Polyorganosiloxane, polyorganosiloxane composition and cured product thereof, and electrolytic solution for electrolytic capacitor containing polyorganosiloxane and electrolytic capacitor using the same

Abstract

A polyorganosiloxane, represented by formula (1) and having an alkoxy group bonded to silicon and reactive functional groups other than alkoxy groups, R 1 To R 6 The polyorganosiloxane is independently selected from organic functional groups and hydrogen atoms, with an alkoxy content of 0.07–4% by weight bonded to silicon, and 3–12 reactive functional groups bonded to silicon per 1000 molecular weight. The functional groups include at least one selected from methacryloyl, acryloyl, acyl, cyclic ether, and hydrosilyl hydrogen atoms. After being depressurized to 0.15 torr and heated at 110°C for 2 hours, the weight of the polyorganosiloxane decreases to less than 5% by weight. 1 R 2 R 3 R 6 Each of these can be an organic functional group other than an alkoxy or hydroxyl group, or a hydrogen atom. (R) 1 R 2 R 3 SiO 1 / 2 ) a (R) 4 R 5 SiO 2 / 2 ) b (R) 6 SiO 3 / 2 ) c (SiO) 4 / 2 ) d (O) 1 / 2 R 7 ) e (O) 1 / 2 H) f …(1)

Description

[0001] This application is a divisional application of the following application.

[0002] Invention Title: Polyorganosiloxane, Polyorganosiloxane Composition and Cured Product Thereof, Electrolyte for Electrolytic Capacitor Containing Polyorganosiloxane and Electrolytic Capacitor Using the Same

[0003] Application date: December 13, 2017

[0004] Application No.: 201780077352.9 (PCT / JP2017 / 044799) Technical Field

[0005] This invention relates to polyorganosiloxanes having novel structures, particularly polyorganosiloxanes having structures suitable for optical components, and further to electrolytes for electrolytic capacitors containing polyorganosiloxanes and electrolytic capacitors using these electrolytes. Background Technology

[0006] Polyorganosiloxanes are used in many industries due to their high degree of design freedom and ability to have various functions.

[0007] For example, Patent Document 1 discloses a polyorganosiloxane with a polyhedral structure, proposing a polyorganosiloxane that has improved not only in terms of heat resistance, light resistance, and chemical stability, but also in terms of formability and processability.

[0008] In addition, Patent Document 2 discloses a silsesquioxane with a cage-like structure, which exhibits good low-temperature fluidity and is suitable for sealing semiconductors and the like.

[0009] Furthermore, plastic materials, due to their lightweight and ease of molding, can improve productivity and are therefore gradually replacing inorganic glass in optical materials. In particular, lenses used in cameras and smartphones are made of plastic. To obtain a clear image, a high Abbe number is required for the lens material; additionally, a high refractive index is required to reduce the lens film thickness for higher precision. However, as described in Non-Patent Documents 1 and 2, generally, materials with high refractive indices tend to have lower Abbe numbers, making it difficult to achieve both high refractive index and high Abbe number simultaneously.

[0010] To achieve both high refractive index and high Abbe number, it is known that halogens other than fluorine, alicyclic olefins, sulfur atoms, etc., can be introduced into the structure. However, plastic lenses with these functional groups have insufficient heat resistance, thus preventing the reduction of assembly steps and increased productivity as described in Patent Document 3, where electronic components are centrally assembled in a reflow oven. Furthermore, it is required that the lens material maintain stable optical properties to the surrounding environment, but as described in Non-Patent Document 3, it is known that when the lens absorbs moisture, the uneven distribution of refractive index can cause changes in wavefront aberration, necessitating a material with low hygroscopicity.

[0011] As a means of solving these problems, some have proposed using polyorganosiloxanes as optical components, which offer high design freedom and can have various functions.

[0012] For example, Patent Document 4 discloses a polyorganosiloxane modified with cycloalkyl groups, proposing to achieve a high refractive index and high Abbe number silicone resin lens as an optical property by introducing the effect of alicyclic olefins.

[0013] In addition, Patent Document 5 discloses an addition-curing silicone resin composition containing a polyorganohydrosiloxane having a silane backbone (-Si-C6H4-Si-) in its molecular chain, and proposes a sealant for optical components with high Abbe number and high brightness.

[0014] On the other hand, Patent Document 3 proposes an organic-inorganic composite material based on a cage-like silsesquioxane structure as a lens material suitable for centralized mounting of lens assemblies.

[0015] Furthermore, in electrolytic capacitors, a so-called valve metal capable of forming an insulating oxide film layer such as aluminum or tantalum is used as the anode. After forming this insulating oxide film as a dielectric layer on its surface through anodizing or similar processes, it is used as the anode-side electrode. Then, as an example, it is generally known that... Figure 1 The illustrated wound element structure arranges the cathode-side electrode foil (2) and the anode-side electrode foil (1) opposite to each other, with a diaphragm (3) positioned between the anode-side electrode foil and the cathode-side electrode foil, which holds the electrolyte. It is then loaded into a container such as... Figure 2 The outer shell (5) made of materials such as aluminum is sealed using phenolic resin laminate, polypropylene, polyphenylene sulfide and other sealing plates (7) and rubber pads (6) such as butyl rubber, ethylene propylene rubber, silicone rubber and other rubber pads (6).

[0016] In aluminum electrolytic capacitors using alumina as the dielectric, the anode electrode is typically etched to increase its surface area. The electrolyte makes close contact with the uneven surface of this anode electrode, functioning as a substantial cathode to transmit the electric field from the cathode electrode. Therefore, the conductivity and temperature characteristics of the electrolyte become important factors determining the electrical characteristics of the electrolytic capacitor (impedance, dielectric loss (tanδ), equivalent series resistance (ESR), etc.). Furthermore, the electrolyte is required to repair deterioration or damage to the insulating oxide film, which affects the leakage current (LC) and lifespan of the electrolytic capacitor. Thus, the electrolyte becomes a crucial component influencing the characteristics of the electrolytic capacitor.

[0017] Since the conductivity of the electrolyte is directly related to the energy loss and impedance characteristics of the electrolytic capacitor, an electrolyte with high conductivity is preferred. On the other hand, due to increased safety requirements, electrolytic capacitors with higher withstand voltages are needed so that short circuits or fires will not occur even under harsh conditions where abnormal voltages exceeding the rated voltage are applied to the electrolytic capacitor. However, generally, as the conductivity of the electrolyte used increases, the withstand voltage of the electrolytic capacitor tends to decrease, which makes it difficult to develop electrolytic capacitors (Non-Patent Literature 4).

[0018] Therefore, it is known that in order to obtain high voltage resistance while using an electrolyte with high conductivity, and further to obtain high reliability in temperature characteristics and long-term use, silane coupling agents or silane coupling agent oligomers, modified silicones, etc. are added as electrolyte additives (Patent Documents 6-8).

[0019] In addition, some have proposed a technique to improve voltage resistance while maintaining high conductivity of the electrolyte by adding silica particles to the electrolyte (Patent Documents 9-11).

[0020] Existing technical documents

[0021] Patent documents

[0022] [Patent Document 1] Japanese Patent Application Publication No. 2015-129288

[0023] [Patent Document 2] Japanese Patent Application Publication No. 2012-233174

[0024] [Patent Document 3] Japanese Patent Application Publication No. 2011-158797

[0025] [Patent Document 4] Japanese Patent Application Publication No. 2012-8201

[0026] [Patent Document 5] Japanese Patent Application Publication No. 2015-101645

[0027] [Patent Document 6] Japanese Patent Application Publication No. 3-257811

[0028] [Patent Document 7] Japanese Patent Application Publication No. 6-310378

[0029] [Patent Document 8] Japanese Patent Application Publication No. 1-245508

[0030] [Patent Document 9] Japanese Patent Application Publication No. 1-232713

[0031] [Patent Document 10] Japanese Patent Application Publication No. 6-151250

[0032] [Patent Document 11] Japanese Patent Application Publication No. 2003-203827

[0033] Non-patent literature

[0034] [Non-Patent Literature 1] "Refractive Index Prediction System for Transparent Resins" by Nobuhisa Tani, Relay Polymers, 2009, Vol. 30, No. 1, pp. 33-40

[0035] [Non-Patent Literature 2] "Synthesis and Properties of Sulfur-Containing Cyclic Polyolefins" by Takashi Okada, TOSOH Research & Technology Review Vol.52 (2008), pp.11-18

[0036] [Non-Patent Document 3] "Simulation of Moisture Absorption in Plastic Objective Lenses for Optical Discs" Masaya Kobayashi, KONICA TECHNICAL REPORT VOL3 JAN. (1990) Vol.3 P74-80

[0037] [Non-Patent Literature 4] Yu Hui et al., Novel Capacitors, Volume 3, Page 55, 1996 Summary of the Invention

[0038] The problem that the invention aims to solve

[0039] Although the polyorganosiloxane disclosed in the aforementioned patent document 1 is a polyorganosiloxane with improved heat resistance, light resistance, chemical stability, and formability, its mechanical properties such as elastic modulus or hardness and flash point have not been studied.

[0040] Furthermore, the silsesquioxane disclosed in the aforementioned Patent Document 2 is suitable for sealing semiconductors, etc. Although hardness has been studied, it is not sufficient, and flash point has not been studied.

[0041] Furthermore, polyorganosiloxanes with polyhedral structures, such as those in Patent Document 1 or Patent Document 2, are usually solids, and even when they are liquids, their viscosity is very high.

[0042] The first objective of this invention is to provide novel polyorganosiloxanes that take into account mechanical properties such as flash point, coefficient of linear expansion, viscosity, etc., which are different from previously proposed polyorganosiloxanes.

[0043] Furthermore, the polyorganosiloxane disclosed in Patent Document 3, like Non-Patent Document 1, obviously has a high refractive index and a high Abbe number by having a cyclohexyl group in its structure. There is no information on increasing the Abbe number by (meth)acryloyl groups. In addition, there is no evaluation of the simulated reflow soldering process.

[0044] Furthermore, neither of the aforementioned patent documents 4 nor 5 contains information on increasing the Abbe number through (meth)acryloyl groups, nor does it describe the evaluation of simulated reflow soldering processes. Moreover, both are complex compounds, cumbersome to manufacture, and have low productivity (yield or finished product rate), which contradicts the purpose of using plastic lenses to improve productivity.

[0045] In this invention, unlike previously proposed methods, the second objective is to provide a novel polyorganosiloxane modified with (meth)acryloyl groups to achieve a material with high refractive index, high Abbe number, and low hygroscopicity, as well as a material in the mixed cured product of the polyorganosiloxane and acrylic resin that can withstand concentrated mounting in a reflow soldering process.

[0046] Furthermore, the third objective of this invention is to manufacture the polyorganosiloxane with high productivity.

[0047] Furthermore, regarding the effect of using silane coupling agents as additives, it is believed that the silicon compound layer obtained by silane coupling agents inhibits the hydration reaction on the oxide film surface of the electrode, thus suppressing the reduction of electrostatic capacitance. However, silane coupling agents typically have small molecular weights and are not easy to form a sufficiently cross-linked structure, resulting in a limited protective effect on the electrode surface and an inability to suppress leakage current during high-temperature use.

[0048] In an effort to improve it, some researchers have studied the oligomerization of silane coupling agents to form a uniform protective layer, thereby improving its stability at high temperatures, but this approach is not yet fully effective.

[0049] Electrolytes containing modified silicones exhibit excellent solubility and stability in electrolyte solvents, but the silicone portion has a linear structure, making it difficult to obtain a layer that can protect the electrode and resulting in low voltage resistance.

[0050] Furthermore, while electrolytes containing silica particles exhibit high initial voltage withstand capability, they show problems in long-term lifespan, such as voltage degradation during life tests. One reason for this is the poor dispersion stability of silica particles in the electrolyte solvent, leading to gelation. Therefore, solvents with excellent dispersion stability or solubility of silica particles need to be selected, which limits the types of solvents that can be used in electrolytes.

[0051] In this invention, the fourth objective is to provide an electrolyte for electrolytic capacitors that solves the above-mentioned problems and an electrolytic capacitor using the same.

[0052] Methods for solving problems

[0053] To address the first problem mentioned above, the inventors, through dedicated research, focused on the flash point or viscosity of polyorganosiloxanes with reactive functional groups, as well as the mechanical properties or coefficient of linear expansion of the cured products. They discovered that when the weight loss during heating is below a certain amount, significantly increasing the flash point reduces the coefficient of linear expansion of the cured product, further bringing the amount of curable functional groups within a specific range, thereby significantly improving the strength of the cured product. Furthermore, they found that the maximum absorption wavenumber in a specific wavenumber region of infrared absorption spectroscopy has a significant impact on the viscosity of polyorganosiloxanes, ultimately leading to the completion of this invention.

[0054] That is, the first aspect of the present invention is as follows.

[0055] (A1) A polyorganosiloxane, which is the M unit (R) relative to the total silicon. 1 R 2 R 3 SiO 1 / 2 The content of ) is above 10 mol%, relative to the total silicon T units (R 6 SiO 3 / 2 A polyorganosiloxane having a silicon-bonded alkoxy group and other reactive functional groups, with a silicon-bonded alkoxy group content of 80 mol% or less, and having a silicon-bonded alkoxy group content of 0.07 to 4 wt% relative to the total weight of the polyorganosiloxane, and having 3 to 12 silicon-bonded reactive functional groups per 1000 molecular weight of the polyorganosiloxane, after being heated at 110°C for 2 hours under reduced pressure to 0.15 torr, has a weight reduction of 5 wt% or less. Wherein R 1 R 2 R 3 R 6 Organic functional groups or hydrogen atoms other than alkoxy and hydroxyl groups can be the same or different.

[0056] (A2) The polyorganosiloxane according to (A1) has a content of the above-mentioned M units relative to the total silicon of 60 mol% or less.

[0057] (A3) A polyorganosiloxane, which is based on (SiO2) 4 / 2 The Q unit shown is a necessary component of a polyorganosiloxane containing reactive functional groups other than alkoxy groups bonded to silicon. The polyorganosiloxane has 3–12 reactive functional groups bonded to silicon per 1000 molecular weight, and its infrared absorption spectroscopy analysis shows a wavenumber of 1030–1060 cm⁻¹. -1 The region has the maximum absorption wavenumber of Si-O stretching vibration, and the weight of the polyorganosiloxane component is reduced to less than 5% by weight after heating at 110°C for 2 hours under reduced pressure of 0.15 torr.

[0058] (A4) The polyorganosiloxane according to (A1) to (A3) has an M unit content of 10 mol% or more and 60 mol% or less relative to the total silicon.

[0059] (A5) A polyorganosiloxane, which is a polyorganosiloxane represented by the following general formula (101), with a wavenumber of 1030–1060 cm⁻¹ in infrared absorption spectroscopy analysis. -1 The region with the maximum absorption wavenumber of Si-O stretching vibration, after being heated at 110°C for 2 hours under reduced pressure of 0.15 torr, the weight of the polyorganosiloxane decreased to less than 5% by weight.

[0060] (R) 101 R 102 R 103 SiO 1 / 2 ) M1 (R) 104 R 105 R 106 SiO 1 / 2 ) M2

[0061] (R) 107 R 108 SiO 2 / 2 ) D1 (R) 109 R 106 SiO 2 / 2 ) D2

[0062] (R) 110 SiO 3 / 2 ) T1 (R) 106 SiO 3 / 2 ) T2 (SiO) 4 / 2 ) Q

[0063] (O) 1 / 2 R 110 ) Y1 (O) 1 / 2 R 106 ) Y2 ···(101)

[0064] Here, in the above general formula (101),

[0065] R 101 ~R 105 R 107 ~R 110 Each of these groups is independently selected from organic functional groups, reactive functional groups, or hydrogen atoms. R 106It is an organic group containing reactive functional groups, which may be the same or different, and is different from R. 101 ~R 105 R 107 ~R 110 Reactive functional groups.

[0066] R 110 It does not contain reactive functional groups and is composed of organic groups selected from those with 1 to 20 carbon atoms and hydrogen atoms.

[0067] The coefficients M1, D1, T1, and Q are all greater than 0 and less than 0.6.

[0068] M1+M2>0, T1+T2+Q>0,

[0069] M2+D2+T2>0.25, M1+M2+D1+D2+T1+T2+Q=1,

[0070] The coefficients Y1 and Y2 are 0 or positive.

[0071] (A6) The polyorganosiloxane according to (A1) to (A5), wherein the above-mentioned reactive functional group or R bonded to silicon 106 It includes at least one group selected from the group consisting of alkenyl, methacrylyl, acryloyl, acyl and cyclic ether groups, and hydrogen atoms that form hydrosilyl with silicon.

[0072] (A7) The polyorganosiloxanes according to (A1) to (A6) have a reactive functional group of vinyl.

[0073] (A8) The polyorganosiloxane according to (A1) to (A6), characterized in that the reactive functional group or organic group R 106 One molecule has one or more functional groups selected from the group shown in the following structural formulas [2], [3], [4] and [5].

[0074]

Chemistry 1

[0075]

[0076] In this formula, X is a divalent organic functional group that may contain branched and / or cyclic structures. Furthermore, when X bonds to a silicon atom, the atom at the end of X and directly bonded to silicon is a carbon atom. Similarly, when an oxygen atom directly bonded to silicon bonds to X, the atom at the end of X and directly bonded to the oxygen atom is a carbon atom.

[0077] (A9) The polyorganosiloxane according to (A8), characterized in that the reactive functional group or the above-mentioned R 106One molecule has one or more functional groups selected from (meth)acryloyloxypropyl or (meth)acryloyloxyoctyl.

[0078] (A10) The polyorganosiloxane according to any one of (A1) to (A9) is liquid at 40°C.

[0079] (A11) The polyorganosiloxane according to any one of (A1) to (A10) has a viscosity of 5 mPa·s or more and 20,000 mPa·s or less at 25°C.

[0080] (A12) The polyorganosiloxane according to any one of (A1) to (A11) has a number-average molecular weight Mn of 600 or more and 5000 or less as a result of GPC determination based on polystyrene conversion.

[0081] (A13) The polyorganosiloxane according to any one of (A1) to (A12), M unit or (R 101 R 102 R 103 SiO 1 / 2 It contains at least trimethylsiloxy or dimethylsiloxy.

[0082] (A14) The polyorganosiloxane according to any one of (A1) to (A13), wherein it is an MQ resin.

[0083] (A15) The polyorganosiloxane according to any one of (A1) to (A14), which is an MTQ resin.

[0084] (A16) A composition comprising the polyorganosiloxane of any one of (A1) to (A15).

[0085] (A17) A cured product obtained by curing any one of the polyorganosiloxanes described in (A1) to (A15) or any one of the compositions described in (A16).

[0086] Furthermore, through dedicated research aimed at solving the aforementioned second and third problems, the inventors discovered, as a breakthrough from the common understanding that high refractive index leads to a decrease in Abbe number, that when polyorganosiloxanes are modified with a certain amount or more of organic groups containing (meth)acryloyl groups, a region exists in the cured product obtained by (meth)acryloyl polymerization where both the refractive index and Abbe number increase. Further, it was found that the polyorganosiloxane with high refractive index and high Abbe number exhibits low hygroscopicity. Moreover, compared to polyorganosiloxanes with low (meth)acryloyl group modification, which often exhibit separation and poor compatibility when mixed with acrylic resins, the polyorganosiloxane of this invention exhibits excellent compatibility, thus yielding a transparent and clear cured product. Furthermore, it becomes a material that, compared to the acrylic resin before mixing, can increase the glass transition temperature and possesses reflow soldering resistance. In addition, it was realized that the polyorganosiloxane of this invention can use common raw materials, eliminating the need for special structures such as cage-like silsesquioxanes, resulting in high productivity, thus completing this invention.

[0087] That is, the second aspect of the present invention is as follows.

[0088] (B1) A polyorganosiloxane, which is any one of (A1) to (A15) above, wherein M2 + D2 + T2 ≥ 0.4, and the reactive functional group is an organic group containing (meth)acryloyl.

[0089] (B2) According to the polyorganosiloxane described in (B1), the above coefficient M1 is greater than 0.

[0090] (B3) According to (B1) or (B2) the polyorganosiloxane, the above coefficient Q is greater than 0.

[0091] (B4) The polyorganosiloxane according to any one of (B1) to (B3) wherein the coefficient M1 is 0.09 or more and 0.5 or less, and the coefficient Q is 0.04 or more and 0.4 or less.

[0092] (B5) The polyorganosiloxane according to any one of (B1) to (B4) wherein the above coefficient Y1 is 0 or more and 0.25 or less.

[0093] (B6) The polyorganosiloxane according to any one of (B1) to (B5) has a coefficient Y1 of 0.01 or more and 0.1 or less.

[0094] (B7) The polyorganosiloxane according to any one of (B1) to (B6), wherein the above R 101 ~R 105 and R 107 ~R 110 Each is independently a methyl group.

[0095] (B8) The polyorganosiloxane according to any one of (B1) to (B7) has a viscosity of 10 to 100,000 mPa·s at 25°C.

[0096] (B9) A polyorganosiloxane composition comprising any one of the polyorganosiloxanes described in (B1) to (B8), and a (meth)acrylate compound containing a (meth)acryloyl group and / or a polymer obtained by polymerizing such (meth)acryloyl groups.

[0097] (B10) The polyorganosiloxane composition according to (B9) further contains a polymerization initiator.

[0098] (B11) A cured product obtained by curing the polyorganosiloxane composition described in (B10).

[0099] (B12) An optical component comprising the polyorganosiloxane composition of (B9) or (B10) or the cured product of (B11).

[0100] Furthermore, in order to solve the fourth problem mentioned above, the inventors, through dedicated research, discovered that polyorganosiloxanes with specific structures modified by reactive functional groups have excellent solubility in various solvents, which can achieve high stability as an electrolyte and obtain electrolytic capacitors with high voltage resistance, thus completing the present invention.

[0101] That is, the third aspect of the present invention is as follows.

[0102] (C1) An electrolyte for an electrolytic capacitor, comprising a polyorganosiloxane as shown in the following formula (201).

[0103] (R) 201 R 202 R 203 SiO 1 / 2 ) a (R) 204 R 205 SiO 2 / 2 ) b (R) 206 SiO 3 / 2 ) c (SiO) 4 / 2 ) d (O) 1 / 2 R 207 ) e (O) 1 / 2 H) f ···(201)

[0104] (Here, in the above equation (201), R) 201 To R 206Each of the following is independently a hydrocarbon group having 1 to 10 carbon atoms, a group with a reactive functional group, or a hydrogen atom; R 207 It is an organic group with 1 to 8 carbon atoms. Among them, R 201 To R 206 At least one of them is a group or hydrogen atom with a reactive functional group. The reactive functional group can be directly bonded to silicon, or it can be bonded by a linker other than a siloxane bond. (a + b + c + d = 1, a ≥ 0.1, b ≤ 0.5, c + d ≥ 0.1, e + f ≤ 1.0)

[0105] (C2) An electrolyte for an electrolytic capacitor, comprising a polyorganosiloxane, wherein the polyorganosiloxane is any one of (A1) to (A15).

[0106] (C3) An electrolyte for an electrolytic capacitor, comprising a polyorganosiloxane, wherein the polyorganosiloxane is any one of (B1) to (B8).

[0107] (C4) The electrolyte for an electrolytic capacitor according to any one of (C1) to (C3), wherein the reactive functional group comprises at least one group selected from the group consisting of alkenyl, methacryl, acryloyl, acyl, cyclic ether, hydroxyl, acetoxy, monohydroxysilyl, dihydroxysilyl, trihydroxysilyl, monoalkoxysilyl, dialkoxysilyl and trialkoxysilyl, and hydrogen atoms that form silanes with silicon.

[0108] (C5) The electrolyte for electrolytic capacitors according to any one of (C1) to (C4) has 3 to 12 reactive functional groups per 1000 molecular weight of polyorganosiloxane.

[0109] (C6) The electrolyte for electrolytic capacitors according to any one of (C1) to (C5) has a number-average molecular weight Mn of 600 or more and 50,000 or less, as a result of GPC determination based on polystyrene conversion.

[0110] (C7) The electrolyte for an electrolytic capacitor according to any one of (C1) to (C6) contains ethylene glycol and / or γ-butyrolactone.

[0111] (C8) The electrolyte for an electrolytic capacitor according to any one of (C1) to (C7) contains an onium salt of an organic acid and / or an inorganic acid.

[0112] (C9) An aluminum electrolytic capacitor, characterized in that it uses an anode, a cathode made of aluminum, and an electrolyte according to any one of (C1) to (C8).

[0113] The effects of the invention

[0114] The inventors focused on the flash point and viscosity of polyorganosiloxanes with reactive functional groups, as well as the mechanical properties and coefficient of linear expansion of the cured products. They discovered that when the weight loss during heating is below a certain amount, significantly increasing the flash point and decreasing the coefficient of linear expansion of the cured product, and further controlling the amount of curable functional groups within a specific range, can significantly improve the mechanical properties of the cured product. Furthermore, they found that the maximum absorption wavenumber in a specific wavenumber region of infrared absorption spectroscopy has a significant impact on the viscosity of polyorganosiloxanes, ultimately leading to this invention.

