Solid-state imaging device substrate

Abstract

To provide a solid-state imaging device substrate that, when used in the manufacture of a substrate stack, has improved reliability in thermal shock tests.SOLUTION: A ribbed substrate for a solid-state imaging device includes a ribbed material on a transparent substrate, and the ribbed material is formed from a semi-cured or cured product of a patterned curable composition, the curable composition contains a curable compound having a polymerizable functional group and a photopolymerization initiator, and also contains a siloxane compound having an alkali-soluble group, and the cured product of the curable composition has a tensile fracture strain of 18% or more in an atmosphere of 100°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a substrate for a solid-state imaging device. [Background technology]

[0002] Image sensors such as CMOS sensors and CCD sensors are used in digital cameras, smartphones, etc. In recent years, their use has increased with the spread of surveillance cameras in automobiles and factories, and there has been an increasing demand for smaller and higher-definition sensors.

[0003] A solid-state imaging device constituting an image sensor is, for example, a substrate laminate having a hollow structure in which a semiconductor element substrate having a light-receiving element and a glass substrate are bonded together with an adhesive. A substrate laminate having a hollow structure can be obtained, for example, by applying a liquid adhesive such as epoxy resin or acrylic resin to the periphery of a semiconductor element substrate, placing a glass sealing substrate, and then heating to harden the liquid adhesive. Furthermore, a method of using a photosensitive composition instead of the liquid adhesive has also been investigated in order to improve pattern accuracy.

[0004] For example, Patent Document 1 describes a method for producing a substrate laminate, which includes the steps of forming a coating film by applying a photosensitive composition to a first substrate (e.g., a glass substrate), patterning the resulting coating film, laminating the first substrate and a second substrate (e.g., a semiconductor device substrate) via the patterned coating film (hereinafter, sometimes referred to as a "patterned film") to form a laminate, and heating the resulting laminate to bond the first substrate and the second substrate. Patent Document 1 also describes that the photosensitive composition contains a cationically polymerizable compound and a photoacid generator (cationic photopolymerization initiator), and that in the step of patterning the coating film, the coating film is irradiated with light through a photomask to semi-cure the exposed areas of the coating film, and then developed to form a semi-cure patterned film.

[0005] Substrate laminates used in image sensors and the like are required to have high durability, and in particular, reliability in thermal shock tests (such as cracking and peeling of the cured product). However, the technology described in Patent Document 1 leaves room for improvement in the reliability of the manufactured substrate laminates in thermal shock tests. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5491197 Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the above, an object of the present invention is to provide a substrate for a solid-state imaging device that has improved reliability in thermal shock tests when used in the manufacture of a substrate stack. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems and have completed the present invention.

[0009] That is, the present invention has the following configuration. 1) A ribbed substrate for a solid-state imaging device having a rib material on a transparent substrate, the rib material is formed from a semi-cured or cured product of a patterned curable composition, the curable composition contains a curable compound having a polymerizable functional group and a photopolymerization initiator, and also contains a siloxane compound having an alkali-soluble group; A ribbed substrate for a solid-state imaging device, characterized in that the tensile breaking strain of a cured product of the curable composition in an atmosphere at 100°C is 18% or more.

[0010] 2) The ribbed substrate for a solid-state imaging device according to 1), wherein the siloxane compound is a modified polycyclic organosiloxane compound having a polymerizable functional group and a cyclic siloxane structure.

[0011] 3) The ribbed substrate for a solid-state imaging device according to 1) or 2), wherein the siloxane compound is a hydrosilylation reaction product of the following compounds (α) to (γ), and is a modified polycyclic organosiloxane compound having a SiH value of 1.20 mmol / g or less: (α) a cyclic siloxane compound having at least two SiH groups in one molecule; (β) at least one compound selected from the group consisting of an alkenyl compound having a structure represented by the following formula (X1) and / or an alkenyl compound having a phenolic hydroxyl group, (γ) An alkenyl compound having a polymerizable functional group in one molecule. [ka]

[0012] 4) The ribbed substrate for a solid-state imaging device according to any one of 1) to 3), wherein the siloxane compound is a hydrosilylation reaction product of the following compounds (α) to (δ), and is a modified polycyclic organosiloxane compound in which, when the amount of substance of (α) is α moles and the amount of substance of (δ) is δ moles, 0.25≦δ / α≦1.5: (α) a cyclic siloxane compound having at least two SiH groups in one molecule; (β) at least one compound selected from the group consisting of an alkenyl compound having a structure represented by the following formula (X1) and / or an alkenyl compound having a phenolic hydroxyl group, (γ) an alkenyl compound having a polymerizable functional group in one molecule; (δ) A linear siloxane compound having SiH groups at both ends. [ka]

[0013] 5) The ribbed substrate for a solid-state imaging device according to any one of 1) to 4), wherein the siloxane compound is a reaction product with an alkenyl compound having an alcoholic hydroxyl group.

[0014] 6) The ribbed substrate for a solid-state imaging device according to 4) or 5), wherein the linear siloxane compound having SiH groups at both ends used in the reaction is 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane.

[0015] 7) The ribbed substrate for a solid-state imaging device according to any one of 1) to 6), wherein the curable composition has at least two polymerizable functional groups.

[0016] 8) The ribbed substrate for a solid-state imaging device according to any one of 1) to 7), wherein the curable composition contains a compound containing two or more (meth)acryloyl groups.

[0017] 9) The ribbed substrate for a solid-state imaging device according to any one of 1) to 8), wherein the siloxane compound is a modified polycyclic organosiloxane compound having a SiH value of 0.10 mmol / g or more.

[0018] 10) A collective ribbed substrate for a solid-state imaging device, which is an assembly of a plurality of ribbed substrates for a solid-state imaging device according to any one of 1) to 9) separated by dicing spaces. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a substrate for a solid-state imaging device with improved reliability in thermal shock tests. DETAILED DESCRIPTION OF THE INVENTION

[0020] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited thereto. In addition, all academic and patent documents described in this specification are incorporated herein by reference.

[0021] First, the terms used in this specification are explained. "Photopolymerization initiator" refers to a compound that generates cations or radicals as active species upon irradiation with light. "Active species" includes radicals, cations, and anions. "Polymerizable functional group" refers to a functional group that undergoes chain polymerization. "Alkali-soluble group" refers to a functional group that increases solubility in alkaline solutions by interacting with or reacting with alkali. "Polysiloxane structure" refers to a structure in which siloxane units (Si-O-Si) are linked. "Solid content" refers to the non-volatile components in the composition, and "total solid content" refers to the total amount of the components of the composition excluding the solvent.

[0022] Hereinafter, the compound and its derivatives may be collectively referred to by adding "system" after the compound name. When the polymer name is expressed by adding "system" after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative. Acrylates and methacrylates may be collectively referred to as "(meth)acrylates." Acryloyl groups and methacryloyl groups may be collectively referred to as "(meth)acryloyl groups."

[0023] Unless otherwise specified, the components, functional groups, etc. exemplified in this specification may be used alone or in combination of two or more kinds.

[0024] <Solid-state imaging device substrate (solid-state imaging device substrate with grooves)> The substrate of the present invention is a ribbed substrate for a solid-state imaging device, which has a rib material on a transparent substrate, and the rib material is formed from a semi-cured or cured product of a patterned curable composition, and the curable composition contains a curable compound having a polymerizable functional group and a photopolymerization initiator, and also contains a siloxane compound having an alkali-soluble group, and the cured product of the curable composition has a tensile break strain of 18% or more in an atmosphere of 100°C.

