Liquid curable composition, cured product and method for producing individual cured products

Abstract

To provide a liquid curable composition having excellent workability in the coating step and capable of suppressing cracking of a cured product when cutting the cured product.SOLUTION: There is provided a liquid curable composition comprising a curable organopolysiloxane compound, silica fine particles having an average primary particle diameter of 1 nm or more and 20 nm or less, a silane coupling agent having a nitrogen atom in the molecule and a silane coupling agent having an anhydride structure in the molecule, wherein 1 pt.mass of the silica fine particles is added based on 100 pts.mass of the liquid curable composition, 12 pts.mass of the silane coupling agent having a nitrogen atom in the molecule is added based on 100 pts.mass of the solid content of the liquid curable composition, 1.8 pts.mass or more of the silane coupling agent having an anhydride structure in the molecule is added based on 100 pts.mass of the solid content of the liquid curable composition and the viscosity of the liquid curable composition at 23°C is 5 Pa s or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid curable composition, a cured product, and a method for forming individual pieces of the cured product. [Background technology]

[0002] Liquid curable compositions are widely used as raw materials for optical components and molded articles, adhesives for semiconductor elements such as optical semiconductor elements, transistors, and sensors, coating agents, etc., and have been improved in various ways depending on their applications. For example, Patent Document 1 discloses a liquid curable composition improved for use as an adhesive for optical semiconductor elements, etc.

[0003] When using such a liquid curable composition, the liquid curable composition may be applied to a sheet-like substrate, the applied coating liquid may be heated and dried to form a layer of the curable composition, and the layer may be further heated to harden the composition and form a cured product. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2014 / 069508 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a liquid curable composition is applied to a sheet-like substrate, at least one of repelling (collection of the spread liquid) and roughness of the coated surface occurs, which can reduce the workability of the application process. In addition, in order to use the cured product obtained by applying the liquid curable composition to a sheet-like substrate, drying and curing it as an optical component or the like, the cured product is sometimes cut into individual pieces, but when the cured product is cut, cracks (chipping) can occur in the cured product.

[0006] An object of the present invention is to provide a liquid curable composition that has excellent workability in the coating step and that can suppress cracks in the cured product when the cured product is cut. [Means for solving the problem]

[0007] According to the present invention, A liquid curable composition, a curable organopolysiloxane compound; Silica microparticles having an average primary particle diameter of 1 nm or more and 20 nm or less; a silane coupling agent having a nitrogen atom in the molecule; a silane coupling agent having an acid anhydride structure in the molecule, the silica fine particles are added in an amount of 1 part by mass or more relative to 100 parts by mass of the liquid curable composition; the silane coupling agent having a nitrogen atom in the molecule is added in an amount of 12 parts by mass or more per 100 parts by mass of the solid content of the liquid curable composition, the silane coupling agent having an acid anhydride structure in the molecule is added in an amount of 1.8 parts by mass or more per 100 parts by mass of the solid content of the liquid curable composition, A liquid curable composition is provided having a viscosity of 5 Pa·s or more at 23°C. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a liquid curable composition that has excellent workability in the coating step and that can suppress cracks in the cured product when the cured product is cut. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following embodiments do not limit the invention according to the claims, and not all combinations of features described in the embodiments are necessarily essential to the invention. Two or more features among the multiple features described in the embodiments may be arbitrarily combined.

[0010] <Liquid curable composition according to this embodiment> The liquid curable composition according to this embodiment contains a curable organopolysiloxane compound, silica microparticles having an average primary particle diameter of 1 nm to 20 nm, a silane coupling agent having a nitrogen atom in the molecule, and a silane coupling agent having an acid anhydride structure in the molecule. The silica microparticles are added in an amount of 1 part by mass or more per 100 parts by mass of the liquid curable composition. Furthermore, the viscosity of the liquid curable composition at 23°C is 5 Pa·s or more. This reduces repelling and roughening of the coated surface when the liquid curable composition according to this embodiment is applied to a sheet-like substrate, improving workability in the application process.

[0011] Furthermore, in the liquid curable composition according to this embodiment, 12 parts by mass or more of a silane coupling agent having a nitrogen atom in the molecule is added relative to 100 parts by mass of the solid content of the liquid curable composition (components (i.e., active ingredients) excluding the solvent (S) (described below) contained in the liquid curable composition), and 1.8 parts by mass or more of a silane coupling agent having an acid anhydride structure in the molecule is added relative to 100 parts by mass of the solid content of the liquid curable composition. As a result, when the liquid curable composition according to this embodiment is applied to a sheet-like substrate, dried, and cured, the cured product is cut into a lattice pattern to produce individual pieces of the cured product, and cracks in the cured product are suppressed.

[0012] The term "liquid curable composition" refers to a composition that is a viscous liquid and has fluidity at room temperature. Here, room temperature refers to 23°C. The liquid curable composition can be used in a coating process because it has the properties of this state.

[0013] The uses of the liquid curable composition according to this embodiment are not particularly limited, and may include raw materials for optical components and molded articles, adhesives for semiconductor elements such as optical semiconductor elements, transistors, and sensors, etc. In one embodiment, the liquid curable composition can be cut into a grid pattern after curing and used as individual cured pieces. For example, a light-emitting device includes a support member, an insulating substrate provided on the support member and having optical semiconductor elements stacked thereon, and a translucent insulating member bonded to the insulating substrate via an adhesive, and light from the optical semiconductor elements is extracted through the insulating member. A plate-shaped cured product of the liquid curable composition according to this embodiment can be used as an insulating member for such a light-emitting device.

[0014] (viscosity) The liquid curable composition according to this embodiment has a viscosity of 5 Pa·s or more at 23°C. In another embodiment, the viscosity of the liquid curable composition may be 10 Pa·s or more, in yet another embodiment, 20 Pa·s or more, and in yet another embodiment, 30 Pa·s or more. This suppresses repelling and roughening of the coated surface when the liquid curable composition is applied to a sheet-like substrate, improving workability in the application step.

[0015] On the other hand, the upper limit of the viscosity of the liquid curable composition is not particularly limited, but in one embodiment, it can be less than 65 Pa·s, in another embodiment, less than 60 Pa·s, in yet another embodiment, less than 55 Pa·s, and in yet another embodiment, less than 50 Pa·s. This improves workability in forming a layer of the curable composition. In one embodiment, the viscosity range of the liquid curable composition can be 5 Pa·s or more and less than 65 Pa·s, in another embodiment, 10 Pa·s or more and less than 60 Pa·s, in yet another embodiment, 20 Pa·s or more and less than 55 Pa·s, and in yet another embodiment, 30 Pa·s or more and less than 50 Pa·s. This suppresses repelling and roughening of the coated surface when the liquid curable composition is applied to a sheet-like substrate, improving workability in the application process.

[0016] The viscosity of the liquid curable composition can be confirmed, for example, as follows: Using a rheometer, a cone plate with a radius of 50 mm and a cone angle of 0.5° is used, and the viscosity is measured at a shear rate of 2 s at 23°C. -1 At this time, the viscosity is measured.

[0017] (Curable organopolysiloxane compound (A)) The liquid curable composition according to this embodiment contains a curable organopolysiloxane compound (A) (hereinafter, sometimes referred to as "component (A)"). By containing component (A), the liquid curable composition is more likely to exhibit excellent curability and light resistance.

[0018] The curable organopolysiloxane compound (A) is a compound containing a carbon-silicon bond and a siloxane bond (-Si-O-Si-) in the molecule. Because component (A) is a thermosetting compound, it can have at least one functional group selected from the group consisting of functional groups capable of undergoing a condensation reaction upon heating and functional groups capable of undergoing a condensation reaction via hydrolysis. Such functional groups can be at least one selected from the group consisting of hydroxyl groups and alkoxy groups, such as hydroxyl groups or alkoxy groups having 1 to 10 carbon atoms.

[0019] The main chain structure of the curable organopolysiloxane compound (A) is not limited and may be any of linear, ladder, and cage structures. For example, a linear main chain structure may be a structure represented by the following formula (a-1), a ladder main chain structure may be a structure represented by the following formula (a-2), and a cage main chain structure may be a structure represented by the following formula (a-3).

[0020] [ka]

[0021] [ka]

[0022] [ka]

[0023] In formulas (a-1) to (a-3), Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group, and the organic group can be an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group. The multiple Rx in formula (a-1), the multiple Ry in formula (a-2), and the multiple Rz in formula (a-3) may be the same or different. However, two Rx in formula (a-1) cannot both be hydrogen atoms.

[0024] Examples of the alkyl group of the unsubstituted or substituted alkyl group include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, and n-octyl groups.

[0025] Examples of the cycloalkyl group of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0026] Examples of the alkenyl group of the unsubstituted or substituted alkenyl group include alkenyl groups having 2 to 10 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl.

[0027] Examples of the substituent on the alkyl group, cycloalkyl group, and alkenyl group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a thiol group; an epoxy group; a glycidoxy group; a (meth)acryloyloxy group; and unsubstituted or substituted aryl groups such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group.

[0028] Examples of the aryl group of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0029] The lower limit of the number of aryl groups in Rx, Ry, and Rz (organic groups) can be 20% or more in one embodiment, 50% or more in another embodiment, 70% or more in yet another embodiment, and 90% or more in yet another embodiment. This facilitates excellent curability and light resistance, and also facilitates the production of a cured product with a high refractive index, making it suitable for use in devices requiring a high refractive index. The upper limit of the number of aryl groups in the organic groups is not particularly limited, but can be 100% or less in one embodiment. The range of the number of aryl groups can be 20% or more and 100% or less in one embodiment, 50% or more and 100% or less in another embodiment, 70% or more and 100% or less in yet another embodiment, and 90% or more and 100% or less in yet another embodiment.

