Co-modified branched organopolysiloxane, high-energy ray-curable composition comprising same, and use thereof

Abstract

The present invention provides a curing reactive organopolysiloxane having good alkali solubility, and a high energy ray-curable composition comprising the same. A co-modified branched organopolysiloxane represented by the following average unit formula (1): (A3SiO1 / 2) a (A2SiO2 / 2) b (RSiO3 / 2) c (SiO4 / 2) d (in the formula, R is a monovalent hydrocarbon group or the like, A is selected from the group consisting of a group identical to R, a specific phenolic hydroxyl group-containing organic group M1, and a specific carboxylic acid-containing organic group M2, at least one A is M1, at least one A is M2, and a, b, c, and d satisfy the following conditions: 0 < = a, 0 < = b, 0lt; (a + b) and 0 lt; (c + d). ).

Description

Technical Field

[0001] The present invention relates to an alkali-soluble co-modified branched organopolysiloxane that can be cured by actinic rays, such as high-energy rays or electron beams, and a high-energy ray-curable composition containing the same. The co-modified branched organopolysiloxane of 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 polysiloxanes and high-energy ray-curable compositions containing the same are disclosed, it is difficult to say that a curable organopolysiloxane in which the polysiloxane itself has high solubility in an alkaline aqueous solution and exhibits excellent high-energy ray-curability and a high-energy ray-curable composition containing the same 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 curable reactive organopolysiloxane having good alkali solubility and high high-energy ray curability, and a high-energy ray curable composition containing the same.

[0018] Solutions for solving problems

[0019] The present invention has been completed in order to solve the above-mentioned problems. It has been found that a co-modified organopolysiloxane having both an organic group containing a phenolic hydroxyl group and an organic group containing a carboxylic acid on a silicon atom and having a specific branched structure has high solubility in an alkaline aqueous solution, and a high-energy ray-curable composition containing the co-modified organopolysiloxane has excellent coating properties and alkali solubility on a substrate and shows good curing properties, and its cured product (cured film) has sufficient mechanical strength and good transparency, thereby completing the present invention.

[0020] That is, the problem of the present invention can be well solved by using a co-modified branched organopolysiloxane of a specific structure and a curable composition containing the same. The curable composition is a composition that is cured by forming a chemical bond through the curing reactivity (especially the curing reactivity using high-energy rays, etc.) of the specific phenolic hydroxyl group involved in the present invention, and the curing method is not particularly limited, but a high-energy ray-curable composition that undergoes a curing reaction by irradiation with high-energy rays or electron beams is particularly preferred.

[0021] The co-modified branched organopolysiloxane of the present invention is represented by the following average unit formula (1).

[0022] Average unit formula (1):

[0023] (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1)

[0024] {wherein, R is a group selected from a hydrogen atom, a monovalent hydrocarbon group which is unsubstituted or substituted by fluorine, an alkoxy group and a hydroxyl group,

[0025] A is each independently the same group as R,

[0026] is selected from the following formula (21):

[0027] [Chemical formula 1]

[0028]

[0029] (Where R 1 It is a divalent hydrocarbon group with 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3is 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)

[0030] The group M shown 1 ,

[0031] From the following formula (22):

[0032] [Chemical formula 2]

[0033]

[0034] (Where R 1 , X and Z are the same groups as described above,

[0035] 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,

[0036] 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)

[0037] The group M shown 2 ,

[0038] From the following formula (3):

[0039] [Chemical formula 3]

[0040] *-R 4 -X

[0041] (Where R 4 is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is the same group as described above)

[0042] The group J shown, and

[0043] From the following formula (4):

[0044] [Chemical formula 4]

[0045] *-R 4 -Z

[0046] (Where R 4 and Z is the same group as described above)

[0047] In the group L shown

[0048] More than one group, at least one of all A is M 1 , at least one is M 2 , a, b, c, and d are numbers that satisfy the following conditions: 0≤a, 0≤b, 0<(a+b), and 0<(c+d).}

[0049] The number of silicon atoms in the molecule of the co-modified branched organopolysiloxane may be 50 or less, and may be in the range of 5 to 20.

[0050] The co-modified branched organopolysiloxane [the group M in the molecule 1 and 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 hydrophilic groups (Y) containing carboxylic acid in the

[0051] In the formula (21), m1 of the co-modified branched organopolysiloxane may be 1 or 2, and in the formula (22), m2 may be 0 and n may be 1. In the formulas (21) and (22), the co-modified branched organopolysiloxane may be a substance in which k is 0 and the molecule does not contain the group L. Similarly, the co-modified branched organopolysiloxane may be a substance in which the molecule does not contain the group J.

[0052] In the average unit formula (1), a of the co-modified branched organopolysiloxane may be a number greater than 1, and similarly, in the average unit formula (1), b may be 0. Furthermore, in the average unit formula (1), a, b, c, and d of the phenolic hydroxyl group-containing branched organopolysiloxane may be numbers that further satisfy the following condition: 0.5≤a / (b+c+d)≤2.0.

[0053] The co-modified branched organopolysiloxane can be represented by the following average unit formula (1-1) or (1-2).

[0054] Average unit formula (1-1): (A3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1)

[0055] Average unit formula (1-2): (A3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2)

[0056] (In these formulae, R and A are the same groups as described above, and a, c, and d are numbers that satisfy the above conditions.)

[0057] The co-modified branched organopolysiloxane may have a weight average molecular weight of 1,000 or more and 3,000 or less in terms of standard polystyrene as measured by gel permeation chromatography, and a polydispersity index (PDI) related to molecular weight distribution may be 1.5 or less.

[0058] After the co-modified branched organopolysiloxane is applied to a glass plate in a manner to have a thickness of 0.5 μm after coating, the coating film is immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute and then washed with water. The coating film composed of the organopolysiloxane can be a substance that is soluble in an alkaline aqueous solution with a mass reduction rate of 90% by mass or more.

