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

Abstract

Provided are: an organopolysiloxane which has excellent fine patterning properties (including coatability), alkali solubility, and high-energy ray curability, and which, when cured, can form a cured film having high transparency and practically sufficient mechanical strength; a high-energy ray-curable composition comprising the same; and a use of the high-energy ray-curable composition. A curable branched organopolysiloxane represented by an average unit formula: (R3SiO1 / 2) a (R2SiO2 / 2) b (RSiO3 / 2) c (SiO4 / 2) d (O1 / 2Z) e (1) (in the formula, R represents a group selected from the group consisting of a monovalent hydrocarbon group, an alkoxy group, a hydroxyl group, an epoxy group-containing group and a phenolic hydroxyl group-containing group, 0 < = a, 0 < = b, 0 lt; c, 0 < = d, 0 < = e, 0.8 < = c / (a + b + c + d + e), and the molecule has at least one group containing a phenolic hydroxyl group. ), having a weight-average molecular weight of 4,500 or less and a polydispersity of 1.3 or less, and preferably having a cage-shaped molecular structure.

Description

Technical Field

[0001] The present invention relates to an alkali-soluble high-energy ray-curable 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 curable 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. In the area 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. In addition, from the viewpoint of high resolution, especially the uniformity of line width, compounds with low to medium molecular weight and small polydispersity have also received attention. Patent document 3 discloses a resist composition with good stability over time containing an acrylic polymer with a phenol group and a specific acid generator.

[0005] Similarly, utilizing the excellent feature of etching resistance, organosilicon-based resist materials have also been studied. Patent documentation 4 discloses a resist composition composed of a phenol-functional polysiloxane of a hydrogen-functional polysiloxane, an alkenyl-functional polysiloxane and a reaction product of a specific diallyl compound. However, since the linear polysiloxane component is many, the product does not show alkali solubility. In addition, patent documentations 5 and 6 disclose phenol-functional polysilsesquioxanes and resist compositions with a specific structure. These are alkali-soluble, but there are problems with their solubility. Similarly, in patent documentation 7, silsesquioxanes and their uses having a monovalent organic group and a phenolic hydroxyl group with an unsaturated double bond in the molecule are disclosed, but there are problems with their alkali solubility (solubility), coating properties and high-energy ray curability.

[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 and a high-energy ray-curable composition containing the same, in which the polysiloxane itself has a low to medium molecular weight and a small polydispersity, exhibits high solubility in alkaline aqueous solutions and 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: Japanese Patent Application Publication No. 2020-184010 Summary of the invention

[0016] Problems to be solved by the invention

[0017] The present invention is made to solve the above-mentioned problems, and provides an organopolysiloxane, a high-energy ray-curable composition containing the organopolysiloxane, and its use. The organopolysiloxane has good fine patterning properties (including coating properties), alkali solubility and high-energy ray curing properties, and can form a cured film having high transparency and sufficient mechanical strength for practical use by curing.

[0018] Solutions for solving problems

[0019] The present invention is completed to solve the above-mentioned problems. It is found that a curable branched organopolysiloxane having a group containing a phenolic hydroxyl group bonded to a silicon atom and an optional group containing an epoxy group in the molecule, a silsesquioxane unit (so-called T unit) as its main constituent unit and having a low weight-average molecular weight and polydispersity has high solubility in alkaline aqueous solution, and a high-energy ray-curable composition containing the same has excellent coating properties and alkali solubility on a substrate and shows good curability, and its cured product (cured film) has sufficient mechanical strength and good transparency, thereby completing the present invention. The curable branched organopolysiloxane preferably has a relatively small molecule and a low polydispersity, and from the viewpoint of technical effects, it is particularly preferred to have a cage-like molecular structure containing a complete cage.

[0020] It should be noted that the high-energy ray-curable composition of the present invention forms an intermolecular bond and undergoes a curing reaction by irradiation with high-energy rays such as ultraviolet rays, but an optional curing means capable of inducing a curing reaction may be used together with or instead of the high-energy rays. As an example, the high-energy ray-curable composition of the present invention may be cured by electron beam irradiation, and such a composition and curing method are one of the embodiments of the invention intended by the present invention and within the scope of the present invention.

[0021] The curable branched organopolysiloxane of the present invention is represented by the following average unit formula (1), has a weight average molecular weight of 4,500 or less in terms of standard polystyrene as measured by gel permeation chromatography, and has a polydispersity of 1.3 or less.

[0022] (R3SiO 1 / 2 ) a (R2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (O 1 / 2 Z) e (1)

[0023] (In the formula, R is a group selected from an unsubstituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group, a hydroxyl group, a group containing an epoxy group, and a group containing a phenolic hydroxyl group; a, b, c, d, and e are numbers satisfying the following conditions: 0 ≤ a, 0 ≤ b, 0 < c, 0 ≤ d, 0 ≤ e, 0.8 ≤ c / (a + b + c + d + e), and the molecule has at least one group containing a phenolic hydroxyl group.)

[0024] The weight-average molecular weight of the curable branched organopolysiloxane can be 4,000 or less.

[0025] The curable branched organopolysiloxane may also have a = 0, b = 0, and d = 0.

[0026] Preferably, the group containing a phenolic hydroxyl group in the curable branched organopolysiloxane has a structure represented by the following formula (2A) or (2B).

[0027] [Chemical formula 1]

[0028] *-R 1 -X-R 2 -Y-A

[0029] (2A)

[0030] [Chemical formula 2]

[0031] *-R 2 -S-A

[0032] (2B)

[0033] (In the formula, R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is an oxygen atom or a sulfur atom, R 2 is a divalent linking group having 3 to 10 carbon atoms containing an alcoholic hydroxyl group, Y is an oxygen atom or a sulfur atom, the substituent A is a phenolic hydroxyl group represented by the following formula (A1) or a substituted or unsubstituted aromatic hydrocarbon-containing group represented by the following formula (A2), and * is a bonding site to the silicon atom on the organopolysiloxane. Among them, at least one of A is A1.)

[0034] [Chemical formula 3]

[0035]

[0036] [Chemical formula 4]

[0037] -(R 3 ) n -Ar

[0038] (A2)

[0039] (In the formula, R 3is an alkylene group having 1 to 3 carbon atoms, n is 0 or 1, and Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted by a monovalent hydrocarbon group or a halogen group.

