Silylated isocyanurate compound, metal corrosion inhibitor, curable silicone resin composition, and semiconductor device

Abstract

The object of the present invention is to provide a silylated isocyanurate compound that can function as a metal corrosion inhibitor with excellent heat resistance and sulfidation resistance, namely, a silylated isocyanurate compound represented by the following general formula (1), wherein R is independently a substituent selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, group represented by general formula (2-a) or general formula (2-b), and at least one of said R is general formula (2-b).

Description

Technical Field

[0001] This invention relates to a silylated isocyanurate compound used as a metal corrosion inhibitor, a curable silicone resin composition, and a semiconductor device. Background Technology

[0002] In recent years, optoelectronic semiconductor devices have been used in LED lighting, such as outdoor lighting and automotive lighting. The sealing materials for these devices typically use resins with high air permeability or water permeability, such as silicone resin. Therefore, in harsh environments such as outdoors, the silver plating on the electrodes or reflective layers of these devices can corrode due to sulfurous gases or moisture, resulting in a significant decrease in brightness.

[0003] As a countermeasure, studies have been conducted on increasing the refractive index and improving gas barrier properties by introducing aromatic substituents such as phenyl groups (Patent Documents 1-2). However, the introduction of aromatic substituents leads to a decrease in heat resistance.

[0004] Furthermore, as non-corrosive metal corrosion inhibitors, compounds containing N-aromatic hydrocarbons such as benzotriazole and 5-methylbenzimidazole, or metal complexes such as zinc, are known, and the addition of these corrosion inhibitors has been studied and attempted. However, there is a problem that the heat resistance of the resin decreases significantly due to the discoloration of the corrosion inhibitor and the metal ligand (Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-088513

[0008] Patent Document 2: International Publication No. WO2013 / 005859

[0009] Patent Document 3: Japanese Patent Application Publication No. 2012-056251 Summary of the Invention

[0010] The technical problem to be solved by the present invention

[0011] The present invention was made in view of the above-mentioned problems, and its object is to provide a silylated isocyanurate compound that can function as a metal corrosion inhibitor with excellent heat resistance and sulfidation resistance. Furthermore, another object of the present invention is to provide a curable silicone resin composition and a semiconductor device containing a silylated isocyanurate compound with excellent heat resistance and sulfidation resistance.

[0012] Technical means to solve technical problems

[0013] In order to solve the above-mentioned technical problems, the inventors of this application conducted a serious study and found that the organosilicon modified isocyanurate compound represented by the following general formula (1) can solve the above-mentioned technical problems, thereby completing the present invention.

[0014] That is, the present invention provides a silylated isocyanurate compound represented by the following general formula (1).

[0015]

[0016] In the general formula (1), R is independently a substituent selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, group represented by the following general formula (2-a) or the following general formula (2-b), and at least one of the R is of the following general formula (2-b).

[0017]

[0018] In the general formulas (2-a) to (2-b), R 1 Represents an alkyl group with 1 to 8 hydrogen atoms or carbon atoms. q represents an integer from 1 to 10. R 2 The substituents are independently selected from any one of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and groups represented by the following general formula (3), with at least one R. 2 For the following general formula (3), R 4 For hydrogen atoms or OR 2 .

[0019]

[0020] In the general formula (3), R 3 The substituents are independently selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0021] Such silylated isocyanurate compounds are compounds with excellent heat resistance and sulfur resistance.

[0022] In addition, a metal corrosion inhibitor containing a silylated isocyanurate compound represented by the general formula (1) is also provided.

[0023] Addition reaction-cured organosilicon compositions containing the silylated isocyanurate compound of the present invention as an additive can provide cured products with excellent heat resistance and sulfidation resistance, and can be used as metal corrosion inhibitors, etc.

[0024] Furthermore, the present invention provides a curable organosilicon resin composition, the composition comprising:

[0025] (A) An organosilicon compound having at least two alkenyl groups in one molecule;

[0026] (B) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule, wherein the amount of the organosilicon compound is such that the SiH group of component (B) is 0.1 to 4.0 mol of 1 mol of alkenyl group of component (A);

[0027] (C) Platinum group metal catalysts; and

[0028] (D) Silylated isocyanurate compounds represented by the following general formula (1) as metal corrosion inhibitors.

[0029]

[0030] In the general formula (1), R is independently a substituent selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, group represented by the following general formula (2-a) or the following general formula (2-b), and at least one of the R is of the following general formula (2-b).

[0031]

[0032] In the general formulas (2-a) to (2-b), R 1 Represents an alkyl group with 1 to 8 hydrogen atoms or carbon atoms. q represents an integer from 1 to 10. R 2 The substituents are independently selected from any one of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and groups represented by the following general formula (3), with at least one R. 2 For the following general formula (3), R 4 For hydrogen atoms or OR 2 .

[0033]

[0034] In the general formula (3), R 3 The substituents are independently selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0035] Such addition-reaction cured silicone compositions containing silylated isocyanurate compounds as additives can provide cured products with excellent heat resistance and sulfidation resistance.

[0036] At this point, the preferred composition of (A) is: (A1) containing SiO 4 / 2 Unit or R 4 SiO 3 / 2 At least one of the units (R) 4 It is a resinous organopolysiloxane that is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and has at least two alkenyl groups bonded to silicon atoms in one molecule.

[0037] Furthermore, at this time, it is preferable that the (A1) composition is 0-60 mol% SiO2. 4 / 2 Unit, 0–90 mol% R 4 SiO 3 / 2 Unit, 0–50 mol% (R) 4 )2SiO 2 / 2 Unit and 10-50 mol% (R) 4 )3SiO 1 / 2 The SiO2 unit is composed of 4 / 2 Unit and the R 4 SiO 3 / 2 The sum of the units is more than 50 mol% of resinous organopolysiloxanes.

[0038] The organopolysiloxane has a weight-average molecular weight of 1,000 to 5,000, and

[0039] A molecule contains at least two alkenyl groups bonded to silicon atoms.

[0040] The organopolysiloxane has a derivative from the SiO₂ 4 / 2 Unit, the R 4 SiO 3 / 2 Unit, the (R) 4 )2SiO 2 / 2 Unit and the (R) 4 )3SiO 1 / 2 Unitary, uncondensed, and partially residual hydroxyl and alkoxy groups bonded to silicon atoms.

[0041] The amount of the hydroxyl group is 0.001–1.0 mol / 100 g.

[0042] The amount of the alkoxy group bonded to silicon atoms, having 1 to 10 carbon atoms, is less than 1.0 mol / 100g.

[0043] If so, the composition will not become brittle or fail to flow. Furthermore, if the amount of hydroxyl groups bonded to silicon atoms is 0.001 mol / 100g or more, sufficient adhesion can be ensured; if it is 1.0 mol / 100g or less, it will not cause a decrease in storage stability or surface stickiness. Additionally, if the amount of alkoxy groups is 1.0 mol / 100g or less, alcohol gas as a byproduct is less likely to be generated during curing, and voids will not be left in the cured product.

[0044] At this point, in addition to component (A1), component (A) preferably further contains: (A2) an organopolysiloxane in the form of a linear or branched form having two or more alkenyl groups bonded to silicon atoms in one molecule, and having a viscosity of 10 to 100,000 mPa·s at 25°C as determined by the method described in JIS K 7117-1:1999.

[0045] In this way, the viscosity and hardness can be adjusted according to the application. Furthermore, if the viscosity is above 10 mPa·s, the composition will not become brittle, and if it is below 100,000 mPa·s, the workability will not deteriorate.

[0046] At this point, regarding the blending amount of component (A1) and component (A2), it is preferable that when the total amount of components (A1) and (A2) is set to 100% by mass, the amount of component (A1) is 5 to 100% by mass.