[0030] Examples of the substituent on the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth)acryloyloxy group; and unsubstituted or substituted aryl groups such as phenyl group, 4-methylphenyl group, and 4-chlorophenyl group.

[0031] Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-t-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl group.

[0032] Among these, Rx, Ry, and Rz can be a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group, and an example thereof is a phenyl group.

[0033] Furthermore, Rx, Ry, and Rz can be a fluoro group, which is a substituent having a fluorine atom. Examples of the fluoro group include a fluoroalkyl group, a fluorocycloalkyl group, a fluoroalkenyl group, and a fluoroaryl group. The fluoro group may or may not contain a hydrogen atom.

[0034] The lower limit of the number of fluoro groups in Rx, Ry, and Rz (organic groups) can be 10% or more in one embodiment, 20% or more in another embodiment, 30% or more in yet another embodiment, and 40% or more in yet another embodiment. This facilitates the attainment of excellent curability and light resistance, and also facilitates the production of a cured product with a low refractive index, making it suitable for use in devices requiring a low refractive index. The upper limit of the number of fluoro groups in the organic groups is not particularly limited, but can be 90% or less in one embodiment, 80% or less in another embodiment, 70% or less in yet another embodiment, and 60% or less in yet another embodiment. This facilitates the preparation of a more stable curable organopolysiloxane compound (A) and the preparation of a liquid curable composition with stable performance. In one embodiment, the range of the proportion of the number of fluoro groups can be 10% or more and 90% or less, in another embodiment, 20% or more and 80% or less, in yet another embodiment, 30% or more and 70% or less, and in yet another embodiment, 40% or more and 60% or less. By using a curable organopolysiloxane compound (A) in which the proportion of the number of fluoro groups falls within the above range, it becomes easier to obtain a layer of the curable composition that gives a cured product with excellent adhesiveness.

[0035] In one embodiment, the organic groups may be fluoro groups and methyl groups. In one embodiment, the number ratio of fluoro groups may be 10% or more and 90% or less of methyl groups, in another embodiment, 20% or more and 80% or less of methyl groups, in yet another embodiment, 30% or more and 70% or less of fluoro groups, in yet another embodiment, 40% or more and 60% or less of methyl groups, and in yet another embodiment, 50% or more of fluoro groups and 50% or less of methyl groups.

[0036] The curable organopolysiloxane compound (A) can be obtained by a known production method, for example, by polycondensing a silane compound having a hydrolyzable functional group (alkoxy group, halogen atom, etc.).

[0037] The silane compound to be used may be appropriately selected depending on the structure of the desired curable organopolysiloxane compound (A). Examples include bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane; trifunctional silane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyldiethoxymethoxysilane; and tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-s-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, and trimethoxyethoxysilane.

[0038] The weight average molecular weight (Mw) of the curable organopolysiloxane compound (A) can be, in one embodiment, 400 or more, in another embodiment, 600 or more, in yet another embodiment, 800 or more, and in yet another embodiment, 1,000 or more, and in one embodiment, 30,000 or less, in another embodiment, 20,000 or less, in yet another embodiment, 15,000 or less, in yet another embodiment, 10,000 or less, and in yet another embodiment, 5,000 or less. The weight average molecular weight (Mw) of the curable organopolysiloxane compound (A) can be, in one embodiment, 400 or more and 30,000 or less, in another embodiment, 600 or more and 20,000 or less, in yet another embodiment, 800 or more and 15,000 or less, in yet another embodiment, 1,000 or more and 10,000 or less, and in yet another embodiment, 1,000 or more and 5,000 or less. By using a curable organopolysiloxane compound (A) having a mass average molecular weight (Mw) within the above range, it becomes easier to achieve excellent curability and light resistance, and it also becomes easier to obtain a layer of the curable composition that gives a cured product with superior adhesiveness.

[0039] The molecular weight distribution (Mw / Mn) of the curable organopolysiloxane compound (A) is not particularly limited, but in one embodiment it can be 1.0 or more, in another embodiment it can be 1.1 or more, and in one embodiment it can be 10.0 or less, and in another embodiment it can be 6.0 or less. Furthermore, the molecular weight distribution (Mw / Mn) of the curable organopolysiloxane compound (A) can be in the range of 1.0 or more and 10.0 or less, and in another embodiment it can be 1.1 or more and 6.0 or less. By using a curable organopolysiloxane compound (A) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easier to achieve excellent curability and light resistance, and it also becomes easier to obtain a layer of the curable composition that gives a cured product with excellent adhesion.

[0040] The mass average molecular weight (Mw) and number average molecular weight (Mn) of the curable organopolysiloxane compound (A) can be determined, for example, as values ​​converted into standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0041] The content of the curable organopolysiloxane compound (A) is not particularly limited, but the amount may be, relative to 100 parts by mass of the solids content (i.e., active ingredients) of the liquid curable composition, in one embodiment, 40 parts by mass or more, in another embodiment, 60 parts by mass or more, and in yet another embodiment, 70 parts by mass or more; in one embodiment, less than 98 parts by mass, in another embodiment, less than 94 parts by mass, and in yet another embodiment, less than 90 parts by mass. The amount of component (A) may range, relative to 100 parts by mass of the solids content of the liquid curable composition, in one embodiment, from 40 parts by mass to less than 98 parts by mass, from 60 parts by mass to less than 94 parts by mass, and in yet another embodiment, from 70 parts by mass to less than 90 parts by mass. Using component (A) within the above range can more effectively exhibit the effects of adding component (A).

[0042] Polysilsesquioxane Compounds In one embodiment, the curable organopolysiloxane compound (A) can be a polysilsesquioxane compound obtained by polycondensation of a trifunctional organosilane compound. By including a polysilsesquioxane compound as component (A) in a liquid curable composition, it becomes easier to impart excellent curability and light resistance, and it also becomes easier to obtain a layer of the curable composition that gives a cured product with excellent adhesiveness.

[0043] The polysilsesquioxane compound can be a compound having a repeating unit represented by the following formula (a-4): When the liquid curable composition contains a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4) as component (A), it becomes easier to impart excellent curability and light resistance, and it also becomes easier to obtain a layer of the curable composition that gives a cured product with superior adhesiveness.

[0044] [ka]

[0045] In formula (a-4), R 1 represents an organic group. The organic group can be selected from the group consisting of an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted cycloalkyl group, a substituted cycloalkyl group, an unsubstituted alkenyl group, a substituted alkenyl group, an unsubstituted aryl group, a substituted aryl group, and an alkylsilyl group, and can be selected from the group consisting of, for example, an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted aryl group having 6 to 12 carbon atoms.

[0046] Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. 1The number of carbon atoms in the "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by the following formula may be 1 to 6 in one embodiment, and 1 to 3 in another embodiment.

[0047] R 1 The number of carbon atoms in the "substituted alkyl group having 1 to 10 carbon atoms" represented by the formula (I) can be 1 to 6 in one embodiment, and 1 to 3 in another embodiment. Note that this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the alkyl group portion). Therefore, R 1 is a "substituted alkyl group having 1 to 10 carbon atoms", R 1 The number of carbon atoms may exceed 10. Examples of the alkyl group of the "substituted alkyl group having 1 to 10 carbon atoms" include the same alkyl groups as those listed as the "unsubstituted alkyl group having 1 to 10 carbon atoms."

[0048] Examples of the substituent of the "substituted alkyl group having 1 to 10 carbon atoms" include halogen atoms such as fluorine, chlorine, and bromine atoms; a cyano group; and a group represented by the formula OG. The number of atoms (excluding the number of hydrogen atoms) of the substituent of the "substituted alkyl group having 1 to 10 carbon atoms" can be 1 to 30 in one embodiment, and 1 to 20 in another embodiment. Here, G represents a protecting group for a hydroxyl group. The protecting group for a hydroxyl group is not particularly limited, and examples thereof include known protecting groups known as protecting groups for a hydroxyl group. Examples thereof include acyl groups; silyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a t-butyldiphenylsilyl group; acetal groups such as a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydropyran-2-yl group, and a tetrahydrofuran-2-yl group; alkoxycarbonyl groups such as a t-butoxycarbonyl group; and ether groups such as a methyl group, an ethyl group, a t-butyl group, an octyl group, an allyl group, a triphenylmethyl group, a benzyl group, a p-methoxybenzyl group, a fluorenyl group, a trityl group, and a benzhydryl group.

[0049] Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. 1 The number of carbon atoms in the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by the formula (I) can be 6.

[0050] R 1 The number of carbon atoms in the "substituted aryl group having 6 to 12 carbon atoms" represented by the formula (1) can be 6. Note that this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the aryl group portion). Therefore, R 1 is a "substituted aryl group having 6 to 12 carbon atoms", R 1 The number of carbon atoms may exceed 12. Examples of the aryl group in the "substituted aryl group having 6 to 12 carbon atoms" include the same groups as those listed as the "unsubstituted aryl group having 6 to 12 carbon atoms."

[0051] Examples of the substituent in the "substituted aryl group having 6 to 12 carbon atoms" include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl; halogen atoms such as fluorine, chlorine, and bromine; and alkoxy groups such as methoxy and ethoxy. The number of atoms (excluding hydrogen atoms) in the substituent in the "substituted aryl group having 6 to 12 carbon atoms" can be 1 to 30 in one embodiment, and 1 to 20 in another embodiment.

