A substrate stack, an image sensor, and a method for manufacturing a substrate stack.

Abstract

A substrate laminate (10) has a first substrate (11), a second substrate (12), and a cured material layer (13) interposed between the first substrate (11) and the second substrate (12). The cured material layer (13) is patterned, and has a first layer (14) comprising a cured material of a first developable composition, and a second layer (15) comprising a cured material of a second developable composition in this order from the first substrate (11) side. The first developable composition is a developable composition containing a polymerizable first curable compound and a first photopolymerization initiator, and not containing a coloring agent. The second developable composition is a developable composition containing a polymerizable second curable compound, a second photopolymerization initiator, and a coloring agent.

Description

[Technical Field]

[0001] The present invention relates to a substrate stack, an image sensor, and a method for manufacturing a substrate stack. [Background technology]

[0002] Image sensors such as CMOS sensors and CCD sensors are used in digital cameras and smartphones, and in recent years, their use has increased with the proliferation of surveillance cameras in automobiles and factories, and there is an increasing demand for smaller size and higher resolution.

[0003] The substrate laminate constituting the image sensor has a hollow structure in which a semiconductor element substrate having a light-receiving element and a glass substrate are bonded together via patterned layers. A substrate laminate having a hollow structure can be obtained, for example, by the following procedure.

[0004] First, a photosensitive composition is applied to one side of a first substrate (e.g., a glass substrate) to form a coating film on the first substrate. Next, light is irradiated onto the coating film through a photomask to form exposed areas and unexposed areas in the coating film, which are composed of a semi-cured photosensitive composition. Then, the unexposed areas are removed from the first substrate with a developer to form a patterned semi-cured coating film (hereinafter sometimes referred to as a "pattern film") on the first substrate. Next, the first substrate with the pattern film and the second substrate (e.g., a semiconductor device substrate) are bonded together via the pattern film, and the pattern film is cured to bond the first substrate and the second substrate. Through these steps, a substrate laminate having a hollow structure is obtained.

[0005] As the miniaturization of image sensors progresses, reflected light and scattered light at the end of the substrate laminate during imaging may enter the imaging area within the hollow structure, which may cause imaging errors such as flare and ghosting. To solve this problem, a method is adopted to suppress the entry of the above-mentioned reflected light and scattered light into the imaging area within the hollow structure by forming a light-shielding film on a glass substrate. As a method for forming the light-shielding film, the metal vapor deposition method is common, but since the metal vapor deposition method is costly, a light-shielding film made using an inexpensive black resin has also been reported (for example, see Patent Document 1).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] As a method for forming a light-shielding film using a black resin, photolithography capable of fine processing is adopted for the purpose of improving dimensional accuracy. However, through the study by the inventors, it has been found that when a light-shielding film is formed by photolithography using a black resin, problems often occur such as foreign matters derived from the colorant in the black resin remaining on the imaging surface. The above-mentioned foreign matters can cause imaging errors such as reflection during imaging.

[0008] The present invention has been made in view of the above problems, and its object is to provide a substrate laminate capable of suppressing the adhesion of foreign matters derived from a colorant, a manufacturing method thereof, and an image sensor having the substrate laminate.

Means for Solving the Problems

[0009] <Aspects of the Present Invention> The present invention includes the following aspects.

[0010] [1] Step Sa of forming a coating film on the first substrate, Step Sb of forming, on the first substrate, an exposed portion in a semi-cured state and a non-exposed portion by irradiating the coating film with active energy rays through a photomask, Step Sc of forming the patterned coating film on the first substrate by removing the non-exposed portion from the first substrate with a developer, Step Sd1 of bonding the first substrate and the second substrate through the patterned coating film A method for manufacturing a substrate laminate, comprising: The exposed portion in the semi-cured state has, from the first substrate side, a first semi-cured layer composed of a first developable composition in a semi-cured state and a second semi-cured layer composed of a second developable composition in a semi-cured state in this order, The first developable composition is a developable composition containing a first curable compound having polymerizability, a first photoinitiator, and not containing a colorant, The second developable composition is a developable composition containing a second curable compound having polymerizability, a second photoinitiator, and a colorant. A method for manufacturing a substrate laminate.