[0040] In the curable branched organopolysiloxane, X may be an oxygen atom and Y may be a sulfur atom.

[0041] The curable branched organopolysiloxane preferably has a polydispersity of 1.2 or less and has a cage-like molecular structure.

[0042] In the curable branched organopolysiloxane, the average number of silicon atoms per molecule may be 12 or less.

[0043] The curable branched organopolysiloxane preferably has an average of four or more phenolic hydroxyl group-containing groups per molecule.

[0044] After applying a curable branched organopolysiloxane 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. It is preferred that the coating film composed of the organopolysiloxane has a mass reduction rate of 90% by mass or more and is soluble in an alkaline aqueous solution.

[0045] The present invention further provides a high energy ray-curable composition containing at least the following components.

[0046] (A) the curable branched organopolysiloxane,

[0047] (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);

[0048] (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

[0049] (D) Organic solvents

[0050] The present invention further provides an insulating coating agent comprising the high-energy ray-curable composition and a resist material comprising the high-energy ray-curable composition.

[0051] 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.

[0052] 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.

[0053] Effects of the Invention

[0054] The curable branched organopolysiloxane of the present invention has good coating properties on various substrates. In addition, due to its low molecular weight and polydispersity, it shows high solubility to the commonly used alkaline aqueous solution in the development process for forming a pattern of a desired shape. Therefore, in the development process accompanied by selective high-energy ray irradiation, the unreacted / uncured organopolysiloxane and the curable composition comprising it can be easily removed by the washing operation using the alkaline aqueous solution, and high-precision patterning can be achieved by a simple process. Further, the cured product formed by the high-energy ray curable composition comprising the curable branched organopolysiloxane of the present invention has the advantages of being optically transparent and being able to design hardness in a wide range. Therefore, the curable composition involved in the present invention is useful as a resist material using a short-wavelength light source, especially EUV. In addition, it is also 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

[0055] Hereinafter, the configuration of the present invention will be described in further detail.

[0056] The curable branched organopolysiloxane having a specific structure of the present invention has a group containing a phenolic hydroxyl group on at least one silicon atom, and has good solubility in alkaline aqueous solutions (sometimes expressed as "alkali solubility" in the present invention), high-precision patterning properties (including coating properties), and high-energy ray curing properties. 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, etc.

[0057] Here, alkali solubility means that the coating film formed in the development process for forming a pattern of a desired shape 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 soluble in the alkaline aqueous solution.

[0058] More specifically, "soluble in an alkaline aqueous solution" means that after the branched organopolysiloxane according to the present invention is coated on a glass plate in a thickness of 0.5 μm, and 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. In particular, 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 the 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 or the like. When coating is carried out using the organic solvent described later, it is necessary to remove the organic solvent in advance by drying or the like. Further, if it is a composition mainly composed of an organopolysiloxane, the solubility of the high energy ray curable composition containing the organopolysiloxane according to the present invention in an alkaline aqueous solution can be evaluated by the above method. In addition, the water washing step is generally carried out by immersing in a water bath at about room temperature (25 °C) or flowing water at a flow rate similar to that of household tap water for about 10 to 15 seconds so as not to cause adverse effects on the formed pattern and substrate.

[0059] It should be noted that the branched organopolysiloxane of the present invention has a low molecular weight and a small polydispersity. Therefore, compared with the high molecular weight organopolysiloxane composed of the same silsesquioxane units, it has a tendency to further improve the solubility and coatability in an alkaline aqueous solution. When evaluating the solubility of the coating film composed of the organopolysiloxane in an alkaline aqueous solution by the above method, an organopolysiloxane with particularly excellent alkali solubility with a mass reduction rate of the coating film of 98% by mass or more can be obtained.

[0060] The curable branched organopolysiloxane of the present invention is represented by the following average unit formula (1). (R3SiO 1 / 2 ) a (R2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (O 1 / 2 Z) e (1)

[0061] (In the formula, R is a group selected from unsubstituted or fluorine-substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, groups containing epoxy groups, and groups containing phenolic hydroxyl groups, and a, b, c, d, and e are numbers satisfying the following conditions: 0 ≤ a, 0 ≤ b, 0 < c, 0 ≤ d, 0 ≤ e, 0.8 ≤ c / (a + b + c + d + e), and the molecule has at least one group containing a phenolic hydroxyl group.)

[0062] In the curable branched organopolysiloxane represented by the above average unit formula (1), the ratio of each constituent unit has a degree of freedom, but the constituent ratio of the monoorganosiloxane unit (sometimes referred to as T unit or silsesquioxane unit) in all siloxane units satisfies the following formula (3). Considering that the preferred properties of the curable branched organopolysiloxane are a solid with no surface stickiness and a small polydispersity, the monoorganosiloxane unit is the main constituent unit.

[0063] 0.8≤c / (a+b+c+d+e) (3)

[0064] The molecular weight of the curable branched organopolysiloxane of the present invention is 4,500 or less in terms of weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography. This property makes it easy to design a material having excellent alkali solubility and capable of high-precision patterning. The preferred weight average molecular weight is 4,000 or less, more preferably in the range of 1,000 to 4,000, or 1,500 to 4,000.

[0065] On the other hand, the polydispersity (hereinafter sometimes referred to as "PDI") of the curable branched organopolysiloxane is a value defined as the value of "Mw / Mn" using the number average molecular weight (Mn) and the weight average molecular weight (Mw) calculated in terms of standard polystyrene by gel permeation chromatography. The smaller the polydispersity, the narrower the molecular weight distribution and the sharper the molecular weight distribution. Specifically, the polydispersity value of the curable branched organopolysiloxane needs to be 1.3 or less. From the viewpoint of high-precision patterning in the organopolysiloxane involved in the present invention and the high-energy ray-curable composition using the same, in particular, reducing the non-uniformity of line width, the polydispersity value is preferably 1.20 or less, and particularly preferably in the range of 1.00 to 1.20.

[0066] In the curable branched organopolysiloxane of the present invention, the above molecular weight and its polydispersity are essential components. If its weight average molecular weight or its polydispersity exceeds the above upper limit, one or both of the alkali solubility and high-precision patternability (including coating properties) in the organopolysiloxane involved in the present invention and the high-energy ray curable composition using the organopolysiloxane may be impaired, and it cannot be preferably used as a patterning material.