[0052] Among these, R 1 From the viewpoints of facilitating the production of a polysilsesquioxane compound with a stable structure and providing a liquid curable composition with more stable performance, R can be at least one selected from the group consisting of an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and an unsubstituted aryl group having 6 to 12 carbon atoms. 1However, by using a polysilsesquioxane compound that is an unsubstituted alkyl group having 1 to 10 carbon atoms, it becomes easier to achieve excellent curability and light resistance, and it also becomes easier to obtain a layer of the curable composition that gives a cured product with superior adhesiveness.

[0053] Among these, R 1 can be at least one selected from the group consisting of unsubstituted aryl groups having 6 to 12 carbon atoms and substituted aryl groups having 6 to 12 carbon atoms, since this makes it easier to efficiently obtain a curable polysilsesquioxane compound having a high refractive index and makes it easier to use in devices that require a high refractive index. For example, R 1 can be a phenyl group.

[0054] R 1 However, by using a polysilsesquioxane compound having a fluorine atom and an alkyl group (fluoro group) having 1 to 10 carbon atoms, adhesiveness is improved, and a cured product of a layer of the curable composition having a low refractive index is easily obtained, making it easier to use in devices that require a low refractive index. Examples of the alkyl group having 1 to 10 carbon atoms and a fluorine atom include those having the composition formula: C m H (2m-n+1) F n (where m is an integer of 1 to 10, and n is an integer of 1 or more and (2m+1) or less.) Among these, a 3,3,3-trifluoropropyl group is exemplified.

[0055] In addition, polysilsesquioxane compounds are a type of R 1 It may be a polymer having two or more R 1 The compound may be a copolymer having the following formula:

[0056] The content of the repeating units represented by formula (a-4) (i.e., the T sites described below) in the polysilsesquioxane compound can be 50 mol% or more in one embodiment, 70 mol% or more in another embodiment, and 90 mol% or more in yet another embodiment, based on all repeating units. The content of the repeating units represented by formula (a-4) (i.e., the T sites described below) in the polysilsesquioxane compound can be 50 to 100 mol% in one embodiment, 70 to 100 mol% in another embodiment, and 90 to 100 mol% in yet another embodiment, based on all repeating units. For example, the content of the repeating units represented by formula (a-4) (i.e., the T sites described below) in the polysilsesquioxane compound can be 100 mol%. By using a polysilsesquioxane compound containing the repeating units represented by formula (a-4) (T sites) in the above proportion, a layer of a curable composition that gives a cured product with excellent light resistance can be easily obtained. The content of the repeating unit (T site) represented by the formula (a-4) in the polysilsesquioxane compound can be calculated, for example, by the following formula, when NMR peak assignment and area integration are possible: 29 Si-NMR and 1 It can be determined by measuring H-NMR.

[0057] Polysilsesquioxane compounds are soluble in various organic solvents, such as ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and mixed solvents consisting of two or more of these. Therefore, the polysilsesquioxane compounds in a solution state can be prepared using these solvents. 29 Si-NMR and 1 H-NMR can be measured.

[0058] The repeating unit represented by the formula (a-4) can be one represented by the following formula (a-5).

[0059] [ka]

[0060] As shown in formula (a-5), polysilsesquioxane compounds have a structure generally called a T site, in which three oxygen atoms are bonded to a silicon atom and other groups (R 1 ) is bonded to the partial structure.

[0061] In formula (a-5), R 1 is R in the formula (a-4). 1 has the same meaning as *. * represents a Si atom, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, and at least one of the three * is a Si atom. Examples of alkyl groups having 1 to 10 carbon atoms represented by * include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, and t-butyl. Multiple *s may be the same or different.

[0062] Furthermore, the polysilsesquioxane compound is a thermosetting compound that can undergo a condensation reaction and / or hydrolysis upon heating. Therefore, at least one of the *'s in the formula (a-5) of the multiple repeating units (T sites) of the polysilsesquioxane compound can be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and can be, for example, a hydrogen atom.

[0063] In addition, when the polysilsesquioxane compound is soluble in the solvent used for measurement, 29 By measuring Si-NMR, it is possible to confirm the presence of a hydrogen atom or an alkyl group having 1 to 10 carbon atoms at * in the formula (a-5), and whether all three * in the formula (a-5) are repeating units each consisting of a Si atom. 29When Si-NMR peak assignment and area integration are possible, the total number of repeating units in which all three *'s in formula (a-5) are Si atoms relative to the total number of repeating units (T sites) represented by formula (a-4) in the polysilsesquioxane compound can be roughly calculated. From the viewpoint of facilitating the production of a curable composition layer that provides a cured product with stable productivity and stable performance, the total number of repeating units in which all three *'s in formula (a-5) are Si atoms relative to the total number of repeating units (T sites) represented by formula (a-4) in the polysilsesquioxane compound can be 30 mol% or more in one embodiment, 40 mol% or more in another embodiment, and 95 mol% or less in one embodiment, 90 mol% or less in another embodiment. The total number of repeating units in which all three *'s in formula (a-5) are Si atoms relative to the total number of repeating units (T sites) represented by formula (a-4) in the polysilsesquioxane compound can range from 30 to 95 mol% in one embodiment, and from 40 to 90 mol% in another embodiment.

[0064] When the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc., but may be a random copolymer from the viewpoint of ease of production, etc. The structure of the polysilsesquioxane compound may be any of a ladder structure, a double-decker structure, a cage structure, a partially cleaved cage structure, a cyclic structure, and a random structure.

[0065] Furthermore, the polysilsesquioxane compound may be solid at room temperature, but may also be liquid. "Liquid" refers to a state having fluidity, for example, a state in which the viscosity is 10,000 Pa·s or less at room temperature, where room temperature refers to 23°C. A liquid polysilsesquioxane compound can reduce the amount of solvent in a liquid curable composition, and can increase the concentration of the polysilsesquioxane compound in the liquid curable composition.

[0066] The polysilsesquioxane compounds can be used singly or in combination of two or more.

[0067] The method for producing the polysilsesquioxane compound is not particularly limited. For example, a method for producing the polysilsesquioxane compound represented by the following formula (a-6)

[0068] [ka]

[0069] (In the formula, R 1 is R in the formula (a-4). 1 It has the same meaning as R 2 represents an alkyl group having 1 to 10 carbon atoms, and X 1 represents a halogen atom, and p represents an integer of 0 to 3. 2 , and multiple X 1 R may be the same as or different from each other. A polysilsesquioxane compound can be produced by polycondensing at least one silane compound (1) represented by the following formula: 2 Examples of the alkyl group having 1 to 10 carbon atoms represented by * in formula (a-5) above include the same alkyl groups having 1 to 10 carbon atoms represented by * in formula (a-5) above. 1 Examples of the halogen atom include a chlorine atom and a bromine atom.

[0070] Specific examples of the silane compound (1) include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane; and alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, and ethylbromodimethoxysilane. alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane; substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, and 2-cyanoethyltriethoxysilane; 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, and 3,3,3-trifluoropropylchlorodiethoxysilane; Substituted alkylhalogenoalkoxysilane compounds such as trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, and 2-cyanoethyldichloroethoxysilane; substituted alkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane; phenyltrimethoxysilane, 4-methoxyphenyltrimethylsilane, and 4-methoxyphenyltrimethylsilane; substituted or unsubstituted phenyltrialkoxysilane compounds such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane, etc.; substituted or unsubstituted phenylhalogenoalkoxysilane compounds such as phenyltrichlorosilane, 4-methoxyphenyltrichlorosilane, etc.; and the like.These silane compounds (1) can be used singly or in combination of two or more.

[0071] The method for polycondensing the silane compound (1) is not particularly limited. For example, a method can be used in which a predetermined amount of a polycondensation catalyst is added to the silane compound (1) in a solvent or without a solvent, followed by stirring at a predetermined temperature. Specific examples include (a) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (b) a method in which a predetermined amount of a base catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; and (c) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature, followed by adding an excess amount of a base catalyst to make the reaction system basic, followed by stirring at a predetermined temperature. Among these, the polycondensation can be carried out by method (a) or (c), which can efficiently produce the desired polysilsesquioxane compound.

[0072] The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Two or more polycondensation catalysts may be used in combination, and at least an acid catalyst may be used. Examples of acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid may be used.

[0073] Examples of the base catalyst include aqueous ammonia; organic bases such as trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, and imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; and metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate.

[0074] The amount of the polycondensation catalyst used may be 0.05 mol% or more in one embodiment, and 0.1 mol% or more in another embodiment, and 10 mol% or less in one embodiment, and 5 mol% or less in another embodiment, relative to the total molar amount of the silane compound (1). The amount of the polycondensation catalyst used may range from 0.05 to 10 mol% in one embodiment, and from 0.1 to 5 mol% in another embodiment, relative to the total molar amount of the silane compound (1).

[0075] When a solvent is used during polycondensation, the solvent can be appropriately selected depending on the type of silane compound (1). Examples of suitable solvents include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. These solvents can be used alone or in combination. Furthermore, when using the above method (c), after polycondensation reaction in an aqueous system in the presence of an acid catalyst, an organic solvent and a base catalyst (such as aqueous ammonia) can be added to the reaction solution, and further polycondensation reaction can be carried out under neutral or basic conditions.

[0076] The amount of the solvent used may be 0.001 L or more in one embodiment, and 0.01 L or more in another embodiment, and 10 L or less in one embodiment, and 0.9 L or less in another embodiment, per mole of the total amount of the silane compound (1). The amount of the solvent used may range from 0.001 L to 10 L in one embodiment, and from 0.01 L to 0.9 L in another embodiment, per mole of the total amount of the silane compound (1).