[0011] [2] The second substrate has a semiconductor element substrate and a frame material, In the step Sd1, the method for manufacturing a substrate laminate according to [1], wherein the first substrate and the frame material are bonded through the patterned coating film.

[0012] [3] In the step Sd1, after heating the patterned coating film to further cure the first developable composition in the semi-cured state and the second developable composition in the semi-cured state, the cured coating film and the second substrate are bonded with an adhesive. The method for manufacturing a substrate laminate according to [1] or [2].

[0013] [4] A method for manufacturing a substrate laminate according to [1] or [2], wherein in step Sd1, the first substrate and the second substrate are laminated with the patterned coating film in a semi-cured state to form a laminate, and then the laminate is heated to further cure the coating film, thereby bonding the first substrate and the second substrate together.

[0014] [5] A step Sa of forming a coating film on a first substrate, Step Sb involves irradiating the coating film with active energy rays through a photomask to form a semi-cured exposed area and an unexposed area on the first substrate. Step Sc to form the patterned coating film on the first substrate by removing the unexposed areas from the first substrate with a developing solution, Step Sd2 involves bonding the side of the first substrate opposite to the side on which the patterned coating film is formed to the second substrate with an adhesive. A method for manufacturing a substrate laminate comprising, The semi-cured exposure portion has, from the first substrate side, a first semi-cured layer made of a first developable composition in a semi-cured state, and a second semi-cured layer made of a second developable composition in a semi-cured state, in this order. The first developable composition comprises a polymerizable first curable compound and a first photopolymerization initiator, and is a developable composition that does not contain a colorant. A method for producing a substrate laminate, wherein the second developable composition comprises a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0015] [6] The second substrate comprises a semiconductor element substrate and a frame material, The method for manufacturing a substrate laminate according to [5], wherein in step Sd2, the first substrate and the frame material are bonded together with the adhesive.

[0016] [7] A method for manufacturing a substrate laminate according to any one of [1] to [6], wherein in step Sa, the first developable composition is applied to the first substrate, and then the second developable composition is applied to the first film made of the first developable composition to form the coating film comprising the first film and the second film made of the second developable composition.

[0017] [8] The coating film further comprises a third film composed of a third developable composition, The third developable composition comprises a polymerizable third curable compound and a third photopolymerization initiator, and is a developable composition that does not contain a colorant. The method for manufacturing a substrate laminate according to [7], wherein in step Sa, the third developable composition is applied to the side of the second film opposite to the side of the first film.

[0018] [9] A method for manufacturing a substrate laminate according to any one of [1] to [6], wherein in step Sa, the first developable composition is applied to the first substrate, the first film made of the first developable composition is irradiated with an active energy ray, and the second developable composition is applied to the first film after irradiation with the active energy ray to form the coating film comprising the first film and the second film made of the second developable composition.

[0019]

[10] The coating film further comprises a third film composed of a third developable composition, The third developable composition comprises a polymerizable third curable compound and a third photopolymerization initiator, and is a developable composition that does not contain a colorant. The method for manufacturing a substrate laminate according to [9], wherein in step Sa, the third developable composition is applied to the side of the second film opposite to the side of the first film.

[0020]

[11] The method for manufacturing a substrate laminate according to any one of [1] to

[10] , wherein the first developable composition and the second developable composition are alkali soluble.

[0021]

[12] A method for manufacturing a substrate laminate according to any one of [1] to

[11] , wherein the first substrate is a glass substrate.

[0022]

[13] The first curable compound is cationic polymerizable or radical polymerizable, a method for producing a substrate laminate according to any one of [1] to

[12] above.

[0023]

[14] The method for manufacturing a substrate laminate according to any one of [1] to

[13] , wherein the second curable compound is cationic polymerizable or radical polymerizable.

[0024]

[15] The second photopolymerization initiator is a photocationic polymerization initiator, The method for producing a substrate laminate according to any one of [1] to

[14] , wherein the photocationic polymerization initiator has one or more structures selected from the group consisting of a naphthalimide structure and an oximesulfonate structure.