[0047] If so, all characteristics will be improved, resulting in excellent operability.

[0048] Preferably, it further contains a cyclic siloxane represented by the following general formula (4) as component (E), wherein the cyclic siloxane represented by the general formula (4) is 0.1 to 30% by mass relative to the total mass of components (A) and (B).

[0049] So that the amount of all hydrosilyl group in the curable silicone resin composition is 0.1 to 4.0 mol relative to 1 mol of all alkenyl group in the curable silicone resin composition contains a cyclic siloxane represented by the general formula (4).

[0050]

[0051] In the above general formula (4), R 5 Independently, it is a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, where r is an integer of 1 or 2.

[0052] Therefore, by adding component (E), the viscosity, curing properties and curing characteristics can be adjusted.

[0053] At this point, it is preferable that the composition of the present invention contains at least one inorganic white pigment selected from titanium dioxide, zinc oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate.

[0054] Because the curable silicone resin composition of the present invention has excellent weather resistance and transparency, the above-mentioned compounds can be used appropriately.

[0055] Furthermore, a semiconductor device comprising a cured product of a curable silicone resin composition and a semiconductor element is provided.

[0056] The curable silicone resin composition of the present invention provides a cured product with excellent sulfidation resistance, mechanical properties, transparency, crack resistance, and heat resistance. Therefore, it is suitable for use as a lens material, protective coating agent, molding agent, etc., in light-emitting semiconductor devices, and is particularly suitable for sealing LED components such as blue LEDs, white LEDs, and ultraviolet LEDs. Furthermore, due to the excellent heat resistance of the curable silicone resin composition of the present invention, when used as a wavelength conversion film material with the addition of silicate phosphors or quantum dot phosphors, long-term reliability under high humidity can be ensured, providing a light-emitting semiconductor device with good moisture resistance and long-term color rendering.

[0057] At this time, it is preferable that the thickness of the cured material is 1 mm, and the transmittance of the cured material to direct light with a wavelength of 450 nm is more than 70%.

[0058] If a curable silicone resin composition is provided to provide a cured product with such direct light transmittance, it has excellent transparency and is therefore particularly suitable for optical applications such as sealing materials for LEDs.

[0059] In this case, the semiconductor element is preferably a light-emitting element.

[0060] This invention can be applied to light-emitting elements.

[0061] Invention Effects

[0062] As described above, the silylated isocyanurate compound of the present invention is a compound with excellent heat resistance and sulfur resistance. Therefore, the addition reaction curable silicone composition containing the silylated isocyanurate compound of the present invention as an additive can provide a cured product with excellent heat resistance and sulfur resistance. Therefore, the silylated isocyanurate compound of the present invention can be used as a metal corrosion inhibitor, etc. Furthermore, the curable silicone resin composition of the present invention, the addition reaction curable silicone composition (curable silicone resin composition) containing the silylated isocyanurate compound as an additive can provide a cured product with excellent mechanical properties, transparency, crack resistance, heat resistance, and sulfur resistance. Furthermore, the cured product of the curable silicone resin composition of the present invention and the semiconductor device of the semiconductor element are suitable for lens materials, protective coatings, molding agents, etc. of light-emitting semiconductor devices, and can ensure long-term reliability under high humidity, and can provide a light-emitting semiconductor device with good moisture resistance and long-term color rendering. Attached Figure Description

[0063] Figure 1 The compound (mixture) synthesized in Example 1 ([Synthesis Example]) 1 H-NMR spectrum. Detailed Implementation

[0064] The present invention will now be described in detail, but it is not limited thereto.

[0065] The present invention relates to silylated isocyanurate compounds represented by the following general formula (1). In addition, silylated isocyanurate compounds are also referred to as organosilicon-modified isocyanurate compounds or silylated modified isocyanurate compounds.

[0066]

[0067] In the above general formula (1), R is independently a substituent selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, group represented by the following general formula (2-a) or the following general formula (2-b), and at least one of the above R is of the following general formula (2-b).

[0068]

[0069]

[0070] In the above general formulas (2-a) and (2-b), R 1 This indicates an alkyl group having 1 to 8 hydrogen or carbon atoms. Additionally, q represents an integer from 1 to 10. Furthermore, R... 2The substituents are independently selected from any one of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and groups represented by the following general formula (3), with at least one R. 2 For the following general formula (3), R 4 For hydrogen atoms or OR 2 .

[0071]

[0072] In the above general formula (3), R 3 The substituents are independently selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0073] Examples of alkyl groups having 1 to 10 carbon atoms in R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, allyl, 3-butenyl, hexenyl, cyclohexenyl, and octenyl.

[0074] The characteristic of R is that at least one R in the above general formula (1) is of the above general formula (2-b), and the remaining Rs are hydrogen atoms, methyl, allyl, the above general formula (2-a) or the above general formula (2-b). More preferably, the remaining Rs are of the above general formula (2-a) or the above general formula (2-b).

[0075] R in the above general formulas (2-a) and (2-b) 1 Each is an alkyl group having 1 to 8 hydrogen atoms or carbon atoms. Specifically, examples include lower alkyl groups such as methyl, ethyl, propyl, and butyl, and cycloalkyl groups such as cyclohexyl. Among these, hydrogen atoms or methyl groups are preferred.

[0076] Furthermore, R in the above general formulas (2-a) and (2-b) 2 Each group is independently selected from any one of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and groups represented by the above general formula (3). Furthermore, as R 2 Examples of alkyl groups having 1 to 10 carbon atoms include groups identical to those exemplified in R above. 2 The characteristic is that at least one R in the above general formula (2-b) is 2 For the group represented by formula (3) above, the remaining R are preferred. 2 It is a hydrogen atom, a methyl group or a group represented by the above formula (3).

[0077] In the above general formula (3), R 3The substituents are independently selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0078] Examples of alkyl groups having 1 to 10 carbon atoms include groups identical to those exemplified in R above. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, etc. Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, etc. Furthermore, examples of aryl groups having 6 to 10 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, or aralkyl groups such as benzyl, phenethyl, phenylpropyl. Among these groups, methyl, phenyl, and vinyl are preferred.

[0079] In the above general formulas (2-a) and (2-b), q is an integer from 1 to 10, preferably an integer from 1 to 8, and more preferably an integer from 1 to 5.

[0080] As a silylated modified isocyanurate compound represented by the above general formula (1), for example, compounds represented by the following formula can be listed.

[0081]

[0082] [Preparation method of silylated modified isocyanurate compound]

[0083] The silylated modified isocyanurate compounds of the present invention can be prepared, for example, by hydrolyzing triglycidyl isocyanurate with chlorosilane and alkoxysilane. The conditions of the hydrolysis reaction only need to be adjusted appropriately. For example, the reaction ratio of epoxy group to trimethylchlorosilane is 1:1 in molar ratio.

[0084] [Corrosion Inhibitor]

[0085] The silylated isocyanurate compounds of the present invention exhibit excellent performance as corrosion inhibitors for metals. Therefore, it is preferable to prepare metal corrosion inhibitors containing the silylated isocyanurate compounds of the present invention.

[0086] When the silylated isocyanurate compound of the present invention is used as a corrosion inhibitor, it may be added in an amount of 0.001 to 5% by mass, preferably 0.01 to 3% by mass, relative to the resin composition. The composition of the resin composition is not particularly limited, and examples include acrylic resins, epoxy resins, isocyanate resins, urethane resins, olefin resins, or silicone resins. Silicone resins, epoxy resins, urethane resins, and acrylic resins are preferred, with silicone resins being particularly preferred.