[0077] The temperature when polycondensing silane compound (1) is usually in the range from 0°C to the boiling point of the solvent used, and in one embodiment, it can be 20°C or higher, in another embodiment, 30°C or higher, in one embodiment, 100°C or lower, and in another embodiment, 95°C or lower. The temperature when polycondensing silane compound (1) can be in the range from 20°C to 100°C in one embodiment, and 30°C to 95°C in another embodiment. By setting the temperature at or above this lower limit of the reaction temperature, the polycondensation reaction proceeds sufficiently. On the other hand, by setting the temperature at or below this upper limit of the reaction temperature, gelation is suppressed. The reaction is completed within 30 minutes to 30 hours.

[0078] Depending on the type of monomer used, it may be difficult to increase the molecular weight. For example, R 1 is an alkyl group having a fluorine atom, R 1 In such cases, a polysilsesquioxane compound having the desired molecular weight can be more easily obtained by reducing the amount of catalyst and carrying out the reaction under mild conditions for a long period of time.

[0079] After completion of the reaction, neutralization is carried out by adding an aqueous alkali solution such as sodium bicarbonate to the reaction solution when an acid catalyst was used, or by adding an acid such as hydrochloric acid to the reaction solution when a base catalyst was used, and the salt generated during this process is removed by filtration, washing with water, or the like, to obtain the target polysilsesquioxane compound.

[0080] When producing a polysilsesquioxane compound by the above method, the OR of the silane compound (1) 2 or X 1 The portion of the polysilsesquioxane that has not undergone hydrolysis and subsequent condensation reaction remains in the polysilsesquioxane compound.

[0081] When component (A) is, for example, a polysilsesquioxane compound obtained by the polycondensation reaction of silane compound (1), curing proceeds via a condensation reaction, including the reaction with a silane coupling agent (described below). Therefore, the liquid curable composition of this embodiment differs from typical heat-curable silicone adhesives, which cure via an addition reaction in the presence of a precious metal catalyst such as a platinum catalyst. Therefore, liquid curable compositions containing polysilsesquioxane compounds are substantially free of precious metal catalysts or contain only small amounts of precious metal catalysts. Here, "substantially free of precious metal catalysts" means "not intentionally adding any component that could be interpreted as a precious metal catalyst, and the content of precious metal catalysts in the liquid curable composition is, for example, less than 1 ppm by mass, calculated as the mass of catalytic metal element, relative to the amount of active ingredient in the liquid curable composition." Here, "active ingredient" refers to "components contained in the liquid curable composition excluding the solvent (S) (described below)." The liquid curable composition may be one that is substantially free of a precious metal catalyst or has a low content of a precious metal catalyst, from the viewpoint of stable production taking into account formulation variations, etc., from the viewpoint of long-term static stability, and from the viewpoint of the fact that precious metal catalysts are expensive.

[0082] The liquid curable composition of this embodiment contains the curable organopolysiloxane compound (A), and may also contain the components described below.

[0083] (Silane coupling agent (B)) The liquid curable composition of this embodiment contains a silane coupling agent (B) (hereinafter, sometimes referred to as "component (B)"). By including the silane coupling agent (B), the viscosity of the liquid curable composition can be easily adjusted to the above-mentioned range, improving workability in the application process and providing excellent curing properties due to the condensation reaction with component (A) upon heating. The silane coupling agent (B) includes both a silane coupling agent (B1) (hereinafter, sometimes referred to as "component (B1)") having a nitrogen atom in the molecule and a silane coupling agent (B2) (hereinafter, sometimes referred to as "component (B2)") having an acid anhydride structure in the molecule. This reduces cracking in the cured product when the liquid curable composition is applied to a sheet-like substrate, dried, and cured, and the resulting cured product is cut into individual pieces.

[0084] Silane coupling agent (B1) The silane coupling agent (B1) is not particularly limited as long as it is a silane coupling agent having a nitrogen atom in the molecule. Examples thereof include trialkoxysilane compounds represented by the following formula (b-1), dialkoxyalkylsilane compounds or dialkoxyarylsilane compounds represented by the following formula (b-2), etc.

[0085] [ka] JPEG2025141171000008.jpg1266

[0086] In the above formula, R a represents an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a t-butoxy group. a R may be the same or different. b represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a t-butyl group; or an aryl group having or having no substituent, such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 1-naphthyl group.

[0087] R c represents an organic group having a nitrogen atom and 1 to 10 carbon atoms. c R may further be bonded to another group containing a silicon atom. c Specific examples of the organic group having 1 to 10 carbon atoms include an N-2-(aminoethyl)-3-aminopropyl group, a 3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, a 3-ureidopropyl group, and an N-phenyl-aminopropyl group.

[0088] Among the compounds represented by the above formula (b-1) or (b-2), R c In the case where the group (I) is an organic group bonded to another group containing a silicon atom, examples of the compound include those that bond to another silicon atom via an isocyanurate skeleton to form an isocyanurate-based silane coupling agent, and those that bond to another silicon atom via a urea skeleton to form a urea-based silane coupling agent.

[0089] Among these, the silane coupling agent (B1) can be an isocyanurate-based silane coupling agent or a urea-based silane coupling agent, since it is easy to obtain a cured product that is crack-resistant when cut, and can further be one having four or more alkoxy groups bonded to silicon atoms in the molecule. "Having four or more alkoxy groups bonded to silicon atoms" means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is four or more.

[0090] An example of an isocyanurate-based silane coupling agent having four or more alkoxy groups bonded to a silicon atom is a compound represented by the following formula (b-3), and an example of a urea-based silane coupling agent having four or more alkoxy groups bonded to a silicon atom is a compound represented by the following formula (b-4).

[0091] [ka] JPEG2025141171000010.jpg26131

[0092] In the formula, R a represents R in the formulas (b-1) and (b-2). a Each of t1 to t5 independently represents an integer of 1 to 10, and can be an integer of 1 to 6, for example, 3.

[0093] Specific examples of the compound represented by formula (b-3) include 1,3,5-N-tris[(tri(C1 to C6)alkoxy)silyl(C1 to C10)alkyl]isocyanurates such as 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-tri-i-propoxysilylpropyl)isocyanurate, and 1,3,5-N-tris(3-tributoxysilylpropyl)isocyanurate;1,3,5-N-tris(3-dimethoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxy-i-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxy-n-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxymethylsilylpropyl)isocyanurate 1,3,5-N-tris(3-diethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxy-i-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxy-n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxymethylsilylpropyl) isocyanurate , 1,3,5-N-tris(3-di-i-propoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3,5- 1,3,5-N-tris[(di(C1 to C6)alkoxy)silyl(C1 to C10)alkyl]isocyanurates such as N-tris(3-dibutoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxy-i-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxy-n-propylsilylpropyl)isocyanurate, and 1,3,5-N-tris(3-dibutoxyphenylsilylpropyl)isocyanurate; and the like.

[0094] Specific examples of the compound represented by formula (b-4) include N,N'-bis[(tri(C1 to C10)alkoxysilyl)(C1 to C10)alkyl]ureas such as N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, and N,N'-bis(2-trimethoxysilylethyl)urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea; and N,N'-bis[(di(C1 to C6)alkoxy(C6)alkylsilyl(C1 to C10)alkyl)ureas such as N,N'-bis(3-dimethoxyethylsilylpropyl)urea and N,N'-bis(3-diethoxymethylsilylpropyl)urea; and N,N'-bis[(di(C1 to C6)alkoxy(C6 to C20)arylsilyl(C1 to C10)alkyl)ureas such as N,N'-bis(3-dimethoxyphenylsilylpropyl)urea and N,N'-bis(3-diethoxyphenylsilylpropyl)urea. The silane coupling agent (B1) can be used singly or in combination of two or more.

[0095] Among these, the silane coupling agent (B1) that can be used is 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl)isocyanurate (hereinafter, the two are referred to as "isocyanurate compounds"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter, the two are referred to as "urea compounds"), or a combination of the above isocyanurate compound and urea compound.

[0096] The content of the silane coupling agent (B1) in the liquid curable composition may be 12 parts by mass or more in one embodiment, 14 parts by mass or more in another embodiment, and 16 parts by mass or more in yet another embodiment, and may be less than 40 parts by mass in one embodiment, less than 35 parts by mass in another embodiment, and less than 30 parts by mass in yet another embodiment, relative to 100 parts by mass of the solids content (i.e., active ingredient) of the liquid curable composition. The amount of the silane coupling agent (B1) may be in the range of 12 parts by mass or more and less than 40 parts by mass in one embodiment, 14 parts by mass or more and less than 35 parts by mass in another embodiment, and 16 parts by mass or more and less than 30 parts by mass in yet another embodiment, relative to 100 parts by mass of the solids content (i.e., active ingredient) of the liquid curable composition.

[0097] By using the component (B1) in the above range, the effect of adding the component (B1) can be more effectively exerted, making it easier to obtain a cured product that suppresses the generation of cracks when the cured product is cut.

[0098] Silane coupling agent (B2) The silane coupling agent (B2) is not particularly limited as long as it has an acid anhydride structure in the molecule. For example, tri(C1 to C6)alkoxysilyl(C2 to C8)alkyl succinic anhydrides such as 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-(triethoxysilyl)propyl succinic anhydride; di(C1 to C6)alkoxymethylsilyl(C2 to C8)alkyl succinic anhydrides such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride; (carbon) compounds such as 2-(methoxydimethylsilyl)ethyl succinic anhydride. Examples of the silane coupling agent (B2) include (1 to 6) alkoxydimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydrides; trihalogenosilyl (2 to 8 carbon atoms) alkyl succinic anhydrides such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride; dihalogenomethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydrides such as 2-(dichloromethylsilyl)ethyl succinic anhydride; and halogenodimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydrides such as 2-(chlorodimethylsilyl)ethyl succinic anhydride. The silane coupling agent (B2) can be used alone or in combination of two or more.

