of the total area of ​​the cured film) dissolved in the above TMAH dissolution test

[0224] C: The cured coating film is completely dissolved or almost dissolved in the above TMAH dissolution test

[0225] [Example 1] Synthesis of curable branched organopolysiloxane (A-1) having phenolic hydroxyl groups

[0226] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 40.1 g of dimethylsiloxy-terminated phenylsilsesquioxane (silicon-bonded hydrogen content: 0.66 mass%), 10 g of toluene, 46.2 g of tert-butoxystyrene, and a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (platinum content: 4.5 mass%; platinum metal is 2 ppm relative to the matrix) were added, and heated at 70°C for 30 minutes and at 100°C for 2 hours. After confirming the completion of the reaction by infrared spectroscopic analysis, the volatile components were removed to obtain a light yellow oily product. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched phenyl silsesquioxane in which the silicon-bonded hydrogen atoms were replaced by tert-butoxyphenylethyl groups.

[0227] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 84.46 g of branched phenylsilsesquioxane substituted with tert-butoxyphenylethyl and 157 g of a 90% by mass formic acid aqueous solution were added, and heated at 100°C for 5 hours to confirm that the reaction was complete. The volatile components were removed, and after dilution with 100 mL of PGMEA, the product was washed with a sodium bicarbonate aqueous solution and purified water to obtain a PGMEA solution. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0228] [Me2AiSiO 1 / 2 ] 6.0 [PhSiO 3 / 2 ] 4.0

[0229] Among them, Me is methyl, Ph is phenyl, and A represents a (CH2)2C6H4OH group.

[0230] The analysis results of gel permeation chromatography revealed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-1) were 1,700 and 1.36, respectively.

[0231] [Example 2] Synthesis of Curable Branched Organopolysiloxane (A-2) Having Phenolic Hydroxyl Group

[0232] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 32.0 g of dimethylsiloxy-terminated silica (silicon-bonded hydrogen content: 0.97 mass %), 54.3 g of tert-butoxystyrene, and a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (platinum content: 4.5 mass %; platinum metal is 2 ppm relative to the matrix) were added, and heated at 70°C for 30 minutes and at 120°C for 2 hours. After confirming the completion of the reaction by infrared spectroscopic analysis, the volatile components were removed to obtain a light yellow oily product. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was branched silica in which the silicon-bonded hydrogen atoms were replaced by tert-butyloxyphenylethyl groups.

[0233] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 82.8 g of branched silica substituted with tert-butoxyphenylethyl and 157 g of a 90% by mass formic acid aqueous solution were added, and heated at 100°C for 4 hours to confirm that the reaction was complete. The volatile components were removed, and after dilution with 100 mL of PGMEA, the product was washed with a sodium bicarbonate aqueous solution and purified water to obtain a PGMEA solution. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0234] [Me2ASiO 1 / 2 ] 10.7 [SiO 4 / 2 ] 6.0

[0235] Wherein, Me is a methyl group and A represents a (CH2)2C6H4OH group.

[0236] The analysis results of gel permeation chromatography revealed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-2) were 2,400 and 1.14, respectively.

[0237] [Example 3] Synthesis of curable branched organopolysiloxane (A-3) having phenolic hydroxyl groups

[0238] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 13.2 g of dimethylsiloxy-terminated silica (silicon-bonded hydrogen content: 0.97 mass %), 36.7 g of O,O-bistrimethoxysilyl-4-vinylcatechol, and a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (platinum content: 4.5 mass %; platinum metal is 2 ppm relative to the matrix) were added, and heated at 70°C for 30 minutes and at 120°C for 2 hours. After confirming the completion of the reaction by infrared spectroscopic analysis, the volatile components were removed to obtain a light yellow oily product. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was branched silica in which the silicon-bonded hydrogen atoms were replaced by 3,4-bistrimethylsiloxyphenylethyl groups.