[0059] The present invention further provides a curable composition containing the co-modified branched organopolysiloxane, in particular a high-energy ray-curable composition. Specifically,

[0060] Provided is a high energy ray-curable composition containing at least the following components.

[0061] (A) the curable branched organopolysiloxane,

[0062] (B) a photoacid generator in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (A);

[0063] (C) a cross-linking agent in an amount of 0 to 30 parts by mass based on 100 parts by mass of the component (A); and

[0064] (D) Organic solvents

[0065] The present invention further provides an insulating coating agent comprising the high-energy ray-curable composition. In addition, the present invention provides a resist material comprising the high-energy ray-curable composition.

[0066] The present invention further provides a cured product of the high-energy ray-curable composition and a method of using the cured product as an insulating coating.

[0067] The present invention further provides a display device including a layer composed of a cured product of the high-energy ray-curable composition, such as a liquid crystal display, an organic EL display, and an organic EL flexible display.

[0068] Effects of the Invention DETAILED DESCRIPTION

[0069] Hereinafter, the configuration of the present invention will be described in further detail.

[0070] The co-modified branched organopolysiloxane having a specific structure of the present invention has a phenolic hydroxyl group on at least one silicon atom and is soluble in alkaline aqueous solution (sometimes referred to as "alkali-soluble" in the present invention). In addition, the high-energy ray-curable composition of the present invention contains (A) the branched organopolysiloxane, (B) a photoacid generator, and (D) an organic solvent as essential components, and may further optionally contain (C) a crosslinking agent.

[0071] 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.

[0072] More specifically, "soluble in alkaline aqueous solution" means that after the branched organopolysiloxane involved in the present invention is applied to 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 applying 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 the composition is mainly composed of organopolysiloxane, the solubility of the high-energy ray-curable composition containing the organopolysiloxane involved in the present invention relative to 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.

[0073] It should be noted that the co-modified branched siloxane of the present invention comprises a repeating unit selected from the above (A3SiO 1 / 2 ) and (A2SiO 2 / 2), and therefore, compared with an organopolysiloxane consisting only of silsesquioxane units, the solubility in alkaline aqueous solutions tends to be further improved. Regarding a branched organopolysiloxane containing these siloxane units, when the solubility in alkaline aqueous solutions 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.

[0074] The co-modified branched organopolysiloxane of the present invention is represented by the following average unit formula (1). (A3SiO 1 / 2 ) a (A2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1)

[0075] R in the formula is a group selected from a hydrogen atom, a non-substituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group. The non-substituted 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, and octyl groups, but methyl and hexyl are particularly preferred. Examples of the above-mentioned cycloalkyl group include cyclopentyl and cyclohexyl groups. Examples of the above-mentioned arylalkyl group include benzyl and phenethyl groups. Examples of the above-mentioned aryl group include phenyl and naphthyl groups. 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 groups, but 3,3,3-trifluoropropyl is preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0076] A in the formula is independently the same group as the above R,

[0077] is selected from the following formula (21):

[0078] [Chemical formula 5]

[0079]

[0080] (Where R 1 It is a divalent hydrocarbon group with 2 to 6 carbon atoms, X is a hydroxyl group, and Z is -OR 3 (Where R 3is 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)

[0081] The group M shown 1 ,

[0082] From the following formula (22):

[0083] [Chemical formula 6]

[0084]

[0085] (Where R 1 , X and Z are the same groups as above,

[0086] 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,

[0087] 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)

[0088] The group M shown 2 ,

[0089] From the following formula (3):

[0090] [Chemical formula 7]

[0091] *-R 4 -X

[0092] (Where R 4 is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is the same group as above)

[0093] The group J shown, and

[0094] From the following formula (4):

[0095] [Chemical formula 8]

[0096] *-R 4 -Z

[0097] (Where R 4 and Z is the same group as above)

[0098] In the group L shown

[0099] More than one group, at least one of all A is M 1 , at least one is M 2 That is, the co-modified branched organopolysiloxane involved in the present invention must have both M 1 The organic group containing phenolic hydroxyl group and the organic group represented by M 2 The co-modified branched organopolysiloxane of the present invention may contain the group J or not, but preferably does not contain the group L.

[0100] In the co-modified branched organopolysiloxane 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).

[0101] Furthermore, the group M 1 and group M 2 Can be located in (A3SiO 1 / 2 ) unit and (A2SiO 2 / 2 ) units, but in one molecule there is at least one group M 1 and group M 2 By setting the values ​​of a, b, c, and d within appropriate ranges, the high energy radiation curability, alkali solubility, and surface viscosity of the branched organopolysiloxane of the present invention after coating on a substrate can be appropriately controlled. In order to maintain these properties in a good balance, the values ​​of a, b, c, and d are preferably set to satisfy the following formula.

[0102] 0.5≤a / (b+c+d)≤2.0

[0103] Where b is (A2SiO 2 / 2 ) units, but b=0 is also possible. In this case, (A3SiO 1 / 2 ) unit at least one A is a group M 1 , at least one A is a group M 2 .

[0104] 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 of the present invention. That is, 0.5≤a / c≤2.0 and 0.5≤a / d≤2.0. In these ranges, it is easy to appropriately control the above-mentioned properties, i.e., high energy ray curability, alkali solubility, and surface adhesion after coating on a substrate.

[0105] As specific examples of the co-modified branched organopolysiloxane preferably used in the present invention, it is preferred that the co-modified branched organopolysiloxane contains a monoorganosiloxane unit (A3SiO 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.

[0106] Average unit formula (1-1): (A3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1)

[0107] Average unit formula (1-2): (A3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2)

[0108] (In these formulae, R and A are the same groups as above, and a, c and d are numbers satisfying the above conditions.)