[0067] Furthermore, the average number of silicon atoms in the curable branched organopolysiloxane is preferably 12 or less. That is, the branched organopolysiloxane of the present invention may be a branched organopolysiloxane having a single number of silicon atoms, or may be a mixture of two or more branched organopolysiloxanes having different numbers of silicon atoms, but the average number of silicon atoms in all molecules of these curable branched organopolysiloxanes is preferably 12 or less. The more preferred average number of silicon atoms is 10 or less, and even more preferably 8 or less. This characteristic also affects whether high-precision patterning can be performed, and it is preferred that the average number of silicon atoms is small and its deviation is small.

[0068] The curable branched organopolysiloxane of the present invention preferably has a cage-like molecular structure. The cage-like molecular structure refers to a so-called polyhedral cluster structure or a structure similar thereto, also known as a polyhedral oligomeric silsesquioxane, having a symmetrical molecular structure or a molecular structure similar thereto. It is well known that there are regular hexahedral structures with 8 silicon atoms, pentagonal structures with 10 silicon atoms, and heptahedral structures with 12 silicon atoms.

[0069] In the present invention, in the above formula (1), (RSiO 3 / 2 ) c In the branched organopolysiloxane having a cage-like molecular structure with silsesquioxane units as the main constituent units, a, b, c, d and e may satisfy the condition of 0.8≤c / (a+b+c+d+e)≤1.0, and it is particularly preferred that a, b and d are 0. Further, as described later, from the viewpoint of providing a complete cage-like molecular structure, e may be 0, and is preferred. That is, the curable branched organopolysiloxane of the present invention represented by the above formula (1) is particularly preferably composed of only (RSiO 3 / 2 ) c It should be noted that in this case, the number of c is of course consistent with the number of silicon atoms in the molecule.

[0070] In the above formula (1), (O 1 / 2 Z) e RSiO 3 / 2 ) c The unit is the main constituent unit, indicating that the formation may contain (R2SiO 2 / 2 ) b Unit and (SiO 4 / 2 ) dIn the case of a branched organopolysiloxane having a cage-like molecular structure, a portion of the condensation reaction is not completed and the remaining Si-OH and / or Si-O-alkyl group. That is, Z each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, particularly preferably methyl, ethyl or isopropyl.

[0071] When all the condensable reaction groups in the branched organopolysiloxane of formula (1) are bonded to each other to form Si-O-Si bonds, e in formula (1) is 0 (zero). Such a situation is called a complete cage structure. In addition, when r is not 0, in the branched organopolysiloxane of formula (1), all the condensable reaction groups are not bonded to each other to form Si-O-Si bonds, and a part of them becomes SiOZ. Such a situation is called a partial cleavage structure. In the cage-like molecular structure of such a branched organopolysiloxane, a complete cage structure and a partial cleavage structure are known, and both can be used as the branched organopolysiloxane represented by formula (1) of the present invention. However, the branched organopolysiloxane of formula (1) of the present invention is preferably a complete cage structure (i.e., e=0 in formula (1)) or a structure close thereto (for example, e is 15% or less, preferably 10% or less relative to a+b+c+d), and is particularly preferably a complete cage structure. Specific examples of the complete cage structure and the partially cleaved structure of the branched organopolysiloxane are shown in paragraphs

[0047] to

[0049] of JP-A-2010-515778, and the cage-like branched organopolysiloxane of the present invention may have the same chemical structure.

[0072] As described later, all the substituents R in the branched polyorganosiloxane of the present invention represented by the above average unit formula (1) may be groups containing phenolic hydroxyl groups, and preferably, but from the viewpoint that the curing reaction proceeds even without using the crosslinking agent (C), a part of the substituents R may be groups containing epoxy groups. On the other hand, the substituents R other than the groups containing phenolic hydroxyl groups and the groups containing epoxy groups in the average unit formula (1) may be groups selected from unsubstituted or fluorine-substituted monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups. Here, the unsubstituted or fluorine-substituted monovalent hydrocarbon group preferably does not contain a curing-reactive functional group containing a carbon-carbon double bond or a monovalent organic group having a hetero atom such as an epoxy group, an amino group, or a thioether group, and is preferably a group selected from unsubstituted or fluorine-substituted alkyl groups, cycloalkyl groups, arylalkyl groups, and aryl groups having 1 to 20 carbon atoms.

[0073] 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, cyclohexyl, etc. can be listed. As the above-mentioned arylalkyl group, benzyl, phenethyl, etc. can be listed. As the above-mentioned aryl group, phenyl, naphthyl, etc. 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, isopropoxy, etc. can be listed.

[0074] Examples of the epoxy group-containing group of the substituent R include 3-glycidoxypropyl and 3,4-epoxycyclohexylethyl. When the epoxy group-containing group and the phenolic hydroxyl group-containing group are present together in the branched organopolysiloxane of formula (1), the high-energy ray-curable composition of the present invention has the advantage of being able to achieve good high-energy ray curability even without using a crosslinking agent.

[0075] From the viewpoint of easy production of a branched polyorganosiloxane having a small polydispersity, the substituent R is preferably a bulky group, and specifically, an alkyl group having 3 or more carbon atoms, an aryl group, and an epoxy group-containing group are recommended as preferred groups.

[0076] The curable branched polyorganosiloxane of the present invention has a group containing a phenolic hydroxyl group in the molecule. Specifically, it is required that all or part of the substituents R in the average unit formula (1) are groups containing a phenolic hydroxyl group, and at least one of the substituents R is a group containing a phenolic hydroxyl group. Furthermore, the group containing a phenolic hydroxyl group as the substituent R may further have an alcoholic hydroxyl group (also called a methanol group) in the same functional group, and this is preferred. That is, the substituent R involved in the present invention may be a group containing a phenolic hydroxyl group having an average of one or more alcoholic hydroxyl groups and a phenolic hydroxyl group in the functional group, and this is preferred.

[0077] In the present invention, the group containing a phenolic hydroxyl group is preferably a group represented by the following formula (2A) or (2B). 2 The substituent A has an alcoholic hydroxyl group, and at least a part of the substituent A has a phenolic hydroxyl group.

[0078] [Chemical formula 5]

[0079] *-R 1 -XR 2 -YA

[0080] (2A)

[0081] [Chemical formula 6]

[0082] *-R 2 -SA

[0083] (2B)

[0084] Connector R 1 It is a divalent hydrocarbon group having 2 to 6 carbon atoms, and may be linear or branched. Specific examples thereof include ethylene, propylene, 2-methylethylene, butylene, pentylene, and hexylene, and propylene is preferred.