[0087] Furthermore, by dissolving the silylated isocyanurate compound of the present invention in an organic solvent and coating it onto a substrate, it can also exert excellent effects as a corrosion inhibitor for metals. The organic solvent is not particularly limited, and examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and diethylene glycol diethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogenated hydrocarbon solvents such as chloroform, dichloromethane, and 1,2-dichloroethane; alcohol solvents such as methanol, ethanol, isopropanol, isobutanol, and cyclohexanol; carbitol solvents such as carbitol, methyl carbitol, and butyl carbitol; organosiloxane solvents such as octamethylcyclotetrasiloxane and hexamethyldisiloxane; and further, solvents such as acetic acid cellosol and butyl cellosol. These organic solvents can be used alone or in combination with two or more.

[0088] In order to solve the above-mentioned technical problems, the inventors of this application conducted careful research and discovered that by using a curable organosilicon resin composition containing the following components, a curable organopolysiloxane resin composition exhibiting high reaction inhibition effect and stability under high temperature and high humidity conditions can be obtained, thereby completing the present invention:

[0089] (A) An organosilicon compound having at least two alkenyl groups in one molecule;

[0090] (B) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule, wherein the amount of the organosilicon compound is such that the SiH group of component (B) is 0.1 to 4.0 mol of 1 mol of alkenyl group of component (A);

[0091] (C) Platinum group metal catalysts; and

[0092] (D) Silylated isocyanurate compounds represented by the following general formula (1) as metal corrosion inhibitors.

[0093]

[0094] In the general formula (1), R is independently a substituent selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, group represented by the following general formula (2-a) or the following general formula (2-b), and at least one of the R is of the following general formula (2-b).

[0095]

[0096] In the general formulas (2-a) to (2-b), R 1 Represents an alkyl group with 1 to 8 hydrogen atoms or carbon atoms. q represents an integer from 1 to 10. R 2 The substituents are independently selected from any one of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and groups represented by the following general formula (3), with at least one R. 2 For the following general formula (3), R 4 For hydrogen atoms or OR 2 .

[0097]

[0098] In the general formula (3), R 3 The substituents are independently selected from any one of hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0099] [(A) Alkenyl-containing organosilicon compounds]

[0100] The alkenyl-containing organosilicon compound that is a component of (A) of the present invention is characterized in that it has at least 2, preferably 2 to 5, alkenyl groups in one molecule. Preferably, the alkenyl groups are capable of undergoing addition reactions with hydrosilyl groups.

[0101] The aforementioned component (A) can be any one of a linear or branched organopolysiloxane (as component (A2) described later) or a resinous (network) organopolysiloxane (as component (A1) described later). Each component can be used alone or in combination with two or more, but it is preferable to include the resinous (network) organopolysiloxane (A1). Furthermore, it is even more preferable to include both component (A1) and component (A2). The following provides a detailed description of each component.

[0102] [(A1) Resinous (network-like) organopolysiloxane]

[0103] The (A1) component of this invention contains SiO 4 / 2 Unit or R 4 SiO 3 / 2 At least one of the units (R) 4The weight-average molecular weight (Mw) of a resinous (network-like) organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule is preferably 1,000 to 5,000, more preferably 1,100 to 3,000, and is preferably 1,000 to 5,000. If the molecular weight (Mw) is 1,000 or higher, the composition will not become brittle; if the molecular weight (Mw) is 5,000 or lower, the viscosity of the composition will not increase and it will not flow.

[0104] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, allyl, 3-butenyl, hexenyl, cyclohexenyl, and octenyl.

[0105] Examples of alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 5, include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, etc., with vinyl being preferred. The aforementioned alkenyl groups are bonded to at least 2 silicon atoms in a molecule, preferably to 2 to 5 silicon atoms.

[0106] Examples of aryl groups having 6 to 10 carbon atoms, preferably 6 to 8, include aryl groups such as phenyl, tolyl, and xylyl, as well as aralkyl groups such as benzyl, phenethyl, and phenylpropyl, with phenyl being the most preferred. It is preferable to have one or more of the aforementioned aryl groups in one molecule, more preferably 2 to 100.

[0107] In addition, the weight-average molecular weight (Mw) in this invention refers to the weight-average molecular weight of polystyrene as a standard obtained by gel permeation chromatography (GPC) under the following conditions.

[0108] [Measurement Conditions]

[0109] Developing solvent: Tetrahydrofuran (THF)

[0110] Flow rate: 0.6 mL / min

[0111] Detector: Differential refractive index detector (RI)

[0112] Column: TSK Guardcolumn SuperH-L

[0113] TSKgel SuperH4000(6.0mmI.D.×15cm×1),

[0114] TSKgel SuperH3000(6.0mmI.D.×15cm×1),

[0115] TSKgel SuperH2000(6.0mmI.D.×15cm×2),

[0116] (All manufactured by TOSOH CORPORATION)

[0117] Column temperature: 40℃

[0118] Sample injection volume: 20 μL (0.5% by mass THF solution).

[0119] Furthermore, the amount of alkenyl groups contained in component (A1) is typically 0.01 to 0.5 mol / 100g, preferably 0.05 to 0.3 mol / 100g, and more preferably 0.10 to 0.25 mol / 100g.

[0120] If the amount of alkenyl groups bonded to silicon atoms is 0.01 mol / 100g or more, it has sufficient crosslinking points for hardening the composition; if it is 0.5 mol / 100g or less, the crosslinking density will not increase excessively and the toughness will be lost, which is therefore preferred.

[0121] Furthermore, the amount of hydroxyl groups bonded to silicon atoms in component (A1) is preferably 0.001 to 1.0 mol / 100g, more preferably 0.005 to 0.8 mol / 100g, and even more preferably 0.008 to 0.6 mol / 100g.

[0122] If the amount of hydroxyl groups bonded to silicon atoms is 0.001 mol / 100g or more, sufficient adhesion can be ensured; if it is less than 1.0 mol / 100g, it will not cause a decrease in storage stability or surface stickiness, and is therefore preferred.

[0123] Furthermore, in component (A1), the amount of alkoxy groups bonded to silicon atoms, having 1 to 10 carbon atoms, preferably 1 to 5, is generally preferably 1.0 mol / 100g or less, more preferably 0.8 mol / 100g or less, and even more preferably 0.5 mol / 100g or less.

[0124] If the amount of alkoxy groups is less than 1.0 mol / 100g, alcohol gas as a byproduct will not be easily generated during curing, and no voids will be left in the cured product.

[0125] Furthermore, the amount of hydroxyl and alkoxy groups bonded to silicon atoms in this invention refers to the amount of hydroxyl and alkoxy groups bonded to silicon atoms through… 1 H-NMR and 29 The value measured by Si-NMR.

[0126] In addition, when preparing the resinous organopolysiloxane of component (A1), a portion of the material used to obtain each siloxane unit (Q unit, T unit, D unit, M unit) described later will remain without condensation, and the hydroxyl and alkoxy groups bonded to silicon atoms mentioned above originate from this.

[0127] Furthermore, containing SiO 4 / 2 Unit or R 4 SiO 3 / 2 Unit (R) 4 The (A1) component is preferably composed of at least one of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 10 carbon atoms: typically 0 to 60 mol%, preferably 0 to 50 mol% SiO2. 4 / 2 Unit (Q unit), typically 0–90 mol%, preferably 30–80 mol% R 4 SiO 3 / 2 Unit (T unit), typically 0–50 mol%, preferably 0–20 mol% (R unit). 4 )2SiO 2 / 2 Unit (D unit) and typically 0–50 mol%, preferably 10–30 mol% (R) 4 )3SiO 1 / 2 Organopolysiloxanes with a resin structure composed of units (M units), preferably SiO 4 / 2 Unit and R 4 SiO 3 / 2 The sum of the units is 50 mol% or more, more preferably 60 to 90 mol%.