[0099] Among these, the silane coupling agent (B2) may be a tri(C1 to C6)alkoxysilyl(C2 to C8)alkyl succinic anhydride, such as 3-(trimethoxysilyl)propyl succinic anhydride or 3-(triethoxysilyl)propyl succinic anhydride.

[0100] The content of the silane coupling agent (B2) in the liquid curable composition can be 1.8 parts by mass or more in one embodiment, and 2 parts by mass or more in another embodiment, and less than 10 parts by mass in one embodiment, less than 8 parts by mass in another embodiment, and less than 6 parts by mass in yet another embodiment, relative to 100 parts by mass of the solid content (i.e., active ingredient) of the liquid curable composition. The amount of the silane coupling agent (B2) can be in the range of 1.8 parts by mass or more and less than 10 parts by mass in one embodiment, 1.8 parts by mass or more and less than 8 parts by mass in another embodiment, and 2 parts by mass or more and less than 6 parts by mass in yet another embodiment, relative to 100 parts by mass of the solid content (i.e., active ingredient) of the liquid curable composition.

[0101] By using the component (B2) in the above range, the effect of adding the component (B2) can be more effectively exhibited, making it easier to obtain a cured product that is less likely to crack when cut.

[0102] The total content of the (B) component is not particularly limited, but may be, relative to 100 parts by mass of the solids content (i.e., active ingredients) of the liquid curable composition, in one embodiment, 17 parts by mass or more, in another embodiment, 19 parts by mass or more, and in yet another embodiment, 21 parts by mass or more; or may be less than 50 parts by mass, in another embodiment, less than 43 parts by mass, and in yet another embodiment, less than 36 parts by mass. The total content of the (B) component may be, relative to 100 parts by mass of the solids content (i.e., active ingredients) of the liquid curable composition, in one embodiment, 17 parts by mass or more but less than 50 parts by mass, in another embodiment, 19 parts by mass or more but less than 43 parts by mass, and in yet another embodiment, 21 parts by mass or more but less than 36 parts by mass. Using the (B) component within this range makes it easier to obtain a cured product that suppresses the generation of cracks when the cured product is cut.

[0103] (Solvent (S)) The liquid curable composition of this embodiment may contain a solvent (S). The solvent (S) is not particularly limited as long as it can dissolve or disperse the active ingredient of the liquid curable composition. The solvent (S) may contain an organic solvent having a boiling point of 254°C or higher (hereinafter, sometimes referred to as "organic solvent (SH)"). Here, the "boiling point" refers to the "boiling point at 1013 hPa."

[0104] The liquid curable composition may contain a solvent other than the organic solvent (SH). The solvent other than the organic solvent (SH) may be a solvent having a boiling point of 70°C or higher but lower than 254°C (hereinafter, this may be referred to as "organic solvent (SL)"). The organic solvent (SL) is not particularly limited as long as it has a boiling point of 70°C or higher but lower than 254°C and is capable of dissolving or dispersing the components of the liquid curable composition. In one embodiment, the organic solvent (SL) may have a boiling point of 70°C or higher but lower than 200°C, and in another embodiment, it may have a boiling point of 70°C or higher but lower than 170°C, which further suppresses the generation of bubbles (voids) in the cured product.

[0105] Specific examples of the organic solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol-n-butyl ether (boiling point 229°C), dipropylene glycol methyl ether acetate (boiling point 209°C), diethylene glycol butyl methyl ether (boiling point 212°C), dipropylene glycol-n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), ), triethylene glycol dimethyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 218°C), diethylene glycol-n-butyl ether (boiling point 230°C), ethylene glycol monophenyl ether (boiling point 245°C), tripropylene glycol methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 249°C), benzyl alcohol (boiling point 204.9°C), phenethyl alcohol (boiling point 219 to 221°C), ethylene glycol Examples of suitable organic solvents include diethylene glycol monobutyl ether acetate (boiling point 192°C), ethylene glycol monoethyl ether (boiling point 134.8°C), ethylene glycol monomethyl ether (boiling point 124.5°C), propylene glycol monomethyl ether acetate (boiling point 146°C), cyclopentanone (boiling point 130°C), cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195 to 197°C), cyclohexanol (boiling point 161°C), cyclohexadienone (boiling point 104 to 104.5°C), and methyl ethyl ketone (boiling point 80°C). Among these, the organic solvent (SL) may be diethylene glycol monobutyl ether acetate, cyclohexanone, or methyl ethyl ketone, from the viewpoint of easy mixing of the active ingredient.

[0106] The liquid curable composition may contain the solvent (S) in an amount such that the solids content (i.e., active ingredient) concentration is, in one embodiment, 80% by mass or more, and in another embodiment, 85% by mass or more. In one embodiment, the liquid curable composition may contain the solvent (S) in an amount such that the solids content concentration is less than 95% by mass, and in another embodiment, less than 90% by mass. The liquid curable composition may contain the solvent (S) in an amount such that the solids content concentration is, in one embodiment, 80% by mass or more but less than 95% by mass, and in another embodiment, 85% by mass or more but less than 90% by mass. This makes it easier to adjust the viscosity of the liquid curable composition and further suppresses the generation of bubbles (voids) in the cured product.

[0107] When the solid content concentration is within this range, the active ingredient can be easily mixed well and the workability in the application step is excellent. Furthermore, the liquid curable composition can be stored in a container such as a 18 liter can, a pail can, or a drum, and when the solid content concentration is within this range, the liquid curable composition can be easily filled into the container.

[0108] (Fine particles (C)) The liquid curable composition of this embodiment contains fine particles (C) (hereinafter, sometimes referred to as "component (C)"). The fine particles (C) contain silica fine particles (C1) having an average primary particle diameter of 20 nm or less.

[0109] Silica fine particles (C1) The inclusion of silica fine particles (C1) suppresses repelling and roughening of the coated surface when the liquid curable composition is applied to a sheet-like substrate, thereby improving workability in the application process. The average primary particle diameter of the silica fine particles (C1) can be 20 nm or less in one embodiment, 15 nm or less in another embodiment, and 10 nm or less in yet another embodiment. This suppresses aggregation of the liquid curable composition, suppresses repelling and roughening of the coated surface when the liquid curable composition is applied to a sheet-like substrate, and improves workability in the application process. Furthermore, the average primary particle diameter of the silica fine particles (C1) can be 1 nm or more in one embodiment, 2 nm or more in another embodiment, and 5 nm or more in yet another embodiment. This suppresses aggregation of the silica fine particles, which can result in the same effect as if larger particles were used, suppresses aggregation of the liquid curable composition, suppresses repelling and roughening of the coated surface when the liquid curable composition is applied to a sheet-like substrate, and improves workability in the application process. The average primary particle diameter of the silica fine particles (C1) can be in the range of 1 nm to 20 nm in one embodiment, 2 nm to 15 nm in another embodiment, and 5 nm to 10 nm in yet another embodiment. The average primary particle diameter of the silica fine particles (C1) is determined by randomly selecting 2,000 silica fine particles (C1) and observing the primary particles using a transmission electron microscope, and averaging the particle diameter (nm) data obtained for the 2,000 particles. The average value is calculated by rounding off to one decimal place.

[0110] In one embodiment, the specific surface area of ​​the silica fine particles (C1) is 100 m 2 / g or more, in another embodiment, 200m 2 / g or more, and in yet another embodiment, 300m 2 / g or more, and in one embodiment, 2500 m 2 / g or less, in another embodiment, 1000m 2 / g or less, and in yet another embodiment, 500m 2 In one embodiment, the range of the specific surface area of ​​the silica fine particles (D1) is 100 m / g or less.2 / g or more 2500m 2 / g or less, in another embodiment, 200m 2 / g or more 1000m 2 / g or less, and in yet another embodiment, 300m 2 / g or more 500m 2 / g or less.

[0111] The content of the silica fine particles (C1) can be, relative to 100 parts by mass of the liquid curable composition, 1 part by mass or more in one embodiment, 2 parts by mass or more in another embodiment, and 2.5 parts by mass or more in yet another embodiment; and can be less than 20 parts by mass in one embodiment, less than 12 parts by mass in another embodiment, and less than 6 parts by mass in yet another embodiment. The amount of the silica fine particles (C1) can be, relative to 100 parts by mass of the liquid curable composition, 1 part by mass or more and less than 20 parts by mass in one embodiment, 2 parts by mass or more and less than 12 parts by mass in another embodiment, and 2.5 parts by mass or more and less than 6 parts by mass in yet another embodiment. By using the silica fine particles (C1) in the above range, the effect of adding the silica fine particles (C1) can be more effectively exhibited.

[0112] The shape of the silica fine particles (C1) may be any of spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fibrous, etc., and can be spherical. Here, "spherical" means "almost spherical, including true spherical, spheroidal, oval, confetti-like, cocoon-like, and other polyhedral shapes that can approximate a sphere."

[0113] The silica fine particles (C1) can be surface-modified silica, because they are relatively easy to mix into a liquid curable composition and can easily produce a liquid curable composition that is easier to work with in the coating process. Hydrophobic surface-modified silica can be obtained. Examples of hydrophobic surface-modified silica include silica having a trialkylsilyl group having 1 to 20 tricarbon atoms (e.g., trimethylsilyl), an alkylsilyl group having 1 to 20 dicarbon atoms (e.g., dimethylsilyl), or an alkylsilyl group having 1 to 20 carbon atoms (e.g., octylsilyl), bonded to the surface; and silica whose surface has been treated with silicone oil. Hydrophobic surface-modified silica can be obtained, for example, by surface-modifying silica particles with a silane coupling agent having a trialkylsilyl group having 1 to 20 tricarbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms, or by treating silica particles with silicone oil.