[0115] Through the first aspect of the present invention, a polyorganosiloxane with a high flash point before curing, low temperature dependence of the elastic modulus after curing, and minimal weight loss upon heating can be obtained. Low flash points present challenges for safe handling under normal conditions and are classified as higher-risk materials under fire safety laws, resulting in higher storage and transportation costs. Therefore, the benefits of obtaining a polyorganosiloxane with a high flash point are significant. Furthermore, the low coefficient of linear expansion of the cured material equates to stable performance over a wide temperature range, further enhancing its excellent mechanical properties and greatly contributing to product reliability. Moreover, the minimal weight loss upon heating the cured material reduces the likelihood of heat loss (thickness reduction) or embrittlement over time.

[0116] Furthermore, the first method of this invention yields a low-viscosity polyorganosiloxane. The low viscosity significantly improves processability and increases the freedom of process design, while also drastically reducing the time required for weighing, mixing, and molding. Further reductions in cleaning time and detergent usage are also foreseeable. Because the cured material exhibits significantly improved thermal shock resistance, it can withstand more processes than ever before, resulting in a significant increase in process design freedom.

[0117] Furthermore, through the second aspect of the present invention, by including (meth)acryloyl groups in the structure of the organosiloxane, a cured product can be easily obtained using a polymerization initiator. The cured product exhibits high optical properties, particularly high refractive index and Abbe number, and low hygroscopicity and coefficient of linear expansion, thus providing a polyorganosiloxane suitable for use as optical components such as lenses. The polyorganosiloxane of the present invention can be used alone or mixed with other resins, particularly preferably with acrylic resins. In the preferred embodiment of the present invention, it can be used as a plastic lens with reflow solderability.

[0118] Furthermore, the inventors have discovered that polyorganosiloxanes with specific structures modified with functional groups exhibit excellent solubility in various solvents, enabling them to achieve high stability as electrolytes and obtain electrolytic capacitors with high voltage resistance.

[0119] The underlying principle is not yet clear, but the polyorganosiloxanes of the specific structure of this invention use M units, T units, and / or Q units in their structure, and do not exceed the necessary amount of D units. Therefore, they can be considered to have a moderately cross-linked structure, branched structure, and cyclic structure, resulting in higher strength and uniformity as a protective layer for electrodes, and achieving high voltage resistance. Furthermore, conventional polyorganosiloxanes, due to their very low polarity, have low compatibility with solutes or solvents in electrolytes when used directly, leading to aggregation or separation. However, through modification with reactive functional groups, their solubility in various organic solvents used in electrolytes increases, allowing them to be used in any electrolyte. Moreover, it is believed that through condensation reactions of hydroxysilyl or alkoxysilyl groups, or through reactions or interactions between hydroxysilyl or alkoxysilyl groups and reactive functional groups, or through reactions or interactions between hydroxysilyl or alkoxysilyl groups and the electrode surface, the strength of the electrode protective layer or its adhesion to the electrode also becomes higher, resulting in high voltage resistance. Through the third aspect of the present invention, an electrolyte for electrolytic capacitors containing a polyorganosiloxane that exhibits excellent solubility in various solvents, high stability as an electrolyte, and high voltage resistance can be provided, as well as an electrolytic capacitor using the same. Attached Figure Description

[0120]

【 Figure 1 [Image 1] is an explanatory diagram showing the structure of the central portion of an example wound electrolytic capacitor.

[0121]

【 Figure 2 The diagram shows the structure of an example electrolytic capacitor with a casing.

[0122]

【 Figure 3 The diagram shows the relationship between (meth)acryloyl group content and Abbe number and refractive index.

[0123]

【 Figure 4 This displays the temperature distribution under reflow soldering conditions.

[0124]

【 Figure 5 [This refers to the polyorganosiloxane obtained in Synthesis Example 3-1 of the present invention.] 1 A graph showing the H-NMR measurement results.

[0125]

【 Figure 6 [This refers to the polyorganosiloxane obtained in Synthesis Example 3-2 of the present invention.] 1 A graph showing the H-NMR measurement results.

[0126]

【 Figure 7 [This refers to the polyorganosiloxane obtained in Synthesis Examples 3-3 of the present invention.] 1 A graph showing the H-NMR measurement results.

[0127]

【 Figure 8[This refers to the polyorganosiloxanes obtained in Synthesis Examples 3-4 of the present invention.] 1 A graph showing the H-NMR measurement results.

[0128]

【 Figure 9 [This refers to the polyorganosiloxanes obtained in Synthesis Examples 3-5 of the present invention.] 1 A graph showing the H-NMR measurement results. Detailed Implementation

[0129] The embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments and can be implemented in various modifications within the scope of its spirit.

[0130] (Polyorganosiloxane)

[0131] Polyorganosiloxanes refer to polymers with siloxane bonds as the main chain, for example, represented by the general formula (1) shown below.

[0132] (R) 1 R 2 R 3 SiO 1 / 2 ) a (R) 4 R 5 SiO 2 / 2 ) b (R) 6 SiO 3 / 2 ) c (SiO) 4 / 2 ) d (O) 1 / 2 R 7 ) e (O) 1 / 2 H) f ···(1)

[0133] Here, in the above equation (1), R 1 To R 6 Each is independently selected from an organic functional group and a hydrogen atom, and satisfies a + b + c + d = 1. Furthermore, R... 7 It is an organic group selected from 1 to 7 carbon atoms.

[0134] This embodiment relates to a polyorganosiloxane (hereinafter also referred to as polysiloxane A), which is an M unit (R) relative to the total silicon. 1 R 2 R 3 SiO 1 / 2 The content of ) is above 10 mol%, relative to the total silicon T units (R 6 SiO 3 / 2The polyorganosiloxane having a content of 80 mol% or less and having alkoxy groups bonded to silicon and reactive functional groups other than alkoxy groups, wherein the content of the aforementioned alkoxy groups bonded to silicon relative to the total weight of the polyorganosiloxane is 0.07 to 4 wt%, and the number of the aforementioned reactive functional groups bonded to silicon per 1000 molecular weight of the polyorganosiloxane is 3 to 12, and the weight of the polyorganosiloxane reduced to 5 wt% or less after heating at an internal temperature of 110°C for 2 hours under reduced pressure of 0.15 torr. Furthermore, another polyorganosiloxane according to this embodiment (hereinafter also referred to as polysiloxane B) is based on (SiO2) 4 / 2 The Q unit shown is a necessary component of a polyorganosiloxane containing reactive functional groups bonded to silicon. The number of reactive functional groups bonded to silicon per 1000 molecular weight of the polyorganosiloxane is 3–12. In infrared absorption spectroscopy analysis, the wavenumber is 1030–1060 cm⁻¹. -1 The region has the maximum absorption wavenumber of Si-O stretching vibration, and the weight of the polyorganosiloxane component is reduced to less than 5% by weight after heating at 110°C for 2 hours under reduced pressure of 0.15 torr.

[0135] In these polyorganopolysiloxanes, the so-called reactive functional group bonded to silicon is not limited to groups directly bonded to silicon, but can also refer to groups formed by bonding a group containing a reactive functional group to silicon, but preferably a group directly bonded to silicon.

[0136] In polyorganosiloxane A, in general formula (1), the proportion of M units, a, is 0.1 or more, preferably 0.2 or more. Furthermore, a is less than 1, preferably 0.6 or less, and more preferably 0.3 or less. By making a ≥ 0.1, that is, by making the M units below an appropriate upper limit, the molecular weight of the polyorganosiloxane can be easily controlled. More specifically, it is easy to keep the molecular weight within an appropriate range that is not too small, which can suppress the increase of low-boiling-point components and prevent the flash point from decreasing, and is therefore preferred.

[0137] Furthermore, in general formula (1), c, representing the proportion of T units, is 0 or more, preferably 0.15 or more, more preferably 0.4 or more, and as an upper limit, c is 0.8 or less, preferably 0.65 or less. Because c is within the above-mentioned range in formula (1), the cured product of polyorganosiloxane A has appropriate rigidity, which is therefore preferred. In particular, by keeping the value of c below 0.8, the viscosity of the polyorganosiloxane can be maintained within a range that is easy to handle, and the brittleness of the cured product can be improved, which is also preferred.

[0138] Polyorganosiloxane A may contain (SiO) 4 / 2The Q unit shown in formula (1) is preferably 0 or more, preferably 0.7 or less, and more preferably 0.5 or less. In general formula (1), by keeping d within the above range, the viscosity of the polysiloxane can be prevented from becoming too high, and the cured product of polysiloxane A has appropriate rigidity, which is therefore preferred. Furthermore, polysiloxane A may contain (R... 4 R 5 O 2 / 2 In the D unit shown in formula (1), b can be 0 or more, but preferably 0.3 or less, and more preferably 0.1 or less. By being within such a range, it is easy to maintain a high rigidity of the cured material.

[0139] The polyorganosiloxane A can be an MQ resin composed of M and Q units, an MT resin composed of M and T units, an MDT resin composed of M, D, and T units, an MDQ resin composed of M, D, and Q units, an MTQ resin composed of M, T, and Q units, or an MDTQ resin composed of M, D, T, and Q units. Furthermore, when MTQ resin is formulated into compositions for various applications, it is preferable that it contains MT resin at a content of 60% by weight or less relative to the total amount of the polyorganosiloxane composition. By containing an appropriate amount of MT resin, suitable softness can be imparted.

[0140] Among them, the polyorganosiloxane A, which is composed only of M units and D units, has a low boiling point when the M units exceed 10 mol% relative to the total silicon, that is, when a exceeds 0.1, b is greater than 0, and c and d are 0 in formula (1), and the weight reduction is large after heating for 2 hours under reduced pressure of 0.15 torr and internal temperature of 110°C. Therefore, it is not included in this invention.

[0141] Relative to the total weight of polyorganosiloxane A, the content of alkoxy groups bonded to silicon in polyorganosiloxane A is 0.07% by weight or more, preferably 0.5% by weight or more, 4% by weight or less, and preferably 2% by weight or less. Polyorganosiloxane A containing alkoxy groups within the above range can suppress the aggregation between polyorganosiloxane A molecules through the steric hindrance of the alkoxy groups, thus remaining a liquid rather than a solid and exhibiting moderate fluidity. Therefore, it is easy to mix with other resins, etc., and the benefit of greatly improved productivity in manufacturing compositions can be obtained. When the amount of alkoxy groups is below the lower limit specified in this invention, the viscosity becomes too high and it becomes a solid, and the aforementioned benefit of improved productivity cannot be obtained. On the other hand, by keeping the content of alkoxy groups below the upper limit, the stability of long-term storage can be improved. Furthermore, since the phenomenon of alkoxy group desorption and alcohol formation caused by heating is suppressed, it is preferable for the safety and health of operators. In addition, alkoxy groups are not easily desorbed when the cured product is heated, so embrittlement caused by the reduction of cured product thickness is less likely to occur. Furthermore, this also makes it less prone to embrittlement over time.

[0142] In addition, there are no particular restrictions on the type of alkoxy group, but methoxy, ethoxy, isopropoxy, etc. are preferred.

[0143] Polysiloxane A is a polysiloxane having reactive functional groups other than alkoxy groups that bond with silicon. The lower limit for the number of silicon-bonded reactive functional groups per 1000 molecular weight of polyorganosiloxane A is 3 or more, more preferably 4 or more, and the upper limit is preferably 12 or less, more preferably 9 or less. By keeping the reactive functional groups above the lower limit, it is easier to improve the strength of the cured product when the polysiloxane is cured. On the other hand, by keeping the reactive functional groups below the upper limit, the brittleness of the cured product when the polysiloxane is cured can be improved.

[0144] (Determination of the number of reactive functional groups per 1000 molecular weight)

[0145] The content of silicon-bonded alkoxy groups in polyorganosiloxanes, and the number of silicon-bonded reactive functional groups per 1000 molecular weight, are calculated as follows. Furthermore, the number of trimethylsiloxy groups per 1000 molecular weight can also be determined in the same manner.

[0146] Weigh 50 mg of the polyorganosiloxane to be tested, and accurately weigh 15 mg of toluene as an internal standard. Further, dissolve it in 1 g of dichloroform and analyze using a 400 MHz converter. 1The 1H-NMR (AL-400, manufactured by NEC Corporation) was set to a relaxation delay of 20 seconds for measurement. Based on the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene and the weighing value, the alkoxy content and the reactive functional group content per 1g (mmol / g) were calculated, i.e., the number of reactive functional groups per 1000 molecular weight of the polyorganosiloxane. At this point, it is necessary to remove organic matter not bonded to the polyorganosiloxane, or impurities such as water and metals, to less than 0.1% by weight to avoid affecting the measurement results. If the impurities exceed 0.1% by weight, they are removed by distillation, filtration, or other purification methods before preparing the sample for measurement. 1 H-NMR. When difficult to remove, by 1 The impurity content calculated by ¹H-NMR determination or other analytical methods is not included as part of the polyorganosiloxane calculation. Instead, the actual sample weight is calculated by subtracting the impurity from the weighed sample weight. Furthermore, as an internal standard, any substance other than toluene, such as N,N-dimethylformamide or tribromoethane, that does not react with polyorganosiloxane can be used.

[0147] Polyorganosiloxane A, after being heated for 2 hours at a reduced pressure of 0.15 torr and an internal temperature of 110°C, exhibits a weight reduction of 5% by weight or less, preferably 3% by weight or less. By keeping the weight reduction below the upper limit mentioned above, a relatively high flash point of the polyorganosiloxane can be maintained. This avoids the risk of unsafe handling under normal conditions due to a low flash point, and allows it to be classified as a higher-risk material in fire safety regulations, thus reducing storage and transportation costs. Furthermore, since the weight reduction during curing or in the cured product is also minimal, advantages such as low temperature dependence of the cured product's storage modulus, a wider usable temperature range, and less embrittlement due to thickness reduction can be obtained.

[0148] The weight reduction during depressurization heating can be measured as follows.

[0149] Measurement 1 ¹H-NMR was used to calculate the weight of components other than the polysiloxane, such as the organic solvent. A rotor was placed in a flask and its weight was measured. Subsequently, the polysiloxane was added to the flask, and its weight was measured. The flask was heated in an oil bath, and the rotor was rotated using a magnetic stirrer until the liquid surface was fluid. The pressure was then reduced using an oil-filled vacuum pump. After 2 hours, the mixture was cooled to room temperature and restored to atmospheric pressure. The oil adhering to the flask was thoroughly wiped off, and the weight of the polysiloxane in the flask was measured. This weight was subtracted from the previously measured weights of the flask and rotor, and the weight of the evaporated components was calculated. The polysiloxane after this operation was then measured. 1H-NMR was used to calculate the weight of components other than the polyorganosiloxane, such as the organic solvent. The weight reduction before and after the operation was then calculated. 1 The H-NMR determination results allow for the calculation of the amounts of components other than the polyorganosiloxane and the amount of polyorganosiloxane volatilized, based on the weight of the volatilized product. Alternatively, all volatilized distillate can be recovered using a cold trap, and its weight measured. 1 H-NMR.

[0150] In addition, the present invention also includes the following embodiments.

[0151] As another embodiment of the present invention, polyorganosiloxane B contains (SiO2) 4 / 2 The Q unit shown in (1) is an essential component. That is, the polyorganosiloxane B is in formula (1) where d is greater than 0, preferably 0.1 or more, more preferably 0.15 or more. Furthermore, d is less than 1, preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. By having the Q unit, preferably having it at or above the lower limit value, the strength of the cured product during curing is improved. In addition, by keeping the Q unit below the upper limit value, the viscosity of the polyorganosiloxane will not become too high, and the cured product will not easily become brittle.

[0152] Polyorganosiloxane B is a polysiloxane having reactive functional groups other than alkoxy groups that are bonded to silicon. The content of the reactive functional groups is preferably in the same range as that of polyorganosiloxane A, for the same reasons.

[0153] In infrared absorption spectroscopy analysis, polyorganosiloxane B showed a wavelength range of 1030–1060 cm⁻¹. -1 The region contains the maximum absorption wavenumber of Si-O stretching vibration. In infrared absorption spectroscopy, by using the maximum absorption wavenumber of Si-O stretching vibration within the aforementioned wavenumber region, the extremely rigid structure of cage-like silsesquioxanes can be avoided. The maximum absorption wavenumber refers to the wavenumber with the maximum absorbance in a specific region; in this embodiment, the wavenumber is 1000–1200 cm⁻¹. -1 The wavenumber with the highest absorbance in the region is taken as the maximum absorption wavenumber.

[0154] The maximum absorption wavenumber obtained from infrared absorption spectroscopy analysis can be determined using a Fourier transform infrared spectrometer via the ATR method (total internal reflection measurement).

[0155] Furthermore, in infrared absorption spectroscopy analysis, the wavenumber is preferably in the range of 1070–1150 cm⁻¹. -1The region does not exhibit absorption peaks for Si-O stretching vibrations. By using the maximum absorption wavenumber in the aforementioned wavenumber region where Si-O stretching vibrations are absent, the extremely rigid structure characteristic of cage-like silsesquioxanes can be avoided. In the case of rigid structures like cage-like silsesquioxanes, the cured product does not deform under external stress, exhibiting a single rigid body; therefore, internal heat transfer in the resin is minimal, and the repulsive force does not decrease. Furthermore, in the wavenumber range of 1070–1150 cm⁻¹... -1 Characteristic absorption bands from organic molecules other than Si-O can exist within this region. Examples of characteristic absorption bands from organic molecules include CO from hydroxyl groups, COC from esters, COC from acid anhydrides, COC from ethers, CN from amines, sulfonic acids, sulfoxides, CF from fluorine compounds, P=O or PO from phosphorus compounds, and SO4 from inorganic salts. 2- or ClO4 - The resulting absorption bands are all structures with high absorption intensity. It is important not to confuse these with the Si-O stretching vibrations.

[0156] Polyorganosiloxane B, after being heated for 2 hours at a reduced pressure of 0.15 torr and an internal temperature of 110°C, exhibits a weight reduction of 5% by weight or less, preferably 3% by weight or less. A significant weight reduction under these conditions results in a lower flash point for the polyorganosiloxane. A low flash point makes safe handling under normal conditions difficult, placing it in a higher hazard category under fire safety laws, and increasing storage and transportation costs. Furthermore, the weight reduction during curing or in the cured product is also significant, leading to undesirable conditions such as a high temperature dependence of the cured product's storage modulus, limited usable temperature, and embrittlement due to thickness reduction.

[0157] In polyorganosiloxane B, in formula (1), a, which represents the proportion of M units, is preferably 0.1 or more, more preferably 0.2 or more. Furthermore, a is less than 1, preferably 0.6 or less, more preferably 0.3 or less. By having a at or above the aforementioned lower limit, i.e., containing an appropriate amount or more of M units, the molecular weight is easily controlled, and excessively high viscosity can be prevented. On the other hand, by keeping a below the upper limit, i.e., within a range where excessive M units are not possible, the molecular weight of the polyorganosiloxane is easily kept within an appropriate range where it is not too small, thus suppressing the increase of low-boiling-point components and preventing a decrease in flash point, which is therefore preferred.

[0158] There are no particular restrictions on the type of alkoxy groups bonded to silicon in polyorganosiloxane A and polyorganosiloxane B; they can contain branched or cyclic structures. However, when using alkoxy groups with large molecular weights, the weight of alkoxy groups desorbed during heating of the polyorganosiloxane or its cured product increases. Therefore, alkoxy groups with small molecular weights are preferred. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc., are preferred.

[0159] The types of reactive functional groups other than the alkoxy group bonded to silicon in polyorganosiloxane A and polyorganosiloxane B are not particularly limited. They can contain branched structures or cyclic structures. From a reactivity point of view, alkenyl, methacryl, acyl, cyclic ether groups, and hydrogen atoms that form hydrosilyl groups with silicon are preferred. Only one type can be used, or multiple types can be used in combination. As an alkenyl group, vinyl is particularly preferred; as a methacryl, methacryloxypropyl is particularly preferred; as an acyl, acyloxypropyl is particularly preferred; as a cyclic ether group, a group having an epoxy group is particularly preferred. As an epoxy group, glycidoxy, alicyclic epoxy, or a group converted to an epoxy group by oxidizing an alkenyl group are suitable.

[0160] Furthermore, as another preferred group to incorporate, phenyl is expected to improve compatibility with other resins and increase the refractive index, among other adjustable optical properties. Moreover, by incorporating long-chain alkyl groups, specifically alkyl groups with 5 to 30 carbon atoms, improved compatibility with other resins is anticipated.

[0161] In addition, the present invention also includes the following embodiments.

[0162] As another embodiment of the present invention, the essential component of the polyorganosiloxane C is represented by the following general formula (101), and in infrared absorption spectroscopy analysis, at wavenumbers of 1030 to 1060 cm⁻¹ -1 The region with the maximum absorption wavenumber of Si-O stretching vibration, after being heated at 110°C for 2 hours under reduced pressure of 0.15 torr, the weight of the polyorganosiloxane decreased to less than 5% by weight.

[0163] (R) 101 R 102 R 103 SiO 1 / 2 ) M1 (R) 104 R 105 R 106 SiO 1 / 2 ) M2

[0164] (R) 107 R 108 SiO 2 / 2 ) D1 (R) 109 R 106 SiO 2 / 2 ) D2

[0165] (R) 110 SiO 3 / 2 ) T1 (R)106 SiO 3 / 2 ) T2 (SiO) 4 / 2 ) Q

[0166] (O) 1 / 2 R 110 ) Y1 (O) 1 / 2 R 106 ) Y2 ···(101)

[0167] Here, in the above formula

[101] ,

[0168] R 101 ~R 105 R 107 ~R 110 R is a group independently selected from organic functional groups, reactive functional groups, and hydrogen atoms. 106 Is with R 101 ~R 105 R 107 ~R 110 Different organic groups with reactive functional groups can be the same or different.

[0169] R 110 Is with R 106 Different functional groups are selected from organic groups with 1 to 20 carbon atoms and groups with hydrogen atoms.

[0170] The coefficients M1, D1, T1, and Q are all greater than or equal to 0 and less than 0.6.

[0171] M1+M2>0, T1+T2+Q>0,

[0172] M2+D2+T2>0.25, M1+M2+D1+D2+T1+T2+Q=1,

[0173] The coefficients Y1 and Y2 are 0 or positive values.

[0174] Furthermore, R is preferred. 106 It does not contain (meth)acryloyl groups.

[0175] The general formula (101) will be explained below.

[0176] In general formula (101), coefficients M1 and M2 represent the proportion of M units where one oxygen atom is bonded to a silicon atom. Similarly, D1 and D2 represent the proportion of D units where two oxygen atoms are bonded to a silicon atom, T1 and T2 represent the proportion of T units where three oxygen atoms are bonded to a silicon atom, and Q represents the proportion of Q units where four oxygen atoms are bonded to a silicon atom.

[0177] Furthermore, M2, D2, and T2 represent R bonds on silicon atoms, respectively. 106 That is, different from R 101 ~R 105 R 107 ~R 110 The ratio of M, D, and T units of organic groups containing reactive functional groups.

[0178] Then, M1 + M2 > 0 means that there must be an M unit.

[0179] T1 + T2 + Q > 0 indicates that either a T unit or a Q unit is required.

[0180] Then M2+D2+T2>0.25 and M1+M2+D1+D2+T1+T2+Q=1 indicate that R is bonded to the silicon atom. 106 That is, different from R 101 ~R 105 R 107 ~R 110 The proportion of M, D, and T units containing reactive functional groups relative to the sum of M, D, T, and Q units is greater than 25 mol%.

[0181] In addition, Y1 represents the content of alkoxy or silanol groups bonded to silicon.

[0182] Y2 represents R, which is different from that bonded to silicon. 101 ~R 105 R 107 ~R 110 The content of organic groups containing reactive functional groups.

[0183] To improve the compatibility with other resins, one of the effects of this invention, the proportion of M² + D² + T², which is the main unit having reactive functional groups, needs to be greater than 0.25, typically 0.33 or more, preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 or more. Furthermore, from the viewpoint of increasing the content of reactive functional groups and improving the storage stability of the liquid, it is preferable that reactive functional groups are present in either the M or T unit. Therefore, it is preferable that M² + T² > 0.25, more preferably that M² + T² is 0.4 or more, even more preferably that M² + T² is 0.5 or more, and particularly preferably 0.6 or more.

[0184] As a reactive functional group other than the primary reactive functional group, R, without impairing compatibility with other resins or liquid storage stability, 101 ~R 105 R 107 ~R 110 It may contain organic groups that include other reactive functional groups.