[0025] A (collective) transparent substrate on which multiple pattern films for ribs are formed is sometimes referred to as a "collective ribbed substrate," a collective ribbed substrate diced into individual pieces is sometimes referred to as a "ribbed substrate," and the pattern film formed on a ribbed substrate is sometimes referred to as a "rib material." A "collective ribbed substrate" is an assembly of multiple ribbed substrates separated by dicing spaces. "Ribbed substrates" and "collective ribbed substrates" are sometimes collectively referred to as a "first substrate." Furthermore, a substrate on which solid-state imaging semiconductor elements are stacked is sometimes referred to as a "second substrate," and "second substrate" includes both the collective substrate on which multiple solid-state imaging semiconductor elements are stacked before dicing and the individualized substrates.

[0026] Forming a pattern film in a semi-cured state is sometimes referred to as "B-staging." The "semi-cured state" refers to a state in which there is still room for further curing of the pattern film in the step of heating the laminate.

[0027] <Curable composition> The curable composition according to the present invention is a curable composition characterized by containing a curable compound having a polymerizable functional group and a photopolymerization initiator, and also containing a siloxane compound having an alkali-soluble group, and the cured product has a tensile break strain of 18% or more in an atmosphere at 100°C.

[0028] The curable composition of the present invention contains a siloxane compound having an alkali-soluble group (hereinafter, sometimes referred to as "component (A)"), a curable compound having a polymerizable functional group (hereinafter, sometimes referred to as "component (B)"), and a photopolymerization initiator (hereinafter, sometimes referred to as "component (C)").

[0029] [Siloxane compound having an alkali-soluble group (component (A))] (Component (A)) is a modified polycyclic organosiloxane compound having a polymerizable functional group and a cyclic siloxane structure. A "polycyclic siloxane structure" refers to a cyclic molecular structure skeleton having siloxane units (Si-O-Si) as ring components. Having each structure represented by the following formula (X2) or a hydroxyl group in the same molecule makes it soluble in an alkaline aqueous solution, potentially enabling its use as an alkaline-developable resist material. The straight line extending from the nitrogen atom in each structure represented by (X2) above does not represent a methyl group, but rather indicates that the nitrogen atom is bonded to another group (site). [ka]

[0030] Component (A) is preferably a modified polycyclic organosiloxane having a SiH value of 1.20 mmol / g or less, more preferably a modified polycyclic organosiloxane having a SiH value of 0.10 mmol / g or more and 1.20 mmol / g or less, more preferably a SiH value of 0.50 mmol / g or less, even more preferably a SiH value of 0.15 mmol / g or less.

[0031] Component (A) may have a monocyclic structure or a polycyclic structure. The polycyclic structure may be a polyhedral structure. Among the siloxane units constituting the ring, the T units (XSiO 3 / 2 ) or Q units (SiO 4 / 2 The higher the content of the M unit (XSiO), the higher the hardness of the resulting cured layer tends to be and the more excellent the heat resistance. 1 / 2 ) or D unit (X2SiO 2 / 2 The higher the content of ), the more flexible the resulting cured product layer tends to be and the more reduced the residual stress. Here, X represents an organic group.

[0032] Component (A) used in the curable composition of the present invention further has at least two polymerizable functional groups in one molecule. The polymerizable functional groups herein refer to functional groups that polymerize or crosslink when exposed to external light or thermal energy, and the type of reaction or crosslinking is not particularly limited.

[0033] The weight-average molecular weight of component (A) used in the curable compound of the present invention is preferably 10,000 or more and 50,000 or less, more preferably 20,000 or more and 40,000 or less, and even more preferably 25,000 or more and 35,000 or less. When the weight-average molecular weight is 10,000 or more, a cured layer with excellent heat resistance tends to be obtained. On the other hand, when the weight-average molecular weight is 50,000 or less, the removability of the unexposed area during development is increased, and therefore patterning ability tends to be improved.

[0034] Component (A) (modified polycyclic organosiloxane compound: specifically, a polymerizable compound having a polymerizable functional group, an alkali-soluble group, and a polycyclic siloxane structure in one molecule) can be obtained, for example, by a hydrosilylation reaction containing the following compounds (α), (β), and (γ) as essential components. Compound (α): A polycyclic siloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule. Compound (β): A compound having a carbon-carbon double bond reactive with a SiH group and an alkali-soluble group in one molecule (an alkenyl compound having a structure represented by (X1) and / or an alkenyl compound having a phenolic hydroxyl group). Compound (γ): A compound having a carbon-carbon double bond reactive with SiH groups and a polymerizable functional group in one molecule (an alkenyl compound having a polymerizable functional group in one molecule). [ka]

[0035] Furthermore, it is more preferable to synthesize component (A) by a hydrosilylation reaction using the following compound (δ) and compounds (α), (β), and (γ) as starting materials, since this tends to improve reliability in thermal shock tests. Compound (δ): A linear siloxane compound with SiH groups (hydrosilyl groups) at both ends

[0036] (Compound (α)) Compound (α) is a polycyclic siloxane compound having at least two SiH groups per molecule, and examples thereof include compounds described in International Publication No. 96 / 15194, which are cyclic compounds having at least two SiH groups per molecule. The polycyclic siloxane may have a polycyclic structure, and the polycyclic structure may be a polyhedral structure. In order to form a cured layer with high heat resistance and mechanical strength, compound (α) is preferably a polycyclic siloxane having three or more SiH groups per molecule. From the viewpoint of heat resistance and light resistance, the group present on the Si atom is preferably either a hydrogen atom or a methyl group.

[0037] The cyclic polysiloxane is represented by, for example, the following general formula (1).

[0038] [ka]

[0039] In general formula (1), R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms, m represents an integer of 2 to 10, and n represents an integer of 0 to 10. To facilitate the hydrosilylation reaction, m is preferably 3 or greater. To facilitate the hydrosilylation reaction, m+n is preferably 3 to 12. To facilitate the hydrosilylation reaction, n is preferably 0.

[0040] R 1 , R 2 and R 3R is preferably an organic group composed of an element selected from the group consisting of C, H, and O. 1 , R 2 and R 3 Examples of R include alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, oxyalkyl groups, and aryl groups. Among these, chain alkyl groups such as methyl groups, ethyl groups, propyl groups, hexyl groups, octyl groups, decyl groups, and dodecyl groups, cyclic alkyl groups such as cyclohexyl groups and norbornyl groups, and phenyl groups are preferred. From the viewpoint of availability of cyclic polysiloxanes, R 1 , R 2 and R 3 As R, a chain alkyl group having 1 to 6 carbon atoms or a phenyl group is preferred. 1 , R 2 and R 3 As the alkyl group, a chain alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred.

[0041] Examples of cyclic polysiloxanes represented by general formula (1) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Among these, from the viewpoint of availability and reactivity of the SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in the general formula (1), m = 4, n = 0, and R 1 is a methyl group).

[0042] Compound (α) can be obtained by a known synthesis method. For example, a cyclic polysiloxane represented by general formula (1) can be synthesized by a method described in International Publication No. 96 / 15194 or the like. A cyclic polysiloxane having a polyhedral skeleton can be synthesized by a method described in Japanese Patent Application Laid-Open Nos. 2004-359933, 2004-143449, and 2006-269402, for example. Alternatively, a commercially available polycyclic siloxane compound may be used as compound (α).

[0043] (Compound (β)) Compound (β) is a compound having, in one molecule, a carbon-carbon double bond reactive with a SiH group and an alkali-soluble group. The alkali-soluble group in compound (β) is the same as the alkali-soluble group in the curable composition described above, and the preferred embodiments are also the same. That is, compound (β) preferably has, as the alkali-soluble group, one or more selected from the group consisting of an X2 group and a phenolic hydroxyl group, and more preferably has an X2 group.