[0085] The linking group X is an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

[0086] Connector R 2 It is a linear, branched or cyclic divalent linking group having 3 to 10 carbon atoms and containing an alcoholic hydroxyl group. Specifically, the divalent groups exemplified by the following structural formula (4) are mentioned.

[0087] In addition, the linking group Y is an oxygen atom or a sulfur atom, and is preferably a sulfur atom.

[0088] [Chemical formula 7]

[0089]

[0090] (Wherein, * indicates the bonding site)

[0091] Furthermore, the substituent A is a phenolic hydroxyl group represented by the following formula (A1) or a substituted or unsubstituted aromatic hydrocarbon-containing group represented by the following formula (A2), wherein at least one of A is A1.

[0092] On the other hand, * is a bonding site to a silicon atom on the organopolysiloxane.

[0093] [Chemical formula 8]

[0094]

[0095] [Chemical formula 9]

[0096] -(R 3 ) n -Ar

[0097] (A2)

[0098] (Where R 3 is an alkylene group having 1 to 3 carbon atoms, n is 0 or 1, and Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted by a monovalent hydrocarbon group or a halogen group.

[0099] By introducing the substituent A2 into the group containing a phenolic hydroxyl group, the softening point of the branched polyorganosiloxane and the surface viscosity during film production can be adjusted. 3 , methylene, ethylene, propylene, preferably methylene. The number of alkylene groups in these substituents A2 may be zero, preferably zero.

[0100] Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted by a monovalent hydrocarbon group or a halogen group include phenyl, o-tolyl, p-tolyl, o-chlorophenyl, p-chlorophenyl, 1-naphthyl, 2-naphthyl, 1-methyl-2-naphthyl, 6-methyl-2-naphthyl, 2-methyl-1-naphthyl, 2-anthryl and 9-anthryl, but 1-naphthyl and 2-naphthyl are preferably used.

[0101] There is no limitation on the amount of A2 in the molecule, but from the viewpoint of maintaining good alkali solubility and high energy ray curability of the branched polyorganosiloxane, the value of [molar concentration of A2] / [molar concentration of A] is preferably 0.5 or less, more preferably 0.2 or less, and still more preferably 0.1 or less.

[0102] The curable branched organopolysiloxane of the present invention has at least one phenolic hydroxyl group in the molecule, but the average value is preferably 4 or more. That is, the branched organopolysiloxane of the present invention can be a branched organopolysiloxane having a single number of phenolic hydroxyl groups, or can be a mixture of two or more branched organopolysiloxanes having different numbers of phenolic hydroxyl groups, but it is preferred that the average number of phenolic hydroxyl groups in all molecules of these curable branched organopolysiloxanes is 4 or more. Thus, good high-energy ray curing and excellent alkali solubility can be provided. The average number of groups containing phenolic hydroxyl groups is preferably an average of five or more, more preferably six or more. In particular, when the number of Si atoms is 12 or less, the number of substituents R on the Si atom is set as the upper limit, and it is preferred that the molecule has an average of 4 to 12 groups containing phenolic hydroxyl groups.

[0103] There is no particular limitation on the position of the group containing a phenolic hydroxyl group in the curable branched polyorganosiloxane of the present invention, and any R in the average unit formula (1) can be applied. However, as described above, considering that the above formula (3) is satisfied and there are preferably four or more groups containing a phenolic hydroxyl group, a monoorganosiloxane unit (RSiO 3 / 2 ) wherein all or part of R is a group containing a phenolic hydroxyl group.

[0104] The method for producing the curable branched organopolysiloxane of the present invention is not particularly limited. As a typical production method, the following production method 1) or 2) can be used.

[0105] 1) producing a branched organopolysiloxane having a predetermined molecular weight and a small polydispersity by a controlled hydrolysis / condensation reaction between a pre-produced alkoxysilane containing a phenolic hydroxyl group and other alkoxysilanes as an optional component;

[0106] 2) Using a single or multiple alkoxysilanes, a reactive branched organopolysiloxane having a specified molecular weight and a small polydispersity is produced by controlled hydrolysis / condensation reaction, and a compound containing a phenolic hydroxyl group and a compound containing an aromatic hydrocarbon as an optional component are introduced by chemical reaction. At this time, by adjusting the ratio of the amount of substances in the chemical reaction, reactive functional groups such as epoxy groups in the reactive branched organopolysiloxane as a precursor can be left in the molecule, which is preferred.

[0107] It should be noted that, in the present invention, the manufacturing method of 2) can be preferably applied. In addition, since the product does not contain heavy metals such as platinum atoms, any of the above manufacturing methods has advantages in the case of being applied to electronic materials, especially electronic materials in the semiconductor field.

[0108] The method 2) is further described by giving specific examples. In the presence of a basic catalyst, a mixture of a trialkoxysilane having a reactive functional group (e.g., a group containing an epoxy group) and optionally other trialkoxysilanes is subjected to a controlled hydrolysis / condensation reaction to produce a branched organopolysiloxane having an epoxy group with a small polydispersity. The molecular weight of the product can be controlled by the type and amount of the solvent used during the reaction and the amount of water used.

[0109] Preferably, a curable branched organopolysiloxane having a group containing a phenolic hydroxyl group can be produced by an addition reaction between the obtained branched organopolysiloxane having an epoxy group-containing group and a phenol compound containing a mercapto group and an optionally used compound having both a mercapto group and an aromatic hydrocarbon group. In this case, all the epoxy group-containing groups of the branched organopolysiloxane can be reacted, or a curable branched organopolysiloxane having at least one phenolic hydroxyl group and an epoxy group-containing group can be produced by leaving a part of the epoxy group-containing groups.

[0110] [High Energy Ray Curable Composition]

[0111] The high energy ray curable composition of the present invention contains the following four components: Component (A) is the main component of the present invention described in detail, and component (C) is an optional component.

[0112] (A) the above-mentioned curable branched organopolysiloxane,

[0113] (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);

[0114] (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

[0115] (D) Organic solvents

[0116] [Component (B): photoacid generator]

[0117] 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.

[0118] 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.

[0119] 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 intended photocuring reaction occurs, but 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 curable branched organopolysiloxane (A) of the present invention.