[0114] Furthermore, the fine particles (C) may contain fine particles other than the silica fine particles (C1). That is, the fine particles (C) may be silica fine particles (C1) alone or in combination with one or more of the following fine particles. This makes it easier to obtain a cured product with superior heat resistance. Examples of such fine particles include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, organic components, and silicones. Furthermore, the fine particles (C) used may be surface-modified.

[0115] Metal refers to an element belonging to Group 1 (excluding H), Groups 2 to 11, Group 12 (excluding Hg), Group 13 (excluding B), Group 14 (excluding C and Si), Group 15 (excluding N, P, As and Sb), or Group 16 (excluding O, S, Se, Te and Po) of the periodic table.

[0116] Examples of metal oxides include titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. Metal oxide fine particles also include sol particles made of these metal oxides.

[0117] Examples of minerals include smectite, bentonite, etc. Examples of smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite.

[0118] Examples of metal carbonates include calcium carbonate and magnesium carbonate, examples of metal sulfates include calcium sulfate and barium sulfate, examples of metal hydroxides include aluminum hydroxide, and examples of metal silicates include aluminum silicate, calcium silicate, magnesium silicate, etc. Examples of organic components include acrylic polymers.

[0119] Silicone refers to an artificial polymer compound having a main skeleton formed by siloxane bonds, such as dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

[0120] The average primary particle diameter of the fine particles other than the silica fine particles (C1) can be, in one embodiment, 0.005 μm or more, in another embodiment, 0.006 μm or more, and in yet another embodiment, 0.007 μm or more; and in one embodiment, 7 μm or less, in another embodiment, 2 μm or less, in yet another embodiment, 0.1 μm or less, and in yet another embodiment, 0.05 μm or less. The average primary particle diameter of the fine particles (C) can be, in one embodiment, 0.005 μm or more and 7 μm or less, in another embodiment, 0.006 μm or more and 2 μm or less, in yet another embodiment, 0.007 μm or more and 0.1 μm or less, and in yet another embodiment, 0.007 μm or more and 0.05 μm or less. The average primary particle diameter of the fine particles (C) is determined by randomly selecting 2,000 fine particles (C) and observing their primary particles using a transmission electron microscope, and averaging the particle diameter (nm) data obtained for the 2,000 particles. The average value is calculated by rounding off to the nearest integer.

[0121] In one embodiment, the specific surface area of ​​the fine particles other than the silica fine particles (C1) is 0.1 m 2 / g or more, in another embodiment, 0.5m 2 / g or more, and in yet another embodiment, 1 m 2 / g or more, and in yet another embodiment, 50m 2 / g or more, and in one embodiment, 500m 2 / g or less, in another embodiment, 400 m 2 / g or less, and in yet another embodiment, 300m 2 / g or less, and in yet another embodiment, 220m 2 In one embodiment, the range of the specific surface area of ​​the fine particles (C) can be 0.1 m / g or less. 2 / g or more 500m 2 / g or less, in another embodiment, 0.5 m 2 / g or more 400m 2 / g or less, and in yet another embodiment, 1m 2 / g or more 300m 2 / g or less, and in yet another embodiment, 50m2 / g or more 220m 2 / g or less.

[0122] The shape of the fine particles other than the silica fine particles (C1) may be any of spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fibrous, etc., and can be spherical. Here, "spherical" means "almost spherical, including true spherical, spheroidal, oval, confetti-like, cocoon-like, and other polyhedral shapes that can approximate a sphere."

[0123] The content of the (C) component is not particularly limited, but may be 1 part by mass or more in one embodiment, 2 parts by mass or more in another embodiment, and 2.5 parts by mass or more in yet another embodiment, relative to 100 parts by mass of the liquid curable composition. In one embodiment, the content may be less than 25 parts by mass, less than 15 parts by mass in another embodiment, and less than 10 parts by mass in yet another embodiment. The amount of the (C) component may be in the range of 1 part by mass or more but less than 25 parts by mass, in another embodiment, 2 parts by mass or more but less than 15 parts by mass, and in yet another embodiment, 2.5 parts by mass or more but less than 10 parts by mass relative to 100 parts by mass of the liquid curable composition. Using the (C) component within the above range can more effectively exhibit the effects of adding the (C) component.

[0124] (Other ingredients (D)) The liquid curable composition of this embodiment may contain another component (D). Examples of component (D) include antioxidants, ultraviolet absorbers, and light stabilizers. The antioxidant is added to prevent oxidative degradation during heating. Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0125] Examples of phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, etc. Examples of phenol-based antioxidants include monophenols, bisphenols, polymeric phenols, etc. Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc.

[0126] These antioxidants may be used alone or in combination of two or more. The amount of antioxidant used may be 3 parts by mass or less per 100 parts by mass of the solid content of the liquid curable composition.

[0127] The ultraviolet absorber is added to improve the light resistance of the resulting liquid curable composition. Examples of ultraviolet absorbers include salicylic acids, benzophenones, benzotriazoles, and hindered amines. These ultraviolet absorbers can be used alone or in combination of two or more. The amount of ultraviolet absorber used can be 3 parts by mass or less per 100 parts by mass of the solid content of the liquid curable composition.

[0128] The light stabilizer is added to improve the light resistance of the resulting liquid curable composition. Examples of light stabilizers include hindered amines such as poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidine)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imino}]. These light stabilizers can be used alone or in combination of two or more. The amount of light stabilizer used can be 5 parts by mass or less per 100 parts by mass of the solid content of the liquid curable composition.

[0129] The total amount of the other components (D) other than the components (A), (B), and (C), and the solvent (S), used may be 10 parts by mass or less per 100 parts by mass of the solid content of the liquid curable composition.

[0130] <Cured product according to this embodiment> The cured product according to this embodiment is a cured product of the liquid curable composition according to this embodiment (more specifically, a cured product of a layer of the curable composition formed from the liquid curable composition according to this embodiment), and may contain the same components as those shown in the section <Liquid curable composition according to this embodiment>, except that the component (A) and the component (B) are compounds formed by a condensation reaction among those shown in the section <Liquid curable composition according to this embodiment>. Note that the cured product does not contain a solvent (S) or is substantially free of a solvent (S), depending on the curing conditions.

[0131] (Compound obtained by condensation reaction of curable organopolysiloxane compound (A) and silane coupling agent (B)) The cured product according to this embodiment contains a compound resulting from a condensation reaction between a curable organopolysiloxane compound (A) and a silane coupling agent (B). The curable organopolysiloxane compound (A) and the silane coupling agent (B) may undergo hydrolysis before undergoing a condensation reaction. In one embodiment, the compound resulting from a condensation reaction between a curable organopolysiloxane compound and a silane coupling agent (B) is a compound resulting from a condensation reaction between a polysilsesquioxane compound and a silane coupling agent. The structure and functional groups of the curable organopolysiloxane compound (A) may be the same as those exemplified in the section entitled "Liquid Curable Composition According to This Embodiment."

[0132] (Fine particles (C) and other components (D)) The cured product according to this embodiment contains fine particles (C) and other components (D). The structures, functional groups, contents, physical properties, etc. of the fine particles (C) and other components (D) can be the same as those exemplified in the section <Liquid curable composition according to this embodiment>.

[0133] The cured product according to this embodiment is a cured product of a layer of a curable composition, and therefore has a plate-like shape. That is, it is a plate-like cured product. In one embodiment, the plate-like cured product has multiple surfaces, for example, a pair of main surfaces (a first main surface and a second main surface) and multiple side surfaces extending between the pair of main surfaces. The main surfaces refer to the surfaces with the first and second largest areas. The plate-like cured product can be a rectangular or circular plate.

[0134] The thickness of the plate-shaped cured product, which is the distance between the pair of main surfaces, is not particularly limited, and can be 500 μm or less in one embodiment, 400 μm or less in another embodiment, and 300 μm or less in yet another embodiment, and can be 50 μm or more in one embodiment, 75 μm or more in another embodiment, and 90 μm or more in yet another embodiment. The thickness of the plate-shaped cured product can range from 50 μm to 500 μm in one embodiment, from 75 μm to 400 μm in another embodiment, and from 90 μm to 300 μm in yet another embodiment. Having a thickness within the above range makes it easy to use in optical components, etc.

[0135] <Method for producing the liquid curable composition according to this embodiment> The liquid curable composition of the present embodiment can be produced, for example, by a production method including the following steps (AI) and (AII).

[0136] (Process (AI)) Step (AI) is a step of polycondensing at least one compound represented by the above formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound.

[0137] (Process (AII)) Step (AII) is a step of obtaining a liquid curable composition using the polysilsesquioxane compound obtained in step (AI).

[0138] Examples of a method for obtaining a polysilsesquioxane compound by polycondensing at least one compound represented by the above formula (a-6) in the presence of a polycondensation catalyst in step (AI) include the same methods as those exemplified in the section <Liquid curable composition according to the present embodiment>.

[0139] In step (AII), a method for obtaining a liquid curable composition using a polysilsesquioxane compound includes, for example, mixing the polysilsesquioxane compound, the component (B), the component (C), and, if desired, the component (D) with a solvent (S), degassing, and dissolving. The mixing and degassing methods are not particularly limited, and known methods can be used. The order of mixing is also not particularly limited. According to the production method including steps (AI) and (AII), the liquid curable composition of this embodiment can be produced efficiently and simply.