[0128] The above R 4 Independently, it is a substituted or unsubstituted monovalent alkyl group having 1 to 10 carbon atoms, preferably 2 to 5; an alkenyl group having 2 to 10 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, preferably the above (A1) component with R. 4 SiO 3 / 2 Substituent R in unit (T unit) bonding 4 Having at least one phenyl group, and (R 4 )3SiO 1 / 2 Substituent R bonded to unit (M unit) 4 At least one of them is an alkenyl group having 2 to 10 carbon atoms.

[0129] Specifically, R is one of the M-unit, D-unit, and T-unit. 4Examples of such groups include lower alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl; and groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, bromine, and chlorine, or by cyano groups, such as chloromethyl, cyanoethyl, and 3,3,3-trifluoropropyl. Among these, methyl, phenyl, and vinyl are preferred.

[0130] As a method for obtaining SiO 4 / 2 The material of the unit (Q unit) may be, for example, sodium silicate, tetraalkoxysilane or their condensation reactants, but is not limited thereto.

[0131] As used to obtain R 4 SiO 3 / 2 The material of the unit (T unit) may be, for example, an organosilicon compound or its condensation reaction product, such as an organotrichlorosilane or an organotrialkoxysilane represented by the following structural formula, but is not limited thereto.

[0132]

[0133] In the above formula, Me represents a methyl group.

[0134] As used to obtain (R) 4 )2SiO 2 / 2 The material of the unit (D unit) may be, for example, an organosilicon compound such as an organodichlorosilane or an organodialkoxysilane represented by the following structural formula, but is not limited thereto.

[0135]

[0136] In the above formula, Me represents methyl. n is an integer from 5 to 80, m is an integer from 5 to 80, and n+m≤78.

[0137]

[0138] In the above formula, Me represents a methyl group.

[0139] As used to obtain (R) 4 )3SiO 1 / 2 The material of the unit (M unit) may be, for example, organosilicon compounds such as triorganochlorosilanes, triorganoalkoxysilanes, and hexaorganodisiloxanes represented by the following structural formulas, but is not limited thereto.

[0140]

[0141] In the above formula, Me represents a methyl group.

[0142] [(A2) Straight-chain or branched organopolysiloxanes]

[0143] The (A2) component is a linear or branched organopolysiloxane having two or more alkenyl groups in one molecule that are bonded to silicon atoms, with a number of 2 to 10 carbon atoms, and a viscosity of 10 to 100,000 mPa·s at 25°C as determined by the method described in JIS K 7117-1:1999.

[0144] By adding component (A2) to the curable silicone resin composition of the present invention, the viscosity and hardness can be adjusted according to the application.

[0145] Examples of alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 5, include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, etc., with vinyl being the most preferred. It is preferable to have 2 or more of the above-mentioned alkenyl groups in one molecule, more preferably 2 to 5.

[0146] Preferably, the viscosity of the above-mentioned organopolysiloxane at 25°C, as determined by the method described in JIS K 7117-1:1999, is 10 to 100,000 mPa·s, more preferably 100 to 50,000 mPa·s, and even more preferably 1,000 to 30,000 mPa·s.

[0147] If the viscosity is above 10 mPa·s, the composition will not become brittle; if it is below 100,000 mPa·s, the workability will not deteriorate.

[0148] Specifically, the following components can be cited as examples of the aforementioned organopolysiloxanes, but are not limited to these.

[0149]

[0150] In the above formula, x, y, and z are each integers greater than or equal to 0, and are numbers that satisfy x + y ≥ 1.

[0151]

[0152] In the above formula, x, y, and z are each integers greater than or equal to 0, and are numbers that satisfy x + y ≥ 1.

[0153]

[0154] In the above formula, x, y, and z are each integers greater than or equal to 0, and are numbers that satisfy x + y ≥ 1.

[0155]

[0156] In the above formula, s, t, u, and p are each integer greater than or equal to 0, and are numbers that satisfy s+t+u+p≥ 1.

[0157] At this point, when the total amount of components (A1) and (A2) is set to 100% by mass, the amount of component (A2) added is preferably 0 to 95% by mass, more preferably 5 to 90% by mass. That is, component (A1) is preferably 5 to 100% by mass, more preferably 10 to 95% by mass. If set within the range described above, the operability is excellent.

[0158] [(B) Organosilicon compounds containing silane]

[0159] (B) is an organosilicon compound having at least 2, preferably 2 to 5, hydrogen atoms (hydrosilyl groups) bonded to silicon atoms in one molecule, wherein the organosilicon compound has an amount such that 1 mol of the SiH group of the (B) component is 0.1 to 4.0 mol, preferably 0.5 to 2.0 mol, and more preferably 0.7 to 1.5 mol of 1 mol of alkenyl groups contained in the (A) component.

[0160] The above-mentioned component (B) is an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. It is preferably selected from organohydrogen polysiloxanes having one or more aryl groups bonded to silicon. In addition, the above-mentioned component (B) is as shown in the average composition formula (5) below.

[0161] R 6 a H b SiO (4-a-b) / 2 (5)

[0162] In the formula, R 6 The groups are monovalent hydrocarbon groups of the same or different kinds, with 1 to 10 unsubstituted or substituted carbon atoms. a and b are preferably positive numbers that satisfy 0.7≤a≤2.1, 0.001≤b≤1.0, and 0.8≤a+b≤3.0. More preferably, they are positive numbers that satisfy 1.0≤a≤2.0, 0.01≤b≤1.0, and 1.5≤a+b≤2.5.

[0163] As R 6 Specifically, examples include saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, and pentyl; saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; and aromatic hydrocarbon groups such as benzyl, phenethyl, and phenylpropyl. These groups are those in which some or all of the hydrogen atoms bonded to the carbon atom are replaced by halogen atoms such as fluorine, bromine, and chlorine, for example, trifluoropropyl and chloropropyl halogenated hydrocarbon groups. Among these groups, saturated hydrocarbon groups such as methyl, ethyl, and propyl, and phenyl, having 1 to 5 carbon atoms, are preferred.

[0164] The organohydropolysiloxane of component (B) above contains at least two (usually 2 to 200) hydrogen atoms bonded to silicon atoms (hydrosilyl group), preferably three or more (usually 3 to 100). Component (B) reacts with component (A) and acts as a crosslinking agent.

[0165] There are no particular restrictions on the molecular structure of the above-mentioned component (B). For example, any molecular structure, such as linear, cyclic, branched, or three-dimensional network (resin-like), can be used as component (B).

[0166] When component (B) above has a linear structure, the hydrosilyl group can bond to silicon atoms at any point on the molecular chain end and side chain, or at both points. Furthermore, the number of silicon atoms (or degree of polymerization) in one molecule is typically 2 to 200, preferably around 3 to 100, and the organohydrosiloxane can be liquid or solid at room temperature (25°C).

[0167] Specific examples of organohydrogen polysiloxanes represented by the above average composition formula (5) include tris(dimethylsiloxy)phenylsilane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-diphenylsiloxane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-diphenylsiloxane-dimethylsiloxane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-methylphenylsiloxane-dimethylsiloxane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-methylphenylsiloxane-dimethylsiloxane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-methylhydrosiloxane-dimethylsiloxane-diphenylsiloxane, a copolymer of trimethylsiloxy-terminated methylhydrosiloxane-methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane, and a copolymer of (CH3)2HSiO 1 / 2 Unit and SiO 4 / 2 Unit and (C6H5)3SiO 1 / 2 Copolymers composed of units, etc.

[0168] In addition, organohydrogen polysiloxanes represented by the following structures may be used, but are not limited to these.

[0169]

[0170] In the above formula, p is an integer greater than or equal to 0, u, v, and w are positive integers, and v ≥ 2.