[0120] [Component (C): cross-linking agent]

[0121] Component (C) is a component that reacts with the phenolic hydroxyl group (and alcoholic hydroxyl group) in component (A) by the action of the acid generated by component (B) by high-energy ray irradiation, thereby contributing to the crosslinking reaction. As component (C), a well-known crosslinking agent formulated in a chemically amplified negative resist composition can be used.

[0122] 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.

[0123] 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 curable branched organopolysiloxane of component (A) of the present invention.

[0124] [Component (D): organic solvent]

[0125] 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 curable branched organopolysiloxane and the 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.

[0126] 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).

[0127] The content of the organic solvent is not particularly limited and is appropriately set according to the miscibility with the curable 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 the 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.

[0128] The cured product obtained by the high-energy ray-curable composition of the present invention can obtain the desired physical properties of the cured product and the curing speed of the curable composition according to the molecular structure of component (A) and the number of phenolic hydroxyl groups per molecule, and according to the molecular structure and addition amount of components (B) and (C), and further, the viscosity of the curable composition can be designed to 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 or an anti-corrosion layer.

[0129] 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.

[0130] [Other additives]

[0131] 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.

[0132] [Thickener]

[0133] 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.

[0134] Examples of the thickener that can be used in the present invention include: an organosilane having a trialkoxysilyloxy group (e.g., trimethoxysilyloxy group, triethoxysilyloxy group) or a trialkoxysilylalkyl group (e.g., trimethoxysilylethyl group, triethoxysilylethyl group) and a hydrosilyl group or an alkenyl group (e.g., vinyl group, allyl group), or an organosiloxane oligomer having a linear structure, a branched structure, or a cyclic structure having about 4 to 20 silicon atoms; an organosiloxane oligomer having a trialkoxysilyloxy group or a trialkoxysilylalkyl group and a methacryloxyalkyl group (e.g., 3-methacryloyloxy group, oxypropyl) 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, a 3-glycidoxypropyl group, a 4-glycidoxybutyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group) 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, a trimethoxysilyl group The organic compound containing an aminoalkyltrialkoxysilane and an epoxy-bonded alkyltrialkoxysilane, and an epoxy-containing ethyl polysilicate, 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.

[0135] 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.

[0136] [Further optional additives]

[0137] 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.

[0138] [Method for producing cured film]

[0139] 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:

[0140] 1) Forming a coating film of the high energy ray curable composition on a substrate.

[0141] 2) The obtained coating film is heated at a temperature of about 100° C. or less for a short time to remove the solvent.

[0142] 3) Perform position selective exposure on the coating film.

[0143] 4) Developing the exposed coating film.

[0144] 5) The patterned cured film is heated at a temperature exceeding 100° C. to completely cure the film.

[0145] If necessary, a short-time heating step may be inserted between 3) and 4).

[0146] The above-mentioned manufacturing method is described in detail.

[0147] 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.

[0148] 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.

[0149] The applied curable composition is usually heated, dried, and the solvent is removed. Typically, there are methods of drying on a hot plate or in an oven at 80 to 120°C, preferably 90 to 100°C for 1 to 2 minutes, leaving it at room temperature for several hours, and heating it in a hot air heater or infrared heater for several tens of minutes to several hours.

[0150] 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 irradiated energy dose 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.

[0151] 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.

[0152] As described above, the curable branched organopolysiloxane and the high-energy ray-curable composition containing the same as the main component according to 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 advantages of enabling simple and high-precision pattern formation and having excellent mechanical strength and transparency of the obtained cured film.

[0153] Generally, it is preferred to post-heat the patterned cured film after development. 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.

[0154] By the above operation, a cured film of the high energy ray-curable composition patterned into a desired shape can be formed.

[0155] [use]

[0156] 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.

[0157] 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.

[0158] 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. Electronic devices include semiconductor devices, magnetic recording heads and other electronic devices. 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.

[0159] Hereinafter, the present invention will be further described based on examples, but the present invention is not limited to the following examples.

[0160] Example

[0161] The synthesis of the curable 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.

[0162] [Appearance of Curable Composition and Cured Product]

[0163] The curable composition and the cured product were visually observed to determine their appearance including transparency.

[0164] [Alkali solubility of curable branched organopolysiloxane]

[0165] 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.

[0166] A: Completely dissolved: The coating is completely removed

[0167] B: Almost dissolved: Some coating film remains (scum) observed

[0168] C: Partial dissolution: A large amount of scum (more than 20% of the coating area) was observed

[0169] D: Insoluble

[0170] [High Energy Ray Curability of Curable Composition]

[0171] 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: 40mJ / cm2) under a high-pressure mercury lamp, and then heated at 150°C for 2 minutes to obtain a cured coating film. The high-energy ray curability was determined according to the following criteria.

[0172] A: The cured coating is insoluble in the above TMAH dissolution test.

[0173] 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

[0174] C: The cured coating film is completely dissolved or almost dissolved in the above TMAH dissolution test

[0175] [Synthesis Example 1] Synthesis of Epoxy-functional Branched Organopolysiloxane (P-1)

[0176] In a 1000mL three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 120.0g of 3-glycidoxypropyltrimethoxysilane, 400g of tetrahydrofuran, 1.0g of a 50% cesium hydroxide aqueous solution and 13.9g of water were placed. The mixture was refluxed at 70°C for 6 hours to carry out a hydrolysis / condensation reaction. After cooling to room temperature, 8.0g of Kyoward (registered trademark) 700PL manufactured by Kyowa Chemical Industry Co., Ltd. was added to the reaction solution and stirred at room temperature for 30 minutes. The solid was filtered out and the volatile components were distilled off under reduced pressure to obtain a colorless oily product. By 13 C and 29 SiNMR spectroscopy and gel permeation chromatography (GPC) analysis confirmed that the product was a branched organopolysiloxane (P-1) in which all the substituents on the silicon atoms were 3-glycidoxypropyl groups. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (PDI) calculated by the GPC method in terms of standard polystyrene were 1,380, 1,480 and 1.07, respectively. In addition, the average number of silicon atoms (the value calculated from the above Mn) was 8.3.