[0109] Functional group M 1 is a group containing a phenolic hydroxyl group represented by the above formula (21), and is a component that imparts curing reactivity, particularly high-energy ray curing, to the branched organopolysiloxane involved in the present invention by having a phenolic hydroxyl group (=substituent X). 3 The acid dissociable group R 3 Protected hydroxyl group. X is a phenolic hydroxyl group and shows hydrophilicity, so in addition to the curing reactivity, it also contributes to the improvement of the above-mentioned alkali solubility. On the other hand, Z does not show hydrophilicity, but is a useful functional group for adjusting the hydrophilicity of the branched organopolysiloxane as a whole. In addition, in formula (21), the number m1 of substituents X on the aromatic ring is a number in the range of 1 to 3, and the number k of substituents Z is a number in the range of 0 to 3, and can also be k=0. In addition, there is no particular limitation on the substitution position of the substituents X and Z on the aromatic ring.

[0110] 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.

[0111] 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 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.

[0112] 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 (R 31 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.

[0113] 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.

[0114] 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 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 of the present invention, and is preferably not contained in the molecule.

[0115] The co-modified branched organopolysiloxane of the present invention is characterized in that it further has a carboxylic acid-containing organic group, namely, M 2In addition to the above functional groups M 1 In addition, by including the functional group M 2 , further improving the alkali solubility of the branched organopolysiloxane of the present invention.

[0116] The functional group M represented by formula (22) 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 co-modified branched organopolysiloxane of the present invention, an ester group can be preferably used.

[0117] 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.

[0118] [Chemical formula 9]

[0119]

[0120] (Wherein, * represents the bonding site)

[0121] In the group Y, the above-mentioned p is 0 or 1, but preferably 1. Further, q is 0 or 1, but preferably 1.

[0122] 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 groups 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 as described above.

[0123] The co-modified branched organopolysiloxane of the present invention has both functional groups M 1 and functional group M 2 However, from the viewpoint of achieving good curability with relatively high energy rays, it is particularly preferred that the functional group M in the entire molecule 1 and functional group M2 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 and 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.

[0124] The functional group J in the co-modified branched organopolysiloxane 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 co-modified branched organopolysiloxane of the present invention, and may not be included in the molecule.

[0125] The functional group L in the co-modified branched organopolysiloxane 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 co-modified branched organopolysiloxane of the present invention, and may not be included in the molecule, but is preferably not included.

[0126] The co-modified branched organopolysiloxane of the present invention preferably has a silicon atom number of 50 or less, more preferably 20 or less, and particularly preferably in the range of 3 to 50, and in the range of 5 to 20, from the viewpoint of controlling the molecular weight distribution of the polysiloxane to a small value in order to improve the coating properties of the curable composition and the lithography properties such as line width uniformity.

[0127] The molecular weight of the co-modified branched organopolysiloxane of the present invention 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 molecular weight is preferably 1,000 to 3,000, more preferably 1,500 to 3,000, and particularly preferably 1,500 to 2,500, as measured by gel permeation chromatography in terms of standard polystyrene.

[0128] Similarly, from the viewpoint of improving the alkali solubility of the co-modified branched organopolysiloxane of the present invention, the polydispersity index (PDI) related to the molecular weight distribution measured by gel permeation chromatography is preferably 1.5 or less, particularly preferably 1.4 or less.

[0129] The co-modified branched organopolysiloxane of the present invention comprises at least one 1 The organic group containing a phenolic hydroxyl group is preferably an organic group containing a phenolic hydroxyl group, but from the viewpoint of imparting good high energy ray curability and excellent alkali solubility, it is preferred that the molecule has at least two hydroxyl groups (X), wherein at least one of the hydroxyl groups (X) in the molecule is derived from the group M 1 The phenolic hydroxyl group, but the other hydroxyl groups can come from multiple groups M 1 , you can also choose to group M 1 or group M 2 The functional group having multiple hydroxyl groups (X) may also be derived from the group J. That is, even in the case of the functional group derived from the group M 1 When there are few phenolic hydroxyl groups (X), the 2 Or, by designing a molecule in which the sum of the numbers of hydroxyl groups in the groups J is large, the high-energy ray curability and alkali solubility of the molecule as a whole can be further improved.

[0130] More specifically, in the co-modified branched organopolysiloxane of the present invention, the group M 1 、Group M 2 The sum of the number of hydroxyl groups (X) of the group J is preferably 2 or more on average, more preferably 3 or more, 4 or more, or 5 or more. It should be noted that among all A in the organopolysiloxane represented by the average unit formula (1), α is a group M represented by the formula (21). 1 , β are groups M represented by formula (22) 2 When γ are groups J represented by formula (4), the sum of the numbers of hydroxyl groups (X) in the molecule is represented by m1×α+m2×β+γ, and the sum of the numbers of X is particularly preferably 2 or more, 3 or more, or 5 or more.

[0131] On the other hand, the co-modified branched organopolysiloxane of the present invention comprises at least one 2 The preferred number of carboxylic acid groups in the molecule depends on the type and number of other substituents of the branched organopolysiloxane, but generally, the introduction of one carboxylic acid group can greatly improve the alkali solubility. If necessary, the introduction of two or more carboxylic acid groups in the molecule can impart excellent alkali solubility.