[0140] <Method for forming a cured product and method for manufacturing individual pieces of a cured product according to this embodiment> The cured product and individual pieces of the cured product of this embodiment can be formed and produced, for example, by a method including the following steps (BI), (BII), and (BIII). (Process (BI)) Step (BI) is a step of applying the liquid curable composition of the present embodiment obtained in step (AII) to a sheet-like substrate such as a release sheet.

[0141] (Process (BII)) Step (BII) is a step of heating the coating film of the liquid curable composition obtained in step (BI) to dry and cure it, thereby obtaining a cured product having a plate-like shape.

[0142] (Process (BIII)) Step (BIII) is a step of cutting the plate-shaped cured product obtained in step (BII) into a lattice pattern and processing it into individual plate-shaped pieces to obtain individual pieces of the cured product.

[0143] In step (BI), the liquid curable composition obtained in step (AII) is applied to a sheet-like substrate such as a release sheet. Applying the liquid curable composition to the release sheet can include (1) applying the liquid curable composition to the release sheet so that it forms a specific shape (such as a circular plate (disk) or a rectangular plate (cuboid)), (2) applying the liquid curable composition so that it covers the entire surface of the release sheet, or (3) preparing a release sheet equipped with a mold having recesses or holes of a specific shape (such as a circular plate (disk) or a rectangular plate (cuboid)), and applying (pouring) the liquid curable composition into the recesses or holes of the mold in the release sheet.

[0144] The method for applying the liquid curable composition onto the release sheet is not particularly limited, and examples thereof include knife coating, blade coating, roll coating, etc. The liquid curable composition is stored in a container such as a 18L can, a pail can, or a drum can, and is used by supplying the liquid curable composition to a coating device.

[0145] The coating thickness of the liquid curable composition is not particularly limited as long as it is equal to or greater than the thickness of the intended plate-shaped cured product. For example, the coating thickness of the liquid curable composition may be 500 μm or less in one embodiment, 400 μm or less in another embodiment, and 300 μm or less in yet another embodiment, or may be 50 μm or more in one embodiment, 75 μm or more in another embodiment, and 90 μm or more in yet another embodiment.

[0146] The release sheet onto which the liquid curable composition is applied is not particularly limited, and can be, for example, a film on which a release agent is formed. The film is not particularly limited, and can be made of an organic material or an inorganic material. Resins can be used as organic materials, and ceramics, glass, metals, etc. can be used as inorganic materials. In one embodiment, examples of the film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film, polyolefin films such as polypropylene film and polymethylpentene film, plastic films such as polycarbonate film, metal foils such as aluminum and stainless steel, paper such as glassine paper, fine paper, coated paper, impregnated paper, and synthetic paper, and laminates thereof.

[0147] The thickness of the release sheet is not particularly limited, and in one embodiment, it can be 20 μm or more, and in another embodiment, it can be 25 μm or more, and in one embodiment, it can be less than 200 μm, and in another embodiment, it can be less than 100 μm.

[0148] The release agent is not particularly limited and is composed of a resin. In one embodiment, examples of the release agent include polyolefins such as polyethylene resins, thermoplastic elastomers such as olefin-based thermoplastic elastomers, fluororesins such as tetrafluoroethylene, and silicone resins such as silicones having dimethylpolysiloxane as a basic skeleton.

[0149] The thickness of the release agent is not particularly limited, and in one embodiment, it can be 30 nm or more, and in another embodiment, 50 nm or more, and in one embodiment, it can be less than 300 nm, and in another embodiment, it can be less than 200 nm.

[0150] The mold used in (3) for applying the liquid curable composition to the release sheet is not particularly limited, and can be, for example, a film having a specific shape of recesses or holes. The film of the mold is also not particularly limited, and can be made of the same material as the film of the release sheet.

[0151] The thickness of the mold film is not particularly limited, and may be any thickness that allows recesses or holes of the desired thickness to be formed in the cured plate. For example, the thickness of the mold film may be 500 μm or less in one embodiment, 400 μm or less in another embodiment, and 300 μm or less in yet another embodiment, or may be 100 μm or more in one embodiment, 200 μm or more in another embodiment, and 250 μm or more in yet another embodiment.

[0152] The mold film may have a release agent formed thereon, and the release agent and its thickness may be the same material and thickness as the release agent of the film of the release sheet.

[0153] In step (BII), the coating film of the liquid curable composition obtained in step (BI) is heated to dry and cure, thereby obtaining a plate-shaped cured product. In the heat drying of the applied liquid curable composition, the heating temperature can be, in one embodiment, 80°C or higher, and in another embodiment, 90°C or higher, and in one embodiment, 120°C or lower, and in another embodiment, 110°C or lower. In one embodiment, the heating temperature can range from 80 to 120°C, and in another embodiment, 90 to 110°C. In one embodiment, the heating time can range from 10 minutes to 1 hour, and in another embodiment, 20 to 30 minutes. One example is drying by heating the coating film of the liquid curable composition at 100°C for 20 minutes.

[0154] In the case of the layer (dried product) of the curable composition obtained by drying the liquid curable composition applied to the mold in (3) in applying the liquid curable composition to the release sheet, if a support member is required when a plate-shaped cured product is formed, a support plate may be placed on the dried product. The support plate is not particularly limited and can be a plate made of a hard material having the same shape as the dried product, such as a glass plate.

[0155] In one embodiment, the heating temperature for heat curing the dried curable composition may be 100°C or higher, and in another embodiment, 120°C or higher, and in one embodiment, 180°C or lower, and in another embodiment, 160°C or lower. The heating temperature for curing may range from 100 to 180°C, and in another embodiment, 120 to 160°C. The heating time for curing may range from 30 minutes to 10 hours, in another embodiment, 1 hour to 7 hours, and in yet another embodiment, 3 hours to 5 hours. As one example, the dried curable composition may be heated at 150°C for 4 hours to form a cured product.

[0156] After forming the plate-shaped cured product, the cured product of the liquid curable composition covering the entire surface of the release sheet in (2) of applying the liquid curable composition to the release sheet (in other words, the cured product of the curable composition layer formed from the liquid curable composition) may be processed into a specific shape (a circular plate shape (disk shape), a square plate shape (rectangular parallelepiped shape)) to facilitate cutting in the step (BIII) described below. The processing method is not particularly limited, and punching is an example.

[0157] After forming the plate-shaped cured product, the cured product of the liquid curable composition formed in the mold in (3) in applying the liquid curable composition to the release sheet and the cured product of the liquid curable composition formed in the mold having the support plate are removed from the mold.

[0158] In one embodiment, the area of ​​the main surface of the plate-shaped cured product is 710 cm , which is about the same as a typical 12-inch wafer.2 In the following, in another embodiment, 400 cm 2 In the following, in another embodiment, 300 cm 2 In one embodiment, the length may be 10 cm or less. 2 In another embodiment, 15 cm 2 In yet another embodiment, 20 cm 2 In one embodiment, the area of ​​the main surface of the plate-shaped cured product can be 10 cm or more. 2 More than 710cm 2 In the following, in another embodiment, 15 cm 2 More than 400cm 2 In the following, in yet another embodiment, 20 cm 2 More than 300cm 2 If the area is within the above range, it becomes easy to use in optical components and the like.

[0159] Step (BIII) is a step in which the plate-shaped cured product obtained in step (BII) is cut into a grid pattern and processed into individual plate-shaped pieces to obtain individual cured product pieces. For cutting, a dicing method conventionally used for cutting semiconductor wafers such as silicon into a grid pattern can be used. The cured product formed on a release sheet is attached to the exposed adhesive surface of the dicing sheet using a laminator or the like to fix it during dicing, and the release sheet is then peeled off. The dicing sheet is not particularly limited, and a conventional dicing sheet can be used. The dicing sheet is attached to a frame and diced into individual plate-shaped pieces having the desired shape using a dicing device. This results in individual cured product pieces cut into a grid pattern on the dicing sheet. The dicing device is not particularly limited, and for example, a blade dicing device using a blade that rotates at high speed can be used. The diced plate-shaped cured product is individually picked up from the dicing sheet.

[0160] The plate-shaped cured product thus obtained can be used as an optical component or a molded product. As described in the liquid curable composition according to the present embodiment, the plate-shaped cured product can be used as an insulating member for a light-emitting device.

[0161] <Summary of the embodiment> The disclosure of the present specification includes the following liquid curable composition, cured product, and method of forming the cured product.

[0162] (1) A liquid curable composition, a curable organopolysiloxane compound; Silica microparticles having an average primary particle diameter of 1 nm or more and 20 nm or less; a silane coupling agent having a nitrogen atom in the molecule; a silane coupling agent having an acid anhydride structure in the molecule, the silica fine particles are added in an amount of 1 part by mass or more relative to 100 parts by mass of the liquid curable composition; the silane coupling agent having a nitrogen atom in the molecule is added in an amount of 12 parts by mass or more per 100 parts by mass of the solid content of the liquid curable composition, The silane coupling agent having an acid anhydride structure in the molecule is added in an amount of 1.8 parts by mass or more per 100 parts by mass of the solid content of the liquid curable composition, and the liquid curable composition has a viscosity of 5 Pa s or more at 23°C.

[0163] (2) The liquid curable composition according to (1), wherein the curable organopolysiloxane compound is a polysilsesquioxane compound.

[0164] (3) The liquid curable composition according to (1) or (2), wherein the liquid curable composition is cut into a lattice shape after curing and used as individual pieces of the cured product.

[0165] (4) The liquid curable composition according to any one of (1) to (3), wherein the liquid curable composition contains 80% by mass or more of a solid content.