[0177] [Synthesis Example 2] Synthesis of Epoxy-functional Branched Organopolysiloxane (P-2)

[0178] In a 1000mL three-necked flask equipped with a thermometer, a stirring device and a nitrogen inlet tube, 120.0g of 3,4-epoxycyclohexylethyltrimethoxysilane, 400g of tetrahydrofuran, 1.0g of a 50% cesium hydroxide aqueous solution and 13.4g of water were placed. The same operation as in Synthesis Example 1 was performed to obtain a colorless oily product. The same characterization as in Synthesis Example 1 was performed to confirm that the product was a branched organic polysiloxane (P-2) in which the substituents on the silicon atoms were all 3,4-epoxycyclohexylethyl. The Mn, Mw and PDI calculated in terms of standard polystyrene by the GPC method were 1,420, 1,460 and 1.03, respectively. In addition, the average number of silicon atoms (the value calculated from the above Mn) was 8.0.

[0179] [Synthesis Example 3 (Example)] Synthesis of phenol-functional branched organopolysiloxane (A-1)

[0180] In a 500 mL three-necked flask equipped with a thermometer, a stirring device and a nitrogen inlet tube, 56.0 g of P-1 obtained in Synthesis Example 1, 38.0 g of 4-mercaptophenol, 5.3 g of 2-naphthalenethiol, 75.0 g of methanol and 120.0 g of propylene glycol monomethyl ether acetate (PGMEA) were placed to prepare a uniform solution. 33.6 g of triethylamine was slowly added to the solution at room temperature, and the reaction was further stirred for 4 hours to terminate the reaction. After adding 21.0 g of acetic acid, the reaction solution was washed three times with 500 mL of water. After treating the organic layer with anhydrous magnesium sulfate, the solid was filtered out to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was performed. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-1) having a structure in which the substituents on the silicon atom were 4-mercaptophenol and 2-naphthol added to 3-glycidoxypropyl at a molar ratio of 90:10. Mn, Mw, and PDI determined by the GPC method in terms of standard polystyrene were 3,410, 3,560, and 1.04, respectively.

[0181] [Synthesis Example 4 (Example)] Synthesis of phenol-functional branched organopolysiloxane (A-2)

[0182] Instead of 56.0g of P-1, 38.0g of 4-mercaptophenol, 5.3g of 2-naphthalenethiol, 75.0g of methanol, 120.0g of PGMEA, 33.6g of triethylamine and 21.0g of acetic acid, 70.0g of P-2, 50.0g of 4-mercaptophenol, 120.0g of PGMEA, 75.0g of methanol, 40.0g of triethylamine and 24.0g of acetic acid were used. The reaction was carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was carried out. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-2) having a structure in which the substituent on the silicon atom was 4-mercaptophenol added to 3,4-epoxycyclohexylethyl. The Mn, Mw and PDI calculated in terms of standard polystyrene by GPC method were 3,470, 3,920 and 1.13, respectively.

[0183] [Synthesis Example 5 (Example)] Synthesis of Phenol-functional Branched Organopolysiloxane (A-3)

[0184] Instead of 56.0g of P-1, 38.0g of 4-mercaptophenol, 5.3g of 2-naphthalenethiol, 75.0g of methanol, 120.0g of PGMEA, 33.6g of triethylamine and 21.0g of acetic acid, 76.0g of P-2, 36.0g of 4-mercaptophenol, 75.0g of methanol, 120.0g of PGMEA, 35.0g of triethylamine and 22.0g of acetic acid were used. The reaction was carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was carried out. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-3) with a structure in which 4-mercaptophenol was added to a 67 mol% substituent on a silicon atom. The Mn, Mw and PDI calculated in terms of standard polystyrene by GPC method were 3,290, 3,390 and 1.03, respectively.

[0185] [Synthesis Example 6 (Example)] Synthesis of Phenol-functional Branched Organopolysiloxane (A-4)

[0186] Instead of 56.0g of P-1, 38.0g of 4-mercaptophenol, 5.3g of 2-naphthalenethiol, 75.0g of methanol, 120.0g of PGMEA, 33.6g of triethylamine and 21.0g of acetic acid, 126.0g of P-2, 89.0g of 2-mercaptophenol, 200.0g of PGMEA, 100.0g of methanol, 72.0g of triethylamine and 43.0g of acetic acid were used, and a 1000mL three-necked flask was used. The reaction was carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was carried out. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-4) having a structure in which the substituent on the silicon atom was 2-mercaptophenol added to 3,4-epoxycyclohexylethyl. Mn, Mw, and PDI determined by the GPC method in terms of standard polystyrene were 2,500, 2,580, and 1.03, respectively.

[0187] [Synthesis Example 7] Synthesis of Epoxy-functional Branched Organopolysiloxane (P-3)

[0188] In a 500mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 220.0g of 3-glycidoxypropyltrimethoxysilane, 150g of toluene, 55g of water, and 1.6g of a 50% aqueous solution of cesium hydroxide were added, and stirred at 80°C for 4 hours. Azeotropic dehydration and demethanolation were performed using toluene, concentrated to a solid content of 60%, and stirred at 115°C for 6 hours. Then, it was allowed to stand at room temperature, 20g of an alkaline adsorbent (KYOWARD (registered trademark) KW-700PL) was added, and after stirring at room temperature for 30 minutes, the solid content was filtered to obtain a solution of a branched polysiloxane with a solid content concentration of 60%. The same characterization as in Synthesis Example 1 was performed to confirm that the product was a toluene solution of a branched polysiloxane (P-3) in which the substituents on the silicon atoms were all 3-glycidoxypropyl groups. Mn, Mw and PDI in terms of standard polystyrene by GPC method were 2,900, 7,250 and 2.50, respectively. The average number of silicon atoms (value calculated from the above Mn) was 17.3.