[0239] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 48.0 g of branched silica substituted with 3,4-bistrimethylsiloxyphenylethyl, 100 mL of tetrahydrofuran, 5 g of a 90% by mass aqueous solution of formic acid, and 10.0 g of purified water were added, and heated at 60°C for 90 minutes to confirm that the reaction was complete. The volatile components were removed and diluted with 100 mL of PGMEA to obtain a PGMEA solution of the product. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0240] [Me2ASiO 1 / 2 ] 10.7 [SiO 4 / 2 ] 6.0

[0241] Wherein, Me is a methyl group and A represents a (CH2)2C6H3(OH)2 group.

[0242] The analysis results of gel permeation chromatography revealed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-3) were 2,400 and 1.04, respectively.

[0243] [Example 4] Synthesis of branched organopolysiloxane (A-4) having phenolic hydroxyl groups and carboxyl-containing groups

[0244] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 58.6 g of the product obtained in Example 1, 90 g of PGMEA, 7.2 g of succinic anhydride and 0.12 g of tetramethylguanidine were added, and heated at 90°C for 4 hours to confirm that the reaction was complete. After cooling to room temperature, 3 g of Kyoward 700PL was added to neutralize the reaction system. The white solid was filtered out to obtain a PGMEA solution of the product.13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0245] [Me2ASiO 1 / 2 ] 4.0 [Me2TSiO 1 / 2 ] 2.0 [PhSiO 3 / 2 ] 4.0

[0246] Among them, Me is methyl, Ph is phenyl, A represents a (CH2)2C6H4OH group, and B represents a (CH2)2C6H4O(C=O)(CH2)2CO2H group.

[0247] The analysis results of gel permeation chromatography revealed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-4) were 1,900 and 1.36, respectively.

[0248] [Example 5] Synthesis of branched organopolysiloxane (A-5) having phenolic hydroxyl groups and carboxyl-containing groups

[0249] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 41.6 g of the product obtained in Example 2, 178 g of PGMEA, 1.7 g of succinic anhydride and 0.03 g of tetramethylguanidine were added, and heated at 90°C for 4 hours to confirm that the reaction was complete. After cooling to room temperature, 1.5 g of Kyoward 700PL was added to neutralize the reaction system. The white solid was filtered out to obtain a PGMEA solution of the product. 13 C and 29 SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0250] [Me2ASiO 1 / 2 ] 9.6 [Me2TSiO 1 / 2 ] 1.1 [SiO 4 / 2 ] 6.0

[0251] Wherein, Me is a methyl group, A represents a (CH2)2C6H4OH group, and T represents a (CH2)2C6H4O(C=O)(CH2)2CO2H group.

[0252] The analysis results of gel permeation chromatography revealed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-5) were 2,400 and 1.36, respectively.

[0253] [Evaluation Examples 1-1 to 1-5, Comparative Evaluation Examples 1-1 to 1-4] Alkali Solubility of Curable Branched Organopolysiloxane

[0254] The alkali solubility was evaluated using a 20 mass % PGMEA solution of the branched organopolysiloxane shown below. The results are summarized in Table 1.

[0255] A-1: Phenolic hydroxyl group-containing branched organopolysiloxane obtained in Synthesis Example 1

[0256] A-2: Phenolic hydroxyl-containing branched organopolysiloxane obtained in Synthesis Example 2

[0257] A-3: Phenolic hydroxyl-containing branched organopolysiloxane obtained in Synthesis Example 3

[0258] A-4: Branched organopolysiloxane having phenolic hydroxyl groups and carboxyl groups obtained in Synthesis Example 4

[0259] A-5: Branched organopolysiloxane having phenolic hydroxyl groups and carboxyl groups obtained in Synthesis Example 5

[0260] P-1: having an average composition similar to that of dimethylsiloxy-terminated phenylsilsesquioxane used in Synthesis Example 1 ([Me2HSiO 1 / 2 ] 5.0 [PhSiO 3 / 2 ] 15.0 ) is a branched organopolysiloxane that is solid at room temperature