[0044] Examples of groups containing a carbon-carbon double bond reactive with SiH groups (hereinafter, sometimes simply referred to as "alkenyl groups") include vinyl groups, allyl groups, methallyl groups, 2-allylphenyl groups, 3-allylphenyl groups, 4-allylphenyl groups, 2-(allyloxy)phenyl groups, 3-(allyloxy)phenyl groups, 4-(allyloxy)phenyl groups, 2-(allyloxy)ethyl groups, 2,2-bis(allyloxymethyl)butyl groups, 3-allyloxy-2,2-bis(allyloxymethyl)propyl groups, and vinyl ether groups. From the viewpoint of reactivity with SiH groups, compound (β) preferably has at least one alkenyl group selected from the group consisting of vinyl groups and allyl groups.

[0045] Specific examples of the compound (β) include diallyl isocyanurate, monoallyl isocyanurate, 2,2'-diallylbisphenol A, vinylphenol, allylphenol, etc. In order to more stably maintain the semi-cured state of the pattern film, the compound (β) is more preferably one or more selected from the group consisting of diallyl isocyanurate and monoallyl isocyanurate, and even more preferably diallyl isocyanurate.

[0046] (Compound (γ)) Compound (γ) is a compound having, in one molecule, a carbon-carbon double bond reactive with a SiH group (hydrosilyl group) and a polymerizable functional group. Compound (γ) preferably has a cationically polymerizable group or a radically polymerizable group as the polymerizable functional group. In particular, compound (γ) preferably has a cationically polymerizable group as the polymerizable functional group, and among the cationically polymerizable groups, it preferably has an epoxy group, more preferably has one or more selected from the group consisting of an alicyclic epoxy group and a glycidyl group, and even more preferably has an alicyclic epoxy group.

[0047] Compound (γ) has a group (alkenyl group) containing a carbon-carbon double bond reactive with a SiH group. Examples of the alkenyl group contained in compound (γ) include the same alkenyl groups as those exemplified as the alkenyl group contained in compound (β), and preferred embodiments are also the same. That is, compound (γ) preferably has, as the alkenyl group, one or more types selected from the group consisting of a vinyl group and an allyl group.

[0048] Specific examples of compound (γ) include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, etc. From the viewpoint of reactivity in cationic polymerization, compound (γ) is preferably a compound having an alicyclic epoxy group, and 1-vinyl-3,4-epoxycyclohexane is particularly preferred.

[0049] (Compound (δ)) The compound (δ) is a linear siloxane compound having SiH groups (hydrosilyl groups) at both ends. Examples of linear siloxane compounds having SiH groups at both ends include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, and dimethylhydrogensiloxane units (H(CH3)2SiO 1 / 2 units), and SiO2 units, SiO 3 / 2 Examples of the compound (δ) include polysiloxanes comprising one or more siloxane units selected from the group consisting of SiO units and SiO. The number of SiH groups in the compound (δ) is preferably two.

[0050] Specific examples of compound (δ) include 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,4-bis(dimethylsilyl)benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,2,2-tetraphenyldisilane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,2-bis(dimethylsilyl)benzene, etc. Among these, from the viewpoint of improving the toughness of the resin, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane or 1,4-bis(dimethylsilyl)benzene is preferred, and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane is more preferred.

[0051] (Other starting materials) In the hydrosilylation reaction, in addition to the above-mentioned compound (α), compound (β), compound (γ), and compound (δ), other starting materials may be used. For example, as the other starting material, an alkenyl group-containing compound different from the above-mentioned compound (β) and compound (γ) (hereinafter, sometimes referred to as "other alkenyl group-containing compound") may be used.

[0052] In order to increase the affinity with the alkaline developer and improve the development rate, component (A) may be synthesized using an alkenyl compound (π) having an alcoholic hydroxyl group. Preferred examples of the alkenyl compound (π) having an alcoholic hydroxyl group include allyl alcohol, 3-allyloxy-1,2-propanediol, and ethylene glycol monoallyl ether. To further improve the development rate, ethylene glycol monoallyl ether is preferred as compound (π).

[0053] To obtain a cured layer with excellent heat resistance, it is preferable to use a compound having two or more alkenyl groups in one molecule (hereinafter, sometimes referred to as "compound (ε)") as the other alkenyl group-containing compound. The use of compound (ε) increases the number of crosslinking points during the hydrosilylation reaction, which tends to improve the heat resistance of the resulting cured product.

[0054] Specific examples of the compound (ε) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, 1,1,2,2-tetraallyloxyethane, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, triethylene glycol divinyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, 1,3,5-tris(allyloxy)adamantane, 1,3,5-tris(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, and oligomers thereof. In order to further improve the heat resistance of the resulting cured product layer, the compound (ε) is preferably diallyl monomethyl isocyanurate.

[0055] To further suppress film loss during development, it is preferable to use a compound having an alkenyl group and a (meth)acryloyl group in one molecule (hereinafter sometimes referred to as "compound (ζ)") as another alkenyl group-containing compound. When compound (ζ) is used, a (meth)acryloyl group is introduced into the compound, which results in a relatively large number of reaction sites for radical polymerization reactions. This can improve the alkali resistance of the semi-cured exposed area.

[0056] Specific examples of compound (ζ) include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, 2-butenyl acrylate, 2-butenyl methacrylate, etc. In order to further suppress film loss during development, compound (ζ) is preferably one or more selected from the group consisting of vinyl acrylate and allyl acrylate, and more preferably allyl acrylate.

[0057] To improve the adhesive strength of the resulting cured product to the substrate, it is preferable to use a compound having one alkenyl group and an isocyanurate in one molecule (hereinafter sometimes referred to as "compound (η)") as another alkenyl group-containing compound. The use of compound (η) introduces a highly polar isocyanurate into the compound, improving the adhesive strength between the resin and the substrate. This improves the adhesive strength of the resulting cured product to the substrate.

[0058] Specific examples of the compound (η) include vinyl isocyanurate, allyl isocyanurate, 2-methyl-2-propene isocyanurate, allyl dimethyl isocyanurate, etc. In order to improve the adhesive strength of the resulting cured product to the substrate, allyl dimethyl isocyanurate is preferred as the compound (η).

[0059] (hydrosilylation reaction) The order and method of the hydrosilylation reaction to obtain a modified polycyclic organosiloxane compound are not particularly limited. For example, a modified polycyclic siloxane compound can be obtained by a hydrosilylation reaction according to the method described in International Publication No. 2009 / 075233 using the above-mentioned compounds (α), (β), (γ), and (δ), and optionally other starting materials. The modified polycyclic organosiloxane compound obtained using the above-mentioned compounds (α), (β), (γ), and (δ), and optionally other starting materials, is, for example, a polymer having multiple cationically polymerizable functional groups and multiple alkali-soluble groups in one molecule and having a polycyclic siloxane structure in the main chain.

[0060] Regarding the ratio of each compound in the hydrosilylation reaction, the total amount of alkenyl groups, A, and the total amount of SiH groups, B, among the starting materials preferably satisfy the relationship 1≦B / A≦30, more preferably 1≦B / A≦10, and even more preferably 1≦B / A≦1.1.

[0061] In order to stably maintain the semi-cured state of the pattern film while increasing the flexibility of the cured product obtained by B-staging, it is preferable to use compound (δ). When the amount of compound (α) in the hydrosilylation reaction is α moles and the amount of compound (δ) is δ moles, it is preferable that 0.25≦δ / α≦1.5, and more preferably 0.50≦δ / α≦1.0.