[0185] Furthermore, as a non-R 106 The proportion of M units, M1, is also preferably present, i.e., M1 > 0. The reason is that replacing the alkoxy and silanol groups of the polyorganosiloxane with M units can improve the storage stability of the polyorganosiloxane, resulting in a low viscosity, which is beneficial when using large-volume R... 106 In polyorganosiloxanes modified with M-units, when alkoxy and silanol groups are substituted with M-units, the sterically unhindered M-units are easily accessible to silicon atoms and do not possess R-units. 106 The M-unit is advantageous for replacement. From the perspective of spatial steric hindrance, R... 101 To R 103 Methyl or hydrogen atoms are particularly preferred, with methyl being the most preferred from the viewpoint of storage stability. Regarding the amount of substitution, from the viewpoint of storage stability, the preferred coefficient M1 is 0.09 or higher. The upper limit is generally 0.6 or lower, preferably 0.5 or lower, and more preferably 0.4 or lower.

[0186] Furthermore, in this invention, from the viewpoint of increasing the (meth)acryloyl group content and improving liquid preservation stability, MQ resin, MTQ resin, and MT resin are preferred. D units may also be added to impart appropriate softness to these resins. To make it a material with high elastic modulus and low linear expansion coefficient, suitable for use as an optical material, D1 ≤ 0.1 is preferred, and D1 ≤ 0.05 is more preferred.

[0187] Q-units represent the most fully oxidized form of silicon, and their inclusion in the structure of polyorganosiloxanes can improve heat resistance. Therefore, MQ resins and MTQ resins containing Q-units in their structure are preferred. The preferred coefficient for the content of Q-units is greater than 0, preferably 0.04 or higher, and typically 0.6 or lower is the upper limit. A higher number of Q-units increases the solid content or viscosity, reducing processability; therefore, 0.4 or lower is more preferable.

[0188] In addition, (O) 1 / 2 R 110 The alkyl or silanol groups bonded to silicon can control the viscosity of polyorganosiloxanes, adjusting it to a suitable viscosity for molding. Silanol groups have the effect of increasing viscosity, while silanol groups can decrease viscosity by converting them to alkoxy groups.

[0189] The coefficient Y1 is 0 or a positive value. From the viewpoint of adjusting to the viscosity required for molding, the coefficient Y1 is usually 0 or above, preferably 0.01 or above, and from the viewpoint of preserving stability or curing shrinkage, it is usually 0.25 or below, preferably 0.2 or below, and more preferably 0.1 or below.

[0190] The coefficient Y2 represents the content of organic groups containing (meth)acryloyl groups bonded to silicon, which helps increase the refractive index and Abbe number, and therefore can be added to the structure of polyorganosiloxanes. By making Y2 > 0.25 instead of M2 + D2 + T2 > 0.25, it can be used as a material with excellent compatibility with other resins. That is, as another aspect of the present invention, the requirement of M2 + D2 + T2 > 0.25 in general formula (101) can be replaced by Y2 > 0.25. Since compounds with (meth)acryloyloxy groups bonded to silicon are easily hydrolyzed and detached by water, the water absorption rate becomes high, so it is preferable to use them in a way that is less affected by moisture.

[0191] That is, it can be made into (meth)acryloyloxy modified Q resin, T resin, MQ resin, MT resin, MTQ resin, and polyorganosiloxane composed of them and D units.

[0192] (About R) 101 ~R 110 )

[0193] Next, the substituents will be explained.

[0194] As one embodiment of the present invention, it is a reactive functional group, or R 106 An organic group substituted with (meth)acryloyl. Preferred groups are those having one or more functional groups selected from the group shown in [2], [3], [4] and [5], but more preferably acryloyloxypropyl, acryloyloxyoctyl, methacryloyloxypropyl, and methacryloyloxyoctyl, with acryloyloxypropyl and methacryloyloxypropyl being the most preferred.

[0195]

Chemistry 2

[0196]

[0197] In this formula, X is a divalent organic functional group, which may contain branched structures and / or cyclic structures. Furthermore, in addition to carbon and hydrogen, X may contain any one of the following groups: oxygen, nitrogen, phosphorus, sulfur, and halogens. When X is bonded to a silicon atom, the atom at the end of X and directly bonded to the silicon atom is a carbon atom. Similarly, when X is bonded to an oxygen atom directly bonded to a silicon atom, the atom at the end of X and directly bonded to the oxygen atom is a carbon atom.

[0198] Furthermore, in this invention, the individual units constituting the M unit, D unit, and T unit do not need to be entirely identical. That is, the units with a ratio of M1 (R...) 101 R 102 R 103 SiO 1 / 2 Within ), for example, it could be a certain R 101It is a hydrogen atom, a certain R 101 It's a different structure like methyl. The same applies to other R and X.

[0199] In addition, R 101 To R 105 R 107 To R 110 Each of these is a group independently selected from an organic functional group and a hydrogen atom. Then R... 101 To R 103 R 107 R 108 R 110 It does not contain (meth)acryloyl groups. This is due to, for example, R 101 To R 103 When the organic group contains (meth)acryloyl, it is impossible to distinguish between the M1 proportion part and the M2 proportion part, hence this stipulation.

[0200] On the other hand, R in the M2 proportion 104 R 105 Even organic groups containing (meth)acryloyl groups do not present this problem and are therefore not subject to this restriction. The same reasoning applies to the D1 and T1 proportion portions. 107 R 108 R 110 It does not contain (meth)acryloyl groups.

[0201] R 101 ~R 105 R 107 ~R 110 Each of the following is preferably composed of alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, octyl, cyclohexyl, alkyl, phenyl, naphthyl, carbazole, styrene, furanyl, polyethylene glycol, glycidyloxypropyl, cyclic epoxy, etc., and more preferably methyl, phenyl, or hydrogen atoms.

[0202] R 110 The term "free of (meth)acryloyl" indicates a group selected from organic groups having 1 to 20 carbon atoms and hydrogen atoms. Methyl is preferred. Furthermore, for the same reasons as polyorganosiloxane A and polyorganosiloxane B, polyorganosiloxane C is preferably selected at a wavenumber of 1030 to 1060 cm⁻¹ in infrared absorption spectroscopy analysis. -1 The region with the maximum absorption wavenumber of Si-O stretching vibration, after being heated at 110°C for 2 hours under reduced pressure of 0.15 torr, the weight of the polyorganosiloxane decreased to less than 5% by weight.

[0203] In polyorganosiloxanes A, B, and C, the type of M unit is not particularly limited and can be a group containing reactive functional groups. Particularly from the viewpoint of the storage stability of the polyorganosiloxane, it is preferable that at least one M unit is a trimethylsiloxy group; more preferably, there are 1 to 4 trimethylsiloxy groups per 1000 molecular weight. If the number of trimethylsiloxy groups is too small, the number of M units other than trimethylsiloxy groups, i.e., M units containing reactive groups, tends to increase spontaneously. Therefore, from the viewpoint of the storage stability of the polyorganosiloxane, it is preferable that the number of trimethylsiloxy groups is within the above range. On the other hand, from the viewpoint of the reactivity of the polyorganosiloxane, it is preferable that the amount of trimethylsiloxy groups in the polyorganosiloxane or in the M units is small; specifically, it is preferable that there is 1 or less trimethylsiloxy group per 1000 molecular weight, and more preferably no trimethylsiloxy groups. If there are too many trimethylsiloxy groups, the number of reactive functional groups decreases. Therefore, when the functionality (curability, etc.) of the reactive functional groups is important, it is preferable that there is 1 or less trimethylsiloxy group.

[0204] Polyorganosiloxane A, polyorganosiloxane B, and polyorganosiloxane C are preferably in a liquid state at 40°C (at normal pressure). Normal pressure refers to pressure equal to atmospheric pressure, approximately one atmosphere. Furthermore, liquid refers to a state of fluidity. Further, from a molding and processing perspective, it is more preferable that they are in a liquid state at 25°C (at normal pressure).

[0205] Furthermore, the viscosity of polyorganosiloxane A, polyorganosiloxane B, and polyorganosiloxane C at 25°C is not particularly limited, as long as the polyorganosiloxane is liquid at 40°C (at normal pressure). It is generally 5 mPa·s or higher at 25°C, preferably 50 mPa·s or higher, more preferably 100 mPa·s or higher, and generally 20,000 mPa·s or lower, preferably 2,000 mPa·s or lower, more preferably 500 mPa·s or lower. By maintaining the viscosity within this range, dripping from the nozzle, dripping during coating, and pinholes can be reduced, and it has appropriate fluidity for easy processing. Unless otherwise specified, the viscosity of this invention refers to the value measured by an E-type viscometer.

[0206] The molecular weight of the polyorganosiloxane is not particularly limited, but the number-average molecular weight (Mn) is typically 600 or more, preferably 800 or more, more preferably 900 or more, and even more preferably 950 or more. It is also typically 10,000 or less, preferably 5,000 or less, and more preferably 2,000 or less. The weight-average molecular weight (Mw) is typically 800 or more, preferably 900 or more, and more preferably 1,000 or more. It is also typically 20,000 or less, preferably 10,000 or less, and more preferably 4,000 or less. By keeping the number-average molecular weight or weight-average molecular weight above the aforementioned lower limit, the volatile components are reduced, resulting in various benefits such as an increased flash point, prevention of dripping from the nozzle due to viscosity optimization, dripping during coating, and non-stick properties. On the other hand, by keeping the number-average molecular weight or weight-average molecular weight below the upper limit, viscosity increases can be prevented, or it can be solidified as needed, making mixing or processing with other components easier.

[0207] Number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) under the following conditions and expressed as conversion values ​​for standard polystyrene. The sample uses approximately 10% by weight of THF solution and is filtered through a 0.45 μm filter before determination. Apparatus: TOSOH HLC-8220 GPC column: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko Corporation), column temperature 40°C, eluent: tetrahydrofuran, flow rate 0.2 mL / min.

[0208] Another embodiment of the present invention is a composition containing the polyorganosiloxane described above and a cured product obtained by curing it. The curing type can include addition polymerization curing, condensation polymerization curing, chain polymerization curing, etc. Hydrosilylation (addition polymerization curing type) that does not produce release components such as water and alcohol and whose reaction is irreversible can be conveniently used, or polyorganosiloxanes (chain polymerization type) that similarly do not produce release components and are cured by ultraviolet light or heat using chain polymerization initiators such as free radical polymerization initiators, and are cured without the production of release components. This is because if release components such as water or alcohol are generated during curing accompanied by polymerization, they tend to remain as bubbles in the cured product, or cause pressure increases within the container during molding, or cause shrinkage or deformation of the molded body due to the volatilization of the release components.

[0209] (Polyorganosiloxane composition)

[0210] Another embodiment of the present invention is a curable composition containing the polyorganosiloxane described above. Depending on the curing type, this composition may appropriately contain a curing catalyst or a chain polymerization initiator. The curing catalyst or chain polymerization initiator is not particularly limited as long as it enables the curing of the polyorganosiloxane described in this invention.

[0211] (Catalyst solidification)

[0212] Examples of addition polymerization catalysts include platinum group metal catalysts such as platinum black, platinum dichloride, chloroplatinic acid, reactants of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum diacetoacetate; complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum(O); complexes of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclosiloxane with platinum(O); palladium-based catalysts; and rhodium-based catalysts. The mixing amount of the addition polymerization catalyst, based on platinum group metals, relative to the total weight of the polyorganosiloxane, is typically 1 ppm or more, preferably 2 ppm or more, typically 100 ppm or less, preferably 50 ppm or less, and more preferably 20 ppm or less. This results in high catalyst activity and high transparency of the cured product. Furthermore, one addition polymerization catalyst can be used alone, or in combination of two or more.

[0213] As a polycondensation catalyst, acids such as hydrochloric acid, nitric acid, sulfuric acid, and organic acids, bases such as ammonia and amines, and metal chelating compounds can be used. Suitable metal chelating compounds can contain any one or more of Ti, Ta, Zr, Al, Hf, Zn, Sn, Pt, and In. Among them, the metal chelating compound preferably contains any one or more of Ti, Al, Zn, Zr, Pt, and In, and more preferably a compound containing Zr and Pt.

[0214] The amount of polycondensation catalyst mixed relative to the total weight of the polyorganosiloxane is typically 1 ppm or more, preferably 2 ppm or more, typically 300 ppm or less, preferably 200 ppm or less, and more preferably 150 ppm or less, based on metal content. Accordingly, the catalyst has high activity and minimal weight loss upon heating and curing. Furthermore, the polycondensation catalyst can be used alone or in combination of two or more types.

[0215] (Chain polymerization initiator)

[0216] Chain polymerization initiators can include free radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, etc., but the method of using free radical polymerization initiators is generally preferred.

[0217] Free radical polymerization initiators can be photopolymerization initiators and thermal polymerization initiators.

[0218] As photopolymerization initiators, alkyl phenyl ketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction photopolymerization initiators, oxime ester photopolymerization initiators, etc. can be used. Alkyl phenyl ketone-based photopolymerization initiators can be used as suitable substances.

[0219] As thermal polymerization initiators, existing known peroxides or azo compounds can be used.

[0220] Organic peroxides can be listed as follows, such as diacyl peroxides, dicarbonates peroxide, esters peroxide, ketals peroxide, dialkyl peroxides, hydrogen peroxide, silyl peroxides, etc. More specifically, examples include cumyl peroxide neodecanoate, 1,1,3,3-tetramethylbutyl peroxide neodecanoate, 1-cyclohexyl-1-methylethyl peroxide neodecanoate, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-butyl peroxide neopentanoate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-hexyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide neoheptanoate, tert-pentyl peroxide-2-ethylhexanoate, di-tert-butyl peroxide hexahydrophthalate, tert-pentyl peroxide-3, 5,5-Trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxynedecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxynedecanoate, tert-amylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di(3-methylbenzoylperoxy)hexane, tert-butylperoxy-2-ethylhexane monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate, dibutylperoxytrimethyl adipate, tert-amylperoxyoctanoate, tert-amylperoxyisononanoate, tert-amylperoxybenzoate, lauroyl peroxide, etc.

[0221] Examples of azo compounds include 2,2'-azobis-2,4-dimethylpentanonitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid), and 1,1'-azobis(1-cyclohexanecarboxynitrile).

[0222] Free radical polymerization initiators can be used alone or in combination of two or more.

[0223] <Antioxidants>

[0224] The curable composition preferably further contains an antioxidant. By containing an antioxidant, the curable composition can suppress heat-induced discoloration of the cured product, such as during reflow soldering.

[0225] Specific examples of antioxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol di[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol di[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Phosphorus-based antioxidants include triphenyl phosphite, triisodecyl phosphite, tri(tetrazyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite; sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, di(tetrazyl)-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearate-3,3'-thiodipropionate, and pentaerythritol tetra(β-lauryl thiopropionate). These antioxidants can be used alone or in combination of two or more.

[0226] (Other ingredients)

[0227] The curable composition of the present invention may contain fillers, curing agents, viscosity modifiers, and other components. These components may be appropriately contained within a range that does not impair the mechanical properties or effects such as flash point, coefficient of linear expansion, and viscosity of the cured polyorganosiloxane involved in this embodiment.

[0228] Furthermore, there is no particular limitation on the viscosity of the cured composition; it can be adjusted to an appropriate viscosity according to the molding method.

[0229] Furthermore, the curable composition of the present invention can be in the form containing MT resin as described above, and can also be in the form containing cage-like silsesquioxanes. When the polyorganosiloxane curable composition contains cage-like silsesquioxanes, the content of cage-like silsesquioxanes is preferably less than 5% by weight. By keeping the content of cage-like silsesquioxanes below the above-mentioned upper limit, cage-like silsesquioxanes are less likely to precipitate, transparency is easily improved, and haze of the cured product described later is easily suppressed. In addition, it is easier to maintain the liquid phase.

[0230] (Curved product of polyorganosiloxane composition)

[0231] The cured product obtained by curing the above-described curable composition is another embodiment of the present invention. The curing method is not particularly limited, and known methods such as heat or ultraviolet light can be appropriately employed depending on the type of polyorganosiloxane.

[0232] The haze of the cured product obtained by curing the above-described curable composition is preferably less than 1%, more preferably less than 0.6%. Within this range, the influence caused by light diffusion is reduced, thus achieving transparency suitable for use in optical resins.

[0233] Haze can be measured using a haze meter based on the measuring apparatus (haze meter) according to "Test method for total light transmittance of plastic-transparent materials - Part 1 Single beam method / compensation method (JIS K 7361)" and "Determination of haze of plastic-transparent materials (JIS K 7136)".

[0234] The yellow index of the cured product obtained by curing the above-mentioned curable composition after treatment at 85°C and 85% relative humidity for 168 hours is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 3. Within this range, the durability under the influence of ambient temperature and humidity is improved when used for optical applications, making it a cured product suitable for optical applications.

[0235] The yellow index can be determined using a measuring apparatus based on "Determination of yellowness and yellowing degree of plastics (JIS K 7373)".

[0236] (Method for manufacturing polyorganosiloxanes)

[0237] The manufacturing method of the polyorganosiloxane involved in this embodiment is not particularly limited, as long as a polyorganosiloxane having the above-described structure can be obtained. For example, it can be any manufacturing method such as disiloxane compound or disilazane compound and their hydrolysis products, alkoxysilane compound or its hydrolysis products, condensation of partially hydrolyzed condensates, condensation of chlorosilane compound or its hydrolysis products, condensation of partially hydrolyzed condensates, ring-opening polymerization of cyclic siloxane compound, chain polymerization starting from anionic polymerization, etc., and multiple manufacturing methods can also be combined. In addition, polyorganosiloxanes having the desired number of reactive functional groups or molecular weight can be fractionated and used by column chromatography or GPC, solvent extraction, distillation to remove unwanted components, etc. Furthermore, when the weight of the polyorganosiloxane component decreases by more than 5% by weight after heating at 110°C for 2 hours under reduced pressure of 0.15 torr, i.e., a large amount of low-boiling-point components are generated, the low-boiling-point components can be removed by heating or reducing pressure to obtain the polyorganosiloxane involved in this embodiment.

[0238] The method for introducing reactive functional groups into the polyorganosiloxanes involved in this embodiment is not particularly limited. For example, reactive functional groups can be introduced from disiloxane compounds, disilazane compounds, alkoxysilane compounds with M, D, or T units, chlorosilane compounds with M, D, or T units, and cyclic siloxane compounds. Furthermore, the introduced reactive functional groups can be converted into other reactive functional groups using chemical methods. For example, it can be used by converting it into other types of reactive functional groups through the following methods: converting a polyorganosiloxane having an alkenyl group into a monofunctional thiol having a reactive functional group through a reaction; converting an alkenyl group into an epoxy group by oxidizing it with an oxidizing agent; converting a polyorganosiloxane having a hydrogen atom directly bonded to a silicon atom into a vinyl compound having a reactive functional group through a reaction; converting a cyclic ether group introduced into a polyorganosiloxane into an alcoholic hydroxyl group by ring opening, etc.

[0239] The polyorganosiloxane described in this embodiment has low viscosity and minimal weight loss during depressurization and heating, resulting in excellent workability. Furthermore, the cured product obtained by curing the polyorganosiloxane described in this embodiment possesses high strength or high thermal shock resistance, making it suitable for a wide range of applications. These applications include, for example, viscosity modifiers, compatibilizers, lubricants, dispersants, coagulants, adhesives, release agents, waterproofing agents, oil repellents, coating agents, surface modifiers, metal surface repair agents, flame retardants, and applications such as sealing materials or substrates for semiconductor devices, primarily inorganic or organic light-emitting elements, coating materials, and optical components.

[0240] Furthermore, the present invention also includes the following embodiments (second embodiment).

[0241] (Polyorganosiloxane)

[0242] To increase the Abbe number of the cured product, which is one of the effects of the present invention, in general formula (101), a functional group having a (meth)acryloyl group is included as a reactive functional group. The proportion of units having a (meth)acryloyl group, M2 + D2 + T2, needs to be greater than 0.25, preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 or more. Furthermore, from the viewpoints of improving compatibility with other acrylic resins, increasing the (meth)acryloyl group content, and improving liquid storage stability, it is preferable that (meth)acryloyl groups are present in the M unit or T unit. Therefore, it is preferable that M2 + T2 > 0.25, more preferably that M2 + T2 is 0.4 or more, even more preferably that M2 + T2 is 0.5 or more, and particularly preferably 0.6 or more.

[0243] Furthermore, the proportion M1 of M units without (meth)acryloyl groups is also preferred, i.e., M1 > 0. The reason is that replacing the alkoxy and silanol groups of polyorganosiloxanes with M units can improve the storage stability of polyorganosiloxanes and reduce viscosity. However, in polyorganosiloxanes modified with bulky groups such as (meth)acryloyl groups, when replacing alkoxy and silanol groups with M units, the sterically less hindranced M units are more easily accessible to silicon atoms, and M units without (meth)acryloyl groups are advantageous for substitution. From a steric hindrance perspective, R... 101 To R 103 Methyl or hydrogen atoms are particularly preferred, with methyl being the most preferred from the viewpoint of storage stability. Regarding the amount of substitution, from the viewpoint of storage stability, the preferred coefficient M1 is 0.09 or higher. The upper limit is generally 0.6 or lower, preferably 0.5 or lower, and more preferably 0.4 or lower.

[0244] Furthermore, in this invention, from the viewpoint of increasing the (meth)acryloyl group content and improving the stability of liquid preservation, MQ resin, MTQ resin, and MT resin are preferred. D units may also be added to impart appropriate softness to these resins. In order to make it a material with high elastic modulus and low linear expansion coefficient, suitable for use as an optical material, D1 ≤ 0.1 is preferred, and D1 ≤ 0.05 is more preferred.

[0245] Q-units represent the most fully oxidized form of silicon, and their inclusion in the structure of polyorganosiloxanes can improve heat resistance. Therefore, MQ resins and MTQ resins containing Q-units in their structure are preferred. The preferred coefficient for the content of Q-units is greater than 0, preferably 0.04 or higher, and typically 0.6 or lower is the upper limit. A higher number of Q-units results in a solid state or increased viscosity, reducing processability; therefore, 0.4 or lower is more preferable.

[0246] In addition, (O) 1 / 2 R 110 () refers to alkoxy or silanol groups bonded to silicon, which can control the viscosity of polyorganosiloxanes and adjust it to a suitable viscosity for molding. Silanol groups have the effect of increasing viscosity, while converting silanol groups to alkoxy groups can reduce viscosity.

[0247] The coefficient Y1 is 0 or a positive value. From the viewpoint of adjusting to the viscosity required for molding, the coefficient Y1 is usually 0 or above, preferably 0.01 or above, and from the viewpoint of preserving stability or curing shrinkage, it is usually 0.25 or below, preferably 0.2 or below, and more preferably 0.1 or below.

[0248] The coefficient Y2 represents the content of organic groups containing (meth)acryloyl groups bonded to silicon, which helps increase the refractive index and Abbe number, and therefore can be added to the structure of polyorganosiloxanes. By replacing M2+D2+T2≧0.25 with Y2≧0.25, it can be used as an optical material. That is, as another aspect of the invention, the requirement of M2+D2+T2≧0.25 in general formula (101) can be replaced by Y2≧0.25. Since compounds with (meth)acryloyloxy groups bonded to silicon are easily hydrolyzed and detached by water, resulting in a higher water absorption rate, it is preferable to use them in a way that is less affected by moisture.

[0249] That is, it can be made into (meth)acryloyloxy modified Q resin, T resin, MQ resin, MT resin, MTQ resin, and polyorganosiloxane composed of them and D units.

[0250] (About R) 101 ~R 110 )

[0251] Next, the substituents will be explained.

[0252] In this invention, it is a reactive functional group, or R 106 An organic group substituted with (meth)acryloyl. Preferred groups are those having one or more functional groups selected from the group shown in [2], [3], [4] and [5], but more preferably acryloyloxypropyl, acryloyloxyoctyl, methacryloyloxypropyl, and methacryloyloxyoctyl, with acryloyloxypropyl and methacryloyloxypropyl being the most preferred.

[0253]

Transformation 3

[0254]

[0255] In this formula, X is a divalent organic functional group, which may contain branched structures and / or cyclic structures. Furthermore, in addition to carbon and hydrogen, X may contain any one of the following groups: oxygen, nitrogen, phosphorus, sulfur, and halogens. When X is bonded to a silicon atom, the atom at the end of X and directly bonded to the silicon atom is a carbon atom. Similarly, when X is bonded to an oxygen atom directly bonded to a silicon atom, the atom at the end of X and directly bonded to the oxygen atom is a carbon atom.

[0256] Furthermore, in this invention, the individual units constituting the M unit, D unit, and T unit do not need to be entirely identical. That is, the units with a ratio of M1 (R...) 101 R 102 R 103 SiO 1 / 2 Within ), for example, it can have a certain R. 101 It is a hydrogen atom, a certain R101 It's a different structure like methyl. The same applies to other R and X.