[0189] [Synthesis Example 8] Synthesis of Phenol-functional Branched Organopolysiloxane (A-5)

[0190] PGMEA accounting for 120% or more of the solid content (mass of P-3) in the solution of P-3 synthesized above is added to the P-3 solution, and toluene and PGMEA are distilled off under reduced pressure to prepare a 50% PGMEA solution of P-3. In 100g of the solution, 37.7g of 4-mercaptophenol, 10.0g of PGMEA, 24.7g of triethylamine and 15.0g of acetic acid are used. Otherwise, the reaction is carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 is carried out. No side reaction occurs, and it is confirmed that the product is a branched organic polysiloxane (A-5) having a structure in which the substituent on the silicon atom is 4-mercaptophenol added to 3-glycidoxypropyl. Mn, Mw and PDI converted to standard polystyrene by GPC method are 5,100, 12,750 and 2.50, respectively. [Synthesis Example 9] Synthesis of Epoxy-functional Branched Organopolysiloxane (P-4)

[0191] In a 1000mL three-necked flask equipped with a thermometer, a stirring device and a nitrogen inlet tube, 27.5g of 3,4-epoxycyclohexylethyltrimethoxysilane, 15.2g of methyltrimethoxysilane, 171g of tetrahydrofuran, 0.8g of 34% potassium hydroxide aqueous solution and 6.1g of water were placed. The mixture was refluxed at 70°C for 6 hours to carry out a hydrolysis / condensation reaction. After cooling to room temperature, 4.8g of Kyoward (registered trademark) 700PL manufactured by Kyowa Chemical Industry Co., Ltd. was added to the reaction solution and stirred at room temperature for 30 minutes. The solid was filtered out and the volatile components were distilled off under reduced pressure to obtain a white solid. The same characterization as in Synthesis Example 1 was performed to confirm that the product was a branched organic polysiloxane (P-4) in which 50 mol% of the substituents on the silicon atom were 3,4-epoxycyclohexylethyl and 50 mol% were methyl. Mn, Mw and PDI in terms of standard polystyrene by GPC method were 925, 1,080 and 1.17, respectively. The average number of silicon atoms (value calculated from the above Mn) was 7.6.

[0192] [Synthesis Example 10] Synthesis of phenol-functional branched organopolysiloxane (A-6)

[0193] Instead of 56.0g of P-1, 38.0g of 4-mercaptophenol, 5.3g of 2-naphthalenethiol, 75.0g of methanol, 120.0g of PGMEA, 33.6g of triethylamine and 21.0g of acetic acid, 12.6g of P-4, 6.5g of 4-mercaptophenol, 12.4g of PGMEA, 20.0g of methanol, 1.0g of triethylamine and 2.0g of acetic acid were used, and a 100mL three-necked flask was used. Except that, the reaction was carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was carried out. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-6) having a structure in which the substituent on the silicon atom was 4-mercaptophenol added to 3,4-epoxycyclohexylethyl. Mn, Mw, and PDI determined by the GPC method in terms of standard polystyrene were 2,220, 2,690, and 1.21, respectively.

[0194] [Synthesis Example 11] Synthesis of Epoxy-functional Branched Organopolysiloxane (P-5)

[0195] In a 1000mL three-necked flask equipped with a thermometer, a stirring device and a nitrogen inlet tube, 27.5g of 3,4-epoxycyclohexylethyltrimethoxysilane, 18.3g of propyltrimethoxysilane, 171g of tetrahydrofuran, 0.8g of 34% potassium hydroxide aqueous solution and 6.1g of water were placed. The mixture was refluxed at 70°C for 6 hours to perform a hydrolysis / condensation reaction. After cooling to room temperature, 4.8g of Kyoward (registered trademark) 700PL manufactured by Kyowa Chemical Industry Co., Ltd. was added to the reaction solution and stirred at room temperature for 30 minutes. The solid was filtered out and the volatile components were distilled off under reduced pressure to obtain a white solid. The same characterization as in Synthesis Example 1 was performed to confirm that the product was a branched organic polysiloxane (P-5) in which 50 mol% of the substituents on the silicon atom were 3,4-epoxycyclohexylethyl and 50 mol% were propyl. Mn, Mw and PDI in terms of standard polystyrene by GPC method were 1120, 1,180 and 1.05, respectively. The average number of silicon atoms (value calculated from the above Mn) was 8.2.

[0196] [Synthesis Example 12] Synthesis of phenol-functional branched organopolysiloxane (A-7)

[0197] Instead of 56.0g of P-1, 38.0g of 4-mercaptophenol, 5.3g of 2-naphthalenethiol, 75.0g of methanol, 120.0g of PGMEA, 33.6g of triethylamine and 21.0g of acetic acid, 14.0g of P-5, 6.5g of 4-mercaptophenol, 16.0g of PGMEA, 20.0g of methanol, 1.0g of triethylamine and 2.0g of acetic acid were used, and a 1000mL three-necked flask was used. Except for this, the reaction was carried out in the same manner as in Synthesis Example 3 to obtain a PGMEA solution of the product. The same characterization as in Synthesis Example 1 was carried out. No side reaction occurred, and it was confirmed that the product was a branched organic polysiloxane (A-7) having a structure in which the substituent on the silicon atom was 4-mercaptophenol added to 3,4-epoxycyclohexylethyl. Mn, Mw, and PDI determined by the GPC method in terms of standard polystyrene were 2,440, 2,900, and 1.19, respectively.

[0198] [Example 1 and Comparative Example 1] Alkali Solubility of Branched Organopolysiloxane

[0199] The alkali solubility was evaluated using 20 mass % PGMEA solutions of the branched organopolysiloxanes shown below, and the results are summarized in Table 1. The compounds corresponding to Examples of the present application are curable branched organopolysiloxanes A-1 to A-4, A-6, and A-7.

[0200] A-1: Curable branched organopolysiloxane obtained in Synthesis Example 3

[0201] A-2: Curable branched organopolysiloxane obtained in Synthesis Example 4

[0202] A-3: Curable branched organopolysiloxane obtained in Synthesis Example 5

[0203] A-4: Curable branched organopolysiloxane obtained in Synthesis Example 6

[0204] A-5: Curable branched organopolysiloxane obtained in Synthesis Example 8

[0205] A-6: Curable branched organopolysiloxane obtained in Synthesis Example 10

[0206] A-7: Curable branched organopolysiloxane obtained in Synthesis Example 12

[0207] P-1: Curable branched organopolysiloxane obtained in Synthesis Example 1

[0208] P-2: Curable branched organopolysiloxane obtained in Synthesis Example 2

[0209] P-3: Curable branched organopolysiloxane obtained in Synthesis Example 7

[0210] P-4: Curable branched organopolysiloxane obtained in Synthesis Example 9

[0211] P-5: Curable branched organopolysiloxane obtained in Synthesis Example 11

[0212] [Table 1]

[0213]

[0214] [Example 2 and Comparative Example 2] Evaluation of Curable Branched Organopolysiloxane Compositions

[0215] 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.