[0166] (5) A cured product of the liquid curable composition according to any one of (1) to (4), The cured product has a plate-like shape, The main surface of the cured product is 710 cm 2 A hardened product having the following area:

[0167] (6) Applying the liquid curable composition according to any one of (1) to (5) to a sheet; heating the liquid curable composition to form a cured product having a plate-like shape; Cutting the cured product into a lattice shape to process it into individual plate-like shapes; A method for producing a hardened product of individual pieces, comprising: [Example]

[0168] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. In each example, parts and percentages are by weight unless otherwise specified.

[0169] (average molecular weight measurement) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the curable organopolysiloxane compound (A) obtained in the Production Examples were measured using the following apparatus under the following conditions, expressed as standard polystyrene equivalent values. Device name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgel GMHXL, TSKgel GMHXL, and TSKgel 2000HXL connected in sequence Solvent: tetrahydrofuran Injection volume: 20μl Measurement temperature: 40℃ Flow rate: 1ml / min Detector: differential refractometer

[0170] (IR spectrum measurement) The IR spectrum of the curable organopolysiloxane compound (A) obtained in the Production Examples was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer).

[0171] (Production Example 1) A 300 ml eggplant-shaped flask was charged with 28.91 g (145.8 mmol) of phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), and then an aqueous solution of 0.0376 g of 35% hydrochloric acid (0.25 mol % based on the total amount of silane compounds) dissolved in 7.874 ml of distilled water was added with stirring. The entire mixture was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours. The reaction solution was then returned to room temperature (23°C), and 50 g of propyl acetate and 100 g of water were added for liquid separation, yielding an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer and the layer was dried. After filtering off the magnesium sulfate, the organic layer was concentrated using an evaporator, and the concentrate was dried under vacuum to yield 17.0 g of curable organopolysiloxane compound (A1). The curable organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw / Mn) of 1.2. The IR spectrum data of the curable organopolysiloxane compound (A1) is shown below. Si-C6H5:698cm -1 , Si-O: 1132 cm -1

[0172] The compounds used in the examples and comparative examples are shown below. (Component (A)) Curable organopolysiloxane compound (A): the organopolysiloxane compound obtained in Production Example 1 (solid at 23°C)

[0173] ((B) component) Silane coupling agent having a nitrogen atom in the molecule (B1): 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-9659") Silane coupling agent having an acid anhydride structure in the molecule (B2): 3-(trimethoxysilyl)propylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-967C")

[0174] ((C) component) Silica microparticles (C): Silica microparticles surface-treated with trimethylsilyl groups (manufactured by Nippon Aerosil Co., Ltd., product name "AEROSIL RX300", average primary particle diameter: 7 nm, specific surface area: 210 m 2 / g)

[0175] (Solvent (S)) Solvent (S): Cyclohexanone (SL) (boiling point: 157°C)

[0176] (Preparation of Liquid Curable Composition) Example 1 In terms of solid content (active ingredient) mass ratio, 100 parts by mass of the curable organopolysiloxane compound (A) was added with 20 parts by mass of a silane coupling agent (B1) having a nitrogen atom in the molecule, 3 parts by mass of a silane coupling agent (B2) having an acid anhydride structure in the molecule, and 5 parts by mass of silica fine particles (C), and further solvent (S) was added to adjust the solid content concentration to 85%, and the entire mixture was thoroughly mixed and degassed to obtain a liquid curable composition.

[0177] Examples 2 to 3 and Comparative Examples 1 to 5 The liquid curable compositions of Examples 2 and 3 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1, except that the types of compounds (component (B) and component (C)) and their blending ratios (mass ratio of solids (active ingredients)) were changed as shown in Table 1 below. Furthermore, in Examples 2 and 3 and Comparative Examples 1 to 5, the liquid curable compositions were also prepared using a solvent (S) so that the solids concentration of the liquid curable compositions was 85%. The parenthesized values ​​for component (B) and component (C) in Table 1 indicate, on the left, the blending ratio of component (B) and component (C) per 100 parts by mass of the solids of the liquid curable composition, and on the right, the blending ratio of component (B) and component (C) per 100 parts by mass of the liquid curable composition.

[0178] (Viscosity evaluation) The liquid curable composition obtained in Example 1 was subjected to a shear rate of 2 s at 23°C using a rheometer (manufactured by Anton Paar, product name "MCR301") with a cone plate having a radius of 50 mm and a cone angle of 0.5°. -1 The viscosity of the liquid curable compositions obtained in Examples 2 and 3 and Comparative Examples 1 to 5 was also measured in the same manner as in Example 1 above.

[0179] [Table 1]

[0180] (Preparation of a layer of curable composition) The liquid curable composition obtained in Example 1 was applied to the release-treated surface of a release sheet (manufactured by Lintec Corporation, product name "SP-PET381031", thickness: 38 μm) in which one side of a polyethylene terephthalate film had been treated with a silicone-based release agent, so that after heat drying the sheet had a thickness of 100 μm±7 μm and an area of ​​25 cm 2 The coating was applied using an applicator so that the coating was 5 cm long x 5 cm wide. The applied layer was heat-treated at 100°C for 20 minutes to obtain a layer of curable composition. In the same manner as in Example 1, layers of the curable compositions of Examples 2 and 3 and Comparative Examples 1 to 5 were obtained from the liquid curable compositions obtained in Examples 2 and 3 and Comparative Examples 1 to 5 (more specifically, layers of the curable composition with a release sheet were obtained).

[0181] (Coatability evaluation) In the preparation of the curable composition layer, the surface of the curable composition layer of Example 1, measuring 100 mm in length and 20 mm in width, was visually observed, and the coatability was evaluated according to the following criteria. ○: No repelling (collection of spreading liquid) and no roughness of the coated surface ×: At least one of cissing and rough coating surface is observed In the same manner as in Example 1, the coatability of the layers of the curable compositions of Examples 2 and 3 and Comparative Examples 1 to 5 was evaluated.

[0182] (Dicing (DC) suitability evaluation) The curable composition layer of Example 1 was cured at 150°C for 4 hours to produce a laminate of the dicing sheet and the cured product. The cured product was attached to a dicing sheet (manufactured by Lintec Corporation, product name "Adwill D-676H"), after which the unnecessary release sheet was removed. The cured product in the laminate obtained above was then diced using a dicing machine (manufactured by DISCO Corporation, product name "DFD6362") and a dicing blade (ZH05-SD2000-N1-90CC) at a dicing blade movement speed of 50 mm / s, a dicing blade rotation speed of 30,000 rpm, and a height of 60 μm. This resulted in multiple 5 mm x 5 mm individual pieces of the cured product (100 μm thick) aligned and fixed on the dicing sheet. The presence or absence of cracks in the cured product was visually inspected, and dicing suitability was evaluated according to the following criteria. ○: No cracks at all ×: There are even a few cracks In the same manner as in Example 1, the dicing suitability of the cured products of Examples 2 and 3 and Comparative Examples 1 to 5 was also evaluated.

[0183] Table 2 shows the results of the evaluation of the coatability and dicing suitability of Examples 1 to 3 and Comparative Examples 1 to 5.

[0184] [Table 2]

[0185] The layers of the curable compositions (layers after heat drying) obtained by drying the liquid curable compositions of Examples 1 to 3 showed excellent results in the evaluation of coatability, and the liquid curable compositions of Examples 1 to 3 were able to improve workability in the coating process. Furthermore, the cured products obtained by drying and curing the liquid curable compositions of Examples 1 to 3 showed excellent results in the evaluation of dicing suitability, and the cured products of the liquid curable compositions of Examples 1 to 3 were suppressed from cracking during dicing.

[0186] On the other hand, the cured products obtained by drying and curing the liquid curable compositions of Comparative Examples 1 to 4 cracked during dicing. Furthermore, the layer of the curable composition obtained by drying the liquid curable composition of Comparative Example 5 (layer after heat drying) suffered from at least one of cissing and roughness of the coated surface during coating. Furthermore, the layer of the curable composition of Comparative Example 5 (layer after heat drying) could not be formed as a layer, and its dicing suitability could not be evaluated.

[0187] Although the embodiments of the invention have been described above, the invention is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the gist of the invention.

Claims

1. A liquid curable composition, a curable organopolysiloxane compound; Silica fine particles having an average primary particle diameter of 1 nm or more and 20 nm or less; a silane coupling agent having a nitrogen atom in the molecule; a silane coupling agent having an acid anhydride structure in the molecule, the silica fine particles are added in an amount of 1 part by mass or more relative to 100 parts by mass of the liquid curable composition, the silane coupling agent having a nitrogen atom in the molecule is added in an amount of 12 parts by mass or more per 100 parts by mass of a solid content of the liquid curable composition, the silane coupling agent having an acid anhydride structure in the molecule is added in an amount of 1.8 parts by mass or more per 100 parts by mass of a solid content of the liquid curable composition, A liquid curable composition having a viscosity of 5 Pa·s or more at 23°C.

2. The liquid curable composition according to claim 1 , wherein the curable organopolysiloxane compound is a polysilsesquioxane compound.

3. The liquid curable composition according to claim 1 , wherein the liquid curable composition is cut into a lattice shape after curing and used as individual pieces of the cured product.

4. The liquid curable composition according to claim 1 , wherein the liquid curable composition contains 80% by mass or more of a solid content.

5. A cured product of the liquid curable composition according to claim 1, The cured product has a plate-like shape, The main surface of the cured product is 710 cm ２ A hardened product having the following area:

6. Applying the liquid curable composition according to claim 1 to a sheet; heating the liquid curable composition to form a cured product having a plate-like shape; Cutting the cured product into a lattice shape to process it into individual plate-like shapes; A method for producing a hardened product of individual pieces, comprising:

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