[0257] In addition, R 101 To R 105 R 107 To R 110 Each of these is a group independently selected from an organic functional group and a hydrogen atom. Then R... 101 To R 103 R 107 R 108 R 110 It does not contain (meth)acryloyl groups. This is due to, for example, R 101 To R 103 When the organic group contains (meth)acryloyl, it is impossible to distinguish between the M1 proportion part and the M2 proportion part, hence this stipulation.

[0258] On the other hand, R, which is part of the M2 ratio 104 R 105 Even organic groups containing (meth)acryloyl groups do not present this problem and are therefore not subject to this restriction. The same reasoning applies to the D1 and T1 proportion portions. 107 R 108 R 110 It does not contain (meth)acryloyl groups.

[0259] R 101 To R 105 R 107 To R 110 The preferred functional groups are alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, octyl, cyclohexyl, phenyl, naphthyl, carbazole, styrene, furanyl, polyethylene glycol, glycidyloxypropyl, cyclic epoxy, etc., and more preferably methyl, phenyl or hydrogen atoms.

[0260] R 110 It indicates that it does not contain a (meth)acryloyl group, and is selected from organic groups with 1 to 20 carbon atoms and hydrogen atoms. Methyl is preferred.

[0261] (Other properties of polyorganosiloxanes)

[0262] As a preferred characteristic of the polyorganosiloxane of the present invention, it is preferably liquid at 25°C, and from a processability point of view, the viscosity at 25°C is preferably 10 to 100,000 mPa·s as measured by an E-type viscometer. Furthermore, to ensure it is liquid, the number-average molecular weight of polystyrene, as determined by gel permeation chromatography (GPC), is preferably 10,000 or less. Further, in the case of being liquid, it is more preferable to have fewer low molecular weight components, and the number-average molecular weight is preferably 1,000 or more. While a higher proportion of low molecular weight components facilitates liquid formation, it can lead to a decrease in the elastic modulus during curing, and furthermore, a significant change in the elastic modulus with temperature variations, potentially causing degradation of the optical components due to temperature changes.

[0263] (Method for manufacturing polyorganosiloxanes)

[0264] The polyorganosiloxane of the present invention can be obtained by hydrolysis and condensation of conventionally produced silicon raw materials, and the raw materials that can be used for manufacturing are exemplified below.

[0265] As an example of an M-unit source, trimethylsilanol, trimethylmethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, dimethylsilanol, dimethylmethoxysilane, tetramethyldisiloxane, tetramethyldisilazane, dimethylvinylsilanol, dimethylvinylmethoxysilane, 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetramethyldisilazane, dimethylmethacryloyloxypropylsilanol, dimethylmethacryloyloxypropylmethoxysilane, 1,3-dimethylacryloyloxypropyltetramethyldisiloxane, dimethylglycidoxypropylsilane Alcohols, dimethylglycidoxypropylmethoxysilane, 1,3-diglycidoxypropyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-diphenyltetramethyldisilazane, dimethylphenylsilanol, dimethylmethoxyphenylsilane, 1,4-di(dimethylmethoxysilyl)benzene, 1,4-di(dimethylethoxysilyl)benzene, and the compounds listed above, for compounds containing silanol hydroxyl or alkoxy groups, compounds bonded by replacing the silanol hydroxyl or alkoxy group with a halogen can be used, and hexamethyldisiloxane is particularly suitable. Furthermore, for the purpose of increasing the refractive index, the above-mentioned compounds containing aromatic compounds are preferred.

[0266] As an example of a D-unit source, dimethyldisilanol, dimethyldimethoxysilane, tetramethyldisiloxane, dimethylsiloxane oligomers, methacryloxypropyldimethoxymethylsilane, methyldimethoxyphenylsilane, diethoxymethylphenylsilane, methylphenyldisilanol, 1,4-di(methyldimethoxysilyl)benzene, 1,4-di(methyldiethoxysilyl)benzene, and compounds in which the silanol hydroxyl or alkoxy group of the above-listed compounds is halogenated and their polymers can be used, with dimethyldimethoxysilane being particularly suitable. Furthermore, for the purpose of increasing the refractive index, the above-mentioned compounds containing aromatic compounds are also preferred.

[0267] As an example of a T-unit source, trimethoxysilanes modified with C1-C20 long-chain alkoxy groups, such as trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, as well as vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, and 3-glycidyl Alkoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane and their ethoxysilane compounds, phenyltrisilanol, 1,4-di(trimethoxysilyl)benzene, 1,4-di(triethoxysilyl)benzene, and in addition to these alkoxysilanes, trichlorosilane or trihydrosilylsilane, trisilanol and their polymers may also be used. Particularly suitable are 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 8-acryloyloxyoctyltrimethoxysilane. Furthermore, for the purpose of increasing the refractive index, the above-mentioned compounds containing aromatic compounds are also preferred.

[0268] As an example of a Q-unit source, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, triethoxymonomethoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxymonopropoxysilane, triethoxymonopropoxysilane, diethoxymonopropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxysilane can be used. Alkoxysilanes such as diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, diethoxymonomethoxymonoethoxysilane, diethoxymonomethoxymonobutoxysilane, diethoxymonoethoxymonobutoxysilane, diethoxymonomethoxymonoethoxysilane, diethoxymonoethoxymonopropoxysilane, and monomethoxymonoethoxymonopropoxymonobutoxysilane, or aryloxysilanes; methyl silicate MS51, MS56, MS57, and MS60 manufactured by Mitsubishi Chemical Corporation as tetramethoxysilane oligomers; and ethyl silicate oligomers ES40 and ES48 manufactured by Tama Chemical Corporation as tetraethoxysilane oligomers, etc., with methyl silicate MS51 being particularly suitable.

[0269] As a catalyst for the hydrolysis and condensation of these silicon raw materials, acid catalysts, base catalysts, or inorganic salts can be used, with acid catalysts being particularly suitable.

[0270] As an example of an acid catalyst, hydrochloric acid, sulfuric acid, trifluoroacetic acid, acetic acid, methacrylic acid, acrylic acid, etc. can be used, with hydrochloric acid being particularly suitable.

[0271] As an example of an alkaline catalyst, ammonia, hexamethyldisilazane, triethylamine, tetraethylammonium hydroxide, diazabicycloundecene, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, etc. can be used, with potassium hydroxide being particularly suitable.

[0272] As inorganic salts, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc. can be used.

[0273] As an example of a solvent used in a hydrolysis-condensation reaction, tetrahydrofuran, toluene, methanol, ethanol, isopropanol, hexane, heptane, etc. can be used, with tetrahydrofuran being particularly preferred. Depending on the solubility of the product, two or more solvents can be used, with a mixture of toluene and methanol, or a mixture of tetrahydrofuran and methanol being particularly preferred.

[0274] As a method for manufacturing MT resin, the M units can be added simultaneously, that is, the raw materials of each MT unit are mixed together at the beginning and hydrolyzed and condensed by a catalyst. Alternatively, the M units can be added afterward, that is, the raw materials of the T units are pre-hydrolyzed and condensed before the raw materials of the M units are added and hydrolyzed and condensed. However, from the viewpoint of suppressing the generation of low molecular weight components, it is preferable to add the M units afterward.

[0275] For alkoxy or silanol groups that remain without hydrolysis and condensation, they can be substituted with organic acids or alcohols as needed. For example, acetic acid, acrylic acid, and methacrylic acid can be used. For example, groups without (meth)acrylyl groups can be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and their structural isomers. Groups containing (meth)acrylyl groups can be 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. From the point of view of stability, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0276] As a method for manufacturing MTQ resin, the M unit can be added simultaneously, that is, the raw materials of each MTQ unit are mixed together at the beginning and hydrolyzed and condensed by a catalyst. Alternatively, the M unit can be added afterward, that is, the raw materials of TQ unit are pre-hydrolyzed and condensed, and then the raw materials of M unit are added for hydrolysis and condensation. Another method is multi-stage synthesis, that is, the raw materials of T unit and M unit are pre-hydrolyzed and condensed, and the raw materials of Q unit and M unit are also pre-hydrolyzed and condensed, and then these hydrolyzed and condensed products are mixed together for further hydrolysis and condensation. However, from the viewpoint of suppressing the generation of low molecular weight components, it is preferable to add the M unit afterward or to synthesize in a multi-stage manner.

[0277] For alkoxy or silanol groups that remain without hydrolysis and condensation, they can be substituted with organic acids or alcohols as needed. For example, acetic acid, acrylic acid, and methacrylic acid can be used. For example, groups without (meth)acrylyl groups can be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and their structural isomers. Groups containing (meth)acrylyl groups can be 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. From the point of view of stability, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0278] As a method for manufacturing MQ resin, the M units can be added simultaneously, that is, the raw materials of each MQ unit are mixed together in advance and hydrolyzed and condensed by a catalyst. Alternatively, the M units can be added afterward, that is, the raw materials of the Q units are hydrolyzed and condensed in advance and then the raw materials of the M units are added for hydrolysis and condensation. However, from the viewpoint of suppressing the generation of low molecular weight components, it is preferable to add them afterward. It is even more preferable to use pre-hydrolyzed and condensed silicates as raw materials.

[0279] For alkoxy or silanol groups that remain without hydrolysis and condensation, they can be substituted with organic acids or alcohols as needed. For example, acetic acid, acrylic acid, and methacrylic acid can be used. For example, groups without (meth)acrylyl groups can be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and their structural isomers. Groups containing (meth)acrylyl groups can be 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. From the point of view of stability, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0280] In addition, it is also preferable to use a raw material with hydrosilyl group in the M unit to hydrolyze and condense MQ resin, and then modify the vinyl compound by hydrosilanization using a platinum catalyst such as Karstedt catalyst.

[0281] One method for manufacturing Q resin is to mix an organic acid or alcohol with a catalyst and synthesize it by replacing the terminal alkoxy group of the Q unit raw material with the organic acid or alcohol.

[0282] As an example of an organic acid, acrylic acid or methacrylic acid can be used; as an example of an alcohol, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate can be used. From the viewpoint of stability, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is preferred.

[0283] In addition, these MT resins, MTQ resins, MQ resins, and Q resins can also be hydrolyzed and condensed with D-unit raw materials to impart toughness.

[0284] Furthermore, when these MT, MTQ, MQ, and Q resins have a rigid structure like cage-type silsesquioxanes, the cured product is hard and brittle, making it difficult to alleviate stress during reflow soldering and leading to cracking. Therefore, a cage-type structure is preferred. With a cage-type structure, infrared absorption spectroscopy analysis shows that in the wavenumber range of 1070–1150 cm⁻¹… -1 The region contains absorption peaks for Si-O stretching vibrations; therefore, by avoiding the maximum absorption wavenumber of Si-O stretching vibrations in the aforementioned wavenumber region, the extremely rigid structure of cage-like silsesquioxanes can be avoided. Furthermore, in the wavenumber range of 1070–1150 cm⁻¹… -1 Within this region, characteristic absorption bands from organic molecules other than Si-O can exist. Examples of characteristic absorption bands from organic molecules include CO from hydroxyl groups, COC from esters, COC from acid anhydrides, COC from ethers, CN from amines, sulfonic acids, sulfoxides, CF from fluorine compounds, P=O or PO from phosphorus compounds, and SO4 from inorganic salts. 2- or ClO4 -The resulting absorption bands are all structures with high absorption intensity. It is important not to confuse these with the Si-O stretching vibrations.

[0285] The amount of water used for hydrolysis is preferably 0.5 equivalents or more, more preferably 0.8 equivalents or more, and even more preferably 1.1 equivalents or more, relative to the total amount of alkoxy groups contained in the MDTQ unit. As an example of the type of water, it can be water contained in commercially available hydrochloric acid, or water purified by distillation or ion exchange resin.

[0286] The preferred structure of the polyorganosiloxane used in this embodiment is MT resin, or MTQ resin, or MQ resin, with MTQ resin being particularly preferred.

[0287] (Polyorganosiloxane composition)

[0288] In addition to the polyorganosiloxanes described above, the polyorganosiloxane composition of this embodiment may also contain monofunctional (meth)acrylate compounds or polyfunctional (meth)acrylate compounds, and / or (meth)acrylate polymers. Furthermore, a polymerization initiator may be included to polymerize and cure the (meth)acrylate compounds. An organic solvent may also be included.

[0289] The following describes the components that may be contained in the polyorganosiloxane composition of the present invention.

[0290] In this invention, "(meth)acryloyl" is a general term for acryloyl and methacryloyl groups, represented by CH2=C(R)-C(=O)-. R represents a hydrogen atom or a methyl group. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid. "(meth)acrylate" is a general term for acrylate and methacrylate.

[0291] (Monofunctional (meth)acrylate compounds)

[0292] Specific examples of monofunctional (meth)acrylate compounds include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, and other (meth)acrylates containing carboxyl groups.

[0293] 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and other (meth)acrylates containing hydroxyl groups;

[0294] Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, decyl methacrylate, lauryl methacrylate, tridecyl methacrylate, octadecyl methacrylate, and other alkyl methacrylates.

[0295] Cyclohexyl methacrylate, dicyclopentenyl methacrylate, 2-dicyclopentenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, 4-tert-butylcyclohexyl methacrylate, and other methacrylates containing alicyclic structures.

[0296] (Meth)acrylates containing aromatic ring structures include phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, nonylphenoxypolyethylene glycol methacrylate, phenoxypolypropylene glycol methacrylate, phenylphenyl methacrylate, phenylphenoxyethyl methacrylate, phenoxybenzyl methacrylate, phenylbenzyl methacrylate, naphthyl methacrylate, and (1-naphthyl)methyl methacrylate.

[0297] Tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, methacryloylmorpholine, and other (meth)acrylates containing heterocyclic structures;

[0298] Alkoxy (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate;

[0299] 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate, etc.

[0300] (Multifunctional (meth)acrylate compounds)

[0301] Specific examples of multifunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and other alkylene glycol di(meth)acrylates;

[0302] Polyalkylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and other polyalkylene glycol di(meth)acrylates;

[0303] Cyclohexanediethanol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, adamantanediol di(meth)acrylate, and other di(meth)acrylates containing alicyclic structures;

[0304] Polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, polyurethane di(meth)acrylate and other difunctional (meth)acrylates;

[0305] Trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, and ε-caprolactone-modified tri((meth)acryloyloxyethyl)isocyanurate.

[0306] di(trimethylolpropane)tetra(meth)acrylate and other 4-functional (meth)acrylates;

[0307] dipentaerythritol penta(meth)acrylate and other 5-functional (meth)acrylates;

[0308] Multifunctional monomers such as dipentaerythritol hexa(meth)acrylate and other 6-functional (meth)acrylates.

[0309] (Meth)acrylic polymers)

[0310] (Meth)acrylate polymers are polymers containing more than 50% by mass (meth)acrylate units in their composition. "Unit" refers to a repeating unit that constitutes the polymer. (Meth)acrylate compounds can be monofunctional or polyfunctional.

[0311] The (meth)acrylic polymer may contain one or more (meth)acrylate units.

[0312] In addition, it may contain monomer units other than (meth)acrylate units. These other monomers can be any monomers that can copolymerize with (meth)acrylates, such as aromatic vinyl monomers like styrene and α-methylstyrene; vinyl cyanide monomers like acrylonitrile; and vinyl ester monomers like vinyl acetate.

[0313] The polymerization method for obtaining (meth)acrylic acid polymers is not particularly limited, and polymerization can be carried out by known methods such as solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization. In this invention, suspension polymerization is preferred because it is relatively easy to control the polymerization reaction or separate the resulting polymer.

[0314] Furthermore, as (meth)acrylic polymers, polymers modified by introducing (meth)acryloyl groups or functional groups containing double bonds such as vinyl groups into the side chains can be used. As chemical modification methods, for example, reactions of carboxyl groups with glycidyl groups or reactions of hydroxyl groups with isocyanate groups can be used.

[0315] As a chemical modification method, when using the reaction of carboxyl groups and glycidyl groups, for example, a method can be used to manufacture (meth)acrylate polymers containing (meth)acrylate units having carboxyl groups, and to react the obtained (meth)acrylate polymers with compounds having glycidyl groups and double bonds, such as (meth)acrylate glycidyl ester.

[0316] For the reaction of (meth)acrylic polymers containing (meth)acrylic monomer units with carboxyl groups with compounds having glycidyl groups and double bonds, a reaction catalyst that shortens the reaction time is preferred. Examples of reaction catalysts include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine. From the viewpoint that the polyorganosiloxane compositions of the present invention are less prone to coloring, quaternary ammonium salts are particularly preferred.

[0317] From the viewpoint of increasing the Abbe number, alkyl methacrylates, methacrylates containing alicyclic structures, alkylene glycol di(methacrylates), and di(methacrylates) containing alicyclic structures are particularly preferred.

[0318] The weight-average molecular weight (Mw) of the (meth)acrylic polymer is preferably 5,000 to 500,000, more preferably 10,000 to 200,000. A weight-average molecular weight of 5,000 or higher improves the strength of the cured product. A weight-average molecular weight of 500,000 or lower reduces the viscosity of the polyorganosiloxane composition of the present invention, thus improving workability.

[0319] (Polymerization initiator)

[0320] Examples of polymerization initiators include photopolymerization initiators, thermal polymerization initiators, and peroxides used in redox polymerization. The type of polymerization initiator can be appropriately selected according to the polymerization method.

[0321] (Photopolymerization initiator)

[0322] Photopolymerization initiators are free radical polymerization initiators used in photopolymerization. Specific examples of photopolymerization initiators include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, and other benzophenone-type compounds; anthraquinone-type compounds such as tert-butylanthraquinone and 2-ethylanthraquinone; 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-1 -{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one and other alkyl phenyl ketone type compounds; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanone, isopropylthioxanone and other thioxanone type compounds; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, di(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other acylphosphine oxide type compounds; methyl phenylglyoxylate and other phenylglyoxylate type compounds, etc.

[0323] Among these, alkylphenyl ketone type compounds are preferred for their ability to suppress coloring of the cured product, and 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1-hydroxycyclohexylphenyl ketone are more preferred. Furthermore, acylphosphine oxide type compounds are preferred for their ease of fully curing the cured product to its interior, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferred for its ability to suppress coloring of the cured product. These photopolymerization initiators can be used alone or in combination of two or more.

[0324] When a cured composition is cured by photopolymerization to obtain a cured product, there is no particular limitation on the wavelength of the light irradiating the cured composition, but ultraviolet light with a wavelength of 200–400 nm is preferred. Specific examples of ultraviolet light sources include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, UV-LED lamps, chemical lamps, black light lamps, etc. After photopolymerization of the cured composition, further post-curing can be performed. Accordingly, the amount of unreacted (meth)acryloyl groups remaining in the cured product can be reduced, and the strength of the cured product can be further improved. As post-curing conditions, 70–150°C for 0.01–24 hours is preferred, and 80–130°C for 0.1–10 hours is more preferred.

[0325] (Thermal polymerization initiator)

[0326] Thermal polymerization initiators are free radical polymerization initiators used in thermal polymerization. Examples of thermal polymerization initiators include organic peroxides and azo compounds.

[0327] Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; ketal peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydrogen peroxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and dicumyl peroxide, di-tert-butyl peroxide, etc. Alkyl peroxides; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; di(4-tert-butylcyclohexyl) peroxide dicarbonate, di(2-ethylhexyl) peroxide dicarbonate, and other peroxide dicarbonates; peroxide esters such as tert-butyl peroxide-2-ethylhexanoate, tert-hexyl peroxide isopropyl monocarbonate, tert-butyl peroxide benzoate, and 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate.

[0328] Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 1,1'-azobis-1-cyclohexanenitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanopentanoic acid, and 2,2'-azobis-(2-amidinylpropane) dihydrochloride, etc.

[0329] These thermal polymerization initiators can be used alone or in combination of two or more. Organic peroxides are preferred as thermal polymerization initiators because they are less likely to generate bubbles in the cured product. Considering the balance between the curing time and pot life of the curable composition, the 10-hour half-life temperature of the organic peroxide is preferably 35–80°C, more preferably 40–75°C, and even more preferably 45–70°C. When the 10-hour half-life temperature is above 35°C, the curable composition is less prone to gelation at room temperature, resulting in a better pot life. On the other hand, when the 10-hour half-life temperature is below 80°C, the curing time of the curable composition can be shortened.

[0330] Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxide-2-ethylhexanoate, tert-butylperoxide-2-ethylhexanoate, and di(4-tert-butylcyclohexyl)peroxide. Commercially available products of 1,1,3,3-tetramethylbutylperoxide-2-ethylhexanoate include Perocta O (trade name, manufactured by Nippon Oil Co., Ltd., 10-hour half-life temperature: 65.3°C). Commercially available products of tert-butylperoxide-2-ethylhexanoate include Perbutyl O (trade name, manufactured by Nippon Oil Co., Ltd., 10-hour half-life temperature: 72.1°C). Commercially available products of di(4-tert-butylcyclohexyl)peroxide include Peroyl TCP (trade name, manufactured by Nippon Oil Co., Ltd., 10-hour half-life temperature: 40.8°C).

[0331] When a cured composition is cured by thermal polymerization to obtain a cured product, the curing conditions are not particularly limited. However, from the viewpoint of easily obtaining a resin for optical components in which coloring is suppressed, the curing temperature is preferably 40 to 200°C, more preferably 60 to 150°C. The curing time (heating time) varies depending on the curing temperature, preferably 1 to 120 minutes, more preferably 1 to 60 minutes.

[0332] After the curable composition is thermally polymerized, it is preferable to further perform post-curing. As post-curing conditions, it is preferable to cure at 50 to 150°C for 0.1 to 10 hours, more preferably at 70 to 130°C for 0.2 to 5 hours.

[0333] (Redox polymerization)

[0334] Redox polymerization typically uses redox-based polymerization initiators. Redox-based polymerization initiators are polymerization initiators that combine peroxides with reducing agents. Examples of peroxides used in redox polymerization include benzoyl peroxide and hydrogen peroxide. These peroxides can be used alone or in combination of two or more. An example of a combination of the above-mentioned peroxides as redox polymerization initiators with a reducing agent is described below.

[0335] (1) A combination of benzoyl peroxide (peroxide) and aromatic tertiary amines (reducing agents) such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxypropyl)-p-toluidine.

[0336] (2) Combination of hydrogen peroxide (peroxide) and metal soaps (reducing agents).

[0337] (3) Combination of hydrogen peroxide (peroxide) and thiourea (reducing agent).

[0338] When a cured composition is cured by redox polymerization to obtain a cured product, it can be cured at room temperature of 5–40°C by using a redox polymerization initiator. The preferred curing temperature is 15–40°C, which can further improve the strength of the resin used for optical components by reducing the amount of unreacted (meth)acryloyl groups remaining in the obtained resin.

[0339] Furthermore, to ensure that the curable composition does not easily gel and can be operated stably, it is preferable to carry out the curing method by first dissolving the reducing agent in the curable composition and adding the peroxide thereto.

[0340] When curing a curable composition, it is preferable to cure the composition in a sealed state to suppress the interference of oxygen on curing. Methods for sealing include, for example, clamping the curable composition with glass or a PET film.

[0341] (Organic solvent)

[0342] Organic solvents may be included for the purpose of diluting the polyorganosiloxanes and compositions of the present invention. There are no particular limitations on the types of organic compounds used, as long as they do not impair the required physical properties of the cured polyorganosiloxanes and compositions of the present invention. Aromatic hydrocarbons with good solubility (e.g., toluene, xylene, ethyl benzoate, ethylbenzene, benzyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol), and esters (e.g., methyl acetate, ethyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, ethyl lactate, methyl lactate) can be used. The solvents used include butyl lactate, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethers (such as isopropyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, methyl tert-butyl ether, tetrahydrofuran), alcohols (such as methanol, ethanol, n-propanol, isopropanol, butanol, sec-butanol, tert-butanol, n-pentanol), halogen solvents (such as dichloromethane, trichloroethylene, tetrachloroethylene, bromopropane, chloroform), and others (such as dimethyl sulfoxide, N,N-dimethylformamide), and two or more solvents may also be used.

[0343] The content is not particularly limited as long as it does not impair the required physical properties of the cured polyorganosiloxane and composition of the present invention. However, when it is desirable to suppress volatile components to a small amount to reduce viscosity, it is preferably more than 0 wt% and less than 25 wt% relative to the total polyorganosiloxane or composition. Furthermore, when it is desirable to obtain a film-cured product, it is preferably more than 75 wt% and less than 100 wt% relative to the total composition.

[0344] (Curved product of polyorganosiloxane composition)

[0345] The polyorganosiloxane composition of the present invention can be cured by heat or light.

[0346] The curing conditions of the polyorganosiloxane composition of the present invention are not particularly limited, and curing can be carried out appropriately by means of the conditions used for curing silicone resin, depending on the type of polymerization initiator, etc.

[0347] (Properties of cured products)

[0348] By curing the polyorganosiloxane and composition of the present invention as described above, a cured product having the following characteristics can be obtained, wherein the polyorganosiloxane of the present invention has units containing (meth)acryloyl groups in an amount of 40 mol% or more relative to the total amount of its M, D, T, and Q units.