[0062] In order to obtain a curable composition with excellent patterning properties, the charge ratio of compound (β) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (β) / (mass of compound (α)+mass of compound (δ))) is preferably 0.1 or more and 0.9 or less, more preferably 0.2 or more and 0.8 or less.

[0063] In order to improve the heat resistance of the cured product obtained by B-staging while stably maintaining the semi-cured state of the pattern film, the charge ratio of compound (γ) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (γ) / (mass of compound (α)+mass of compound (δ))) is preferably 0.05 or more and 1.0 or less, and more preferably 0.2 or more and 0.9 or less.

[0064] When compound (π) is used as a starting material, in order to increase the affinity with the alkaline developer and improve the development rate, the charge ratio of compound (ε) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (ε) / (mass of compound (α)+mass of compound (δ))) is preferably 0.01 or more and 1.0 or less, and more preferably 0.05 or more and 0.7 or less.

[0065] When compound (ε) is used as a starting material, in order to obtain a curable composition with excellent patterning properties while improving the heat resistance of the cured product obtained by B-staging, the charge ratio of compound (ε) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (ε) / (mass of compound (α)+mass of compound (δ))) is preferably 0.01 or more and 0.5 or less, and more preferably 0.05 or more and 0.4 or less.

[0066] When compound (ζ) is used as a starting material, in order to further suppress film loss during development while ensuring the adhesiveness of the pattern film during B-staging, the feed ratio of compound (ζ) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (ζ) / mass of compound (α)+mass of compound (δ)) is preferably 0.1 or more and 0.5 or less, and more preferably 0.2 or more and 0.4 or less.

[0067] When compound (η) is used as a starting material, in order to improve the adhesive strength of the resulting cured product to a substrate, the feed ratio of compound (η) to compound (α) and compound (δ) in the hydrosilylation reaction (mass of compound (η) / mass of compound (α)+mass of compound (δ)) is preferably 0.1 or more and 1.0 or less, more preferably 0.2 or more and 0.7 or less.

[0068] The hydrosilylation reaction may be carried out using a hydrosilylation catalyst such as chloroplatinic acid, a platinum-olefin complex, or a platinum-vinylsiloxane complex. The hydrosilylation catalyst may be used in combination with a co-catalyst. The amount of the hydrosilylation catalyst (amount of substance) added is not particularly limited, but is preferably 10 times the amount of the total amount of alkenyl groups contained in the starting material. -8 more than 10 times -1 times or less, more preferably 10 -6 more than 10 times -2 It is less than double.

[0069] The reaction temperature for hydrosilylation may be set appropriately, and is preferably 30°C or higher and 200°C or lower, more preferably 50°C or higher and 150°C or lower. The oxygen concentration in the gas phase during the hydrosilylation reaction is preferably 3% by volume or lower. From the viewpoint of promoting the hydrosilylation reaction, the gas phase may contain 0.1% by volume or higher and 3% by volume or lower of oxygen.

[0070] A solvent may be used in the hydrosilylation reaction. The solvent may be a single solvent or a mixed solvent of two or more solvents. Examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and halogenated solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. Toluene, xylene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and chloroform are preferred because they are easily removed by distillation after the reaction. A gelation inhibitor may be used in the hydrosilylation reaction, if necessary.

[0071] [Curable compounds having polymerizable functional groups] The curable compound having a polymerizable functional group (hereinafter sometimes referred to as "component (B)") has two or more polymerizable functional groups in one molecule, and as long as it has two or more polymerizable functional groups in one molecule, it can be selected depending on the curing reaction type and used without any particular limitation, and examples include compounds having a polymerizable group such as cationic polymerizable compounds and radical polymerizable compounds. Component (B) is used as a crosslinking agent for the curable composition in this patent.

[0072] Examples of the cationically polymerizable compound include epoxy compounds and oxetane compounds. Examples of the component (B) having two cationically polymerizable groups per molecule include novolak phenol type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, cyclohexyl epoxy group-containing polyorganosiloxanes (cyclic, linear), glycidyl group-containing polyorganosiloxanes (cyclic, linear), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexylmethyl) ... bis(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis{(3-ethyl-3-oxetanyl)methoxy}methyl}benzene, bis{1-ethyl(3-oxetanyl)}methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and the like.

[0073] Examples of the radical polymerizable compound include compounds having a (meth)acryloyl group. Here, the radical polymerizable compound having a (meth)acryloyl group is not limited as long as it is a compound having two or more acryloyl groups or methacryloyl groups in one molecule. Examples of component (B) having two (meth)acryloyl groups in one molecule include triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (more specifically, polypropylene glycol diacrylate, etc.), 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc.

[0074] Examples of the component (B) having three (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin propoxy tri(meth)acrylate.

[0075] Examples of the component (B) having four (meth)acryloyl groups in one molecule include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate.

[0076] When a cationically polymerizable compound is selected as component (B), if the semi-cured pattern film is stored for a long period of time, cationic polymerization may proceed due to residual cations in the pattern film, and curing of the pattern film may proceed to the point where it becomes difficult to bond the substrates together when assembling a substrate laminate.From the viewpoint of being able to store the semi-cured pattern film for a long period of time, a radically polymerizable compound is more preferred as component (B), and a compound containing two or more (meth)acryloyl groups is even more preferred as the radically polymerizable compound.

[0077] From the viewpoint of further improving the durability of the substrate laminate in a thermal shock test, component (B) is more preferably a radical polymerizable compound, and as the radical polymerizable compound, a compound containing two or more (meth)acryloyl groups is even more preferable.

[0078] In order to increase the reactivity of the radical polymerization reaction, thereby increasing the alkali resistance of the semi-cured exposed area and further suppressing film loss during development, a compound having an acryloyl group is preferred as component (B).

[0079] Furthermore, in order to enhance the alkali resistance of the semi-cured exposed area by increasing the reactivity of the radical polymerization reaction and further suppress film loss during development, component (B) may have two or more (meth)acryloyl groups per molecule, but a compound having three or more (meth)acryloyl groups per molecule is preferred from the viewpoint of curability. In order to particularly suppress film loss during development, a compound having three or more acryloyl groups per molecule is more preferred as a compound containing a (meth)acryloyl group.

[0080] In order to ensure the adhesiveness of the pattern film during B-staging, the number of (meth)acryloyl groups contained in one molecule of component (B) is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less.

[0081] Component (B) is preferably a compound containing a (meth)acryloyl group, but the compound containing a (meth)acryloyl group may also have a cationically polymerizable functional group. It may also have an alkali-soluble group. However, in order to improve patterning properties while more stably maintaining the semi-cured state of the pattern film, it is preferable that the curable composition according to the first embodiment does not contain a compound having a cationically polymerizable functional group and an alkali-soluble group in one molecule. In other words, in the curable composition according to the present invention, it is preferable that the compound containing a (meth)acryloyl group is not a compound having a cationically polymerizable functional group and an alkali-soluble group in one molecule.

[0082] The amount of (component (B)) added can be set in various ways, but the amount added is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts, per 100 parts by weight of the modified polyorganosiloxane compound (component (A)). If the amount added is too small, the effect of the addition will not be apparent, and if the amount added is too large, it may have an adverse effect on the physical properties of the cured product.

[0083] [Photopolymerization initiator] The photopolymerization initiator (hereinafter sometimes referred to as "component (C)") may be a cationic polymerization initiator and / or a radical polymerization initiator.

[0084] The cationic polymerization initiator is not particularly limited, and may be an active energy ray cationic polymerization initiator that generates cationic species or Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates cationic species or Lewis acid by heat.