[0132] The method for producing the co-modified branched organopolysiloxane of the present invention is not particularly limited. As typical production methods, the following two methods can be listed: 1) a branched organopolysiloxane having a specified molecular weight and molecular weight distribution is produced by a condensation reaction of multiple organosilicon compounds, and a compound containing a phenolic hydroxyl group or a derivative thereof is introduced by a chemical reaction; 2) an organosilicon compound containing a phenolic hydroxyl group or a derivative thereof is produced, and a branched organopolysiloxane having a specified molecular weight and molecular weight distribution is produced by a condensation reaction with other organosilicon compounds, but it is not limited thereto. In the present invention, the method 1) can be preferably applied. As a specific example, a method of producing a branched organopolysiloxane having a silicon-bonded hydrogen atom and introducing a group containing a phenolic hydroxyl group by a hydrosilylation reaction can be listed. The latter reaction can directly provide the compound containing a phenolic hydroxyl group to the reaction, and can also adopt a method of using a compound with a hydroxyl group protected by an acid dissociable group to introduce a branched organopolysiloxane and then removing the protecting group.

[0133] Particularly preferably, the production method comprises at least the following steps:

[0134] (D3SiO 1 / 2 ) a (D2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (1')

[0135] (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).)

[0136] The step of subjecting the branched organopolysiloxane containing silicon-bonded hydrogen atoms to a hydrosilylation reaction as shown in the above-mentioned embodiment may be a production method having at least the following step (I): subjecting the branched organopolysiloxane containing silicon-bonded hydrogen atoms to a hydrosilylation reaction with a compound represented by the following formula (33):

[0137] [Chemical formula 10]

[0138]

[0139] (Where R 6 is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Z is the same group as above, and k2 is a number in the range of 1 to 3)

[0140] The unsaturated hydrocarbon group-containing compound shown in the figure is subjected to a hydrosilylation reaction,

[0141] Furthermore, it is particularly preferred that the above step (I) is followed by a step (II): the molecule obtained in the step (I) has the following formula (34):

[0142] [Chemical formula 11]

[0143]

[0144] (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)

[0145] The branched organopolysiloxane having the functional group represented by the 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 the formula (34) into the group M represented by the above formula (21). 1 .

[0146] It is particularly preferred that a step (III) is further performed after the step (II) to further introduce a carboxylic acid-containing organic group into the molecule, thereby finally obtaining a compound having the above-mentioned groups M in the molecule. 1 The organic group containing phenolic hydroxyl group and the group M 2 The present invention relates to a co-modified branched organopolysiloxane containing a carboxylic acid-containing organic group, wherein the step (III) is to provide a molecule obtained in the step (II) with 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 .

[0147] [Curable composition]

[0148] The co-modified branched organopolysiloxane of the present invention comprises at least one 1 The curing reaction mechanism is not particularly limited as long as it is a curing reaction involving a phenolic hydroxyl group, but examples thereof include one or more reactions selected from condensation reaction, free radical polymerization reaction, peroxide curing reaction, and high-energy ray curing reaction such as ultraviolet rays, and a curable composition containing the co-modified branched organopolysiloxane of the present invention can be designed.

[0149] [High-energy ray-curable composition]

[0150] The co-modified 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. More specifically, the high-energy ray curable composition of the present invention contains at least the co-modified branched organopolysiloxane of the present invention and a photoacid generator required for curing, and may optionally contain other components.

[0151] 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, as described later, (C) crosslinking agent can be added as needed and is an optional structure. In addition, the amount of organic solvent used can also be appropriately selected for the purpose of adjusting the coating properties of the composition.

[0152] (A) The above co-modified branched organopolysiloxane

[0153] (B) a photoacid generator in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (A);

[0154] (C) a cross-linking agent in an amount of 0 to 30 parts by mass based on 100 parts by mass of the component (A); and

[0155] (D) Organic solvents

[0156] [Component (B): photoacid generator]

[0157] Component (B) is a component that catalyzes the curing reaction of component (A) caused by high-energy rays, and generally, a group of compounds known as photoacid generators for cationic polymerization can be used. As photoacid generators, compounds that can generate Bronsted acids or Lewis acids by irradiation with high-energy rays or electron beams are well known.

[0158] The photoacid generator used in the high-energy radiation curable composition of the present invention can be arbitrarily selected from photoacid generators well known in the art and is not particularly limited to a specific photoacid generator. Among the photoacid generators, strong acid generating compounds such as diazonium salts, sulfonium salts, iodonium salts, and phosphonium salts are known, and these compounds can be used. Examples of photoacid generators include: bis(4-tert-butylphenyl)iodonium hexafluorophosphate, cyclopropyldiphenylsulfonium tetrafluoroborate, dimethylphenacylsulfonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoromethanesulfonate, 2-(3,4-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4, 6-bis(trichloromethyl)-1,3,5-triazine, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5 -triazine, 4-nitrobenzene diazonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyliodonium nitrate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium perfluoro-1-butanesulfonate, N-hydroxy Naphthalimide trifluoromethanesulfonate, p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butylsulfonate, (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, and 4-(phenylthio)phenyldiphenylsulfonium triethyl trifluorophosphate, etc., but are not limited thereto. As the photocationic polymerization initiator, in addition to the above-mentioned compounds, commercially available photoacid generators such as Omnicat 250, Omnicat 270 (all from IGM Resins BV), CPI-310B, IK-1 (all from San-Apro Co., Ltd.), DTS-200 (Midori Chemical Co., Ltd.), TS-01, TS-91 (all from Sanwa Chemical Co., Ltd.) and Irgacure 290 (from BASF) can be listed.

[0159] The amount of the photoacid generator added to the high-energy ray-curable composition of the present invention is not particularly limited as long as the target photocuring reaction occurs, but it is generally preferably used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass, based on 100 parts by mass of the co-modified branched organopolysiloxane (component (A)) of the present invention.

[0160] [Component (C): cross-linking agent]

[0161] Component (C) is a component that reacts with phenolic hydroxyl groups by the action of the acid generated by component (B) by high-energy ray irradiation to contribute to the crosslinking reaction. As component (C), a well-known crosslinking agent formulated in a chemically amplified negative resist composition can be used.