[0349] High Abbe number, high refractive index

[0350] Cured products with high Abbe numbers and high refractive indices, typically 44 or higher, preferably 50 or higher, and more preferably 56 or higher, and refractive indices typically 1.43 or higher, preferably 1.45 or higher, and more preferably 1.50 or higher, can be obtained. Furthermore, when forming a polyorganosiloxane composition, it is possible to obtain monomer-cured products with Abbe numbers and refractive indices higher than those of the (meth)acrylic resin composition used. The determination of the Abbe number and refractive index can be performed by the method described in the examples described later.

[0351] • Low water absorption rate

[0352] After drying the cured material, a cured material with a water absorption rate typically below 2% by mass, preferably below 1% by mass, and more preferably below 0.8% by mass, after being placed in an environment of 85% humidity and 85% RH for 168 hours can be obtained. Furthermore, when it becomes a polyorganosiloxane composition, the water absorption rate can also be lower than that of the monomer-cured (meth)acrylic resin composition used. The water absorption rate can be determined by the method described in the examples below.

[0353] High pencil hardness

[0354] Cured products with a pencil strength typically of H or higher, preferably 3H or higher, and more preferably 8H or higher, can be obtained. Furthermore, when formed as a polyorganosiloxane composition, the pencil hardness can be higher than that of the monomer-cured product of the (meth)acrylic resin composition used. The pencil hardness can be determined by the method described in the examples described later.

[0355] High energy storage modulus

[0356] A cured product with a storage modulus of typically 750 MPa or more, preferably 1000 MPa or more, and more preferably 2000 MPa or more at 100°C can be obtained. Furthermore, when it is a polyorganosiloxane composition, the storage modulus can be higher than that of the monomer cured product of the (meth)acrylic resin composition used. The storage modulus can be determined by the method described in the examples below.

[0357] Colorless and transparent

[0358] Cured products with a total light transmittance of typically 85% or more, preferably 90% or more, and more preferably 95% or more can be obtained. Furthermore, when it is a polyorganosiloxane composition, the total light transmittance of the monomer cured product of the (meth)acrylic resin composition used is not reduced, and a transparent cured product can be obtained.

[0359] Cured products with a yellowness index (YI) typically below 2, preferably below 1, and more preferably below 0.5 can be obtained. Furthermore, when it becomes a polyorganosiloxane composition, the YI of the monomer cured product of the (meth)acrylic resin composition used will not increase, and a colorless cured product can be obtained.

[0360] Cured products with a haze typically below 2, preferably below 1, and more preferably below 0.1 can be obtained. Furthermore, when used as a polyorganosiloxane composition, the haze of the monomer cured product of the (meth)acrylic resin composition used is not increased, and a transparent cured product can be obtained. The total light transmittance, YI, and haze can be measured by the method described in the examples below.

[0361] • High glass transition temperature (high Tg)

[0362] It is possible to obtain cured products with a Tg typically above 100°C, preferably above 200°C, and more preferably with a Tg that cannot be determined. Furthermore, when it becomes a polyorganosiloxane composition, the Tg of the monomer cured product of the (meth)acrylic resin composition used can be increased.

[0363] • Low linear expansion coefficient

[0364] Cured products with a coefficient of linear expansion typically below 200 ppm / K, preferably below 140 ppm / K, and more preferably below 70 ppm / K can be obtained. Furthermore, when it becomes a polyorganosiloxane composition, its coefficient of linear expansion is lower than that of the monomer cured product of the (meth)acrylic resin composition used. The coefficient of linear expansion can be determined by the method described in the examples below.

[0365] High thermal shock resistance

[0366] It can produce cured products with high reflow solderability.

[0367] (Used as an optical component)

[0368] The polyorganosiloxane and polyorganosiloxane composition of the present invention have high Abbe number and high refractive index, excellent optical properties, high strength, and high reflow solderability, thus exhibiting excellent compatibility in manufacturing processes and making them preferred for use as optical components.

[0369] As an optical component, it can be used in various optical components such as plastic lenses such as camera lenses, pickup lenses, spectacle lenses, Fresnel lenses and prism lenses, as well as optical protective films, hard coatings, anti-reflective films, optical fibers, optical waveguides, holograms, prism lenses, and optical semiconductor components. It is particularly suitable for plastic lenses such as camera lenses.

[0370] Furthermore, the present invention also includes the following embodiments (the third embodiment).

[0371] The electrolyte for the electrolytic capacitors shown below contains at least a solvent, a solute, and a polyorganosiloxane of a specific general formula (201).

[0372] (Polyorganosiloxane)

[0373] The polyorganosiloxane involved in this embodiment is shown in the following general formula (201).

[0374] (R) 201 R 202 R 203 SiO 1 / 2 ) a (R) 204 R 205 SiO 2 / 2 ) b (R) 206 SiO 3 / 2 ) c (SiO) 4 / 2 ) d (O) 1 / 2 R 207 ) e (O) 1 / 2 H) f ···(201)

[0375] Here, in the above equation (201), R 201 To R 206 Each of the following is independently a hydrocarbon group having 1 to 10 carbon atoms, a group with a reactive functional group, or a hydrogen atom; R 207 It is an organic group with 1 to 8 carbon atoms. Among them, R 201 To R 206 At least one of them is a group or hydrogen atom with a reactive functional group. The reactive functional group can be directly bonded to silicon or bonded by a linking group other than a siloxane bond. a + b + c + d = 1, a ≥ 0.1, b ≤ 0.5, c + d ≥ 0.1, e + f ≤ 1.0.

[0376] The significance of equation (201) lies in the fact that, in polyorganosiloxanes, a represents the M unit (R) relative to the total silicon. 201 R 202 R 203 SiO 1 / 2 The content of ) is above 10 mol%, and b shows the D-units (R) relative to the total silicon. 201 R 202 R 203 SiO 2 / 2 The content of ) is less than 50 mol%, and c shows the T unit (R) relative to the total silicon. 206 SiO 3 / 2 The content of ) and the Q unit (SiO) shown by d 4 / 2 The total content of ) is above 10 mol%, and assuming the total silicon constituting the polyorganosiloxane backbone is 1, the sum of the content of organic groups bonded to the polyorganosiloxane backbone via oxygen atoms (e) and the content of hydroxyl groups directly bonded to the polyorganosiloxane backbone (f) (e+f) is below 1.0, R 201 To R 206 Each of the following is independently a hydrocarbon group having 1 to 10 carbon atoms, a group with a reactive functional group, or a hydrogen atom; R 207 It is an organic group with 1 to 8 carbon atoms.

[0377] A group having a reactive functional group refers to a reactive functional group that is directly bonded to silicon in formula (201), or a group in formula (201) that has a reactive functional group on silicon through a linker.

[0378] Furthermore, as a standard for representing the proportion of silicon-containing units in the main chain of the polysiloxane in this embodiment, a, b, c, d are defined with the value when a + b + c + d = 1.

[0379] In this embodiment, in formula (201), a, which represents the proportion of M units, is 0.1 or more, preferably 0.2 or more. Furthermore, a is less than 1, preferably 0.8 or less, and more preferably 0.7 or less. By keeping a within the above range, it becomes easier to control the molecular weight of the polyorganosiloxane shown in formula (201). More specifically, it is easier to make the molecular weight within an appropriate range without being too small, while simultaneously achieving a structure with a moderately cross-linked structure, branched structure, or cyclic structure. This can improve the strength or uniformity of the protective layer of the electrode, and is therefore preferred.

[0380] Furthermore, in the polyorganosiloxane represented by formula (201) used in this embodiment, b, which represents the proportion of D units in formula (201), is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, and may also be 0. With b within the above range in formula (201), the polyorganosiloxane becomes a structure with a moderately cross-linked structure, branched structure, or cyclic structure, which can improve the strength or uniformity of the protective layer of the electrode, and is therefore preferred.

[0381] Furthermore, in the polyorganosiloxane represented by formula (201) used in this embodiment, regarding c, which represents the proportion of T units, and d, which represents the proportion of Q units, c+d is 0.1 or more, preferably 0.15 or more, and more preferably 0.2 or more. Furthermore, c+d is preferably 0.9 or less, and more preferably 0.8 or less. In formula (201), by ensuring that c+d is within the above-mentioned range, the polyorganosiloxane represented by formula (201) becomes a structure with a moderately cross-linked structure, branched structure, or cyclic structure, which can improve the strength or uniformity of the protective layer of the electrode, and is therefore preferred.

[0382] Furthermore, the upper limit of the total e+f of the organic groups and hydroxyl groups bonded by oxygen atoms on the parent polyorganosiloxane modified with reactive functional groups is 1.0, preferably 0.5 or less, more preferably 0.2 or less. This value within the aforementioned range is preferred based on improving the storage stability of the parent polyorganosiloxane. Moreover, when e+f is 0.001 or higher, reactions or interactions occur with reactive functional groups or the electrode surface, which can be considered to increase the strength of the electrode protective layer or the adhesion to the electrode, and is therefore preferred.

[0383] Furthermore, in equation (201), R 201 To R 206 Each of these can be independently a hydrocarbon group having 1 to 10 carbon atoms, a group with a reactive functional group, or a hydrogen atom. Among them, R... 201 To R 206 At least one of them is a group or hydrogen atom with a reactive functional group. The reactive functional group can be directly bonded to silicon or bonded by a linking group other than a siloxane bond.

[0384] For hydrocarbon groups with 1 to 10 carbon atoms, there are no particular limitations as long as the number of carbon atoms is within this range. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. In addition, there are groups with branched structures such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, 2,3-dimethyl-2-butyl, and 2-ethylhexyl, as well as groups with cyclic structures such as cyclohexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenethyl, 1-phenylethyl, and naphthyl.

[0385] The type of reactive functional group is not particularly limited, and it may contain branched or cyclic structures. However, from the viewpoint of solubility or stability, reaction or interaction with the electrode surface, strength as an electrode protective layer, or adhesion to the electrode, it is preferable to contain at least one group selected from the group consisting of alkenyl, methacryl, acryloyl, acyl, cyclic ether, hydroxyl, acetoxy, monohydroxysilyl, dihydroxysilyl, trihydroxysilyl, monoalkoxysilyl, dialkoxysilyl, and trialkoxysilyl, as well as hydrogen atoms that form silanes with silicon. Only one of these groups may be used, or multiple groups may be used in combination.

[0386] More preferably, it is at least one group selected from the group consisting of cyclic ether groups, hydroxyl groups, monohydroxysilyl groups, dihydroxysilyl groups, trihydroxysilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups. As a cyclic ether group, a group having an epoxy group is particularly preferred. As an epoxy group, glycidoxy groups, alicyclic epoxy groups, epoxy groups converted from alkenyl groups by oxidation, etc., can be suitably used, and epoxy groups derived from alkenyl ring conversion are particularly preferred.

[0387] These reactive functional groups are believed to improve the solubility or dispersion stability of polyorganosiloxanes in the solvents used, or to interact or react with solutes in electrolytes or capacitors, to interact or condense with each other, or to react or interact with electrode surfaces, thereby showing an effect of improving voltage withstand. By adding polyorganosiloxanes with these reactive functional groups, the problem of gelation caused by reaction with solvents or solutes when adding organically modified silica particles can be avoided, thus improving voltage withstand.

[0388] These reactive functional groups can be directly bonded to silicon in formula (201), or they can be bonded to linking groups other than siloxane bonds. There are no particular limitations as long as the linking group does not contain siloxane bonds; generally, divalent organic groups are preferred. These groups can contain branched, cyclic, or both, and can also contain heteroatoms such as oxygen, nitrogen, sulfur, and phosphorus atoms. Specifically, suitable examples include straight-chain or branched alkylene groups with 1 to 10 carbon atoms, cyclic hydrocarbon groups such as cyclohexene and phenylene, and oligoethylene glycol groups such as glycol groups, diethylene glycol groups, and triethylene glycol groups. When the linking group contains oxygen atoms, the atoms in the linking chain that are directly bonded to silicon in the polyorganosiloxane are atoms other than oxygen atoms.

[0389] These reactive functional groups are preferably 3 to 12 per 1000 molecular weight in formula (201). The lower limit is 3 or more, more preferably 4 or more, and the upper limit is preferably 12 or less, more preferably 9 or less. By ensuring that the reactive functional groups are within the above range, the ratio of the polysiloxane portion to the reactive functional group portion in the entire structure of the polyorganosiloxane shown in formula (201) is appropriate, thus balancing solubility in solvents with the strength or uniformity of the electrode protective layer, and is therefore preferred. Furthermore, various M-units, D-units, and T-units can be used, for example, as (R... 201 R 202 R 203 SiO 1 / 2 The M unit shown can simultaneously use R. 201 R 202 R 203 All units are methyl groups, and R 201 R 202 R is methyl 203 Units with reactive functional groups.

[0390] R 207 There are no particular limitations on the number of organic groups with 1 to 8 carbon atoms, but hydrocarbon groups and acyl groups are preferred. As hydrocarbon groups, in addition to straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl, groups with branched structures such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, 2,3-dimethyl-2-butyl, and 2-ethylhexyl, as well as groups with cyclic structures such as cyclohexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenethyl, and 1-phenylethyl, are particularly preferred. As acyl groups, examples include formyl, acetyl, propionyl, and benzoyl, with acetyl being particularly preferred.

[0391] (Determination of the number of reactive functional groups bonded to silicon per 1000 molecular weight)

[0392] The number of silicon-bonded reactive functional groups per 1000 molecular weight of the polyorganosiloxane represented by formula (201) used in this embodiment is determined as follows.

[0393] Weigh 50 mg of the polyorganosiloxane to be tested, and accurately weigh 15 mg of toluene as an internal standard. Further, dissolve it in 1 g of dichloroform and analyze using a 400 MHz converter. 1 The 1H-NMR (AL-400, manufactured by NEC Corporation) was set to a relaxation delay of 20 seconds for measurement. Based on the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene, and the weighing value, the reactive functional group content per 1g (mmol / g) was calculated, i.e., the number of reactive functional groups per 1000 molecular weight of the polyorganosiloxane. At this point, it is necessary to remove organic matter, water, metals, and other impurities not bonded to the polyorganosiloxane to less than 0.1% by mass to avoid affecting the measurement results. If the content exceeds 0.1% by mass, it is removed by distillation, filtration, or other purification methods before preparing the sample for measurement. 1 H-NMR. When difficult to remove, by 1 The impurity content is calculated by ¹H-NMR determination or other analytical methods, but it is not included as part of the polyorganosiloxane calculation. Instead, the weight of the sample minus the impurity is used as the actual sample weight for calculation. Furthermore, as an internal standard, any substance other than toluene, such as N,N-dimethylformamide or tribromoethane, that does not react with the polyorganosiloxane of this invention can be used.

[0394] Furthermore, the polyorganosiloxane of formula (201) used in this embodiment may contain hydroxyl silanes remaining without condensation within the range of formula (201) or organic groups bonded to the polyorganosiloxane via oxygen atoms. The hydroxyl silanes remaining in the polyorganosiloxane or the organic groups bonded to the polyorganosiloxane via oxygen atoms contribute to condensation reactions or interactions with reactive functional groups and electrodes, and may also improve voltage withstand. In addition, these hydroxyl groups directly bonded to the parent polyorganosiloxane and organic groups bonded via oxygen atoms may also be introduced individually as reactive functional groups via linking groups other than siloxane bonds.

[0395] The molecular weight of the polyorganosiloxane represented by formula (201) used in this embodiment is not particularly limited. The number-average molecular weight Mn is generally 600 or more, preferably 800 or more, more preferably 900 or more, and even more preferably 950 or more. In addition, it is generally 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. The weight-average molecular weight Mw is generally 800 or more, preferably 900 or more, more preferably 1,000 or more. In addition, it is generally 100,000 or less, preferably 80,000 or less, and even more preferably 50,000 or less. By making the number-average molecular weight or weight-average molecular weight above the above-mentioned lower limit, the stability of the protective layer on the electrode surface is improved. On the other hand, by making the number-average molecular weight or weight-average molecular weight below the upper limit, the solubility in the solvent or the compatibility with the solute is improved, and the stability of the electrolyte is improved.

[0396] Number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) under the following conditions and expressed as conversion values ​​for standard polystyrene. The sample was prepared using approximately 10% by mass THF solution and filtered through a 0.45 μm filter before determination (Apparatus: TOSOH HLC-8220 GPC column: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko Corporation), column temperature 40°C, eluent: tetrahydrofuran, flow rate 0.2 mL / min).

[0397] (Method for manufacturing polyorganosiloxanes)

[0398] The manufacturing method of the polyorganosiloxane represented by formula (201) used in this embodiment is not particularly limited as long as a polyorganosiloxane having the above structure can be obtained. For example, it can be any manufacturing method such as condensing a disiloxane compound or disilazane compound and their hydrolysis products, an alkoxysilane compound and its hydrolysis products, a partially hydrolyzed condensate, a chlorosilane compound or its hydrolysis products, a partially hydrolyzed condensate, a ring-opening polymerization of a cyclic siloxane compound, a chain polymerization starting with anionic polymerization, etc., and multiple manufacturing methods can also be combined. In addition, polyorganosiloxanes with the desired number of reactive functional groups or molecular weight can be fractionated and used by column chromatography or GPC, solvent extraction, distillation to remove unwanted components, etc.

[0399] The method for introducing reactive functional groups into the polyorganosiloxane of formula (201) used in this embodiment is not particularly limited. For example, a disiloxane compound having reactive functional groups, a disilazane compound having reactive functional groups, an alkoxysilane compound having M, D, or T units having reactive functional groups, a chlorosilane compound having M, D, or T units having reactive functional groups, or a cyclic siloxane compound having reactive functional groups can be used as a starting material to introduce reactive functional groups. In addition, the introduced reactive functional groups can be converted into other reactive functional groups by chemical methods. For example, it can be converted to other reactive functional groups for use by the following methods: by reacting a polyorganosiloxane having an alkenyl group with a monofunctional thiol having a reactive functional group to convert it to another type of reactive functional group; by oxidizing the alkenyl group with an oxidizing agent to convert it to an epoxy group; by reacting a polyorganosiloxane having a hydrogen atom directly bonded to a silicon atom with a vinyl compound having a reactive functional group to convert it to another type of reactive functional group; by ring-opening a cyclic ether group introduced into a polyorganosiloxane to convert it to an alcoholic hydroxyl group; by hydrolyzing an alkoxy group present in a polyorganosiloxane to convert it to a hydroxysilyl group, etc.

[0400] Methods for converting alkenyl groups to epoxy groups include reacting the alkenyl group with an oxidizing agent, and converting the alkenyl group to a haloalcohol followed by ring-opening with a base to form an epoxy group. Oxidizing agents used in epoxidation include organic peracids such as m-chloroperoxybenzoic acid and peracetic acid, combinations of hydrogen peroxide with metal catalysts, combinations of hydrogen peroxide with compounds containing nitrile groups, and diethylene oxide compounds such as dimethyldiethylene oxide.

[0401] (solvent)

[0402] The electrolyte in this embodiment contains a solvent, which can be any solvent commonly used in electrolytic capacitors. Specific examples include alcohol solvents such as ethylene glycol, glycerol, and methyl cellosolve; lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone; amide solvents such as N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; carbonate solvents such as ethylene carbonate, propylene carbonate, and butyl carbonate; nitrile solvents such as 3-methoxypropionitrile and glutaronitrile; and phosphate solvents such as trimethyl phosphate and triethyl phosphate. Sulfonate solvents such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, ethyl isopropyl sulfone, ethyl butyl sulfone, sulfolane, 3-methyl sulfolane, and 2,4-dimethyl sulfolane; sulfoxide solvents such as dimethyl sulfoxide, methyl ethyl sulfoxide, and diethyl sulfoxide; urea solvents such as 1,3-dimethyl-2-imidazolinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; and carbamate solvents such as 3-methyl-2-oxazolidinone, or mixtures thereof. Among these, ethylene glycol and γ-butyrolactone are preferred organic solvents that have high solubility for various solutes and can produce electrolytes with excellent temperature characteristics.

[0403] (Solute)

[0404] The electrolyte in this embodiment contains a solute, which can be any solute used in conventional electrolytic capacitors. Specific examples of solutes that can be used in this invention include onium salts of organic acids and / or inorganic acids.

[0405] Specific examples of organic acids include aromatic monocarboxylic acids such as benzoic acid, tolueneic acid, cuminic acid, tert-butylbenzoic acid, salicylic acid, and benzoic acid; aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, 7-phenyl-7-methoxy-1-octanecarboxylic acid, and 6-phenyl-6-methoxy-1-heptanecarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, 4-methylphthalic acid, and 4-nitrophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, citralic acid, dimethylmaleic acid, and 1,2-cyclohexene dicarboxylic acid; and oxalic acid, malonic acid, succinic acid, and pentahydrate. Dicarboxylic acids, including adipic acid, pimelic acid, octanoic acid, azelaic acid, sebaceous acid, undecanoic acid, dodecanoic acid, tridecanoic acid, and other straight-chain saturated aliphatic dicarboxylic acids; dimethylmalonic acid, diethylmalonic acid, dipropylmalonic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-methyl adipic acid, 2,2,4-trimethyl adipic acid, 2,4,4-trimethyl adipic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, 7-methyl-7-methylester-1,9-decanedicarboxylic acid. Carboxylic acids, 2,8-nonanedicarboxylic acid, 7,8,11,12-tetramethyl-1,18-octadecanedicarboxylic acid, 1-methyl-3-ethyl-1,7-heptanedicarboxylic acid, 1,3-dimethyl-1,7-heptanedicarboxylic acid, 5-methyl-1,7-octanedicarboxylic acid, 7,12-dimethyl-1,18-octadecanedicarboxylic acid, 7-ethyl-1,16-hexadecanedicarboxylic acid, 7,8-dimethyl-1,14-tetradecanedicarboxylic acid, 1,6-heptanedicarboxylic acid, 6-methyl-6-methylester-1,8-nonanedicarboxylic acid, 1,8- Branched saturated aliphatic dicarboxylic acids such as nonanedicarboxylic acid, 8-methyl-8-methyl ester-1,10-undecanedicarboxylic acid, 6-ethyl-1,4-tetradecanedicarboxylic acid, and cyclohexanedicarboxylic acid; tricarboxylic acids such as 7-methyl-1,7,9-decanetricarboxylic acid, 6-methyl-1,6,8-nonanetricarboxylic acid, and 8-methyl-1,8,10-undecanetricarboxylic acid; acidic phosphate esters such as dibutyl phosphate and di(2-ethylhexyl) phosphate; acidic phosphonates such as 2-ethylhexylphosphonate, or mixtures thereof. In addition, specific examples of inorganic acid components include boric acid and phosphoric acid.

[0406] Among the aforementioned organic and inorganic acid components, for low-voltage capacitors with a rated voltage of 100V or less, phthalic acid, maleic acid, benzoic acid, and adipic acid are preferred as they provide electrolytes with high conductivity. For high-voltage capacitors with a rated voltage of 300V or more, azelaic acid, sebaceous acid, 1,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, and boric acid are preferred as they provide electrolytes with high voltage resistance. For medium-voltage capacitors with a rated voltage exceeding 100V but less than 300V, benzoic acid, adipic acid, and azelaic acid are preferred as they provide electrolytes with appropriate conductivity and voltage resistance.

[0407] Specific examples of onium salts include ammonium; monoalkylammoniums such as methylammonium and ethylammonium; dialkylammoniums such as dimethylammonium, diethylammonium, and ethylmethylammonium; tertiary ammoniums such as trimethylammonium, ethyldimethylammonium, diethylmethylammonium, and triethylammonium; tetramethylammonium, triethylmethylammonium, tetraethylammonium, N,N-dimethylpyrrolidineonium, N-ethyl-N-methylpyrrolidineonium, N,N-diethylpyrrolidineonium, N,N-tetramethylenepyrrolidineonium, N,N-dimethylpiperidineonium, N-ethyl-N-methylpiperidineonium, N,N-diethylpiperidineonium, N,N-tetramethylenepiperidineonium, and N,N-pentanediamine. Quaternary ammonium compounds such as methylpiperidinium and N,N-spirodipyrrolidinium; 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,3-diethyl-2-methylimidazolium, 1,2-dimethyl-3-n-propylimidazolium, 1-n-butyl-3-methylimidazolium, 1-methyl-3-n-propyl-2,4-dimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,2,3,4,5- Quaternary ammonium imidazoline compounds such as pentamethylimidazoline and 2-ethyl-1,3-dimethylimidazoline; 1,3-dimethylimidazoline, 1,2,3-trimethylimidazoline, 1-ethyl-3-methylimidazoline, 1-ethyl-2,3-dimethylimidazoline, 1,3-diethylimidazoline, 1,2-diethyl-3-methylimidazoline, 1,3-diethyl-2-methylimidazoline, 1,2-dimethyl-3-n-propylimidazoline, 1-n-butyl-3-methylimidazoline, 1-methyl-3-n-propyl-2,4-dimethylimidazoline, 1,2,3 ... Quaternary ammonium imidazoline compounds such as 4-tetramethylimidazoline and 2-ethyl-1,3-dimethylimidazoline; tetrahydropyrimidine compounds such as 1,3-dimethyltetrahydropyrimidine, 1,3-diethyltetrahydropyrimidine, 1-ethyl-3-methyltetrahydropyrimidine, 1,2,3-trimethyltetrahydropyrimidine, 1,2,3-triethyltetrahydropyrimidine, 1-ethyl-2,3-dimethyltetrahydropyrimidine, 2-ethyl-1,3-dimethyltetrahydropyrimidine, 1,2-diethyl-3-methyltetrahydropyrimidine, and 1,3-diethyl-2-methyltetrahydropyrimidine, or mixtures thereof.