[0025]

[16] The method for manufacturing a substrate laminate according to any one of [1] to

[15] , wherein the second developable composition further comprises a sensitizer.

[0026]

[17] A substrate laminate having a first substrate, a second substrate, and a cured material layer interposed between the first substrate and the second substrate, The cured layer is patterned and, starting from the first substrate side, has a first layer composed of a cured product of a first developable composition, and a second layer composed of a cured product of a second developable composition, in that order. The first developable composition comprises a polymerizable first curable compound and a first photopolymerization initiator, and is a developable composition that does not contain a colorant. The substrate laminate is a substrate laminate in which the second developable composition comprises a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0027]

[18] The substrate laminate according to

[17] , further comprising an adhesive layer for bonding the cured material layer and the second substrate.

[0028]

[19] A substrate laminate having a first substrate, a second substrate, an adhesive layer for bonding the first substrate and the second substrate, and a cured material layer disposed on the side of the first substrate opposite to the side of the second substrate, The cured layer is patterned and, starting from the first substrate side, has a first layer composed of a cured product of a first developable composition, and a second layer composed of a cured product of a second developable composition, in that order. The first developable composition comprises a polymerizable first curable compound and a first photopolymerization initiator, and is a developable composition that does not contain a colorant. The substrate laminate is a substrate laminate in which the second developable composition comprises a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0029]

[20] An image sensor comprising a substrate laminate as described in any one of

[17] to

[19] above. [Effects of the Invention]

[0030] According to the present invention, it is possible to provide a substrate laminate that can suppress the adhesion of foreign substances derived from colorants, a method for manufacturing the same, and an image sensor having the substrate laminate. [Brief explanation of the drawing]

[0031] [Figure 1] This is a cross-sectional view showing an example of a substrate laminate according to the present invention. [Figure 2] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 3] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 4] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 5] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 6] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 7] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 8] This is a cross-sectional view showing another example of a substrate laminate according to the present invention. [Figure 9] This is a plan view showing the first substrate after the formation of a cured layer, when manufacturing an example of a substrate laminate according to the present invention. [Figure 10] This is a plan view showing a first substrate after the cured layer has been formed and the substrate has been separated into individual pieces, when manufacturing an example of a substrate laminate according to the present invention. [Figure 11] A, B, and C are cross-sectional views showing a step-by-step example of a method for manufacturing a substrate laminate according to the present invention. [Figure 12] A, B, and C are cross-sectional views showing a step-by-step example of a method for manufacturing a substrate laminate according to the present invention. [Figure 13] A, B, and C are cross-sectional views showing a step-by-step example of a method for manufacturing a substrate laminate according to the present invention. [Figure 14] A, B, and C are cross-sectional views showing different steps of the manufacturing method for a substrate laminate according to the present invention. [Figure 15] A, B, and C are cross-sectional views showing different steps of the manufacturing method for a substrate laminate according to the present invention. [Modes for carrying out the invention]

[0032] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited thereto. Furthermore, all academic and patent documents cited herein are incorporated herein by reference.

[0033] First, let's explain the terms used in this specification. "Photopolymerization initiator" refers to a compound that generates active species (specifically, radicals, cations, anions, etc.) when irradiated with active energy rays. "Photocationic polymerization initiator" refers to a compound that generates cations (acids) as active species when irradiated with active energy rays. "Photoradical polymerization initiator" refers to a compound that generates radicals as active species when irradiated with active energy rays. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, electron beams, X-rays, alpha rays, beta rays, gamma rays, etc.