[0171] The amount of component (B) added is such that the amount of silyl group in component (B) is 0.1 to 4.0 mol, preferably 0.5 to 3.0 mol, and more preferably 0.8 to 2.0 mol, relative to 1 mol of alkenyl group bonded to silicon atoms in the organosilicon resin composition.

[0172] If the amount of component (B) added is less than 0.1 mol of silane in component (B), the composition of the present invention will not undergo a curing reaction, making it difficult to obtain a silicone cured product. Furthermore, the crosslinking density of the resulting cured product will become too low, resulting in insufficient mechanical strength and adversely affecting heat resistance. On the other hand, if the amount added is more than 4.0 mol of the aforementioned silane, a large amount of unreacted silane will remain in the cured product, causing changes in physical properties over time or a decrease in the heat resistance of the cured product. Furthermore, this can lead to foaming caused by dehydrogenation reactions in the cured product.

[0173] [(C) Platinum group metal catalysts]

[0174] The platinum group metal catalyst in component (C) of the present invention is a component incorporated to induce an addition curing reaction in the composition of the present invention, and is a platinum, palladium, or rhodium catalyst. Any conventionally known catalyst that promotes the hydrogenation silylation reaction can be used as a platinum group metal catalyst. Examples of platinum catalysts, such as platinum, platinum black, and chloroplatinic acid, are cited considering cost, including H₂PtCl₆·p'H₂O, K₂PtCl₆, KHPtCl₆·p'H₂O, K₂PtCl₄, K₂PtCl₄·p'H₂O, PtO₂·p'H₂O, PtCl₄·p'H₂O, PtCl₂, H₂PtCl₄·p'H₂O (where p' is a positive integer), or complexes of these components with hydrocarbons such as olefins, alcohols, or vinyl-containing organopolysiloxanes. These catalysts can be used alone or in combination of two or more.

[0175] The amount of component (C) can be the effective amount for curing. Generally, relative to the total amount of components (A) and (B) above, the amount of platinum group metal is preferably in the range of 0.1 to 500 ppm by mass, and particularly preferably in the range of 0.5 to 100 ppm.

[0176] [(D) Metal corrosion inhibitor]

[0177] The metal corrosion inhibitor of component (D) of the present invention is a silylated isocyanurate compound represented by the above general formula (1).

[0178] [Preparation method of silylated modified isocyanurate compound]

[0179] The silylated modified isocyanurate compounds of the present invention can be prepared, for example, by hydrolyzing triglycidyl isocyanurate with chlorosilane and alkoxysilane. The conditions of the hydrolysis reaction only need to be adjusted appropriately. For example, the reaction ratio of epoxy group to trimethylchlorosilane is 1:1 in molar ratio.

[0180] The aforementioned silylated isocyanurate compound exhibits excellent performance as a corrosion inhibitor for metals. When using this silylated isocyanurate compound as a corrosion inhibitor, it can be added in an amount of 0.001 to 5% by mass, preferably 0.01 to 3% by mass, relative to the resin composition.

[0181] In addition to components (A) to (D) above, the curable silicone resin composition of the present invention may also contain components (E) and (F) below.

[0182] [(E) Cyclic polysiloxane]

[0183] (E) The component is a cyclic polysiloxane represented by the following general formula (4). By adding this cyclic polysiloxane to the composition of the present invention, the viscosity, curability and curing properties are adjusted.

[0184]

[0185] In the above general formula (4), R 5 Independently, it is a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, where r is an integer of 1 or 2.

[0186] As mentioned above, R 5 Examples of alkyl groups having 1 to 10 carbon atoms, preferably 1 to 5, include methyl, ethyl, propyl, butyl, pentyl, etc.; examples of alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 8, include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, etc.; examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms, preferably 6 to 8, include aryl groups such as phenyl, tolyl, xylyl, benzyl, phenethyl, phenylpropyl, etc., and aralkyl groups such as phenyl. As R 5 Preferably, hydrogen atoms, vinyl groups, methyl groups, and phenyl groups are present, but hydrogen atoms and vinyl groups do not coexist in a single molecule.

[0187] The amount of cyclic polysiloxane added relative to component (A) above is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass. Furthermore, when component (E) above has an alkenyl group and / or hydrogen atoms directly bonded to silicon atoms, the amount of cyclic polysiloxane added is preferably such that, relative to 1 mol of all alkenyl groups in the composition of the present invention, the amount of all hydrosilyl groups in the composition is 0.1 to 4.0 mol, preferably 0.5 to 2.0 mol.

[0188] As a specific example of the cyclic organopolysiloxane represented by the above general formula (4), cyclic polysiloxanes represented by the following structures can be used, but are not limited thereto.

[0189]

[0190] In the above formula, Me represents a methyl group.

[0191] [(F) Fluorescent material, white pigment]

[0192] Furthermore, (F) phosphors and white pigments may be further incorporated into the curable silicone resin composition of the present invention. Because the curable silicone resin composition of the present invention exhibits excellent weather resistance, even when containing phosphors, it does not cause a significant decrease in fluorescence properties as is common in the past.

[0193] The amount of phosphor and white pigment added is preferably 0 to 500 parts by mass relative to the total of 100 parts by mass of components (A) and (B), and more preferably 0 to 300 parts by mass.

[0194] At this time, as a white pigment, it is preferable to contain at least one inorganic white pigment selected from titanium dioxide, zinc oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate. The white pigment can be appropriately incorporated in an amount of 600 parts by mass or less (e.g., 0 to 600 parts by mass, usually 1 to 600 parts by mass, preferably 10 to 400 parts by mass) relative to the total of 100 parts by mass of the components (A) to (D) above.

[0195] [(G) Other]

[0196] Other additives include, for example, reinforcing inorganic fillers such as silica, glass fiber, and fumed silica; non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, cerium fatty acid, barium fatty acid, cerium alkoxide, and barium alkoxide; and nanofillers such as silica (SiO2), alumina (Al2O3), iron oxide (FeO2), iron tetroxide (Fe3O4), lead oxide (PbO2), tin oxide (SnO2), cerium oxide (Ce2O3, CeO2), calcium oxide (CaO), manganese tetroxide (Mn3O4), and barium oxide (BaO). These additives can be appropriately incorporated into the mixture in an amount of 600 parts by mass or less (e.g., 0 to 600 parts by mass, typically 1 to 600 parts by mass, preferably 10 to 400 parts by mass) relative to the total of 100 parts by mass of the components (A) to (D) above.

[0197] The curable silicone resin composition of the present invention can be applied to a specified substrate and then cured, depending on the application. Regarding curing conditions, although it is sufficiently cured at room temperature (25°C), heat curing can be performed as needed. The temperature for heating can be set, for example, from 60 to 200°C.

[0198] Furthermore, the curable silicone resin composition of the present invention preferably provides a cured product with a thickness of 1 mm, i.e., a cured product with a transmittance of 70% or more, preferably 80% or more, at a wavelength of 400 to 800 nm, particularly at a wavelength of 450 nm, as measured according to JIS K 7361-1. Additionally, a spectrophotometer U-4100 manufactured by Hitachi High-Tech Corporation can be used, for example, to measure the transmittance.

[0199] Furthermore, the curable silicone resin composition of the present invention preferably provides a cured product that is heat-cured from the curable silicone resin composition and has a refractive index in the range of 1.43 to 1.57 at 23°C and 589 nm as determined by JIS K 7142:2014 A method.

[0200] If a cured material with the aforementioned direct light transmittance or refractive index is provided, it exhibits excellent transparency and is therefore particularly suitable for optical applications such as sealing materials for LEDs.

[0201] If such a curable silicone resin composition of the present invention is used, a cured product with excellent mechanical properties, transparency, crack resistance, heat resistance, and sulfidation resistance is provided.

[0202] Semiconductor Devices

[0203] Furthermore, the present invention provides a semiconductor device obtained by sealing a semiconductor element using a cured product of the curable silicone resin composition of the present invention described above.