[0085] As a cationic polymerization initiator, cationic or protonic acid catalysts such as sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, iodonium salts, trifluoroacid salts, boron trifluoride ether complex compounds, boron trifluoride, etc. can be used. They are highly stable until they generate cationic species by heating, so they can be called latent curing catalysts. Polymerization activity varies depending on the type of substituent and the type of anion of the onium salt. In particular, for anions, BF - <AsF 6- <PF 6- <SbF 6- <B(C6F5) 4- It is known that polymerization activity increases in this order. In addition, aluminum complexes and silanol compounds, and aluminum complexes and certain phenolic compounds such as bisphenol S are known to act as cationic polymerization catalysts.

[0086] Among aromatic onium salts that are also used as active energy ray cationic polymerization initiators, some generate cationic species upon heating, and these can also be used as thermal cationic polymerization initiators. Examples include San-Aid SI-60L, SI-80L, and SI-100L (Sanshin Chemical Industry Co., Ltd.) and RHODORSIL PI2074 (Rhodia). Among these cationic polymerization initiators, aromatic onium salts are preferred because of their excellent handling properties and excellent balance between latency and curability.

[0087] The amount of cationic polymerization initiator used is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the modified polyorganosiloxane compound (component (A)). If the amount of cationic polymerization initiator is too small, curing may take a long time or a sufficiently cured product may not be obtained. If the amount of initiator is too large, the color of the initiator may remain in the cured product, or the cured product may become discolored or bulge due to rapid curing, and the heat and light resistance of the cured product may be impaired, which is undesirable.

[0088] The radical polymerization initiator is not particularly limited, and may be any active energy ray radical polymerization initiator that generates radical species by active energy rays or a thermal radical polymerization initiator that generates radical species by heat.

[0089] Specific examples of the radical polymerization initiator include acetophenone-based compounds, acylphosphine oxide-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, biimidazole-based compounds, polynuclear quinone-based compounds, triazine-based compounds, oxime ester-based compounds, titanocene-based compounds, xanthone-based compounds, thioxanthone-based compounds, ketal-based compounds, azo-based compounds, peroxides, 2,3-dialkyldione-based compounds, disulfide-based compounds, fluoroamine-based compounds, etc. In order to further suppress film loss during development, one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, and oxime ester-based compounds are preferred.

[0090] Examples of acetophenone compounds include 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4'-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2'-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-(4'-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4'-morpholinophenyl)butan-1-one, and 1-hydroxycyclohexyl phenyl ketone.

[0091] Examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0092] Examples of oxime ester compounds include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like.

[0093] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0094] Examples of benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0095] Examples of the α-diketone compounds include methyl benzoyl formate.

[0096] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'- Tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole phenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like.

[0097] Examples of polynuclear quinone compounds include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1,4-naphthoquinone.

[0098] Examples of xanthone compounds include xanthone, thioxanthone, and 2-chlorothioxanthone.

[0099] Examples of triazine compounds include 1,3,5-tris(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-methoxyphenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(2'-furylethylidene)-4,6-bis(trichloromethyl) 2-(4'-methoxynaphthyl)-s-triazine, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(2'-thiophenylethylidene)-4,6-bis(trichloromethyl)-s-triazine.

[0100] To further suppress film loss during development, the amount of radical polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, per 100 parts by mass of component (B). Furthermore, to ensure the adhesiveness of the pattern film during B-staging, the amount of radical polymerization initiator is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, per 100 parts by mass of component (B).

[0101] [solvent] The curable composition according to the present invention may contain a solvent. For example, the curable composition according to the first embodiment can be obtained by dissolving or dispersing the above-mentioned components (A), (B), and (C), and other components described below as necessary, in a solvent.

[0102] Specific examples of the solvent include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ester solvents such as ethyl acetate and isobutyl isobutyrate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol solvents such as propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and ethylene glycol diethyl ether; and halogenated solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. From the viewpoint of the coatability (film-forming stability) of the curable composition, the solvent is preferably an ester solvent, and more preferably isobutyl isobutyrate.

[0103] From the viewpoint of the coatability (film-forming stability) of the curable composition, the amount of the solvent is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the modified polycyclic organosiloxane.

[0104] [Other ingredients] The curable composition according to the present invention may contain components other than those described above (other components) within the scope that does not impair the objects and effects of the present invention. However, in order to further suppress film loss during development and more stably maintain the semi-cured state of the pattern film, the total amount of the above-mentioned components is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more and 100% by mass or less, based on the total solid content of the curable composition. Examples of other components include radical scavengers, colorants, sensitizers, fillers, adhesion improvers, coupling agents such as silane coupling agents, anti-deterioration agents, release agents, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-repellent agents, thixotropy imparting agents, tackifiers, storage stability improvers, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers, conductivity imparting agents, antistatic agents, radiation shielding agents, nucleating agents, lubricants, metal deactivators, and thermal conductivity imparting agents.

[0105] <Tensile breaking strain> The composition of the present invention must have a tensile break strain of 18% or more, more preferably 20% or more, and even more preferably 21% or more, in a tensile test at 100°C. A tensile break strain of less than 18% is undesirable because, when a substrate laminate is produced, the curable composition may not be able to withstand the stress generated in a thermal shock test, resulting in cracking or peeling. In this specification, the tensile break strain in a tensile test is a value measured in accordance with JIS K7127:1999. Specifically, it is measured, for example, as follows: The test curable composition is applied to a glass substrate to a thickness of 100 μm. The coating is then prebaked on a hot plate at 85°C for 5 minutes and 120°C for 10 minutes, after which the coating is exposed to light using a manual exposure machine ("MA-1300" manufactured by Dai Nippon Kaken Co., Ltd., lamp: high-pressure mercury lamp) at an accumulated exposure dose of 3000 mJ / cm2. The semi-cured coating film after exposure is then peeled off from the substrate and cut into the shape of a Type 2 test piece as specified in JIS K7127:1999. It is then heated in an oven at 200°C for 2 hours. The film thus obtained is conditioned for at least 48 hours in an environment at a temperature of 100±2°C to form a tensile test sample. The above test piece is used to measure the tensile yield strength and tensile breaking strain in accordance with JIS K7127:1999. The ambient temperature for the tensile test is 100±2°C. The tensile test can be performed using a universal material testing machine (model: 59R5582) manufactured by Istron Co., Ltd., for example. The tensile speed is 1 mm / min.

[0106] <Resist, cured product, and solid-state imaging device substrate using the curable composition> Next, a resist using a curable compound, a cured product thereof, and a method for manufacturing a substrate for a solid-state imaging device using the same will be described.

[0107] The manufacturing method includes a coating film forming step, an exposure step, and a development step. In the coating film forming step, a coating film is formed by applying a curable composition onto a first substrate. In the exposure step, the coating film is irradiated with light through a photomask, thereby forming exposed areas and non-exposed areas in the coating film, which are made of the curable composition in a semi-cured state. In the development step, an alkaline developer is used to remove the non-exposed areas from the substrate, thereby forming a patterned coating film on the first substrate.

[0108] [Coating film formation process] The method for preparing the curable composition is not particularly limited, and various methods are possible for preparation. The various components may be mixed and prepared immediately before curing, or all components may be mixed and prepared in advance in a one-part state and stored at low temperature.

[0109] In the coating film forming step, a coating film is formed by applying the prepared curable composition onto a substrate. Methods for applying the curable composition onto a substrate include spin coating, roll coating, printing, and bar coating. The thickness of the laminate used in an image sensor is, for example, 0.01 μm to 200 μm, preferably 0.1 μm to 150 μm, and more preferably 5 μm to 150 μm.

[0110] Examples of the substrate include a silicon wafer, a glass substrate, a resin substrate (such as a transparent resin substrate), a ceramic substrate, a semiconductor element substrate, etc. Examples of the semiconductor element substrate include a sensor substrate (more specifically, an image sensor substrate, etc.).