[0162] Examples of component (C) preferably used in the present invention include: a compound group having multiple alkoxymethyl groups on the amino group of amino compounds such as melamine, methylguanamine, urea, ethyleneurea, and glycoluril. Specifically, hexamethoxymethylmelamine, tetramethoxymethylmonohydroxymethylmelamine, tetramethoxymethylglycouril, tetrabutoxymethylglycouril, and dimethoxymethyldimethoxyethyleneurea, etc. can be listed. Among these, urea compounds, tetramethoxymethylglycouril, tetrabutoxymethylglycouril, and dimethoxymethyldimethoxyethyleneurea can be preferably used. As component (C), in addition to the above compounds, commercially available crosslinking agents such as Nikalac MW-390, MX-270, MX-279, and MX-280 (all from Sanwa Chemical Co., Ltd.) can also be listed.

[0163] The amount of the crosslinking agent added to the high-energy ray-curable composition of the present invention is not particularly limited as long as the target photocuring reaction can be carried out. That is, it is also possible not to add it. Generally, it is preferred to use the crosslinking agent in an amount of 0 to 30 parts by mass, preferably 5 to 30 parts by mass, and particularly preferably 10 to 30 parts by mass, relative to 100 parts by mass of the co-modified branched organopolysiloxane of component (A) of the present invention.

[0164] [Component (D): organic solvent]

[0165] The high energy ray curable composition of the present invention preferably contains (D) an organic solvent in order to adjust the coating properties of the co-modified branched organopolysiloxane, coating conditions, overall viscosity of the composition, film thickness of the coating film, improve the dispersibility of the photoacid generator, etc. As the organic solvent involved, organic solvents conventionally prepared in various high energy ray curable compositions can be used without particular limitation.

[0166] 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; aromatic hydrocarbons such as toluene, xylene, mesitylene, isopropylbenzene, propylbenzene, diethylbenzene, 1,3-diisopropylbenzene; aromatic ethers such as anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 3,4-dimethoxytoluene, 1,4-bis(methoxymethyl)benzene and the like. The organic solvent may be used alone, or a plurality of organic solvents may be used together in consideration of the miscibility with the components (A) to (C).

[0167] The content of the organic solvent is not particularly limited and is appropriately set according to the miscibility with the co-modified branched organopolysiloxane (A), the film thickness of the coating formed by the high-energy ray curable composition, etc. Usually, 50 to 10,000 parts by mass are used relative to 100 parts by mass of component (A). That is, the solute concentration of the curable branched organopolysiloxane is preferably in the range of 1 to 50% by mass, and more preferably in the range of 2 to 40% by mass.

[0168] The cured product obtained by the high-energy ray-curable composition of the present invention can be obtained according to the molecular structure of component (A) and the number of phenolic hydroxyl groups, alcoholic hydroxyl groups and carboxyl groups in each molecule, and according to the molecular structure and addition amount of components (B) and (C), the desired physical properties of the cured product and the curing speed of the curable composition can be obtained, and further, the viscosity of the curable composition can be designed to be a desired value according to the blending amount of component (D). In addition, the cured product obtained by curing the high-energy ray-curable composition of the present invention is also included in the scope of the present invention. The shape of the cured product obtained by the curable composition of the present invention is not particularly limited, and can be a thin film coating, or a sheet-like molded product, and can also be used as a sealing material or an intermediate layer of a laminate or a display device. The cured product obtained by the composition of the present invention is preferably in the form of a thin film coating, and is particularly preferably a thin film insulating coating.

[0169] The high-energy ray-curable composition of the present invention is suitable for use as a coating agent, particularly as an insulating coating agent for electronic devices and electrical equipment, and is also suitable for use as a resist material using short-wavelength light such as EUV and excimer laser as a light source.

[0170] [Other additives]

[0171] In addition to the above-mentioned components, further additives may be added to the composition of the present invention as desired. Examples of the additives include the following, but are not limited thereto.

[0172] [Thickener]

[0173] In the high-energy ray-curable composition of the present invention, in order to improve the adhesion and closeness to the substrate in contact with the composition, a tackifier can be added. In the case where the curable composition of the present invention is used for coating agents, sealing materials, etc., which require adhesion or closeness to the substrate, it is preferred to add a tackifier to the curable composition of the present invention. As a tackifier, as long as it does not hinder the curing reaction of the composition of the present invention, an optional well-known tackifier can be used.

[0174] Examples of the thickener that can be used in the present invention include: an organosilane having a trialkoxysilyloxy group (e.g., a trimethoxysilyloxy group, a triethoxysilyloxy group) or a trialkoxysilylalkyl group (e.g., a trimethoxysilylethyl group, a triethoxysilylethyl group) and a hydrosilyl group or an alkenyl group (e.g., a vinyl group, an allyl group), or an organosiloxane oligomer having a linear structure, a branched structure, or a cyclic structure and having about 4 to 20 silicon atoms; an organosiloxane oligomer having a trialkoxysilyloxy group or a trialkoxysilylalkyl group and a methacryloxyalkyl group (e.g., a 3-methacryloxy group ... propyl) or an organosiloxane oligomer having a linear structure, branched structure or cyclic structure with about 4 to 20 silicon atoms; an organosilane having a trialkoxysilyloxy group or a trialkoxysilylalkyl group and an epoxy-bonded alkyl group (for example, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl) or an organosiloxane oligomer having a linear structure, branched structure or cyclic structure with about 4 to 20 silicon atoms; an organosilane having two or more trialkoxysilyl groups (for example, trimethoxysilyl alkyl, triethoxysilyl) organic compounds; reaction products of aminoalkyltrialkoxysilane and epoxy-bonded alkyltrialkoxysilane, epoxy-containing ethyl polysilicates, specifically, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 1,6- Bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,3-bis[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, a reaction product of 3-glycidoxypropyltriethoxysilane and 3-aminopropyltriethoxysilane, a condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer and 3-glycidoxypropyltrimethoxysilane, a condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer and 3-methacryloxypropyltriethoxysilane, and tris(3-trimethoxysilylpropyl)isocyanurate.