[0408] For capacitors used in medium and high voltage applications, ammonia is preferred as a solvent for obtaining an electrolyte with high voltage resistance, when combined with dicarboxylic acids such as ethylene glycol solvent and 1,6-decanedicarboxylic acid.

[0409] For low-voltage capacitors, 1,2,3,4-tetramethylimidazoline, 1-ethyl-2,3-dimethylimidazoline, tetramethylammonium, triethylmethylammonium, and tetraethylammonium are preferred among the combinations of γ-butyrolactone solvent and phthalic acid, which can produce electrolytes with high conductivity.

[0410] The amount of solute used is preferably in the range of 5 to 30% by mass relative to the total weight of solvent and solute.

[0411] Furthermore, the polyorganosiloxane represented by formula (201) used in this embodiment preferably contains about 0.5% to 18% by mass relative to the total electrolyte, more preferably 1% or more by mass, more preferably 5% or more by mass, and more preferably 15% or less by mass, more preferably 10% or less by mass.

[0412] Furthermore, in this embodiment, water may be included in the electrolyte for purposes such as improving chemical convertibility. The water content is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.01 to 10% by mass. In addition, other additives may be included in the electrolyte as needed. Other additives include boron compounds such as boric acid and boron-polyol complexes (ethylene glycol, mannitol, sorbitol, etc.); phosphoric acid, acidic phosphate esters (dibutyl phosphate, di(2-ethylhexyl) phosphate), acidic phosphonates (2-ethylhexylphosphonate, etc.); and nitro compounds such as p-nitrobenzoic acid and m-nitroacetophenone.

[0413] The electrolyte in this embodiment can be, for example... Figure 1 , Figure 2 The image shows a wound aluminum electrolytic capacitor, with the electrolyte impregnated in the diaphragm (also called a separator) indicated by 3. This diaphragm is typically made of kraft paper, Manila paper, etc.

[0414] Example

[0415] The present invention will be specifically described below through examples, but the present invention is not limited thereto. Furthermore, the materials used and the methods for measuring the evaluation items in the examples are described below. Unless otherwise specified, parts and percentages in the examples are mass standards.

[0416] [Evaluation I: Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-6]

[0417] [Measurement Method]

[0418] 1. Determination of the number of reactive functional groups in polyorganosiloxanes

[0419] Weigh 50 mg of the polyorganosiloxane to be tested, and accurately weigh 15 mg of toluene as an internal standard. Further, dissolve it in 1 g of dichloroform and analyze using a 400 MHz converter. 1The 1H-NMR (AL-400, manufactured by NEC Corporation) was set to a relaxation delay of 20 seconds for measurement. Based on the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene, and the weighing value, the alkoxy content and the reactive functional group content per 1g (mmol / g) were calculated, i.e., the number of reactive functional groups per 1000 molecular weight of the polyorganosiloxane. At this point, it is necessary to remove organic matter, water, metals, and other impurities not bonded to the polyorganosiloxane to less than 0.1% by weight to avoid affecting the measurement results. If the impurities exceed 0.1% by weight, they should be removed by distillation, filtration, or other purification methods before preparing the sample for measurement. 1 H-NMR. When difficult to remove, by 1 The impurity content calculated by ¹H-NMR determination or other analytical methods is not included as part of the polyorganosiloxane calculation. Instead, the actual sample weight is calculated by subtracting the impurity from the weighed sample weight. Furthermore, as an internal standard, any substance other than toluene, such as N,N-dimethylformamide or tribromoethane, that does not react with polyorganosiloxane can be used.

[0420] 2. 29 Si-NMR determination method

[0421] Device: JNM-ECS400 (manufactured by Nippon Electronics Co., Ltd.), TUNABLE (10), Si-free, AT10 probe

[0422] Measurement conditions: relaxation delay / 15 seconds, scan count / 1024, measurement mode / non-gated decoupled pulse method (NNE), rotation / none, measurement temperature / 25℃

[0423] • Sample preparation: Add 0.5 wt% tris(2,4-pentanedionato)chromium III to dichloroform to obtain 29 Solvent for Si-NMR determination. Weigh 1.5 g of the polyorganosiloxane to be measured and add it to 2.5 ml of the above-mentioned solvent. 29 The sample is dissolved in a solvent for Si-NMR determination and then placed into a 10 mm Φ Teflon (registered trademark) NMR sample tube.

[0424] 3. Determination of molecular weight

[0425] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of each polyorganosiloxane were determined by gel permeation chromatography (GPC) under the following conditions and expressed as conversion values ​​to standard polystyrene. The sample was prepared using approximately 10% by weight of THF solution and filtered through a 0.45 μm filter before measurement.

[0426] Device: TOSOH HLC-8220 GPC

[0427] Chromatographic columns: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko Co., Ltd.), column temperature 40℃

[0428] Eluent: Tetrahydrofuran, flow rate 0.3 mL / min

[0429] 4. Infrared absorption measurement (IR measurement)

[0430] Fourier Transform Infrared Spectroscopy

[0431] • Apparatus: Nic-Plan, Thermo Fisher Scientific

[0432] • Resolution: 4cm -1

[0433] • Number of scans: 64

[0434] The maximum absorption wavenumber was determined using the ATR (Attenuated Total Reflection) method.

[0435] 5. Measurement of weight loss during reduced pressure heating

[0436] Measurement 1 ¹H-NMR was used to calculate the weight of components other than the polysiloxane, such as the organic solvent. A rotor was placed in a flask and its weight was measured. Subsequently, the polysiloxane was added to the flask, and its weight was measured. The flask was heated in an oil bath, and the rotor was rotated using a magnetic stirrer until the liquid surface was fluid. The temperature was raised to 110°C, and the pressure was reduced using an oil-filled vacuum pump. A vacuum pump with a pressure reduction capability of 0.15 Torr was used. After 2 hours, the mixture was cooled to room temperature and restored to atmospheric pressure. The oil adhering to the flask was thoroughly wiped off, and the weight of the polysiloxane in the flask was measured. This weight was subtracted from the previously measured weights of the flask and rotor, and the weight of the evaporated components was calculated. The polysiloxane after this operation was measured. 1 H-NMR was used to calculate the weight of components other than the polyorganosiloxane, such as organic solvents. The weight reduction of the polyorganosiloxane was calculated by subtracting the amount of components other than the polyorganosiloxane from the weight of the volatile components.

[0437] Method for confirming properties at 6.40℃

[0438] Add 100g of each polysiloxane and a rotor with a diameter of 8mm and a length of 30mm to a 500ml eggplant-shaped flask. While stirring with a magnetic stirrer, heat the flask in an oil bath until the internal temperature reaches 40°C. Then, when a glass rod touches the polysiloxane, the liquid state is defined as oil adhering to the glass rod, and after tilting the eggplant-shaped flask at 90° for 30 minutes, more than 90% of the liquid flows from the bottom to the side of the flask.

[0439] 7. Viscosity Measurement

[0440] The value was measured at 25°C using a Brookfield viscometer (Type E viscometer).

[0441] 8. Flash Point Determination Method

[0442] For flash point determination, the value measured using the Pensky-Martens closed-cup method based on JIS K 2265-3:2007 or ISO 2719:2002 for flash points below 80°C, and the Cleveland open-cup method based on JIS K 2265-4:2007 or ISO 2592:2000 for flash points above 80°C, is taken as the flash point. Additionally, for VQ2012 manufactured by SILTECH COR., the SILTECH COR. catalog value of 49°C is taken as the flash point.

[0443] 9. Method for determining the coefficient of linear expansion

[0444] The coefficient of linear expansion of the cured material was measured using a thickness of 1 mm, through the following apparatus, mode, and temperature program. The average coefficient of linear expansion during the second heating from 50°C to 100°C was taken as the measured value.

[0445] Device: TMA / SS6100 manufactured by Seiko Nanotech Co., Ltd.

[0446] Mode: Compression mode

[0447] Temperature program: 1. Increase the temperature from 30°C to 120°C at a rate of 5°C / minute.

[0448] 2.120℃ for 5 minutes

[0449] 3. Cool from 120℃ to 30℃ at a rate of 50℃ / minute.

[0450] 4. Keep at 30℃ for 5 minutes

[0451] 5. Increase the temperature from 30℃ to 120℃ at a rate of 5℃ / minute.

[0452] 6. Hold at 120℃ for 5 minutes

[0453] 10. Three-point bending modulus determination method

[0454] Equipment: AG-Xplus Benchtop Precision Universal Testing Machine, manufactured by Shimadzu Corporation.

[0455] Weighing sensor: 5kN

[0456] Measuring fixture: Plastic three-point bending test fixture

[0457] Test piece: 2mm thick, 14.25mm wide, 30mm long

[0458] Distance between lower support points: 17.6mm

[0459] Loading speed: 0.5 mm / minute

[0460] 11. Shore D hardness

[0461] The measurements were performed using an Asker rubber hardness tester (Type D) based on JIS K 6253.

[0462] [Sample Preparation]

[0463] [The silicone resin used]

[0464] The reagents, chemicals, and solvents used in the synthesis are described below.

[0465] Hexamethyldisiloxane (manufactured by NuSil Technology, product name: S-7205)

[0466] 1,3-Divinyltetramethyldisiloxane (manufactured by NuSil Technology, product name: PLY-70)

[0467] Tetraethoxysilane (manufactured by KISHIDA Chemical Co., Ltd.)

[0468] Ethyl silicate ES-40 (manufactured by Nippon Colcote Co., Ltd.)

[0469] Methyl silicate MS-51 (manufactured by Mitsubishi Chemical Corporation)

[0470] (3-Methacryloxypropyl)trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503)

[0471] Tetrahydrofuran (manufactured by KISHIDA Chemical Co., Ltd.)

[0472] Toluene (manufactured by KISHIDA Chemical Co., Ltd.)

[0473] Ethanol (manufactured by KISHIDA Chemical Co., Ltd.)

[0474] Methanol (manufactured by KISHIDA Chemical Co., Ltd.)

[0475] 1N hydrochloric acid (manufactured by KISHIDA Chemical Co., Ltd.)

[0476] Heptane (manufactured by KISHIDA Chemical Co., Ltd.)

[0477] (1) Polyorganosiloxane 1

[0478] 18.3 parts by weight of hexamethyldisiloxane, 64.3 parts by weight of 1,3-divinyltetramethyldisiloxane, and 105 parts by weight of tetraethoxysilane were dissolved in 187 parts by weight of tetrahydrofuran. A mixture of 24.7 parts by weight of 1N hydrochloric acid and 24.7 parts by weight of ethanol was then added, and the mixture was stirred at 40°C for 4 hours. After dilution with 374 parts by weight of heptane, the mixture was washed with deionized water. The solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no further distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain 185.7 parts by weight of the target polyorganosiloxane.

[0479] (2) Polyorganosiloxane 2

[0480] 18.3 parts by weight of hexamethyldisiloxane, 64.3 parts by weight of 1,3-divinyltetramethyldisiloxane, and 74.7 parts by weight of ethyl silicate ES-40 were dissolved in 157 parts by weight of tetrahydrofuran. A mixture of 17.9 parts by weight of 1N hydrochloric acid and 17.9 parts by weight of ethanol was then added, and the mixture was stirred at 40°C for 4 hours. After dilution with 315 parts by weight of heptane, 87.2 parts by weight of the target polyorganosiloxane 2 were obtained by performing the same treatment as in the synthesis of polyorganosiloxane 1.

[0481] (3) Polyorganosiloxane 3

[0482] 277 parts by weight of 1,3-divinyltetramethyldisiloxane and 132 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 205 parts by weight of toluene and 205 parts by weight of methanol. Then, a mixture of 46.0 parts by weight of 1N hydrochloric acid and 37.6 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 409 parts by weight of heptane, the target polyorganosiloxane 3 was obtained by performing the same treatment as in the synthesis of the aforementioned polyorganosiloxane 1.

[0483] (4) Polyorganosiloxane 4

[0484] 2.6 parts by weight of hexamethyldisiloxane, 9.16 parts by weight of 1,3-divinyltetramethyldisiloxane, and 8.24 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 10.0 parts by weight of toluene and 10.0 parts by weight of methanol. Then, a mixture of 5.10 parts by weight of 1N hydrochloric acid and 2.55 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 17.5 parts by weight of heptane, the target polyorganosiloxane 4 was obtained by performing the same treatment as in the synthesis of the aforementioned polyorganosiloxane 1.

[0485] (5) Polyorganosiloxane 5

[0486] 33.8 parts by weight of hexamethyldisiloxane, 295 parts by weight of (3-methacryloyloxypropyl)trimethoxysilane, and 11.4 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 170 parts by weight of toluene and 170 parts by weight of methanol. Then, a mixture of 79.2 parts by weight of 1N hydrochloric acid and 79.2 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 466 parts by weight of toluene, the target polyorganosiloxane 5,216 parts by weight was obtained by performing the same treatment as in the synthesis of the aforementioned polyorganosiloxane 1.

[0487] (6) Polyorganosiloxane 6

[0488] Except for the absence of the depressurization treatment at 110°C and 0.15 torr, the same synthesis as polyorganosiloxane 1 was performed to obtain 100 parts by weight of the target polyorganosiloxane 6.

[0489] (7) Polyorganosiloxane 7

[0490] Silmer VQ2012, manufactured by SILTECH COR., is used directly as polyorganosiloxane 7. It is sold as a liquid vinyl substitute for MQ resin and is considered the closest commercially available product to the present invention.

[0491] (8) Polyorganosiloxane 8

[0492] 207 parts by weight of hexamethyldisiloxane, 87.5 parts by weight of 1,3-divinyltetramethyldisiloxane, and 186 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 180 parts by weight of toluene and 180 parts by weight of methanol. Then, a mixture of 37.7 parts by weight of 1N hydrochloric acid and 37.7 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 151 parts by weight of heptane, the target polyorganosiloxane 8 was obtained by performing the same treatment as in the synthesis of the aforementioned polyorganosiloxane 1.

[0493] (9) Polyorganosiloxane 9

[0494] 210 parts by weight of hexamethyldisiloxane, 17.9 parts by weight of 1,3-divinyltetramethyldisiloxane, and 172 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 200 parts by weight of toluene and 200 parts by weight of methanol. Then, a mixture of 107 parts by weight of 1N hydrochloric acid and 53.7 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 350 parts by weight of heptane, the target polyorganosiloxane 9 was obtained by performing the same treatment as in the synthesis of the aforementioned polyorganosiloxane 1.

[0495] (10) Polyorganosiloxane 10

[0496] The product manufactured by HYBRID PLASTICS INC. under the trade name Vinyl POSS Cage Mixture (OL1170) is used directly as polyorganosiloxane 10.

[0497] (11) Polyorganosiloxane 11

[0498] The trade name Methalryl POSS Cage Mixture (MA0735) manufactured by HYBRID PLASTICS INC. is used directly as polyorganosiloxane 11.

[0499] [Method 1 for manufacturing solidified products]

[0500] A mixture of 80 parts by weight of the polyorganosiloxane synthesized by the above method, 20 parts by weight of vinyl silicone (manufactured by NuSil Technology Co., Ltd., trade name: PLY7511), and 0.5 parts by weight of dicumyl peroxide (manufactured by Nippon Oil Co., Ltd., trade name: Park Milk D) was prepared. The resulting mixture was sandwiched between glass plates separated by a 1 mm partition, and the temperature was increased from 40°C to 140°C at a rate of 5°C / min, and maintained at 140°C for 2 hours. After cooling to 40°C, the upper glass plate was removed, and the temperature was further increased from 40°C to 190°C at a rate of 5°C / min, and maintained at 190°C for 2 hours. After cooling to below 40°C, the remaining glass plate was removed, yielding a cured polyorganosiloxane composition.

[0501] [Method 2 for manufacturing solidified products]

[0502] 100 parts by weight of the polyorganosiloxane synthesized by the above method were mixed with 3 parts by weight of 2-hydroxy-2-methylphenylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.). The resulting mixture was sandwiched between glass plates with a 1 mm partition. A high-pressure mercury lamp (cumulative luminous flux 3000 mJ / cm²) was used, employing a FUSION UV SYSTEMS, INC. I6P1 / LH lamp. 2 After being irradiated with light, the glass plate used is removed to obtain a cured polyorganosiloxane.

[0503] [Method 3 for manufacturing solidified products]

[0504] Relative to 100 parts by weight of the vinyl-containing polyorganosiloxane synthesized by the above method and 100 parts by weight of the two-terminated vinyl-modified silicone (manufactured by NuSil Technology, trade name: PLY-7500), a hydrosilyl-modified silicone (manufactured by NuSil Technology, trade name: XL-1) was added in a vinyl to hydrosilyl molar ratio of 1:1. A 2% by weight xylene solution (manufactured by Aldrich) of Karstedt catalyst (3 ppm by weight, based on platinum) was further added, along with 6 ppm of 1-ethynyl-1-cyclohexanol. The resulting mixture is referred to as mixture A. Relative to 15 parts by weight of mixture A, 83 parts by weight of spherical silica (manufactured by Denka Co., Ltd., trade name: FB-5D) and 2 parts by weight of terminal trimethylsilyl-modified fumed silica (manufactured by Aerosil Co., Ltd., Japan, trade name: RX-200) as inorganic fillers were added. After mixing using a centrifugal defoaming mixer, the mixture was filled into a mold with a width of 14.25 mm, a length of 30 mm, and a thickness of 2 mm. Then, it was heated at 200°C and a pressure of 50 kg / cm². 2 Apply pressure for 3 minutes to obtain a cured polyorganosiloxane composition.

[0505] Polyorganosiloxanes were prepared according to Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 in Table 1 using the above method, and cured products were manufactured according to Cured Product Manufacturing Methods 1 to 3.

[0506] The various measured values ​​of the above-mentioned polyorganosiloxanes and cured products are shown in Table 1.

[0507] In the polyorganosiloxane of Comparative Example 1-1, there are a large number of alkoxy groups bonded to silicon, and the weight reduction after heating at 110°C for 2 hours is also significant.

[0508] The polyorganosiloxanes of Comparative Examples 1-2 are the closest commercially available products to the present invention known to the applicant, but they exhibit a large weight reduction after being heated at 110°C for 2 hours.

[0509] In Comparative Examples 1-3 and 1-4, the number of reactive functional groups is insufficient compared to the requirements of the present invention.

[0510] In Comparative Examples 1-5 and 1-6, the maximum absorption wavenumbers of the Si-O vibrations in the infrared absorption spectroscopy analysis are different, indicating that they are cage-like silsesquioxanes with substituents. These are essentially solids.

[0511] Table 1

[0512]

[0513] [Inspection]

[0514] [Coefficient of linear expansion]

[0515] Although the polyorganosiloxanes 1, 2, and 4 used in Examples 1-1, 1-2, and 1-4 have similar contents of various types of silicon and types and amounts of reactive functional groups compared to polyorganosiloxane 6 used in Comparative Example 1-1, Examples 1-1, 1-2, and 1-4, the weight loss during heating and depressurization in Examples 1-1, 1-2, and 1-4 is extremely small. Under such circumstances, the coefficient of linear expansion of the cured product is smaller. Therefore, it can be seen that less weight loss during heating and depressurization has the advantage of being able to produce cured products with good dimensional stability over a wide temperature range.

[0516] [Flash point]

[0517] Although the polyorganosiloxane 4 used in Examples 1-4 has similar content of various types of silicon and types and amounts of reactive functional groups compared to the polyorganosiloxane 7 used in Comparative Examples 1-2, it exhibits less weight loss upon heating and depressurization. Under these circumstances, the flash point is significantly increased. According to the Fire Safety Law's classification of hazardous materials, polyorganosiloxane 6 is classified as Class IV, Petroleum Sub-Class II (non-water soluble), while polyorganosiloxane 4 is classified as Class IV, Petroleum Sub-Class III (non-water soluble). Therefore, a smaller weight loss upon heating and depressurization allows for safer handling, placing it in a lower-risk category even within the Fire Safety Law's hazardous materials classification. This results in lower storage and transportation costs.

[0518] [Viscosity]

[0519] The wavenumbers of polyorganosiloxane 10 and polyorganosiloxane 11 used in Comparative Examples 1-5 and 1-6 in infrared absorption spectroscopy analysis were 1030–1150 cm⁻¹. -1 In this region, the wave number is 1075–1150 cm⁻¹, which is unique to cage-like structures. -1 The region exhibits the maximum absorption wavenumber of Si-O stretching vibration. On the other hand, the polyorganosiloxanes used in other embodiments and comparative examples showed wavenumbers of 1030–1070 cm⁻¹ in infrared absorption spectroscopy analysis. -1 The region exhibits the maximum absorption wavenumber of Si-O stretching vibrations and does not possess a cage-like structure. Viscosity measurements of these samples show wavenumbers ranging from 1030 to 1070 cm⁻¹. -1 Polyorganosiloxanes exhibiting the maximum absorption wavenumber of Si-O stretching vibration within the specified region, i.e., polyorganosiloxanes without a cage-like structure, have lower viscosity. On the other hand, wavenumbers of 1075–1150 cm⁻¹... -1Polyorganosiloxanes with the maximum absorption wavenumber of Si-O stretching vibration in the region, i.e., polyorganosiloxanes with a cage-like structure, have high viscosity or are solids. Therefore, the polyorganosiloxanes of the present invention, being low-viscosity liquids, have excellent processability, significantly reducing the time required for weighing, mixing, and molding. Furthermore, they also offer advantages such as reduced cleaning time and less detergent required.

[0520] [Three-point flexural modulus and Shore D hardness]

[0521] In Examples 1-3 and 1-4, the polyorganosiloxanes 3 and 4 contain 3 to 12 vinyl groups as reactive functional groups per 1000 molecular weight of polyorganosiloxane. On the other hand, the polyorganosiloxanes 8 and 9 used in Comparative Examples 1-3 and 1-4, while having the same type of reactive functional groups as polyorganosiloxanes 3 and 4, contain fewer than 3 to 12. Cured products made using these polyorganosiloxanes show that by increasing the number of reactive functional groups per 1000 molecular weight of polyorganosiloxane to 3 to 12, the three-point flexural modulus and Shore D hardness are increased. Therefore, using the polyorganosiloxanes of the present invention to manufacture cured products has the advantage of obtaining materials with high elasticity and high hardness.

[0522] [Evaluation II: Examples 2-1 to 2-22, Comparative Examples 2-1 to 2-11]

[0523] [Measurement Method]

[0524] 1. Determination of the number of reactive functional groups in polyorganosiloxanes

[0525] The number of reactive functional groups in polyorganosiloxanes was determined using the same method as described above.

[0526] 2. 29 Si-NMR determination method

[0527] Perform using the same method as described above. 29 Determination of Si-NMR.

[0528] 3. Determination of molecular weight

[0529] The molecular weight was determined using the same method as described above.

[0530] 4. Determination of refractive index

[0531] 4-1. Refractive index determination of liquid samples before curing: The refractive index at the sodium D line wavelength was determined at 20°C using an automatic refractometer (RX-7000α) manufactured by Atago Co., Ltd.

[0532] 4-2. Determination of the refractive index of the cured material:

[0533] Measurement Method 1. Using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd., at 25°C, 1-bromonaphthalene was used as the intermediate liquid to measure the refractive index and Abbe number.

[0534] Method 2. The refractive index and Abbe number were measured at 23°C using a Carnu precision refractometer KPR2000 manufactured by Shimadzu Corporation, with a mixture of diiodomethane, monobromonaphthalene and liquid paraffin as the intermediate liquid.

[0535] 5. Viscosity Measurement

[0536] Viscosity was measured using the same method described above.

[0537] 6. Gas chromatography determination method

[0538] • Apparatus: GC-14B gas chromatograph manufactured by Shimadzu Corporation

[0539] • Chromatographic column: DB-5, manufactured by Agilent Technologies, Inc.

[0540] • Injection temperature: 290℃

[0541] • Heating method: Increase the temperature from 50℃ to 290℃ at a rate of 10℃ / minute.