[0111] [Exposure process] The coating film is irradiated with light through a photomask to form exposed areas made of a semi-cured curable composition and unexposed areas. In the exposure step, active species are generated in the exposed areas by light irradiation, and functional groups in the exposed areas are polymerized to form the exposed areas in a semi-cured state.

[0112] The light source for photocuring may be a light source that emits light at the absorption wavelength of the polymerization initiator or sensitizer used, and typically includes a light source having a wavelength in the range of 200 to 450 nm, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a carbon arc lamp, or a light-emitting diode. The cumulative exposure dose of the exposed area irradiated with light in the exposure step is preferably 1 mJ / cm. 2 More than 50000mJ / cm 2 or less, more preferably 1 mJ / cm 2 More than 20000mJ / cm 2 The following is the result.

[0113] Furthermore, for the purpose of removing the solvent and improving the physical properties of the cured product, heat may be applied before or after photocuring to pre-bake and after-bake. The curing temperature can be set to various values, but the preferred temperature range is 60 to 400°C, and more preferably 90 to 350°C.

[0114] [Development process] In the development step, the unexposed areas are removed from the substrate using an alkaline developer to form a patterned coating film on the substrate. Examples of the alkaline developer used in the development step include an aqueous solution containing an alkaline component. Examples of the alkaline component contained in the alkaline developer include an alkaline organic component and an alkaline inorganic component. Examples of the alkaline organic component include tetramethylammonium hydroxide (hereinafter sometimes referred to as "TMAH") and choline. Examples of the alkaline inorganic component include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate. To enhance the contrast between the exposed and unexposed areas, the concentration of the alkaline component in the alkaline developer is preferably 25% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. The temperature of the alkaline developer can be adjusted according to the developability of the coating film. Examples of methods for contacting the alkaline developer with the unexposed areas include immersion, puddling, and spraying.

[0115] After contacting the unexposed area with the alkaline developer in the development step, the laminate having the substrate and the exposed area (pattern film) may be washed with water and dried. When drying the laminate, for example, moisture on the surface of the laminate after washing with water can be removed by compressed air, natural drying, or the like.

[0116] After the development step and before the lamination step described below, the pattern film may be heated to a temperature that does not reduce the adhesiveness of the pattern film. The heating temperature can be appropriately set, but is preferably 40° C. or higher and 200° C. or lower.

[0117] <Substrate laminate> A method for manufacturing a substrate laminate using substrates for solid-state imaging devices will be described.

[0118] The manufacturing method includes a lamination step and a heating step. In the lamination step, a first substrate (transparent substrate) and a second substrate are laminated with a patterned coating film interposed therebetween to form a laminate. In the heating step, the laminate is heated to further harden the semi-hardened patterned coating film, thereby bonding the first substrate and the second substrate together.

[0119] [Lamination process] In the lamination step, the first substrate and the second substrate are laminated together via a pattern film to form a laminate.

[0120] [Heating process] In the heating step, the laminate is heated to further harden the semi-hardened pattern film, thereby bonding the first substrate and the second substrate via a hardened layer made of the hardened pattern film. In the heating step, the laminate may be heated while applying a load, for example, in the range of 0.05 MPa to 100 MPa. The heating temperature in the heating step is, for example, 60°C to 300°C. Through the above steps, a substrate laminate is obtained. [Example]

[0121] Examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following.

[0122] [Response rate] In the following Synthesis Examples and Comparative Synthesis Examples, the reaction rates of allyl groups and vinyl groups were measured as follows. Measurements were performed using a 400MHz NMR instrument manufactured by Bruker Biospin. The reaction rate of the allyl group in the synthesis was measured by diluting the reaction mixture with deuterated chloroform to approximately 1% and adding it to an NMR tube. The reaction rate was calculated from the peaks derived from unreacted allyl groups / vinyl groups and the peaks derived from reacted allyl groups / vinyl groups.

[0123] [SiH value] The SiH value was calculated by the following formula (1) by preparing a mixture of the compound and dibromoethane, dissolving it in deuterated chloroform, and performing NMR measurement using a 400 MHz NMR manufactured by Bruker Biospin Corporation. SiH value (mmol / g) = [integral value of the peaks attributable to the SiH groups of the compound] / [integral value of the peaks attributable to the methyl groups of dibromoethane] × 4 × [weight of dibromoethane in the mixture] / [molecular weight of dibromoethane] / [weight of the compound in the mixture] (1) was calculated using

[0124] [Synthesis of modified polycyclic organosiloxane P1] To a mixture of 15 g of diallyl isocyanurate, 10.72 g of diallyl monomethyl isocyanurate, and 99 g of 1,4-dioxane, 0.047 g of a xylene solution of platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan, a solution containing 3 wt% platinum) was added to obtain solution S1. Separately, 33.06 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 66 g of toluene to obtain solution S2.

[0125] Then, in a nitrogen atmosphere containing 3% by volume of oxygen, solution S2 was heated to a temperature of 105°C in a 500 mL four-neck flask, and solution S1 was added dropwise to solution S2 over 1 hour. After completion of the addition, the mixture was stirred for 1 hour while maintaining the temperature at 105°C, thereby obtaining solution S3. The reaction rate of the alkenyl groups in the compound contained in the obtained solution S3 was measured by 1H-NMR, and the reaction rate was found to be 95% or higher.

[0126] Separately, 26.23 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 26.23 g of toluene to obtain a solution S4.

[0127] Then, in a nitrogen atmosphere containing 3% by volume of oxygen, solution S3 was heated to a temperature of 105°C, and solution S4 was added dropwise to solution S3 over 30 minutes. After the dropwise addition was completed, the mixture was stirred for 1 hour while maintaining the temperature at 105°C, thereby obtaining solution S5. The reaction rate of the alkenyl group of the compound contained in the obtained solution S5 was measured by 1H-NMR, and the reaction rate was found to be 95% or higher.

[0128] Solution S5 was then cooled, and the solvents (toluene, xylene, and 1,4-dioxane) were removed from Solution S5 by vacuum distillation to obtain a solid. Isobutyl isobutyrate (hereinafter referred to as "IBIB") was then added to the resulting solid to obtain Solution SP1 (P1 concentration: 70 wt%) containing modified polycyclic organosiloxane P1. P1 was a polysiloxane compound containing multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and possessing a cyclic polysiloxane structure in the main chain. Furthermore, the unreacted SiH groups in P1 accounted for 18.11% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per 1 g, was 1.17 mmol / g.

[0129] [Synthesis of modified polycyclic organosiloxane P2] Solution SP2 (P2 concentration: 70 wt%) containing P2 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except that 37.19 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 37.19 g of toluene to obtain solution S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and a cyclic polysiloxane structure in the main chain. Furthermore, the unreacted SiH groups in curable compound P2 were 2.05% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per 1 g, was 0.12 mmol / g.

[0130] [Synthesis of modified polycyclic organosiloxane P3] To a mixture of 15 g of diallyl isocyanurate, 6.43 g of diallyl monomethyl isocyanurate, and 99 g of 1,4-dioxane, 0.039 g of a xylene solution of platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan, a solution containing 3 wt% platinum) was added to obtain solution S1. Furthermore, 14.49 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 13.36 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane were dissolved in 66 g of toluene to obtain solution S2. Furthermore, 14.14 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 14.14 g of toluene to obtain solution S4. Solution SP3 (P3 concentration: 70 wt%) containing P3 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except for the preparation of S1, S2, and S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and was a polysiloxane compound with a cyclic polysiloxane structure and a linear siloxane structure in the main chain. Furthermore, the unreacted SiH groups in P3 were 2.05% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per 1 g, was 0.10 mmol / g.