[0175] The amount of the thickener added to the high-energy ray-curable composition of the present invention is not particularly limited, but is preferably in the range of 0.01 to 5 parts by mass, or in the range of 0.01 to 2 parts by mass, relative to 100 parts by mass of component (A), because it does not promote the curing characteristics of the curable composition or discoloration of the cured product.

[0176] [Further optional additives]

[0177] In the high-energy radiation curable composition of the present invention, other additives may be added as desired in addition to or in place of the above-mentioned tackifier. As additives that can be used, there may be listed: leveling agents, silane coupling agents not included in the substances listed as the above-mentioned tackifiers, high-energy radiation absorbers, antioxidants, polymerization inhibitors, fillers (functional fillers such as reinforcing fillers, insulating fillers, and thermally conductive fillers), etc. As required, appropriate additives may be added to the composition of the present invention. In addition, in the composition of the present invention, as required, particularly when used as a sealing material, a thixotropy imparting agent may also be added.

[0178] [Method for producing cured film]

[0179] The method for producing the cured film is not particularly limited as long as it is a method that can cure the film composed of the above-mentioned high-energy ray-curable composition. A well-known photolithography process can be applied, and a patterned cured film is preferably produced. As a typical production method, a method comprising the following steps is recommended:

[0180] 1) Forming a coating film of the high energy ray curable composition on a substrate.

[0181] 2) The obtained coating film is heated at a temperature of about 100° C. or less for a short time to remove the solvent.

[0182] 3) Perform position selective exposure on the coating film.

[0183] 4) Developing the exposed coating film.

[0184] 5) Heating the patterned cured film at a temperature exceeding 100°C to completely cure the film

[0185] If necessary, a short heating step can be inserted between 3) and 4).

[0186] The above-mentioned manufacturing method is described in detail.

[0187] The substrate is not particularly limited, and various substrates such as a glass substrate, a silicone substrate, and a glass substrate coated with a transparent conductive film can be used.

[0188] In order to apply the high energy ray curable composition on a substrate, a well-known method using a coating device such as a spin coater, a roll coater, a bar coater, or a slit coater can be applied.

[0189] The applied curable composition is usually heated, dried, and the solvent is removed (=prebaking step). Typically, there are methods of drying on a hot plate at 80 to 120° C., preferably 90 to 100° C. for 1 to 2 minutes, leaving it at room temperature for several hours, heating it in a hot air heater or infrared heater for several tens of minutes to several hours, etc.

[0190] The position selective exposure of the coating film is usually carried out through a photomask, etc., using a high-energy ray light source including a high-pressure mercury lamp, a metal halide lamp, an LED lamp, a laser light source such as an excimer laser, and a well-known active energy line light source such as UEV. Depending on the characteristics of the curable composition, negative and positive photomasks can be used respectively. The energy dose irradiated depends on the structure of the curable composition, but is typically around 50 to 2,000 mJ / cm2. Furthermore, as needed, the exposed composition coating film can also be subjected to a heat treatment (post-exposure baking [PEB]) to increase the degree of curing. The conditions at this time are usually 100 to 150°C for 1 to 1.5 minutes.

[0191] In order to form a pattern of a desired shape, a developer is used for development. As a developer, alkaline aqueous solutions and organic solvents are known, but alkaline aqueous solutions are mainly used for development. Alkaline aqueous solutions can use both aqueous solutions of inorganic alkalis and aqueous solutions of organic alkalis. As preferred developers, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts can be listed, and aqueous solutions of tetramethylammonium hydroxide (TMAH) are particularly preferred. The developing method is not particularly limited, and for example, an immersion method, a spray method, etc. can be applied.

[0192] As described above, the co-modified branched organopolysiloxane and the high-energy ray-curable composition containing the co-modified branched organopolysiloxane as the main component of the present invention have excellent high-energy ray curability and, on the other hand, are remarkably excellent in alkali solubility. Therefore, particularly when subjected to a development step using an alkaline aqueous solution, they have the following advantages: a pattern can be formed simply and with high precision, and the obtained cured film has excellent mechanical strength and transparency.

[0193] The patterned cured film after development may be post-heated as necessary. The post-heating temperature is not particularly limited as long as the patterned cured film does not thermally decompose or deform, but is preferably 150 to 250°C, more preferably 150 to 200°C.

[0194] By the above operation, a cured film of the high energy ray-curable composition patterned into a desired shape can be formed.

[0195] [use]

[0196] The high-energy ray-curable composition of the present invention is particularly useful as a material and a resist material for forming an insulating layer constituting various articles, especially electronic devices and electrical equipment. In addition, the curable composition of the present invention is also suitable as a material for forming an insulating layer of a display device such as a touch panel and a display because the transparency of the cured product obtained therefrom is good. In this case, the insulating layer can also form a desired optional pattern as described above as needed. Therefore, a display device such as a touch panel and a display including an insulating layer obtained by curing the high-energy ray-curable composition of the present invention is also an embodiment of the present invention.

[0197] In addition, after applying the curable composition of the present invention to an article, it is cured to form an insulating coating (insulating film). Therefore, the composition of the present invention can be used as an insulating coating agent. In addition, the cured product formed by curing the curable composition of the present invention can also be used as an insulating coating.