[0261] P-2: having an average composition similar to that of dimethylsiloxy-terminated phenylsilsesquioxane used in Synthesis Example 1 ([Me2HSiO 1 / 2 ] 6.0 [PhSiO 3 / 2 ] 4.0 ) is a branched organopolysiloxane that is liquid at room temperature

[0262] P-3: having an average composition similar to that of dimethylsiloxy-terminated silica used in Synthesis Example 2 ([Me2HSiO 1 / 2 ] 29.0 [SiO 4 / 2 ] 36.0 ) is a branched organopolysiloxane that is solid at room temperature

[0263] P-4: having an average composition similar to that of dimethylsiloxy-terminated silica used in Synthesis Example 2 ([Me2HSiO 1 / 2 ] 10.7 [SiO 4 / 2 ] 6.0 ) is a branched organopolysiloxane that is liquid at room temperature

[0264] [Table 1]

[0265]

[0266] *1: Since a solid coating film could not be formed, evaluation was not possible.

[0267] *2: Cannot form a uniform coating film, so cannot be evaluated

[0268] [Evaluation Examples 2 to 4 and Comparative Evaluation Example 2] Evaluation of Curable Branched Organopolysiloxane Compositions

[0269] The following branched organopolysiloxane PGMEA solution, crosslinking agent and curing catalyst were mixed according to the composition shown in Table 2 (parts by mass; branched organopolysiloxane converted to solid content), and filtered with a membrane filter having a pore size of 0.2 μm to prepare each high energy ray curable composition.

[0270] Curable branched organopolysiloxane:

[0271] A-3: Curable branched organopolysiloxane obtained in Example 3

[0272] A-5: Curable branched organopolysiloxane obtained in Example 5

[0273] P-1: with ([Me2HSiO 1 / 2 ] 5.0 [PhSiO 3 / 2 ] 15.0 ) structure at room temperature solid branched organopolysiloxane

[0274] Photoacid generator:

[0275] B-1: tri-p-tolylsulfonium trifluoromethanesulfonate (TS-01; manufactured by Sanwa Chemical Co., Ltd.) Curing agent:

[0276] C-1: Tetramethoxymethyl glycoluril (Nicalac MX-270; manufactured by Sanwa Chemical Co., Ltd.)

[0277] [Table 2]

[0278]

[0279] [Summarize]

[0280] As shown in Table 1, the coating films formed from the phenolic hydroxyl group-containing branched organopolysiloxane (including co-modified type) obtained by the production method of the present invention showed practically usable alkali solubility, and several of them (A-2 to A-5) showed particularly excellent alkali solubility. It should be noted that the curable branched organopolysiloxanes involved in the comparative examples all had poor alkali solubility or were insoluble in alkali and could not be used for development using alkaline aqueous solutions.

[0281] In addition, as shown in Table 2, the high-energy ray-curable organopolysiloxane composition (Evaluation Examples 2 to 4) using the branched organopolysiloxane containing a phenolic hydroxyl group (including a co-modified type) obtained by the production method of the present invention has good high-energy ray curability. Furthermore, the cured coating formed by high-energy ray irradiation is transparent and shows sufficiently high coating toughness. On the other hand, the branched organopolysiloxane without a phenolic hydroxyl group (Comparative Evaluation Example 2) has poor alkali solubility and no curability, and is therefore difficult to use in the photopatterning process.

[0282] Industrial Applicability

[0283] The branched organopolysiloxane containing phenolic hydroxyl groups obtained by the production method of the present invention and the curable composition containing the same as the main component, especially the high-energy ray curable composition, have excellent high-energy ray curability and excellent alkali solubility. Therefore, especially in the case of a development process using an alkaline aqueous solution, it has the following advantages: it can form a simple and high-precision pattern, and the mechanical strength and transparency of the obtained cured film are excellent. Therefore, the organopolysiloxane is particularly suitable as a material for forming an insulating layer of a display device such as a touch panel and a display, especially a flexible display, especially a patterning material, a coating material, and a resist material.