[0204] As described above, since the curable silicone resin composition of the present invention provides a cured product with excellent transparency or heat resistance, it is suitable for use as a lens material, protective coating agent, molding agent, etc., in light-emitting semiconductor devices, and is particularly suitable for sealing LED elements such as blue LEDs, white LEDs, and ultraviolet LEDs. Furthermore, since the curable silicone resin composition of the present invention has excellent heat resistance, when used as a wavelength conversion film material with the addition of silicate phosphors or quantum dot phosphors, long-term reliability under high humidity can be ensured, providing a light-emitting semiconductor device with good moisture resistance and long-term color rendering. As described above, it is preferable to use the aforementioned semiconductor element as a light-emitting element.

[0205] When sealing light-emitting semiconductor elements such as LEDs using the curable silicone resin composition of the present invention, for example, the curable silicone resin composition of the present invention can be applied to an LED element mounted on a premolded package formed of thermoplastic resin, and the composition can be cured on the LED element, thereby sealing the LED element with the cured product of the curable silicone resin composition. Alternatively, the LED element can be coated with a varnish prepared by dissolving the composition in an organic solvent such as toluene, xylene, or PGMEA.

[0206] The curable silicone resin composition of the present invention is most suitable for optical applications such as display materials, optical recording media materials, optical instrument materials, optical component materials, optical fiber materials, optoelectronic functional organic materials, and semiconductor integrated circuit peripheral materials due to its excellent heat resistance, sulfidation resistance, UV resistance, transparency, crack resistance, and long-term reliability.

[0207] Example

[0208] The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited to the examples described below. Additionally, parts represent parts by weight, Me represents methyl, Vi represents vinyl, and Ph represents phenyl.

[0209] Furthermore, in the embodiments, a device manufactured by BRUKER (device name: AVANCEIII 400M) was used, with deuterated chloroform as the solvent and chloroform as the internal standard. 1 H-NMR determination.

[0210] (Example 1)

[0211] [Synthesis example]

[0212] 297.3 g (1.0 mol) of triglycidyl isocyanurate was added to a reaction vessel and dissolved in 350 g of toluene. 217.3 g (2.0 mol) of trimethylchlorosilane was then added, and the mixture was heated to 80 °C. 18 g (1.0 mol) of water was added dropwise over 30 minutes. After the addition was complete, the mixture was further heated and stirred at 80 °C for 3 hours. Tris(pentafluorophenyl)borane was then added as a catalyst to initiate the chemical reaction.

[0213] After heating, the mixture was cooled to room temperature (25°C) and washed with a 10% (w / w) sodium sulfate aqueous solution. Then, 50 g of a magnesium-aluminum solid solution (trade name: KW-2200, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 1 hour to adsorb and remove tris(pentafluorophenyl)borane. KW-2200 was removed by pressure filtration, and residual solvent was removed by distillation under reduced pressure to obtain a mixture of silylated isocyanurate compounds represented by formulas (A') and (B') below.

[0214]

[0215]

[0216] Figure 1 The mixture is shown 1 H-NMR spectrum. Additionally, the peaks in the spectrum are shown below.

[0217] 1 H-NMR(CDCl3)ppm: δ0.00(9H), δ2.5-2.7(2.7H), δ3.1(1.3H), δ3.5(1.7H), δ3.6-3.8(1.8H), δ3.8-4.1(6H), δ3.8-4.1(6H), δ4.1-4.3(0.9H).

[0218] [Preparation of Organosilicon Resin Compositions]

[0219] 157 parts by mass of a linear dimethyl polysiloxane (viscosity: 5,000 mPa·s, vinyl equivalent: 0.006 mol / 100 g) with vinyl-terminated ends, and 50 parts by mass of CH2=CH(CH3)2SiO2 (6.9 mol%) were prepared. 1 / 2 Unit, 37.3 mol% (CH3)3SiO 1 / 2 Unit, 55.8 mol% SiO 4 / 2 The resinous (network chain) organopolysiloxane (weight average molecular weight: 5,200, vinyl equivalent of 0.095 mol / 100 g) of the unit composition, 8.1 parts by mass of the average structural formula is a mixture of organohydrogen polysiloxane represented by the following formula (C') until homogeneous.

[0220]

[0221] 2.2 parts by mass of the silylated isocyanurate compound synthesized in the synthesis example as a corrosion inhibitor were added to the mixture, and then 0.2 parts by mass of platinum(0)-1,3-divinyltetramethyldisiloxane complex (containing 1.0% by mass of platinum) were added and mixed to prepare an organosilicon resin composition.

[0222] [Heat resistance]

[0223] The prepared silicone resin composition was heated at 150°C for 4 hours to obtain a cured product (10mm × 15mm × 1mm). These cured products were then subjected to a heat resistance test at 200°C for 100 hours. The appearance and transmittance at 450nm of the cured product after the heat resistance test were compared with the initial appearance and transmittance (before the test) to evaluate the heat resistance. Furthermore, the initial appearance of the cured product sample was colorless and transparent. Additionally, the appearance of the sample after the heat resistance test was also colorless and transparent.

[0224] The heat resistance test was conducted using an unsaturated high accelerated life testing apparatus (HASTEST PC-242HSR2) manufactured by HIRAYAMA Manufacturing Corporation. Furthermore, transmittance was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Tech Corporation. The results are shown in Table 1.

[0225] [Sulfurization resistance]

[0226] Using the prepared silicone resin composition, a 1cm layer was applied with a thickness of 0.6mm. 2 The silver-plated plate was sealed and cured at 150°C for 4 hours to obtain a sample. This sample, along with 3g of sulfur powder, was placed in a sealed container and placed in a constant temperature bath at 80°C for 50 hours. The initial light reflectance of the silver-plated plate at 450nm was then measured using an X-rite 8200 manufactured by SDG KK. The initial reflectance was 90%.

[0227] The resistance to sulfurization is calculated using the following formula and judged according to the following standards.

[0228] Vulcanization resistance (%) = ((reflectance after vulcanization test [%)) / (initial reflectance [%))) × 100

[0229] (Judgment Criteria)

[0230] ○: Sulfurization resistance is over 90%.

[0231] △: Sulfurization resistance is above 85% and less than 90%.

[0232] ×: Sulfurization resistance less than 85%

[0233] (Comparative Example 1)

[0234] The silicone resin composition was prepared in the same manner as in Example 1, except that the silylated isocyanurate compound of the present invention was not added. Furthermore, the heat resistance and sulfur resistance were evaluated in the same manner as in Example 1. The cured sample was initially colorless and transparent, and the sample after the heat resistance test was also colorless and transparent. In addition, the reflectance changed from 90% (initial value) to 76.1% (after the sulfur resistance test). The results are shown in Table 1.

[0235] (Comparative Example 2)

[0236] Except for the addition of 2.2 parts by weight of benzotriazole to replace the silylated isocyanurate compound of the present invention, the silicone resin composition was prepared in the same manner as in Example 1. Furthermore, the heat resistance and sulfur resistance were evaluated in the same manner as in Example 1. The cured sample initially appeared colorless and transparent, but after the heat resistance test, the sample appeared reddish-brown and transparent with a light transmittance of 86.9%. In addition, the reflectance changed from 90% (initial value) to 87.8% (after the sulfur resistance test).

[0237] The results are shown in Table 1.

[0238] (Comparative Example 3)

[0239] Except for the addition of 2.2 parts by weight of zinc 2-ethylhexanoate to replace the silylated isocyanurate compound of the present invention, the silicone resin composition was prepared in the same manner as in Example 1. Furthermore, the heat resistance and sulfur resistance were evaluated in the same manner as in Example 1. The cured sample initially appeared colorless and transparent, but after the heat resistance test, the sample appeared yellow and transparent with a light transmittance of 90.3%. In addition, the reflectance changed from 90% (initial value) to 85.9% (after the sulfur resistance test).