[0216] Curable branched organopolysiloxane (20 mass % PGMEA solution):

[0217] A-1: Curable branched organopolysiloxane obtained in Synthesis Example 3

[0218] A-2: Curable branched organopolysiloxane obtained in Synthesis Example 4

[0219] A-3: Curable branched organopolysiloxane obtained in Synthesis Example 5

[0220] A-4: Curable branched organopolysiloxane obtained in Synthesis Example 6

[0221] A-5: Curable branched organopolysiloxane obtained in Synthesis Example 8

[0222] A-6: Curable branched organopolysiloxane obtained in Synthesis Example 10

[0223] A-7: Curable branched organopolysiloxane obtained in Synthesis Example 12

[0224] P-1: Curable branched organopolysiloxane obtained in Synthesis Example 1

[0225] P-2: Curable branched organopolysiloxane obtained in Synthesis Example 2

[0226] P-3: Curable branched organopolysiloxane obtained in Synthesis Example 7

[0227] P-4: Curable branched organopolysiloxane obtained in Synthesis Example 9

[0228] P-5: Curable branched organopolysiloxane obtained in Synthesis Example 11

[0229] Photoacid generator:

[0230] B-1: tri-p-tolylsulfonium trifluoromethanesulfonate (TS-01; manufactured by Sanwa Chemical Co., Ltd.) Curing agent:

[0231] C-1: Tetramethoxymethyl glycoluril (Nicalac MX-270; manufactured by Sanwa Chemical Co., Ltd.)

[0232] [Table 2]

[0233]

[0234] As shown in Table 1, the coating films formed from the curable branched organopolysiloxane of the present invention (Example 1: A-1 to A-4, A-6, A-7) showed excellent alkali solubility. In addition, as shown in Table 2, the high-energy ray-curable organopolysiloxane composition of the present invention (Examples 2-1 to 2-8) had good high-energy ray curability. Furthermore, the cured coating films formed by high-energy ray irradiation were transparent and showed sufficiently high coating toughness.

[0235] On the other hand, the coating film formed of the organopolysiloxane having no phenolic hydroxyl group or a molecular weight or polydispersity not included in the scope of the present invention (Comparative Example 1: A-5, P-1 to P-5) has insufficient alkali solubility. Furthermore, it was confirmed that the high-energy ray-curable composition using the branched polyorganosiloxane having no phenolic hydroxyl group (Comparative Examples 2-2 to 2-6) and the branched polyorganosiloxane containing a phenolic hydroxyl group with a large weight average molecular weight and polydispersity (Comparative Example 2-1) had poor alkali solubility and was not suitable as a patterning material.

[0236] Industrial Applicability

[0237] The curable branched organopolysiloxane and the high-energy ray curable composition with the same as the main component of the present invention have excellent high-energy ray curability. On the other hand, due to the low molecular weight and small polydispersity of the main component, the alkali solubility is excellent. Therefore, in the case of a development process using an alkaline aqueous solution, it has the advantages of being able to form a pattern 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 curable branched organopolysiloxane represented by the following average unit formula (1), having a weight-average molecular weight of 4,500 or less in terms of standard polystyrene measured by gel permeation chromatography and a polydispersity of 1.3 or less (R3SiO 1 / 2 ) a (R2SiO 2 / 2 ) b (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (Oh 1 / 2 Z) e (1) (In the formula, R is a group selected from unsubstituted or fluorine-substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, groups containing an epoxy group, and groups containing a phenolic hydroxyl group, and a, b, c, d, and e are numbers satisfying the following conditions: 0 ≤ a, 0 ≤ b, 0 < c, 0 ≤ d, 0 ≤ e, 0.8 ≤ c / (a + b + c + d + e), and the molecule has at least one group containing a phenolic hydroxyl group).

2. The curable branched organopolysiloxane according to claim 1, wherein the weight-average molecular weight is 4,000 or less.

3. The curable branched organopolysiloxane according to claim 1, wherein a is 0, b is 0, and d is 0.

4. The curable branched organopolysiloxane according to claim 1, wherein the group containing a phenolic hydroxyl group is represented by the following formula (2A) or (2B): [Chemical formula 10] *——R 1 -X-R 2 -Y-A (2A) [Chemical formula 11] *—R 2 -S-A (2B) (Where R 1 is a divalent hydrocarbon group having 2 to 6 carbon atoms, X is an oxygen atom or a sulfur atom, R 2 is a divalent linking group having 3 to 10 carbon atoms and containing an alcoholic hydroxyl group, Y is an oxygen atom or a sulfur atom, the substituent A is a phenolic hydroxyl group represented by the following formula (A1) or a substituted or unsubstituted group containing an aromatic hydrocarbon represented by the following formula (A2), and * is a bonding site with a silicon atom on the organopolysiloxane, wherein at least one of A is A1) [Chemical formula 12] [Chemical formula 13] —(R 3 ) n -On (A2) (Where R 3 is an alkylene group having 1 to 3 carbon atoms, n is 0 or 1, and Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may be substituted by a monovalent hydrocarbon group or a halogen group).

5. The curable branched organopolysiloxane according to claim 1, wherein X is an oxygen atom and Y is a sulfur atom.

6. The curable branched organopolysiloxane according to claim 1, wherein the polydispersity is 1.2 or less and it has a cage-like molecular structure.

7. The curable branched organopolysiloxane according to claim 1, wherein the average number of silicon atoms per molecule is 12 or less.

8. The curable branched organopolysiloxane according to claim 1, wherein each molecule has an average of four or more groups containing a phenolic hydroxyl group.

9. The curable branched organopolysiloxane according to claim 1, wherein it has solubility in an alkaline aqueous solution. When the curable branched organopolysiloxane is coated on a glass plate with a coated thickness of 0.5 μm, and the coated film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute and then washed with water, the mass reduction rate of the coated film composed of this organopolysiloxane is 90 mass% or more.

10. A high-energy ray curable composition, which contains the following substances: (A) The curable branched organopolysiloxane according to any one of claims 1 to 9; (B) A photoacid generator in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of component (A); (C) A crosslinking agent in an amount of 0 to 30 parts by mass relative to 100 parts by mass of component (A); and (D) An organic solvent.

11. An insulating coating agent, which contains the high-energy ray curable composition according to claim 10.

12. A resist material, which contains the high-energy ray curable composition according to claim 10.

13. A cured product of the high-energy ray curable composition according to claim 10.

14. A method of using a cured product of the high energy ray-curable composition according to claim 10 as an insulating coating. 15 . A display device comprising a layer composed of a cured product of the high-energy ray-curable composition according to claim 10 .

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