Claims

1. A method for producing a branched organopolysiloxane containing a phenolic hydroxyl group, which has at least the following average unit formula (1'): (D3SiO 1 / 2 ) a (D2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (Not 4 / 2 ) d (1') (wherein, R is a group selected from a hydrogen atom, a non-substituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group, D is a group independently the same as R, at least one of all D is a hydrogen atom, and a, b, c, and d are numbers that satisfy the following conditions: 0≤a, 0≤b, 0<(a+b), and 0<(c+d)) A step of subjecting a branched organopolysiloxane containing silicon-bonded hydrogen atoms to a hydrosilylation reaction, And it is represented by the following average unit formula (1). Average unit formula (1): (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (Not 4 / 2 ) d (1) {wherein, R is the same group as described above, A is each independently the same group as R, is selected from the following formula (21): [Chemical formula 1] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3 is a monovalent group represented by an acid dissociable group), m1 is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site to the silicon atom on the organopolysiloxane) The group M shown 1 , From the following formula (22): [Chemical formula 2] (Where R 1 , X and Z are the same groups as described above, Y is composed of -W p -R 2 q -CO2H (wherein W is selected from O (C = O), NR 5 (C=O) group, S(C=O) group, p is 0 or 1, q is 0 or 1, R 2 It may also be a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain an oxygen atom or a sulfur atom. 5 is a monovalent hydrophilic group represented by a hydrogen atom or a methyl group, m2 is 0 or 1, n is a number in the range of 1 to 3, k is a number in the range of 0 to 3, and * is a bonding site with a silicon atom on the organopolysiloxane) The group M shown 2 , From the following formula (3): [Chemical formula 3] *-R 4 -X (Where R 4 is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is the same group as described above) The group J shown, and From the following formula (4): [Chemical formula 4] *-R 4 -Z (Where R 4 and Z is the same group as described above) The group L shown More than one group in which at least one of all A is M 1 , a, b, c and d are numbers that satisfy the conditions} 2. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 1, wherein: The method comprises at least step (I) of mixing a branched organopolysiloxane having a silicon-bonded hydrogen atom represented by the average unit formula (1') with From the following formula (33): [Chemical formula 5] (Where R 6 is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Z is the same group as described above, and k2 is a number in the range of 1 to 3) The unsaturated hydrocarbon group-containing compound shown is subjected to a hydrosilylation reaction.

3. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 2, wherein: The method further comprises a step (II) of causing the molecule obtained in the step (I) to have the following formula (34): [Chemical formula 6] (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, Z is the same group as above, k2 is the same number as above, and * is the bonding site with the silicon atom on the organopolysiloxane) The branched organopolysiloxane having the functional group represented by formula (34) is reacted with one or more acidic substances to convert at least a part of the group Z into a hydroxyl group (X), thereby converting the functional group represented by formula (34) into the group M represented by formula (21) 1 .

4. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 3, wherein: The method further comprises the step (III), wherein after the step (II), the molecule obtained in the step (II) is provided with a group M represented by the formula (21) 1 The branched organopolysiloxane is reacted with one or more acid anhydrides and the group M 1 A portion of is converted into a group M represented by the formula (22) 2 .

5. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 1, wherein: The number of silicon atoms in the molecule of the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1′) is 50 or less.

6. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 1, wherein The number of silicon atoms in the molecule of the branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1′) is in the range of 5 to 20.

7. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 1, wherein: In the average unit formula (1'), a is a number of 1 or more.

8. The method for producing a branched organopolysiloxane containing a phenolic hydroxyl group according to claim 1, wherein The branched organopolysiloxane containing silicon-bonded hydrogen atoms represented by the average unit formula (1') is composed of Average unit formula (1-1'): (D3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1') or average unit formula (1-2'): (D3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2') (In these formulas, R and D are the same groups as described above, and a, c and d are numbers that satisfy the above conditions) The organopolysiloxane shown.

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