[0131] [Synthesis of modified polycyclic organosiloxane P4] Solution S1 was obtained by adding 0.039 g of a xylene solution of platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan, a solution containing 3 wt% platinum) to a mixture of 15 g of diallyl isocyanurate, 6.43 g of diallyl monomethyl isocyanurate, and 99 g of 1,4-dioxane. Solution S2 was obtained by dissolving 14.49 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 13.36 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in 66 g of toluene. Solution S4 was obtained by dissolving 8.14 g of ethylene glycol monoallyl ether and 4.24 g of 1-vinyl-3,4-epoxycyclohexane in 12.38 g of toluene. Solution SP4 (P4 concentration: 70 wt%) containing P4 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except for the preparation of S1, S2, and S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and was a polysiloxane compound with a cyclic polysiloxane structure and a linear siloxane structure in the main chain. Furthermore, the unreacted SiH groups in P4 were 2.05% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per 1 g, was 0.11 mmol / g.

[0132] [Synthesis of modified polycyclic organosiloxane P5] Solution S1 was obtained by adding 0.039 g of a xylene solution of platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan, a solution containing 3 wt% platinum) to a mixture of 15 g of diallyl isocyanurate, 6.43 g of diallyl monomethyl isocyanurate, and 99 g of 1,4-dioxane. Solution S2 was obtained by dissolving 14.49 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 13.36 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in 66 g of toluene. Solution S4 was obtained by dissolving 7.86 g of allyl dimethyl isocyanurate, 4.07 g of ethylene glycol monoallyl ether, and 4.24 g of 1-vinyl-3,4-epoxycyclohexane in 16.17 g of toluene. Solution SP5 (P5 concentration: 70 wt%) containing P5 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except for the preparation of S1, S2, and S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and had a cyclic polysiloxane structure and a linear siloxane structure in the main chain. Furthermore, the unreacted SiH groups in P5 were 2.05% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per 1 g, was 0.10 mmol / g.

[0133] [Synthesis of modified polycyclic organosiloxane P6] Solution SP6 (P6 concentration: 70 wt%) containing P6 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except that 23.15 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 23.15 g of toluene to obtain solution S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and a cyclic polysiloxane structure in the main chain. Furthermore, the unreacted SiH groups in curable compound P6 accounted for 22.62% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per gram, was 1.52 mmol / g.

[0134] [Synthesis of modified polycyclic organosiloxane P7] Solution SP7 (P7 concentration: 70 wt%) containing P7 was obtained using the same synthetic method as described above in [Synthesis of Modified Polycyclic Organosiloxane P1], except that 11.57 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 11.57 g of toluene to obtain solution S4. The polysiloxane compound had multiple cationically polymerizable functional groups (specifically, alicyclic epoxy groups) and multiple alkali-soluble groups (specifically, X2 groups) per molecule, and a cyclic polysiloxane structure in the main chain. Furthermore, the unreacted SiH groups in curable compound P7 were 39.58% of the initial SiH groups, and the SiH value, which indicates the number of moles of SiH groups per gram, was 3.09 mmol / g.

[0135] [Preparing other ingredients] As materials for the curable composition, the following materials were prepared in addition to the above solutions SP1 to SP7 and IBIB. A benzophenone-based compound as a photoradical polymerization initiator (Omnirad (registered trademark) 651 manufactured by IGM Resins, hereinafter referred to as Omnirad 651) A sulfonium salt compound as a photocationic polymerization initiator ("CPI310FG" manufactured by San-Apro Co., Ltd., hereinafter referred to as "CPI310FG") 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Evonik, hereinafter referred to as "H-TEMPO") as a radical scavenger A hindered amine compound as a cation scavenger (ADEKA Corporation's "ADEKA STAB LA-72," hereinafter referred to as "LA72") A silane coupling agent ("KBM9659" manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter for glass and Si substrates. 2-Methyl-3-butyn-2-ol (MBO, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as "MBO") as a platinum stabilizer Hindered phenolic compound as an antioxidant (BASF's "Irganox 1010"; hereinafter referred to as "Irganox 1010") Tris-(2-acryloxyethyl) isocyanurate ("A9300" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as "A9300") as a photoradical crosslinking agent Alicyclic epoxy compound as a photocationic crosslinking agent (Daicel Corporation's "Celloxide 2081"; hereinafter referred to as "Celloxide 2081")

[0136] [Preparation of Curable Composition] The materials shown in Table 1 were blended in the amounts shown in Table 1 to obtain curable compositions PS1 to PS7 used in the examples and comparative examples. PS5' was blended in the amount shown in Table 2. When blending curable compounds P1 to P7, they were blended as solutions SP1 to SP7, respectively.

[0137] [Table 1] [Table 2]

[0138] [Measurement of tensile fracture strain in an atmosphere of 100°C] The method for measuring the tensile strain at break of the cured products of the curable compositions PS1 to PS7 in an atmosphere at 100° C. will be described below.

[0139] The test curable composition was applied to a glass substrate to a thickness of 100 μm. After pre-baking on a hot plate at 85°C for 5 minutes and 120°C for 10 minutes, the coating was exposed to light using a manual exposure machine ("MA-1300" manufactured by Dai Nippon Kaken Co., Ltd., lamp: high-pressure mercury lamp) at an integrated exposure of 3000 mJ / cm². The semi-cured coating film after exposure was then peeled off from the substrate and cut into a Type 2 specimen (rectangle, 10 mm wide, 150 mm long) as specified in JIS K7127:1999. The specimen was then heated in an oven at 200°C for 2 hours to obtain a cured film. The film was then conditioned for at least 48 hours at 100±2°C to obtain a tensile test sample. Using the sample obtained in this way, a tensile test was performed in a 100°C atmosphere at a pulling rate of 1 mm / min. The tensile test was performed using a universal material testing machine (model: 59R5582) manufactured by Istron Co., Ltd. The tensile breaking strain was calculated in accordance with JIS K7127:1999.

[0140] [Preparation of simulated optical semiconductor device samples] Hereinafter, methods for producing simulated optical semiconductor device samples of Examples 1 to 6 and Comparative Examples 1 and 2 will be described.

[0141] [Patterned film formation] Each curable composition shown in Table 1 was applied to a glass plate as a glass substrate using a spin coater so that the thickness of the coating film after pre-baking would be 100 μm, and the coating was pre-baked by heating on a hot plate at a temperature of 85°C for 5 minutes and then at a temperature of 120°C for 10 minutes, thereby obtaining Sample 1.

[0142] Next, using a manual exposure machine ("MA-1300" manufactured by Nippon Kaken Co., Ltd., lamp: high-pressure mercury lamp), the film was exposed to an integrated exposure dose of 3000 mJ / cm through a photomask on which a grid-like line pattern was formed. 2The coating film of Sample 1 was exposed to light under the conditions above (specifically, soft contact exposure).

[0143] After the exposure, Sample 1 was left to stand in an atmosphere at 25°C for 5 minutes, and then immersed in an aqueous TMAH solution (TMAH concentration: 2.38% by mass) as an alkaline developer for 60 seconds. Sample 1 immersed in the alkaline developer was then rinsed with water for 30 seconds, and the surface moisture was removed with compressed air to obtain Sample 2, which had a semi-cured patterned film in which the coating film was patterned in a grid pattern.

[0144] [Sample 3 (ribbed substrate obtained by dividing Sample 2)] Sample 3 was cut with a dicing device to obtain Sample 3 (a diced sample) (a sample having a surface of 12 mm×12 mm).