[0542] Each polysiloxane and THF were weighed and mixed at a mass ratio of 1:1 before determination. Alternatively, each polysiloxane and a rotor were added to a 1L eggplant-shaped flask, and the mixture was subjected to vacuum distillation using a vacuum pump with a decompression capacity of 10 torr. The mixture was heated to an internal temperature of 110°C and subjected to vacuum distillation for 2 hours. After this distillation, gas chromatography was performed, and the results were compared with the polysiloxane before distillation to confirm the reduced peaks. The confirmation method can be as follows: using the THF peak of the diluted polysiloxane before distillation as a reference peak, confirming the peak intensity of each polysiloxane, normalizing the peaks of the distilled polysiloxane using the reference peak, and further correcting the peak intensity using the weighing values ​​of the distilled polysiloxane and THF, comparing the peak intensities before and after distillation. Peaks with a reduction in intensity of more than 10% are those with a retention time from 0 to 12 minutes.

[0543] 7. Infrared Absorption Spectroscopy (IR Measurement) Method

[0544] The infrared absorption spectrum was measured using the same method as described above.

[0545] 8. Methods for determining haze and yellowness index

[0546] • Device: HM-150 haze meter manufactured by Murakami Color Technology Research Institute Co., Ltd.

[0547] The haze was measured based on JIS K7105.

[0548] Methods for determining the Yellow Index (YI)

[0549] • Apparatus: Konica Minolta Corporation, CM-5 spectrophotometer.

[0550] Yi was evaluated using a permeation assay.

[0551] 9. Pencil hardness

[0552] Pencil hardness was determined using a method based on JIS K5600-5-4.

[0553] 10. Determination of storage modulus and glass transition point

[0554] • Apparatus: RSAII dynamic viscoelasticity measuring apparatus manufactured by TA Instruments.

[0555] • Measurement mode: Tensile mode

[0556] • Measurement frequency: 10Hz

[0557] Measure various solidified materials and calculate the energy storage modulus at 100℃ or 200℃.

[0558] Furthermore, the peak temperature of tanδ is taken as the glass transition point.

[0559] 11. Determination of the coefficient of linear expansion

[0560] The coefficient of linear expansion can be determined using any of the following methods.

[0561] Method 1

[0562] • Apparatus: TA Instruments, Thermomechanical Measurement Apparatus Q400

[0563] • Heating rate: 20℃ / minute

[0564] • Measurement range: 20~200℃

[0565] Calculate the coefficient of linear expansion within the temperature range of 30–150℃.

[0566] Method 2

[0567] • Apparatus: TMA / SS6100 thermomechanical analysis apparatus manufactured by Seiko Nanotechnology Co., Ltd., Japan

[0568] • Heating rate: 5℃ / minute

[0569] • Measurement range: 30~200℃

[0570] Calculate the coefficient of linear expansion in the range of 50 to 100℃.

[0571] 12. Determination of water absorption rate

[0572] • Device

[0573] IR measurement: V780 UV-Vis-NIR spectrophotometer manufactured by Nippon Spectrophotometer Co., Ltd.

[0574] Dryer: Yamatoco Co., Ltd., Rectangular Vacuum Constant Temperature Dryer DP63

[0575] Environmental testing machine: SH-221 small environmental testing machine manufactured by ESPEC Corporation.

[0576] • Dry and moisture-absorbing conditions

[0577] Drying: 50℃ for 24 hours; IR measurement after drying.

[0578] Water absorption: 85℃, 85% IR for 168 hours, IR measurement after moisture absorption.

[0579] The time until the measurement is completed should be within 1 hour.

[0580] • Measurement method

[0581] For a 1 mm thick cured material, the IR was measured after drying and after moisture absorption.

[0582] The water absorption rate is obtained from the difference between the absorption peak area after absorbing moisture and the absorption peak area after drying, which appears in the vicinity of 1850-2000 nm.

[0583] 13. Methods for determining acid value

[0584] The granular (meth)acrylic polymer and slurry composition were dissolved in a mixed solvent of toluene and ethanol, and the amount of potassium hydroxide (mg) neutralized by 1g of (meth)acrylic polymer was determined as the acid value.

[0585] 14. Reflow soldering evaluation

[0586] • Device: SRS-1C reflow simulator manufactured by Malcom Co., Ltd.

[0587] • Reflow soldering conditions: Perform 3 cycles Figure 4The temperature distribution is shown. The peak temperature was maintained at 260°C for 10 seconds.

[0588] • Evaluation: After the experiment, the solidified material was observed under a microscope.

[0589] [Sample Preparation]

[0590] [Synthetic Example 2-1] Synthetic method of polyorganosiloxane

[0591] As raw materials for the polyorganosiloxane, 22g of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, 263g of 3-methacryloyloxypropyltrimethoxysilane KBM503 manufactured by Shin-Etsu Chemical Industry Co., Ltd., and 56g of hexamethyldisiloxane manufactured by Nusil Technology Co., Ltd. were used. 170g of toluene and 170g of methanol were used as solvents, and a mixture of 81g of 1N hydrochloric acid and 81g of methanol was used as a catalyst, along with water. Hydrolysis and condensation were carried out while maintaining a temperature between 15°C and 40°C. Subsequently, after removing the hydrochloric acid with demineralized water, the solvent and water were removed, and filtration yielded 221g of the target liquid polyorganosiloxane.

[0592] Despite using common methods and inexpensive raw materials, a high yield of 65% by mass can be obtained relative to the total amount of the aforementioned polyorganosiloxane raw materials, and variable costs and production costs can be kept low.

[0593] The obtained polyorganosiloxane was analyzed by gas chromatography, confirming the absence of peaks for toluene and methanol, hexamethyldisiloxane, trimethylsilanol, trimethylmethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane. The obtained polyorganosiloxane was then analyzed by... 1 H-NMR and 29 The results, obtained by Si-NMR and GPC analysis, identify the organosiloxane D shown in Table 2. Furthermore, physical properties were determined using an E-type viscometer and a refractometer.

[0594] IR measurements show that the maximum absorption wavenumber from SiO is 1047 cm⁻¹. -1 The '-' indicates that the main structure is not cage-like. It can be seen that the polyorganosiloxanes synthesized by this method are not cage-like structures, or even if cage-like structures exist, they are only present in small quantities to the extent that cage-like characteristic peaks cannot be detected by IR spectroscopy. By appropriately changing the amount of polyorganosiloxane raw materials, the molecular composition ratios and physical properties of the same synthesized polyorganosiloxanes A-C, E-G, I, K, and L are shown in Table 2.

[0595] [Synthetic Example 2-2] Synthetic method of non-cage-type silsesquioxanes

[0596] As a raw material for polyorganosiloxane, 170g of 3-methacryloyloxypropyltrimethoxysilane KBM503 was used, along with 85g of toluene and 85g of methanol as solvents, a mixture of 40g of 1N hydrochloric acid and 40g of methanol as a catalyst, and water. Hydrolysis and condensation were carried out while maintaining a temperature between 15°C and 40°C. Subsequently, after removing the hydrochloric acid with demineralized water, the solvent and water were removed, and filtration yielded 235.6g of liquid polyorganosiloxane. Gas chromatography confirmed that no peaks of toluene, methanol, or 3-methacryloyloxypropyltrimethoxysilane were detected. The obtained polyorganosiloxane was then subjected to… 1 H-NMR and 29 Si-NMR and GPC measurements confirmed that it is polyorganosiloxane J as shown in Table 2. Furthermore, physical properties were determined using an E-type viscometer and a refractive index meter.

[0597] IR measurements show that the maximum absorption wavenumber from SiO is 1045 cm⁻¹. -1 The '0' indicates that the main structure is not cage-like. This means that the polyorganosiloxanes synthesized by this method are not cage-like structures, or even if cage-like structures exist, they are only present in small quantities to the extent that IR measurements cannot detect cage-like characteristic peaks.

[0598] As a cage-type silsesquioxane, polyorganosiloxane H (methacryloyl TA-100 manufactured by Toa Synthetic Co., Ltd.) was used.

[0599] [Synthetic Examples 2-3] Methods for synthesizing polyorganosiloxanes containing two or more T units 1

[0600] As a raw material for polyorganosiloxane, 9g of methyl silicate MS51, 120g of 3-methacryloyloxypropyltrimethoxysilane KBM503, 154g of 8-methacryloyloxyoctyltrimethoxysilane KBM5803, and 27g of hexamethyldisiloxane were used. Toluene and methanol were used as solvents, a mixture of 64g of 1N hydrochloric acid and 64g of methanol was used as a catalyst, and water was added. Hydrolysis and condensation were carried out while maintaining a temperature of 15°C to 40°C. Subsequently, after removing hydrochloric acid with demineralized water, the solvent and water were removed, and 214g of liquid polyorganosiloxane was obtained by filtration. Gas chromatography confirmed that no peaks of toluene, methanol, hexamethyldisiloxane, trimethylsilanol, trimethylmethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 8-methacryloyloxyoctyltrimethoxysilane were detected. The obtained polyorganosiloxane was then subjected to… 1 H-NMR and 29Si-NMR and GPC measurements confirmed that it is the polyorganosiloxane N shown in Table 2. Furthermore, measurements were performed using an E-type viscometer and a refractometer. By appropriately varying the amount of polyorganosiloxane raw materials, the molecular composition ratios and properties of the synthesized polyorganosiloxanes M and O are shown in Table 2.

[0601] [Synthetic Examples 2-4] Methods for synthesizing organopolysiloxanes containing two or more T units 2

[0602] Using decyltrimethoxysilane KBM3103C manufactured by Shin-Etsu Chemical Industry Co., Ltd. instead of 8-methacryloyloxyoctyltrimethoxysilane KBM5803 described in Synthesis Examples 2-3, and with appropriate changes in the amount of polyorganosiloxane raw materials, the molecular composition ratios and physical properties of each synthesized organopolysiloxane P-S are shown in Table 2.

[0603] In addition, decyltrimethoxysilane KBM3103C manufactured by Shin-Etsu Chemical Industry Co., Ltd. was used instead of 3-methacryloyloxypropyltrimethoxysilane KBM503 described in Synthesis Examples 2-3. The amounts of organopolysiloxane raw materials were appropriately changed, and the molecular composition ratios and physical properties of each organopolysiloxane T and U synthesized in the same way are shown in Table 2.

[0604] [Method for preparing polyorganosiloxane cured products]

[0605] As Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2, 100 parts by weight of each of the polyorganosiloxanes shown in Table 3 were mixed with 3 parts by weight of Irgacure 1173 as a photopolymerization initiator, and then sealed with glass. The mixture was then passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was light-cured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. The various physical properties measured for the test piece are shown in Table 3.

[0606] [Method for manufacturing a light-curable paste composition and a method for preparing a cured product]

[0607] In a polymerization apparatus equipped with a stirrer, condenser, and thermometer, 145 parts by mass of deionized water and 0.5 parts by mass of polyvinyl alcohol (saponification degree: 80%, degree of polymerization: 1,700) as a dispersion stabilizer were added and stirred. After the polyvinyl alcohol was completely dissolved, stirring was stopped, and 96 parts by mass of methyl methacrylate, 4 parts by mass of methacrylic acid, 0.3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (manufactured by Otsuka Chemical Co., Ltd., trade name: AMBN) as a polymerization initiator, and 1 part by mass of n-dodecyl mercaptan as a chain transfer agent were added, and stirring was resumed. Nitrogen replacement was carried out under stirring, and the temperature was raised to 80°C for polymerization. After detecting the exothermic peak of polymerization, the temperature was raised to 95°C, and the reaction was carried out for another 0.5 hours, followed by cooling to 30°C. The resulting aqueous suspension was filtered through a 45 μm nylon filter cloth, and the filter was washed with deionized water. After dehydration, the product was dried at 40°C for 24 hours to obtain granular (meth)acrylic polymer (Mw = 40,000, acid value 26 mg KOH / g).

[0608] Next, 60 parts by mass of benzyl methacrylate, 0.04 parts by mass of butylated hydroxytoluene (BHT) as a polymerization inhibitor, 3.2 parts by mass of glycidyl methacrylate as a compound containing glycidyl groups and double bonds, and 0.12 parts by mass of tetrabutylammonium bromide as a reaction catalyst were added to a reaction vessel equipped with a condenser. While stirring the liquid in the reaction vessel, 40 parts by mass of the prepared granular (meth)acrylic polymer were added, and the temperature in the reaction vessel was raised to 95°C. The mixture was stirred for 10 hours while maintaining the temperature, thereby carrying out the reaction of introducing double bonds into the (meth)acrylic polymer. After 10 hours, the mixture was cooled to room temperature to obtain a slurry composition. The acid value of the (meth)acrylic polymer in the slurry composition was 0.5 mg KOH / g.

[0609] As Examples 2-6 to 2-8 and Comparative Examples 2-3 to 2-5, 37 parts by weight of each of the polyorganosiloxanes shown in Table 4, 23 parts by weight of the obtained slurry composition, 37.7 parts by weight of benzyl methacrylate, and 2.3 parts by weight of 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, trade name: IRGACURE 184) as a photopolymerization initiator were stirred and mixed to obtain a photocurable slurry composition.

[0610] Each photocurable paste composition was sealed in glass and passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was light-cured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. The various physical properties of the test piece are shown in Table 4.

[0611] [Method for manufacturing photocurable multifunctional oligomer compositions and cured products]

[0612] As Examples 2-9 to 2-11 and Comparative Examples 2-6 to 2-8, 17 parts by weight of each of the polyorganosiloxanes shown in Table 5, 16.4 parts by weight of benzyl methacrylate, 41 parts by weight of ethoxylated isocyanurate triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: NK Ester A-9300), 24 parts by weight of ε-caprolactone-modified tris(acryloyloxyethyl) isocyanurate (manufactured by Toa Synthetic Co., Ltd., trade name: Aronix M-327), and 1.6 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator were stirred and mixed to obtain a photocurable multifunctional oligomer composition.

[0613] Each photocurable multifunctional oligomer composition was sealed in glass and passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was light-cured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. The various physical properties of the test piece are shown in Table 5.

[0614] [Comparison with sesquioxanes]

[0615] Silsesquioxanes are polyorganosiloxanes composed solely of T units, and can be broadly classified into cage-like structures and non-cage-like structures.

[0616] In the polyorganosiloxane I synthesized in Synthesis Example 2-1 (Example 2-12), the polyorganosiloxane H (Comparative Example 2-9), and the polyorganosiloxane J synthesized in Synthesis Example 2-2 (Comparative Example 2-10), 100 parts by mass of each polyorganosiloxane were mixed with 3 parts by mass of Irgacure 1173 as a photopolymerization initiator, sealed in glass, and passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was then photocured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. The various physical properties of the composition and the test piece before curing are shown in Table 6.

[0617] [Comparison with changes in MTQ unit ratio]

[0618] In the polyorganosiloxanes D, K, and L synthesized in Synthesis Example 2-1 (Examples 2-13 to 2-15), 100 parts by weight of each polyorganosiloxane were mixed with 3 parts by weight of Irgacure 1173 as a photopolymerization initiator, sealed in glass, and passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was then photocured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. Various physical properties of the composition and the test piece before curing are shown in Table 7.

[0619] [Comparison of changing the type of T unit and adding more than two types]

[0620] In the polyorganosiloxanes E, M, N, and O synthesized in Synthesis Examples 2-1 and 2-3 (Examples 2-3, 2-16 to 2-18), 100 parts by weight of each polyorganosiloxane were mixed with 3 parts by weight of Irgacure 1173 as a photopolymerization initiator, sealed in glass, and passed through a high-pressure mercury lamp (cumulative light intensity: 3,000 mJ / cm²). 2 The sample was then photocured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. The various physical properties of the composition and the test piece before curing are shown in Table 8.

[0621] Table 2-1

[0622]

[0623] Table 2-2

[0624]

[0625] Table 3

[0626]

[0627] According to Table 3, as T2 increases from 0.12 to 0.4, the refractive index also increases. On the other hand, as is generally known, the Abbe number decreases. Therefore, when designing polysiloxanes for lens materials, the introduction of methacryloyl groups above this level is not considered. However, surprisingly, when T2 is above 0.4, it is observed that the refractive index increases along with the Abbe number. For methacryloyl groups with a T2 exceeding 0.53, the Abbe number is higher than that when T2 is 0.12. In particular, polysiloxanes with a T2 exceeding 0.53 have high refractive index and Abbe number, making them suitable as lens materials.

[0628] Furthermore, according to Table 3, high values ​​are also observed in mechanical properties such as pencil hardness and storage modulus, indicating that lenses made of robust materials can be manufactured that are not easily damaged. Moreover, due to the low coefficient of linear expansion, the stress generated between the lens and surrounding components is minimal, for example, when the lens assembly is heated during a reflow soldering process, making the lens less prone to breakage. In addition, with a total light transmittance of over 90% and a haze of less than 1, it is a transparent material with minimal turbidity, making the polyorganosiloxane of this invention suitable as a lens material.

[0629] Table 4

[0630]

[0631] According to Table 4, in regions with T2 below 0.25 and few methacryloyl groups, the compatibility with acrylic resin is poor. However, in regions with more methacryloyl groups, it is compatible with acrylic resin, is transparent, has a higher Abbe number than the original acrylic resin, and a higher refractive index, making it suitable as a lens material. Furthermore, mechanical strengths such as pencil hardness or storage modulus are improved. Additionally, the increase in tanδ peak temperature, i.e., improved heat resistance, imparts reflow soldering resistance.

[0632] On the other hand, in the cage-type silsesquioxanes with a T2 of 1 in Comparative Examples 2-5, the cured product with acrylic resin became hard and brittle, making it impossible to determine the Abbe number or refractive index. Furthermore, cracks occurred during reflow soldering. Existing cage-type silsesquioxanes are insufficient to meet the requirements of high Abbe number, high refractive index, and reflow soldering resistance.

[0633] Table 5

[0634]

[0635] According to Table 5, when used as a photocurable multifunctional acrylic oligomer composition, in regions with T2 below 0.25 and few methacryloyl groups, the compatibility with acrylic resin is poor. However, in regions with more methacryloyl groups, it is compatible with acrylic resin, and the Abbe number is higher than that of the original acrylic resin. In the case of photocurable multifunctional acrylic oligomer compositions, it can be seen that there exists an optimal balance point for compatibility, transparency, Abbe number, and refractive index within the range of 0.25 < T2 < 1.

[0636] Table 6

[0637]

[0638] According to Table 6, comparing cage-type and non-cage-type silsesquioxanes with a T2 of 1, it can be seen that the structure containing M and Q units is more suitable for consideration of heat resistance, colorability, and water absorption. Furthermore, the viscosity increases and processability decreases when alkoxy groups are not present; therefore, a structure containing a small amount of alkoxy groups is preferred.

[0639] Table 7

[0640]

[0641] Table 7 compares Examples 2-13 and 2-14, showing that when the M1 unit ratio decreases and the T2 unit ratio is slightly less than the same ratio, the Abbe number increases; adding excessive M1 units leads to a decrease in the Abbe number. Comparing Examples 2-13 and 2-15, it shows that when the M1 unit ratio is the same and the T2 unit ratio is low, the Abbe number decreases. Comparing Examples 2-14 and 2-15, it shows that when the Q unit ratio is the same, the M1 unit ratio is high, and the T2 unit ratio is low, the Abbe number decreases.

[0642] Table 8

[0643]

[0644] According to Table 8, when the total T2 content is equal, even if more than two types of T2 units are used, the same Abbe number will be displayed.

[0645] [Preparation method of acrylic composition and cured product]

[0646] Each mixture shown in Table 9 was sealed with glass and passed through a high-pressure mercury lamp (cumulative luminous intensity: 3,000 mJ / cm²). 2 The sample was light-cured and heated in an oven set to 100°C for 30 minutes to obtain a 1 mm thick test piece. Various physical properties of the test piece are shown in Table 9. The substances used were dicyclopentayl methacrylate (manufactured by Hitachi Chemical Co., Ltd., product name Fanclel FA-513M), polybutanediol (degree of polymerization 28) dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name FA-PTG28M), and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA). As antioxidants, phosphorus-based antioxidants and / or phenolic antioxidants were used.

[0647] Properties such as elastic modulus and glass transition can be modified without impairing the optical properties of methacrylic resins used as matrix resins.

[0648] Table 9

[0649]

[0650] [Evaluation III: Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-4]

[0651] [Measurement Method]

[0652] 1. Determination of the number of reactive functional groups in polyorganosiloxanes

[0653] The number of reactive functional groups in polyorganosiloxanes was determined using the same method as described above.

[0654] 2. 29 Si-NMR determination method

[0655] Perform using the same method as described above. 29 Determination of Si-NMR.

[0656] 3. Determination of MDTQ ratio

[0657] In compounds primarily composed of silicon, the tetrahedral silicon atom (Si) is bonded to the vertices of oxygen atoms (O) or carbon atoms (C). A silicon atom bonded to one oxygen atom is called an M unit, two oxygen atoms a D unit, three oxygen atoms a T unit, and four oxygen atoms a Q unit. 29 In the spectra obtained by Si-NMR measurements, the positions of the signals can be distinguished according to the four units mentioned above. Roughly, the M unit is observed at -20 to 0 ppm, the D unit at 0 to -30 ppm, the T unit at -40 to -80 ppm, and the Q unit at -80 ppm to -130 ppm. Since their signal integral ratios are equal to the ratios of their respective silicon atoms, the ratios of each unit in the MDTQ can be calculated. However, depending on the atoms or groups of atoms bonded to silicon or carbon atoms, there are also cases deviating from these ranges. For example, the signal of silicon atoms directly bonded to hydrogen atoms is mostly observed on the magnetic field side higher than that of silicon atoms bonded to methyl groups. Furthermore, when hydrogen atoms or methyl groups are further bonded to oxygen atoms bonded to silicon atoms, i.e., silicon atoms bonded to hydroxyl or methoxy groups, the signal is observed on the low magnetic field side. Therefore, cases observed outside these ranges should be noted. In such cases, it is possible to detect signals by, for example, by... 1 H- 29 Two-dimensional NMR measurements of silicon confirmed the correlation between the target silicon signal and the proton signal of the groups introduced on the silicon. 29 The signals observed by Si-NMR were assigned to the MDTQ units.

[0658] 4. Determination of molecular weight

[0659] The molecular weight was determined using the same method as described above.

[0660] [Sample Preparation]

[0661] [Types of reagents used]

[0662] The reagents and solvents used in the synthesis are described below.

[0663] Hexamethyldisiloxane (manufactured by NuSil Technology, product name: S-7205)

[0664] 1,3-Divinyltetramethyldisiloxane (manufactured by NuSil Technology, product name: PLY-70)

[0665] 1,1,3,3-Tetramethyldisiloxane (manufactured by NuSil Technology) methyl silicate MS-51 (manufactured by Mitsubishi Chemical Corporation)

[0666] Tetrahydrofuran (manufactured by KISHIDA Chemical Co., Ltd.)

[0667] Ethylene glycol monovinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0668] Diethylene glycol monovinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0669] Toluene (manufactured by KISHIDA Chemical Co., Ltd.)

[0670] Ethanol (manufactured by KISHIDA Chemical Co., Ltd.)

[0671] Methanol (manufactured by KISHIDA Chemical Co., Ltd.)

[0672] Heptane (manufactured by KISHIDA Chemical Co., Ltd.)

[0673] N,N-Dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.)

[0674] 1N hydrochloric acid (manufactured by KISHIDA Chemical Co., Ltd.)

[0675] 8N potassium hydroxide aqueous solution (manufactured by KISHIDA Chemical Co., Ltd.)

[0676] Platinum(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum ~2%; Aldrich)

[0677] m-Cloroperoxybenzoic acid (manufactured by KISHIDA Chemical Co., Ltd.), purity approximately 70%.

[0678] Synthesis of polyorganosiloxanes

[0679] [Synthesis Example 3-1] Polyorganosiloxane 12

[0680] 2.6 parts by weight of hexamethyldisiloxane, 9.16 parts by weight of 1,3-divinyltetramethyldisiloxane, and 8.24 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 10.0 parts by weight of toluene and 10.0 parts by weight of methanol. A mixture of 5.10 parts by weight of 1N hydrochloric acid and 2.55 parts by weight of methanol was added, and the mixture was stirred at 40°C for 4 hours. After dilution with 17.5 parts by weight of heptane, the solution was washed with deionized water. The solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no further distillation was visually observed. Then, the solution was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 12".

[0681] "Polyorganosiloxane 12" 1 H-NMR was performed in the same manner as described in [Determination Method] 1 above to confirm that it is a vinyl-containing polyorganosiloxane. The graphs from the measurements are shown below. Figure 5 As shown. Figure 5 The chart is without an internal standard. When determining the number of reactive functional groups, the sample with toluene added as an internal standard is measured.

[0682] [Synthetic Example 3-2] Polyorganosiloxane 13

[0683] 74 parts by weight of 1,1,3,3-tetramethyldisiloxane and 95 parts by weight of methyl silicate MS-51 were dissolved in a mixed solvent of 84 parts by weight of toluene and 84 parts by weight of methanol. Then, a mixture of 58 parts by weight of 1N hydrochloric acid and 58 parts by weight of methanol was added, and the mixture was stirred at 30°C for 3 hours. Subsequently, the solvent was distilled off, and the product was filtered to obtain "polyorganosiloxane 13".