[0198] The insulating film formed by the curable composition of the present invention can be used for various purposes other than the above-mentioned display device. In particular, it can be used as a component of an electronic device, or can be used as a material used in the process of manufacturing an electronic device. The electronic device includes electronic devices such as semiconductor devices and magnetic recording heads. For example, the curable composition of the present invention can be used as a semiconductor device, such as LSI (Large Scale Integration), system LSI, DRAM (Dynamic Random Access Memory), SDRAM (Synchronous Dynamic Random Access Memory), RDRAM (Rambus Dynamic Random Access Memory), D-RDRAM (Direct Rambus Dynamic Random Access Memory) and multi-chip module (Multichip Module) multilayer wiring board insulation coating, semiconductor interlayer insulation film, etching stopper (Etching Stopper) film, surface protection film, buffer coating, passivation film in LSI, cover coat of flexible copper clad board, solder resist film, surface protection film for optical device.

[0199] Hereinafter, the present invention will be further described based on examples, but the present invention is not limited to the following examples.

[0200] Example

[0201] The synthesis of the co-modified branched organopolysiloxane of the present invention, the preparation and evaluation of the high-energy ray-curable composition, and the preparation and evaluation of the cured product thereof will be described in detail by way of examples.

[0202] [Appearance of Curable Composition and Cured Product]

[0203] The curable composition and the cured product were visually observed to determine their appearance.

[0204] [Alkali solubility of curable branched organopolysiloxane]

[0205] 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.

[0206] A: Completely dissolved: The coating is completely removed

[0207] B: Almost dissolved: Some coating film remains (scum) observed

[0208] C: Partial dissolution: A large amount of scum (more than 20% of the coating area) was observed

[0209] D: Insoluble

[0210] [High Energy Ray Curability of Curable Composition]

[0211] 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 (accumulated 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.

[0212] A: The cured coating is insoluble in the above TMAH dissolution test.

[0213] 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

[0214] C: The cured coating film is completely dissolved or almost dissolved in the above TMAH dissolution test

[0215] [Synthesis Example 1] Synthesis of Curable Branched Organopolysiloxane (A-1) Having Phenolic Hydroxyl Group and Carboxyl Group

[0216] 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.

[0217] 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 20 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.

[0218] [Me2ASiO 1 / 2 ] 6.0 [PhSiO 3 / 2 ] 4.0

[0219] Among them, Me is methyl, Ph is phenyl, and A represents a (CH2)2C6H4OH group.

[0220] According to the analysis results of gel permeation chromatography, the weight average molecular weight (Mw) and polydispersity (PDI) of the above product were 1,700 and 1.36, respectively.

[0221] In a 200mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 58.6g of the above product, 90g of PGMEA, 7.2g of succinic anhydride and 0.12g of tetramethylguanidine were added, and heated at 90°C for 4 hours to confirm that the reaction was complete. After cooling to room temperature, 3g of Kyoward700PL was added to neutralize the reaction system. The white solid was filtered out to obtain a PGMEA solution of the product. 13 C and 29SiNMR spectroscopy analysis confirmed that the product was a branched organopolysiloxane having the following average composition.

[0222] [Me2ASiO 1 / 2 ] 4.0 [Me2TSiO 1 / 2 ] 2.0 [PhSiO 3 / 2 ] 4.0

[0223] Among them, Me is a methyl group, Ph is a phenyl group, A represents a (CH2)2C6H4OH group, and T represents a (CH2)2C6H4O(C=O)(CH2)2CO2H group.

[0224] The analysis results of gel permeation chromatography showed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-1) were 1,900 and 1.36, respectively.

[0225] [Synthesis Example 2] Synthesis of branched organopolysiloxane (A-2) having phenolic hydroxyl groups and carboxyl groups

[0226] 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.

[0227] 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.

[0228] [Me2ASiO 1 / 2 ] 10.7 [SiO 4 / 2 ]6.0

[0229] Wherein, Me is a methyl group and A represents a (CH2)2C6H4OH group.

[0230] According to the analysis results of gel permeation chromatography, the weight average molecular weight (Mw) and polydispersity (PDI) of the above product were 2,400 and 1.14, respectively.

[0231] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 41.6 g of the above product, 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 Kyoward700PL 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.

[0232] [Me2ASiO 1 / 2 ] 9.6 [Me2TSiO 1 / 2 ] 1.1 [SiO 4 / 2 ] 6.0

[0233] Wherein, Me is a methyl group, A represents a (CH2)2C6H4OH group, and T represents a (CH2)2C6H4O(C=O)(CH2)2CO2H group.

[0234] The analysis results of gel permeation chromatography showed that the weight average molecular weight (Mw) and polydispersity (PDI) of (A-2) were 2,400 and 1.36, respectively.

[0235] [Examples 1-1 to 1-2, Comparative Examples 1-1 to 1-4] Alkali Solubility of Curable Branched Organopolysiloxane

[0236] The alkali solubility was evaluated using a 20 mass % PGMEA solution of the branched organopolysiloxane shown below. The results are summarized in Table 1.

[0237] A-1: Branched organopolysiloxane having phenolic hydroxyl groups and carboxyl groups obtained in Synthesis Example 1

[0238] A-2: Branched organopolysiloxane having phenolic hydroxyl groups and carboxyl groups obtained in Synthesis Example 2

[0239] 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

[0240] 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

[0241] 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

[0242] 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

[0243] [Table 1]

[0244]

[0245] *1: Since a solid coating film could not be formed, evaluation was not possible.

[0246] *2: Cannot form a uniform coating film, so cannot be evaluated

[0247] [Examples 2 to 3 and Comparative Example 2] Evaluation of Curable Branched Organopolysiloxane Compositions

[0248] 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.

[0249] Curable branched organopolysiloxane:

[0250] A-2: Branched organopolysiloxane having phenolic hydroxyl groups and carboxyl groups obtained in Synthesis Example 2

[0251] P-1: with ([Me2HSiO 1 / 2] 5.0 [PhSiO 3 / 2 ] 15.0 ) is a branched organic polysiloxane that is solid at room temperature.