[0240] The results are shown in Table 1.

[0241] [Table 1]

[0242]

[0243] As shown in Table 1, Comparative Example 1, which did not contain a corrosion inhibitor, was colorless and transparent after the heat resistance test, demonstrating heat resistance, but its sulfidation resistance decreased significantly. Furthermore, Comparative Examples 2 and 3, whose corrosion inhibitors were benzotriazole and zinc 2-ethylhexanoate, respectively, showed discoloration after the heat resistance test, exhibiting poor resistance to discoloration and a decrease in heat resistance. Their sulfidation resistance also decreased.

[0244] In contrast, the cured product (Example 1) obtained from an addition reaction curing composition containing the silylated isocyanurate compound of the present invention as a corrosion inhibitor exhibits high light transmittance after a heat resistance test and high reflectance after a sulfur resistance test. Therefore, it can be seen that the silylated isocyanurate compound of the present invention is particularly preferred as a corrosion inhibitor for metals or for resin compositions used in semiconductor protective layers.

[0245] As Examples 2-4 and Comparative Examples 4-7, compositions described in detail below were prepared. The physical properties of the prepared compositions and their cured products were measured by the following methods. The results are shown in Table 3.

[0246] [Physical Property Evaluation]

[0247] (1) Properties

[0248] The flowability of each composition before curing was confirmed. 50g of the composition was added to a 100ml glass bottle, which was then placed horizontally and allowed to stand at 25°C for 10 minutes. If the resin flowed during this period, it was considered to be in liquid form.

[0249] (2) Viscosity

[0250] The viscosity of each composition before curing at 25°C was determined by the method described in JIS K 7117-1:1999.

[0251] (3) Refractive index

[0252] Regarding the refractive index of each composition before curing, the refractive index of light with a wavelength of 589 nm was measured at 25°C using a digital refractometer RX-9000α manufactured by ATAGO CO.,LTD.

[0253] (4) Hardness (Type D)

[0254] According to JIS K 6249:2003, the hardness of the cured products obtained by curing each composition at 150°C for 4 hours was determined using a Durometer Type D hardness tester.

[0255] (5) Elongation at break and tensile strength

[0256] In accordance with JIS K 6249:2003, the elongation at break and tensile strength of the cured products obtained by curing each composition at 150℃ for 4 hours were determined.

[0257] (6) Heat resistance

[0258] Each silicone resin composition was heated at 150°C for 4 hours to obtain a cured product (10mm × 15mm × 1mm). These cured products were then subjected to a 100-hour heat resistance test at 200°C. The appearance and transmittance at 450nm of the cured product after the heat resistance test were compared with the initial appearance and transmittance (before the test) to evaluate the heat resistance.

[0259] In the heat resistance test, an unsaturated high accelerated life test apparatus (apparatus name: HASTEST PC-242HSR2) manufactured by HIRAYAMA Manufacturing Corporation was used.

[0260] In addition, transmittance was measured using a spectrophotometer (device name: U-4100) manufactured by Hitachi High-Tech Corporation.

[0261] (7) Resistance to sulfurization

[0262] To achieve a thickness of 0.6 mm, the silicone resin compositions prepared in Examples 2-4 and Comparative Examples 4-7 were used to apply a 1 mm thick silicone resin to a surface with a thickness of 1 mm. 2 The silver-plated plate was sealed and cured at 150°C for 4 hours to obtain a sample. This sample, along with 3g of sulfur powder, was placed in a sealed container and placed in a constant temperature bath at 80°C for 50 hours. The initial light reflectance of the silver-plated plate at 450nm was then measured using an X-rite 8200 (manufactured by SDG KK). The initial reflectance was 90%. Sulfur resistance was calculated using the following formula and judged according to the following standards.

[0263] Vulcanization resistance (%) = ((reflectance after vulcanization test [%)) / (initial reflectance [%))) × 100

[0264] (Judgment Criteria)

[0265] ○: Sulfurization resistance is over 90%.

[0266] △: Sulfurization resistance is above 85% and less than 90%.

[0267] ×: Sulfurization resistance less than 85%

[0268] (Example 2)

[0269] Add the following ingredients and stir thoroughly to prepare a curable silicone resin composition:

[0270] (A1) Composition: 75 mol% PhSiO 3 / 2 Unit, 25 mol% ViPhMeSiO 1 / 2The unit consists of branched phenylmethyl polysiloxane (Mw = 2,500, with 0.04 mol / 100 g of hydroxyl groups bonded to silicon atoms and 0.06 mol / 100 g of alkoxy groups bonded to silicon atoms), in 30 parts;

[0271] (B) Component: The organohydrogen polysiloxane represented by the following formula (6) is an amount in which the ratio of the total number of silicon atoms bonded to hydrogen atoms in component (B) to the total number of silicon atoms bonded to vinyl groups in components (A) and (D) (hereinafter sometimes expressed as the SiH / SiVi ratio) is 1.0.

[0272] (C) Components: 0.01 parts of an octanol-modified solution of chloroplatinic acid (platinum content: 1% by mass); and

[0273] (D) Components: The following formula (7) is 0.05 parts.

[0274] The above components are shown in Table 2.

[0275]

[0276]

[0277] (Example 3)

[0278] Add the following ingredients and stir thoroughly to prepare a silicone rubber composition:

[0279] (A1) Ingredients: 30 parts of the organopolysiloxane used in Example 2;

[0280] (B) Component: The organohydrogen polysiloxane represented by the above formula (6) is an amount in which the ratio of the total number of silicon atoms bonded to hydrogen atoms in component (B) to the total number of silicon atoms bonded to vinyl groups in components (A) and (D) (hereinafter sometimes expressed as SiH / SiVi ratio) is 1.0.

[0281] (C) Components: Octyl alcohol modified solution of chloroplatinic acid (platinum content: 1% by mass), which is 0.01 parts;

[0282] (D) Components: 0.01 parts of the following formula (8); and

[0283] (E) Components: 2 parts of the organosilicon compound represented by the formula (9) below.

[0284] The above components are shown in Table 2.

[0285]

[0286]

[0287] (Example 4)

[0288] Add the following ingredients and stir thoroughly to prepare a silicone rubber composition:

[0289] (A1) Composition: 55 mol% SiO 4 / 2 Unit, 7 mol% ViMeSiO 2 / 2 Unit, 38 mol% Me3SiO 1 / 2 The unit consists of branched methyl polysiloxane (Mw = 5,600, with 0.2 mol / 100 g of hydroxyl groups bonded to silicon atoms and 0.02 mol / 100 g of alkoxy groups bonded to silicon atoms), in 30 parts;

[0290] (A2) Ingredients: 50 parts of the following formula (10);

[0291] (B) Component: The organohydrogen polysiloxane represented by the following formula (11) is an amount in which the ratio of the total number of silicon atoms bonded to hydrogen atoms in component (B) to the total number of silicon atoms bonded to vinyl groups in components (A) and (D) (hereinafter sometimes expressed as SiH / SiVi ratio) is 1.0.

[0292] (C) Components: Octyl alcohol modified solution of chloroplatinic acid (platinum content: 1% by mass), which is 0.01 parts;

[0293] (D) Components: 0.01 parts of the following formula (12); and

[0294] (E) Components: 1 part of the organosilicon compound represented by formula (9) above.

[0295] The above components are shown in Table 2.

[0296]

[0297]

[0298]

[0299] (Comparative Example 4)

[0300] The composition was prepared in the same manner as in Example 2, except that component (D) used in Example 2 was not added. See Table 2 for further details.