[0684] The obtained "polyorganosiloxane 13" 1 The H-NMR was performed in the same manner as in Synthesis Example 3-1, confirming that it is a polyorganosiloxane containing hydrosilyl groups. The graphs from the measurements are shown below. Figure 6 .

[0685] [Synthesis Example 3-3] Polyorganosiloxane 14

[0686] Add 30 parts by weight of the polyorganosiloxane 12 synthesized in Synthesis Example 3-1 above to a 1L four-necked flask. Dissolve the flask in 300ml of chloroform, then heat the flask to approximately 40°C using an oil bath. While stirring, add a total of 56.2 parts by weight of m-chloroperoxybenzoic acid in five separate additions over 9 hours. After the fourth addition, add an additional 50ml of chloroform. 1 H-NMR tracking of the reaction over time, through the above... 1 The conversion rate was determined by the integral ratio of the protons of vinyl groups (δ 5.70–6.25) to the protons of epoxy groups (δ 2.15–3.00) under ¹H-NMR analysis conditions. Heating was stopped when the conversion rate reached 98%. After cooling to an internal temperature of approximately 10°C in an ice bath, the mixture was washed twice with 100 ml of 5% sodium thiosulfate. Further washing was performed twice with 100 ml of saturated sodium bicarbonate and once with 100 ml of water. After confirming the absence of peroxide residues in both the organic and aqueous phases using KI starch paper, the solvent was distilled off to obtain 31.3 parts by weight of polyorganosiloxane 14. Polyorganosiloxane 14 exhibits good solubility in γ-butyrolactone.

[0687] The obtained "polyorganosiloxane 14" 1 The H-NMR was performed in the same manner as in Synthesis Example 3-1, confirming that it is a polyorganosiloxane containing epoxy groups. The graphs from the measurements are shown below. Figure 7 .

[0688] In addition, the above method was used to determine 29The Si-NMR results were used to determine the MDTQ ratio, which was a = 0.62, b = 0, c = 0, and d = 0.38. Furthermore, the e+f ratio was 0.09. Since e and f are often difficult to separate in the measured graphs, the total amount of e and f is considered. Additionally, the number-average molecular weight was 1000, and the number of reactive functional groups per 1000 molecular weight was 4.9.

[0689] [Synthetic Examples 3-4] Polyorganosiloxane 15

[0690] 50 parts by weight of the polyorganosiloxane 13 and 48 parts by weight of ethylene glycol monovinyl ether obtained in Synthesis Example 3-2 were dissolved in 195 parts by weight of toluene. Then, 0.05 parts by weight of a platinum(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (based on platinum concentration) of 2% by weight was added, and the mixture was stirred at 80°C for 6 hours. 1 H-NMR was used to track the changes in the reaction over time, and quantitative observations were made of the above-mentioned... 1 Under ¹H-NMR analysis conditions, the δ values ​​of 4.5–4.9 are due to the complete disappearance of the signal from protons directly bonded to silicon atoms. New signals appear at δ values ​​of 2.5–4.0 and 0.8–1.2, originating from 2-(2-hydroxyethoxy)ethyl groups bonded to silicon atoms. After cooling to room temperature, 50 parts by weight of silica gel are added and stirred for 30 minutes. The solvent in the filtrate is then distilled off to obtain polyorganosiloxane 15. Polyorganosiloxane 15 exhibits good solubility in ethylene glycol and γ-butyrolactone.

[0691] The obtained "polyorganosiloxane 4" 1 The H-NMR was performed in the same manner as in Synthesis Example 3-1, confirming that it is a polyorganosiloxane containing ethylene glycol groups. The graphs from the measurements are shown below. Figure 8 Furthermore, the above method was used to determine... 29 The Si-NMR results were used to determine the MDTQ ratio, which was a = 0.56, b = 0, c = 0, and d = 0.44. Furthermore, e + f was 0.05. The number-average molecular weight was 2400, and the functional group content per 1000 molecular weight was 4.7.

[0692] [Synthetic Examples 3-5] Polyorganosiloxane 16

[0693] 50 parts by weight of the polyorganosiloxane 13 and 71 parts by weight of diethylene glycol monovinyl ether obtained in Synthesis Example 3-2 were dissolved in 195 parts by weight of toluene. Then, 0.05 parts by weight of a platinum(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (based on platinum concentration) of 2% by weight was added, and the mixture was stirred at 110°C for 8 hours. 1 H-NMR was used to track the changes in the reaction over time, and quantitative observations were made of the above-mentioned... 1Under ¹H-NMR analysis conditions, the δ values ​​of 4.5–4.9 are due to the complete disappearance of the signal from protons directly bonded to silicon atoms, while new signals appear at δ values ​​of 2.4–4.2 and 0.8–1.2, due to the presence of 2-(2-(2-hydroxyethoxy)ethoxy)ethyl groups bonded to silicon atoms. After cooling to room temperature, 50 parts by weight of silica gel were added and stirred for 30 minutes, followed by filtration. The solvent in the filtrate was distilled off to obtain polyorganosiloxane 16. Polyorganosiloxane 16 exhibits good solubility in ethylene glycol and γ-butyrolactone.

[0694] The obtained "polyorganosiloxane 16" 1 The H-NMR was performed in the same manner as in Synthesis Example 3-1, confirming that it is a polyorganosiloxane containing diethylene glycol groups. The graphs from the measurements are shown below. Figure 9 Furthermore, the above method was used to determine... 29 The Si-NMR results were used to determine the MDTQ ratio, which was a = 0.56, b = 0, c = 0, and d = 0.44. Furthermore, e + f was 0.05. The number-average molecular weight was 3000, and the number of reactive functional groups per 1000 molecular weight was 3.7.

[0695] <Example 3-1>

[0696] (Electrolyte preparation)

[0697] A base electrolyte was prepared by adding γ-butyrolactone (90 parts by mass) to 10 parts by mass of 1-ethyl-2,3-dimethylimidazoline phthalate. Polyorganosiloxane 14 (6 parts by mass) was then added to this base electrolyte, and water was further added to adjust the moisture content to 1% to prepare the final electrolyte. The electrolyte composition was 1-ethyl-2,3-dimethylimidazoline phthalate (9.4% by mass), γ-butyrolactone (84.1% by mass), polyorganosiloxane (5.6% by mass), and water (1.0% by mass).

[0698] (Determination of electrolyte conductivity and capacitor withstand voltage)

[0699] The conductivity of the electrolyte prepared in this way was measured in a constant temperature bath at 25°C using a multi-functional water quality meter (MM-60R) manufactured by DKK East Asia.

[0700] The result is that the conductivity (25℃) of the electrolyte containing polyorganosiloxane 14 is 6.3 mS·cm. -1 .

[0701] Then make Figure 1 An aluminum electrolytic capacitor of this structure is manufactured by impregnating a wound element with an electrolyte solution, housing the wound element in an aluminum casing, and sealing it with peroxide-cured butyl rubber. Figure 2 ).

[0702] In the voltage-time rise curve of this aluminum electrolytic capacitor at 125℃ when a constant current of 10mA is applied, the voltage value at which the first spike or flicker is observed is taken as the withstand voltage value, and the measured result is 200V. The specifications of the aluminum electrolytic capacitor element used are: case size 10φ×20L, rated voltage 200V, and capacitance 20μF.

[0703] <Examples 3-2, 3-3>

[0704] Except for using the polyorganosiloxanes 15 and 16 obtained in Synthetic Examples 3-4 and 3-5 respectively, the electrolyte was prepared in the same manner as in Example 3-1, and the conductivity and withstand voltage were measured. The results are shown in Table 10.

[0705] <Comparative Example 3-1>

[0706] Except for the absence of polyorganosiloxane, the measurements were performed in the same manner as in Example 3-1. The results are shown in Table 10. It can be determined that the withstand voltage without the addition is 85V.

[0707] <Comparative Example 3-2>

[0708] As a substitute for polyorganosiloxane, a commercially available silane coupling agent with epoxy groups (molecular weight 236, T-unit only) was added, and the measurements were performed in the same manner as in Examples 3-1. The withstand voltage was 102V, which was slightly improved but not as good as in the examples. The results are shown in Table 10.

[0709] <Comparative Example 3-3>

[0710] As a substitute for polyorganosiloxane, a commercially available epoxy-modified silicone (molecular weight 800, a=0.29, b=0.71, c=d=0, number of reactive functional groups 2.5) was added, and the determination was performed in the same manner as in Example 3-1. The results are shown in Table 10.

[0711] <Comparative Examples 3-4>

[0712] As a substitute for polyorganosiloxane, an organomodified silica sol modified with epoxy groups as described in Japanese Patent Application Publication No. 10-241999 (the structures of the modified functional groups are shown in Table 10) was added, and the same measurements were performed as in Example 3-1. However, gelation occurred, making it impossible to evaluate it as a capacitor. The results are shown in Table 10.

[0713] Table 10

[0714]

[0715] For the electrolyte of Comparative Example 3-1 without the addition of polyorganosiloxane, the withstand voltage is a relatively low 85V. In Examples 3-1 to 3-3 with the addition of the polyorganosiloxane of the present invention, the conductivity is at the same level but the withstand voltage shows a higher value of 120 to 200V.

[0716] In Comparative Example 3-2, which shows an example of adding a known silane coupling agent, the increase in withstand voltage is smaller compared to that of the present invention. This is believed to be because compounds like silane coupling agents have small molecular weights and do not easily form sufficient cross-linked structures, thus providing less protection to the electrode surface.

[0717] For the electrolyte of Comparative Example 3-3, which contains a known modified silicone, it can be made soluble in γ-butyrolactone by modifying it with reactive functional groups. However, the silicone structure is linear, meaning that the proportion of D units (b) is too large. It is assumed that it is not easy to obtain a layer that can protect the electrode, and the voltage withstand capability cannot be improved.

[0718] Furthermore, the electrolytes of Comparative Examples 3-4, which had organically modified silica sol added, exhibited poor stability and gelled.

[0719] [Evaluation IV: Examples 4-1 to 4-5, Comparative Example 4-1]

[0720] [Measurement Method]

[0721] 1. Determination of the number of reactive functional groups in polyorganosiloxanes

[0722] The number of reactive functional groups in polyorganosiloxanes was determined using the same method as described above.

[0723] 2. 29 Si-NMR determination method

[0724] Perform using the same method as described above. 29 Determination of Si-NMR.

[0725] 3. Determination of MDTQ ratio

[0726] Using the same method as described above, from 29 The results were calculated from the Si-NMR measurements.

[0727] 4. Determination of molecular weight

[0728] The molecular weight was determined using the same method as described above.

[0729] 5. Measurement of weight loss during reduced pressure heating

[0730] The weight loss during depressurization heating was measured using the same method as described above.

[0731] Methods for confirming properties at 6.40℃

[0732] The properties at 40℃ were confirmed using the same method as described above.

[0733] 7. Viscosity Measurement

[0734] Viscosity at 25°C was determined using the same method as described above.

[0735] [Sample Preparation]

[0736] [Types of reagents used]

[0737] The reagents and solvents used in the synthesis are described below.

[0738] Hexamethyldisiloxane (manufactured by NuSil Technology, product name: S-7205)

[0739] 1,3-Divinyltetramethyldisiloxane (manufactured by NuSil Technology, product name: PLY-70)

[0740] 1,1,3,3-Tetramethyldisiloxane (manufactured by NuSil Technology)

[0741] Phenylacetyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KMB-103)

[0742] Hexyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0743] Decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KMB-3103)

[0744] Methyl silicate MS-51 (manufactured by Mitsubishi Chemical Corporation)

[0745] Tetrahydrofuran (manufactured by KISHIDA Chemical Co., Ltd.)

[0746] Toluene (manufactured by KISHIDA Chemical Co., Ltd.)

[0747] Methanol (manufactured by KISHIDA Chemical Co., Ltd.)

[0748] N,N-Dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.)

[0749] 1N hydrochloric acid (manufactured by KISHIDA Chemical Co., Ltd.)

[0750] Polysiloxane 18 (using OctaPhenyl POSS (MA0840) manufactured by HYBRID PLASTICS INC. directly as Polysiloxane 18.)

[0751] Synthesis of polyorganosiloxanes

[0752] [Synthetic Example 4-1] Polyorganosiloxane 17

[0753] As a raw material for polyorganosiloxane, 105 parts by weight of hexamethyldisiloxane, 225 parts by weight of phenyltrimethoxysilane, and 12 parts by weight of methyl silicate MS-51 were used. Toluene and methanol were used as solvents, and a mixture of 75 parts by weight of 1N hydrochloric acid and 75 parts by weight of methanol was used as a catalyst, along with water. Hydrolysis and condensation were carried out while maintaining the temperature between 20°C and 40°C. After washing with demineralized water to remove hydrochloric acid, the solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no solvent distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 17".

[0754] [Synthetic Example 4-2] Polyorganosiloxane 19

[0755] As a raw material for polyorganosiloxane, 12 parts by weight of hexamethyldisiloxane, 25 parts by weight of phenyltrimethoxysilane, 33 parts by weight of decyltrimethoxysilane, and 4.1 parts by weight of methyl silicate MS-51 were used. 29 parts by weight of tetrahydrofuran was used as the solvent, and a mixture of 17 parts by weight of 1N hydrochloric acid and 17 parts by weight of methanol was used as the catalyst, along with water. Hydrolysis and condensation were carried out while maintaining the temperature between 20°C and 40°C. After washing with demineralized water to remove hydrochloric acid, the solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no solvent distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 19".

[0756] [Synthetic Example 4-3] Polyorganosiloxane 20

[0757] As a raw material for polyorganosiloxane, 47 parts by weight of 1,3-divinyltetramethyldisiloxane, 25 parts by weight of phenyltrimethoxysilane, 150 parts by weight of decyltrimethoxysilane, and 7.3 parts by weight of methyl silicate MS-51 were used. 115 parts by weight of toluene and 115 parts by weight of methanol were used as solvents. A mixture of 46 parts by weight of 1N hydrochloric acid and 46 parts by weight of methanol was used as a catalyst, along with water. Hydrolysis and condensation were carried out while maintaining the temperature between 20°C and 40°C. After washing with demineralized water to remove hydrochloric acid, the solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no solvent distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 20".

[0758] [Synthetic Example 4-4] Polyorganosiloxane 21

[0759] As a raw material for polyorganosiloxane, 50 parts by weight of 1,3-divinyltetramethyldisiloxane, 119 parts by weight of phenyltrimethoxysilane, 35 parts by weight of decyltrimethoxysilane, and 7.7 parts by weight of methyl silicate MS-51 were used. Toluene and methanol were used as solvents, and a mixture of 49 parts by weight of 1N hydrochloric acid and 49 parts by weight of methanol was used as a catalyst, along with water. Hydrolysis and condensation were carried out while maintaining the temperature between 20°C and 40°C. After washing with demineralized water to remove hydrochloric acid, the solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no solvent distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 21".

[0760] [Synthetic Examples 4-5] Polyorganosiloxane 22

[0761] As a raw material for polyorganosiloxane, 52 parts by weight of 1,3-divinyltetramethyldisiloxane, 28 parts by weight of phenyltrimethoxysilane, 130 parts by weight of hexyltrimethoxysilane, and 8.1 parts by weight of methyl silicate MS-51 were used. Toluene and methanol were used as solvents, and a mixture of 49 parts by weight of 1N hydrochloric acid and 49 parts by weight of methanol was used as a catalyst, along with water. Hydrolysis and condensation were carried out while maintaining the temperature between 20°C and 40°C. After washing with demineralized water to remove hydrochloric acid, the solvent was distilled off using a rotary evaporator at 76°C and a reduced pressure of 15 Torr until no solvent distillation was visually observed. Then, the mixture was heated at 110°C and a reduced pressure of 0.15 Torr for 2 hours to obtain "polyorganosiloxane 22".

[0762] According to Example 4-1 and Comparative Examples 4-1 to 4-5 in Table 11, polyorganosiloxanes were prepared by the above method, and the measured values ​​of various tests performed on them are shown in Table 11.

[0763] Table 11

[0764]

[0765] The polyorganosiloxane 18, which is a cage-like silsesquioxane containing phenyl groups, shown in Comparative Example 4-1 of Table 11, is a solid. Polyorganosiloxanes that typically contain a large amount of T-unit silicon and a large amount of phenyl groups are mostly solids. On the other hand, the polyorganosiloxane 17 of the present invention shown in Example 4-1, although containing a large amount of T-units and a large amount of phenyl groups, remains in a liquid state, indicating that the present invention can provide a liquid polyorganosiloxane with excellent processability. Furthermore, the polyorganosiloxanes 19-22 shown in Examples 4-2 to 4-5 also remain in a liquid state. Considering that polyorganosiloxanes containing a large amount of phenyl groups and long-chain alkyl groups can easily become solids through the interaction between phenyl groups or the crystallization between long-chain alkyl groups, the present invention can provide a liquid polyorganosiloxane containing phenyl groups and long-chain alkyl groups with excellent processability. Furthermore, when polyorganosiloxanes are mixed with organic resins, separation or turbidity usually occurs due to poor compatibility with the organic resins. However, it is expected that the polyorganosiloxanes 17 and 19 to 22 shown in Examples 4-1 to 4-5 have good compatibility with the organic resins.

[0766] Industrial utilization potential

[0767] The electrolyte containing the polyorganosiloxane specific to this invention provides an electrolyte with superior properties of high voltage resistance, compared to various known additives, when used as an electrolyte for electrolytic capacitors.

[0768] Symbol Explanation

[0769] 1: Anode side electrode foil

[0770] 2: Cathode side electrode foil

[0771] 3: Diaphragm

[0772] 4: Lead-out terminals

[0773] 5: Outer shell

[0774] 6: Rubber pad

[0775] 7: Sealing plate

[0776] 8: External terminals of the electrodes

[0777] 9: Component fixing agent

[0778] 10: Capacitor Components

Claims

1. A polyorganosiloxane, represented by the general formula (1) shown below, having an alkoxy group bonded to silicon and reactive functional groups other than the alkoxy group, (R 1 R 2 R 3 SiO 1 / 2 ) a (R 4 R 5 SiO 2 / 2 ) b (R 6 SiO 3 / 2 ) c (SiO 4 / 2 ) d (Oh 1 / 2 R 7 ) e (Oh 1 / 2 H) f …(1) In equation (1), R 1 To R 6 Independently selected from organic functional groups and hydrogen atoms, and satisfying a + b + c + d = 1, in addition, R 7 It is an organic group selected from 1 to 7 carbon atoms, represented by R. 1 R 2 R 3 SiO 1 / 2 The scale a of the M unit shown is 0.1 or higher, with R 6 SiO 3 / 2 The proportion of T units shown is c is 0.15 or more and 0.8 or less, the content of silicon-bonded alkoxy groups relative to the total weight of the polyorganosiloxane is 0.07 to 4% by weight, the number of silicon-bonded reactive functional groups per 1000 molecular weight of the polyorganosiloxane is 3 to 12, the silicon-bonded reactive functional groups contain at least one group selected from the group consisting of methacryl, acryloyl, acyl and cyclic ether groups and hydrogen atoms that form hydrosilyl groups with silicon, and the weight of the polyorganosiloxane is reduced to 5% by weight or less after being heated at 110°C for 2 hours under reduced pressure to 0.15 torr; wherein R 1 R 2 R 3 R 6 Each can be an organic functional group other than alkoxy and hydroxyl, or a hydrogen atom, either the same or different.

2. The polyorganosiloxane according to claim 1, wherein a represents the proportion of M units and is 0.6 or less.

3. The polyorganosiloxane according to claim 1, wherein the proportion of T units is c is 0.4 or more.

4. The polyorganosiloxane according to claim 1, wherein the number of the reactive functional groups bonded to silicon per 1000 molecular weight of the polyorganosiloxane is 4 to 9.

5. The polyorganosiloxane according to claim 1 or 2, wherein it is liquid at 40°C.

6. The polyorganosiloxane according to claim 1 or 2, wherein the viscosity at 25°C is 5 mPa·s or more and 20,000 mPa·s or less.

7. The polyorganosiloxane according to claim 1 or 2, as a GPC determination result based on polystyrene conversion, has a number-average molecular weight Mn of 600 or more and 5000 or less.

8. The polyorganosiloxane according to claim 1, wherein the M unit contains at least trimethylsiloxy or dimethylsiloxy.

9. The polyorganosiloxane according to claim 1 or 2, wherein it is an MTQ resin.

10. The polyorganosiloxane according to claim 1, wherein the content of the silicon-bonded alkoxy groups relative to the total weight of the polyorganosiloxane is 0.07 to 2% by weight.

11. A composition comprising the polyorganosiloxane according to any one of claims 1 to 10.

12. A cured product formed by curing any polyorganosiloxane according to any one of claims 1 to 10 or any composition according to claim 11.

13. A polyorganosiloxane, which is a polyorganosiloxane represented by the following general formula (101), wherein, in infrared absorption spectroscopy analysis, the wavelength range is 1030–1060 cm⁻¹. -1 The region exhibits the maximum absorption wavenumber of Si-O stretching vibrations. After heating at 110°C for 2 hours under reduced pressure of 0.15 torr, the weight of the polyorganosiloxane decreased to less than 5% by weight. (R 101 R 102 R 103 SiO 1 / 2 ) M1 (R 104 R 105 R 106 SiO 1 / 2 ) M2 (R 107 R 108 SiO 2 / 2 ) D1 (R 109 R 106 SiO 2 / 2 ) D2 (R 110 SiO 3 / 2 ) T1 (R 106 SiO 3 / 2 ) T2 (SiO 4 / 2 ) Q (O 1 / 2 R 110 ) Y1 (O 1 / 2 R 106 ) Y2 ···(101) Here, in the general formula (101), R 101 ~R 105 R 107 ~R 110 Each of the following is an independent group selected from organic functional groups, reactive functional groups, or hydrogen atoms, R 106 It is an organic group containing a reactive functional group, which may be the same as or different from R. 101 ~R 105 R 107 ~R 110 The reactive functional groups, R 110 It does not contain reactive functional groups and is composed of organic groups selected from organic groups having 1 to 20 carbon atoms and groups containing hydrogen atoms. The coefficients M1, D1, T1, and Q are all greater than 0 and less than 0.

6. M1+M2>0, T1+T2+Q>0, M2+D2+T2>0.25, M1+M2+D1+D2+T1+T2+Q=1, The coefficients Y1 and Y2 are 0 or positive values.

14. The polyorganosiloxane according to claim 13, wherein M2+D2+T2≧0.4, and the reactive functional group is an organic group containing (meth)acryloyl.

15. The polyorganosiloxane according to claim 13, wherein R 106 It is an organic group containing (meth)acryloyl.

16. The polyorganosiloxane according to claim 13, wherein R 106 A molecule contains one or more functional groups selected from the groups shown in [2], [3], [4] and [5] below. in, In the formula, X is a divalent organic functional group that may contain branched and / or cyclic structures. Furthermore, when X is bonded to a silicon atom, the atom that is the end of X and directly connected to silicon is a carbon atom. In addition, when an oxygen atom that is directly connected to silicon is bonded to X, the atom that is the end of X and directly connected to the oxygen atom is a carbon atom.

17. The polyorganosiloxane according to claim 13, wherein R 106 One molecule has one or more functional groups selected from (meth)acryloyloxypropyl or (meth)acryloyloxyoctyl.

18. The polyorganosiloxane according to claim 13, R 101 ~R 103 R 107 R 108 and R 110 It does not contain (meth)acryloyl groups.

19. The polyorganosiloxane according to claim 13, wherein the coefficient D1 is 0.1 or less.

20. The polyorganosiloxane according to claim 13, wherein the coefficient M1 is greater than 0.

21. The polyorganosiloxane according to claim 13, wherein the coefficient Q is greater than 0.

22. The polyorganosiloxane according to claim 13, wherein the coefficient M1 is 0.09 or more and 0.5 or less, and the coefficient Q is 0.04 or more and 0.4 or less.

23. The polyorganosiloxane according to claim 13, wherein the coefficient Y1 is 0 or more and 0.25 or less.

24. The polyorganosiloxane according to claim 13, wherein the coefficient Y1 is 0.01 or more and 0.1 or less.

25. The polyorganosiloxane according to claim 13, wherein R 101 ~R 105 and R 107 ~R 110 Each is independently a methyl group.

26. The polyorganosiloxane according to claim 13 has a viscosity of 10 to 100,000 mPa·s at 25°C.

27. A polyorganosiloxane composition comprising the polyorganosiloxane of any one of claims 13 to 26, and a (meth)acrylate compound containing (meth)acryloyl groups and / or a polymer formed by polymerizing these (meth)acryloyl groups.

28. The polyorganosiloxane composition according to claim 27, further comprising a polymerization initiator.

29. A cured product formed by curing the polyorganosiloxane composition of claim 27 or 28.

30. An optical component comprising the polyorganosiloxane composition of claim 27 or 28, or the cured product of claim 29.

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