[0252] Photoacid generator:

[0253] B-1: tri-p-tolylsulfonium trifluoromethanesulfonate (product name: TS-01; manufactured by Sanwa Chemical Co., Ltd.)

[0254] Curing agent:

[0255] C-1: Tetramethoxymethyl glycoluril (product name: Nicalac MX-270; manufactured by Sanwa Chemical Co., Ltd.)

[0256] [Table 2]

[0257] Element Example 2 Example 3 Comparative Example 2 (A-2; as solid component) 100 100 (P-1) 100 (B-1) 2 2 2 (C-1) 10 10 total 112 102 112 Appearance of curable composition transparent transparent transparent High energy ray curing A A C Appearance of cured product transparent transparent Uncured Alkali Solubility A A D

[0258] [Summarize]

[0259] As shown in Table 1, the coating film formed from the co-modified branched organopolysiloxane of the present invention exhibits particularly excellent alkali solubility. It should be noted that the curable branched organopolysiloxanes of the comparative examples all have poor alkali solubility or are insoluble in alkali and cannot be used for development with an alkaline aqueous solution.

[0260] In addition, as shown in Table 2, the high-energy ray-curable organopolysiloxane composition (Examples 2 and 3) using 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 polyorganosiloxane (Comparative Example 2) having no phenolic hydroxyl group and carboxyl group has poor alkali solubility and is not curable, so it is difficult to use in the photolithography patterning process.

[0261] Industrial Applicability

[0262] The co-modified branched organopolysiloxane and the high-energy ray curable composition with the co-modified branched organopolysiloxane as the main component of the present invention have excellent high-energy ray curability due to the phenolic hydroxyl group in the molecule. On the other hand, the alkali solubility is particularly excellent due to the presence of a carboxylic acid-containing organic group in the molecule. Therefore, especially in the case of a development process using an alkaline aqueous solution, the co-modified branched organopolysiloxane and the high-energy ray curable composition with the co-modified branched organopolysiloxane as the main component have the following advantages: the pattern can be formed simply and accurately, 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 co-modified branched organopolysiloxane, which 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 a group selected from a hydrogen atom, a monovalent hydrocarbon group which is unsubstituted or substituted by fluorine, an alkoxy group and a hydroxyl group, A is each independently the same group as R, is selected from the following formula (21): [Chemical formula 1] (Where R 1 It is a divalent hydrocarbon group with 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 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) In the group L shown More than one group, at least one of all A is M 1 , at least one is M 2 , a, b, c and d are numbers satisfying the following conditions: 0≤a, 0≤b, 0<(a+b) and 0<(c+d)}.

2. The co-modified branched organopolysiloxane according to claim 1, wherein The number of silicon atoms in the molecule is 50 or less.

3. The co-modified branched organopolysiloxane according to claim 1, wherein: The number of silicon atoms in the molecule is in the range of 5 to 20.

4. The co-modified branched organopolysiloxane according to claim 1, wherein [The group M in the molecule 1 and 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.

5. The co-modified branched organopolysiloxane according to claim 1, wherein: In the formula (21), m1 is a number of 1 or 2, and In the formula (22), m2 is 0 and n is 1.

6. The co-modified branched organopolysiloxane according to claim 1, wherein: In the average unit formula (1), a is a number of 1 or more.

7. The co-modified branched organopolysiloxane according to claim 1, wherein: In the average unit formula (1), b is 0.

8. The co-modified branched organopolysiloxane according to claim 1, wherein In the average unit formula (1), a, b, c, and d are numbers that further satisfy the following condition: 0.5≤a / (b+c+d)≤2.

0.

9. The co-modified branched organopolysiloxane according to claim 1, wherein: The co-modified branched organopolysiloxane is represented by the following average unit formula (1-1) or (1-2). Average unit formula (1-1): (A3SiO 1 / 2 ) a (RSiO 3 / 2 ) c (1-1) Average unit formula (1-2): (A3SiO 1 / 2 ) a (SiO 4 / 2 ) d (1-2) (In these formulas, R and A are the same groups as described above, and a, c and d are numbers that satisfy the above conditions) 10. The co-modified branched organopolysiloxane according to claim 1, wherein: The weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography is 1,000 or more and 3,000 or less, and the polydispersity index (PDI) related to the molecular weight distribution is 1.5 or less.

11. The co-modified branched organopolysiloxane according to claim 1, wherein In the formula (21) and the formula (22), k is 0 and the group L is not contained in the molecule.

12. The co-modified branched organopolysiloxane according to claim 1, wherein: The group J is not contained in the molecule.

13. The co-modified branched organopolysiloxane according to claim 1, wherein: The invention has solubility in an alkaline aqueous solution, wherein after the co-modified branched organopolysiloxane is applied on a glass plate in a manner to have a thickness of 0.5 μm after coating, the coating film is immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (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. 14 . A curable composition comprising the co-modified branched organopolysiloxane according to claim 1 .

15. A high-energy ray-curable composition comprising: (A) the co-modified branched organopolysiloxane according to any one of claims 1 to 13, (B) a photoacid generator in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (A); (C) a cross-linking agent in an amount of 0 to 30 parts by mass based on 100 parts by mass of the component (A); and (D) Organic solvent. 16 . An insulating coating agent comprising the high-energy ray-curable composition according to claim 15 . 17 . A resist material comprising the high energy ray-curable composition according to claim 15 . 18 . A cured product, which is a cured product of the high-energy ray-curable composition according to claim 15 .

19. A method of using the cured product according to claim 18 as an insulating coating.

20. A display device comprising a layer consisting of the cured product according to claim 18.

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