[0301] (Comparative Example 5)

[0302] The composition was prepared in the same manner as in Example 2, except that 0.05 parts of triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation) were used in place of component (D) used in Example 2. The results are also shown in Table 2.

[0303] (Comparative Example 6)

[0304] The composition was prepared in the same manner as in Example 2, except that 0.05 parts of triglycidyl isocyanurate (manufactured by Nissan Chemical Corporation) were used in place of component (D) used in Example 2. The composition is also shown in Table 2.

[0305] (Comparative Example 7)

[0306] The composition was prepared in the same manner as in Example 2, except that 0.05 parts of monoallyl diglycidyl isocyanurate (manufactured by SHIKOKU CHEMICALSCORPORATION) were used in place of component (D) in Example 2. The composition is also shown in Table 2.

[0307]

[0308] [Table 3]

[0309]

[0310] As shown in Table 3, the sulfur resistance of Comparative Example 4, which did not contain component (D), deteriorated. Furthermore, the heat resistance of Comparative Examples 5-7, which contained isocyanurate derivatives without silane as component (D), deteriorated, and no improvement in sulfur resistance was observed.

[0311] On the other hand, as shown in Table 3, in Examples 2 to 4, which used the silylated isocyanurate compound of the present invention as component (D), a cured product was obtained that was transparent and had sufficient hardness, excellent elongation at break and tensile strength, as well as excellent heat resistance and HAST resistance.

[0312] As described above, the curable silicone resin composition of the present invention can provide a cured product with excellent heat resistance and sulfidation resistance.

[0313] Industrial applicability

[0314] The silylated isocyanurate compounds of the present invention exhibit excellent performance as corrosion inhibitors for metals. In particular, due to their excellent resistance to discoloration after heat resistance testing, they are especially suitable as corrosion inhibitors for resin compositions used in applications requiring durability or transparency, such as sealants for optoelectronic semiconductors.

[0315] Furthermore, this invention is not limited to the above embodiments. The above embodiments are illustrative examples, and any technical solution having a substantially identical structure and achieving the same effect as the technical concept described in the claims of this invention is included within the scope of protection of this invention.

Claims

1. A silylated isocyanurate compound, represented by the following general formula (1), In the general formula (1), R is independently a substituent selected from any one of the groups represented by general formula (2-a) or general formula (2-b) below, and at least one of said R is of general formula (2-b). In the general formulas (2-a) to (2-b), R 1 Represents a hydrogen atom; q represents an integer from 1 to 5; R 2 Each of the substituents is independently selected from hydrogen atoms and groups represented by the following general formula (3), and at least one R 2 For the following general formula (3), R 4 OR 2 , In the general formula (3), R 3 Alkyl groups having 1 to 10 carbon atoms can be represented independently.

2. A metal corrosion inhibitor, characterized in that, The metal corrosion inhibitor contains the silylated isocyanurate compound as described in claim 1.

3. A curable organosilicon resin composition, characterized in that, It contains: (A) An organosilicon compound having at least two alkenyl groups in one molecule; (B) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule, wherein the amount of the organosilicon compound is such that 1 mol of the SiH group of component (B) is 0.1 to 4.0 mol relative to 1 mol of the alkenyl group of component (A); (C) A platinum group metal catalyst, wherein the total amount of platinum group metals relative to the total amount of components (A) and (B) is 0.1 to 500 ppm by mass; and (D) The silylated isocyanurate compound of claim 1 as a metal corrosion inhibitor, wherein the content relative to the curable silicone resin composition is 0.001 to 5% by mass. The component (A) is: (A1) contains SiO 4 / 2 Unit or R 4 SiO 3 / 2 A resinous organopolysiloxane comprising at least one of the units, and having at least two alkenyl groups bonded to silicon atoms in one molecule, wherein R 4 It is an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms. Component (B) is shown in the following average composition formula (5). In equation (5), R 6 , where 1 to 10 carbon atoms are monovalent hydrocarbon groups of the same or different kinds, where some or all of the hydrogen atoms bonded to carbon atoms are replaced by halogen atoms, and a and b are positive numbers satisfying 0.7≤a≤2.1, 0.001≤b≤1.0, and 0.8≤a+b≤3.

0.

4. The curable silicone resin composition according to claim 3, characterized in that, The (A1) composition is composed of 0-60 mol% SiO2. 4 / 2 Unit, 0~90 mol% R 4 SiO 3 / 2 Unit, 0~50 mol% (R) 4 )2SiO 2 / 2 Unit and 10~50 mol% (R 4 )3SiO 1 / 2 The SiO2 unit is composed of 4 / 2 Unit and the R 4 SiO 3 / 2 The sum of the units is more than 50 mol% of resin-like organopolysiloxanes. The organopolysiloxane has a weight-average molecular weight of 1,000 to 5,000, and A molecule contains at least two alkenyl groups bonded to silicon atoms. The organopolysiloxane has a derivative from the SiO₂ 4 / 2 Unit, the R 4 SiO 3 / 2 Unit, the (R) 4 )2SiO 2 / 2 Unit and the (R) 4 )3SiO 1 / 2 Unitary, uncondensed, and partially residual hydroxyl and alkoxy groups bonded to silicon atoms. The amount of the hydroxyl group is 0.001~1.0 mol / 100g. The amount of the alkoxy group bonded to silicon atoms, having 1 to 10 carbon atoms, is less than 1.0 mol / 100g.

5. The curable silicone resin composition according to claim 3, characterized in that, In addition to component (A1), component (A) further comprises: (A2) A linear or branched organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and having a viscosity of 10 to 100,000 mPa·s at 25°C as determined by the method described in JIS K7117-1:1999.

6. The curable silicone resin composition according to claim 4, characterized in that, In addition to component (A1), component (A) further comprises: (A2) A linear or branched organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and having a viscosity of 10 to 100,000 mPa·s at 25°C as determined by the method described in JIS K7117-1:1999.

7. The curable silicone resin composition according to claim 5, characterized in that, Regarding the blending amount of component (A1) and component (A2), when the total amount of components (A1) and (A2) is set to 100% by mass, component (A1) is 5 to 95% by mass.

8. The curable silicone resin composition according to claim 6, characterized in that, Regarding the blending amount of component (A1) and component (A2), when the total amount of components (A1) and (A2) is set to 100% by mass, component (A1) is 5 to 95% by mass.

9. The curable silicone resin composition according to any one of claims 3 to 8, further comprising a cyclic siloxane represented by the following general formula (4) as component (E), wherein the cyclic siloxane represented by general formula (4) is 0.1 to 30% by mass relative to the total mass of components (A) and (B). So that the total amount of all hydrosilyl groups in the curable silicone resin composition is 0.1 to 4.0 mol relative to 1 mol of all alkenyl groups in the curable silicone resin composition, contains a cyclic siloxane represented by the general formula (4). In the above general formula (4), R 5 Independently, it is a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, where r is an integer of 1 or 2.

10. The curable organosilicon resin composition according to any one of claims 3 to 8, characterized in that, The curable silicone resin composition contains at least one inorganic white pigment selected from titanium dioxide, zinc oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate.

11. The curable silicone resin composition according to claim 9, characterized in that, The curable silicone resin composition contains at least one inorganic white pigment selected from titanium dioxide, zinc oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate.

12. A semiconductor device comprising a cured product of the curable silicone resin composition according to any one of claims 3 to 11 and a semiconductor element.

13. The semiconductor device according to claim 12, characterized in that, The thickness of the cured material is 1 mm, and the transmittance of the cured material to direct light with a wavelength of 450 nm is more than 70%.

14. The semiconductor device according to claim 12, characterized in that, The semiconductor element is a light-emitting element.

15. The semiconductor device according to claim 13, characterized in that, The semiconductor element is a light-emitting element.

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