[0145] [Adhesion process] Next, using a flip-chip bonder (Athlete FA's "CB-505"), the ribbed substrate obtained by the above procedure was laminated with a simulated semiconductor substrate obtained by bonding a silicon wafer to a glass epoxy substrate. Specifically, the simulated semiconductor substrate was set on the stage of the flip-chip bonder, and the side of the ribbed substrate without the rib material was adsorbed and fixed with a collet. The collet was then moved to a position on the simulated semiconductor substrate while checking with the camera attached to the flip-chip bonder. The ribbed substrate and simulated semiconductor substrate were then bonded together under the following conditions: collet temperature was 90°C, stage temperature was 90°C, and a load of 4N was applied for 30 seconds, yielding Sample 4, a laminate of the ribbed substrate and the simulated semiconductor substrate.

[0146] Next, the laminate of Sample 4 was heated in an oven at 200°C for 2 hours. This bonded the rib material and the semiconductor substrate laminate. Next, the periphery of the rib material of the heated laminate of Sample 4 was sealed with black sealing resin manufactured by Henkel, and heated in an oven at 165°C for 2 hours to obtain Sample 5. After heating, Sample 5 was heated at 240°C for 5 minutes and then at 260°C for 15 minutes to create a simulated sample of an optical semiconductor device with a hollow structure.

[0147] [evaluation] The evaluation methods and results of the patterning properties and reliability of Examples 1 to 8 and Comparative Examples 1 and 2 will be described below.

[0148] [Patterning property evaluation test] The pattern shape of Sample 2 was observed using a 3D measuring laser microscope (LEXT OLS4000, manufactured by Olympus Corporation) and evaluated according to the following criteria. ⊚: No residue was found in the 50 μm line and space. ◯: Residues were generated in the lines and spaces spaced at 50 μm intervals, but not in the lines and spaces spaced at 100 μm intervals. ×: Other than ◎ and 〇 The results are shown in Table 3 below.

[0149] [Delamination evaluation criteria in thermal shock tests] ⊚: No peeling of the rib material was observed in either of the two simulated samples. ○: Peeling of the rib material (more specifically, partial peeling) was confirmed in one of the two simulated samples, but the number of peeled areas (total of peeled areas on the two simulated samples) was one. ×: Peeling of the rib material (more specifically, partial peeling) was confirmed in at least one of the two simulated samples, and the number of peeled areas (total number of peeled areas in the two simulated samples) was two or more. The results are shown in Table 3 below.

[0150] [Crack evaluation criteria in thermal shock tests] ⊚: No cracks were observed in the rib material in either of the two simulated samples. Good: Cracks (more specifically, partial cracks) were found in the rib material of one of the two simulated samples, but the number of cracks (total number of cracks in the two simulated samples) was one. ×: Cracks (more specifically, partial cracks) were found in the rib material of at least one of the two simulated samples, and the number of cracks (total number of cracks in the two simulated samples) was two or more. The results are shown in Table 3 below.

[0151] [Table 3]

[0152] In Comparative Examples 1 and 2, errors occurred at 100 cycles, but improvements were observed in both peeling and cracking in Examples 1 to 6. This is thought to be because the tensile fracture strain in a 100°C atmosphere increased, which alleviated the stress generated during the thermal shock test at high temperatures, making errors less likely to occur.

[0153] In Examples 3, 4, 5, and 6, which used P3, P4, and P5, which had linear siloxanes introduced, the tensile fracture strain in an atmosphere at 100°C was even greater than in Example 2, which did not have linear siloxanes introduced, and improvements were also seen in the thermal shock test. This is thought to be because the introduction of linear siloxanes further improved the flexibility of the resin.

[0154] On the other hand, because 1-vinyl-3,4-epoxycyclohexane has a hydrophobic epoxy group, the more the amount introduced, the lower its solubility in alkaline aqueous solution, and residues began to appear between the ribs. In Examples 4, 5, and 6, when part of the 1-vinyl-3,4-epoxycyclohexane was replaced with ethylene glycol monoallyl ether, which has a hydrophilic hydroxy group, the solubility in alkaline aqueous solution increased and no residues were observed.

[0155] Furthermore, in Example 5, when P5 was used in which some of the 1-vinyl-3,4-epoxycyclohexane and ethylene glycol monoallyl ether were replaced with allyl dimethyl isocyanurate, the effect of isocyanurate in improving the adhesive strength to the substrate was observed, and neither peeling nor cracking was observed after 500 cycles.

[0156] On the other hand, in Example 6, P5 was used, but the crosslinking agent was changed to the cationic crosslinking agent Celloxide 2081. When the resin was cured using a cationic polymerization system and tested, the results were slightly worse than those of Example 5, which was conducted using a radical polymerization system.

[0157] The above results demonstrate that the present invention can provide an optical semiconductor device with improved reliability as evaluated by thermal shock tests.

Claims

1. A ribbed substrate for a solid-state imaging device having a rib material on a transparent substrate, the rib material is formed from a semi-cured or cured product of a patterned curable composition, the curable composition contains a curable compound having a polymerizable functional group and a photopolymerization initiator, and also contains a siloxane compound having an alkali-soluble group; a cured product of the curable composition having a tensile break strain of 18% or more in an atmosphere at 100°C; Ribbed substrate for solid-state imaging device.

2. 2. The ribbed substrate for a solid-state imaging device according to claim 1, wherein the siloxane compound is a modified polycyclic organosiloxane compound having a polymerizable functional group and a cyclic siloxane structure.

3. The ribbed substrate according to claim 2, wherein the siloxane compound is a modified polycyclic organosiloxane compound that is a hydrosilylation reaction product of the following compounds (α) to (γ) and has a SiH value of 1.20 mmol / g or less: (α) a cyclic siloxane compound having at least two SiH groups in one molecule; (β) at least one compound selected from the group consisting of an alkenyl compound having a structure represented by the following formula (X1) and / or an alkenyl compound having a phenolic hydroxyl group: (γ) An alkenyl compound having a polymerizable functional group in one molecule. 【Chemical 1】

4. The ribbed substrate for a solid-state imaging device according to claim 2, wherein the siloxane compound is a hydrosilylation reaction product of the following compounds (α) to (δ), and is a modified polycyclic organosiloxane compound in which, when the amount of substance of (α) is α moles and the amount of substance of (δ) is δ moles, 0.25≦δ / α≦1.5: (α) a cyclic siloxane compound having at least two SiH groups in one molecule; (β) at least one compound selected from the group consisting of an alkenyl compound having a structure represented by the following formula (X1) and / or an alkenyl compound having a phenolic hydroxyl group: (γ) an alkenyl compound having a polymerizable functional group in one molecule; (δ) A linear siloxane compound having SiH groups at both ends. 【Chemistry 2】

5. 3. The ribbed substrate for a solid-state imaging device according to claim 1, wherein the siloxane compound is a reaction product with an alkenyl compound having an alcoholic hydroxyl group.

6. 5. The ribbed substrate for a solid-state imaging device according to claim 4, wherein the linear siloxane compound having SiH groups at both ends used in the reaction is 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane.

7. 3. The ribbed substrate for a solid-state imaging device according to claim 1, wherein the curable composition has at least two polymerizable functional groups.

8. The ribbed substrate for a solid-state imaging device according to claim 1 or 2, wherein the curable composition contains a compound containing two or more (meth)acryloyl groups.

9. 3. The ribbed substrate for a solid-state imaging device according to claim 1, wherein the siloxane compound is a modified polycyclic organosiloxane compound having a SiH value of 0.10 mmol / g or more.

10. 5. A ribbed substrate for a solid-state imaging device, which is an assembly of a plurality of ribbed substrates for a solid-state imaging device according to claim 1, with dicing spaces interposed therebetween.

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