[0034] "Cationic polymerizable group" refers to a functional group that undergoes a chain polymerization reaction in the presence of a cation. "Radical polymerizable group" refers to a functional group having an unsaturated bond that can be radically polymerized. "Alkali-soluble group" refers to a functional group that increases solubility in alkaline solutions by interacting with or reacting with alkali. "Developerable composition" refers to a composition containing one or more compounds selected from the group consisting of compounds having alkali-soluble groups and compounds soluble in organic solvents. "The developerable composition is alkali-soluble" means that the developerable composition contains a compound having an alkali-soluble group. "The developerable composition is soluble in organic solvents" means that the developerable composition contains a compound soluble in organic solvents. "Sensitizer" refers to a compound that improves exposure sensitivity. "Alicyclic epoxy group" refers to a functional group formed by the bonding of one oxygen atom to two adjacent carbon atoms among the carbon atoms constituting an alicyclic structure, such as the 3,4-epoxycyclohexyl group. A "polysiloxane compound" is a compound having a polysiloxane structure composed of siloxane units (Si-O-Si). Examples of polysiloxane structures include linear polysiloxane structures (specifically, linear polysiloxane structures, branched polysiloxane structures, etc.) and cyclic polysiloxane structures. An "epoxy adhesive" refers to an adhesive that contains a compound having epoxy groups (for example, a compound containing at least two epoxy groups in one molecule) as its main component. A "semi-cured state" refers to a state in which the degree of curing can be further increased by a subsequent process (for example, a heating process). "Solid content" refers to the non-volatile components in a composition, and "total solid content" refers to the total amount of the composition's components excluding the solvent.

[0035] The "thickness" of each layer constituting the substrate stack is the arithmetic mean of 10 measurements obtained by randomly selecting 10 measurement points from electron microscope images of a cross-section obtained by cutting the substrate stack in the thickness direction, and measuring the thickness of the 10 selected measurement points.

[0036] Unless otherwise specified, the "main component" of a material refers to the component that is present in the largest quantity by mass.

[0037] "Alkyl group," "alkenyl group," "alkynyl group," "alkoxy group," "acyl group," "alkylthio group," and "halogenated alkyl group" may all be linear or branched. Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "An organic group (more specifically, an aryl group, etc.) may be substituted with a substituent (more specifically, an alkyl group, etc.)" means that some or all of the hydrogen atoms of the organic group may be substituted with substituents.

[0038] In the following, the compound name may be followed by "system" to refer to the compound and its derivatives collectively. When "system" is followed by a compound name to represent a polymer name, it indicates that the repeating units of the polymer originate from the compound or its derivative. Additionally, acrylic and methacrylic may be collectively referred to as "(meth)acrylic." Similarly, acrylate and methacrylate may be collectively referred to as "(meth)acrylate." Furthermore, acryloyl and methacryloyl may be collectively referred to as "(meth)acryloyl."

[0039] Unless otherwise specified, the components and functional groups exemplified herein may be used individually or in combination of two or more.

[0040] The diagrams referenced in the following explanation are schematic representations of each component for ease of understanding, and the size, number, shape, etc., of each component shown may differ from the actual dimensions due to the limitations of drawing creation. Furthermore, for the sake of explanation, components identical to those described earlier may be denoted by the same reference numerals in later diagrams, and their explanations may be omitted.

[0041] <First Embodiment: Substrate Laminate> A substrate laminate according to the first embodiment of the present invention (hereinafter sometimes referred to as "substrate laminate L1") has a first substrate, a second substrate, and a cured layer interposed between the first substrate and the second substrate. The cured layer is patterned and has, from the first substrate side, a first layer composed of a cured product of a first developable composition, and a second layer composed of a cured product of a second developable composition, in that order. The first developable composition is a developable composition that includes a polymerizable first curable compound and a first photopolymerization initiator, but does not contain a colorant. The second developable composition is a developable composition that includes a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0042] In this specification, "the first developable composition does not contain a colorant" means that the amount of colorant in the first layer, which is made up of the cured product of the first developable composition, is less than 0.1 parts by mass (preferably less than 0.01 parts by mass, more preferably less than 0.001 parts by mass, and even more preferably less than 0.0001 parts by mass) per 100 parts by mass of colorant in the second layer, which is made up of the cured product of the second developable composition.

[0043] According to the substrate laminate L1, the adhesion of foreign matter originating from the coloring agent can be suppressed. The reason for this is presumed to be as follows:

[0044] The substrate laminate L1 can be manufactured by the manufacturing method according to the third embodiment described later. Therefore, when manufacturing the substrate laminate L1, a first film composed of a first developable composition that does not contain a colorant can be formed on the first substrate, and then a second film composed of a second developable composition that contains a colorant can be formed on this first film. This suppresses contact between the second developable composition containing a colorant and the first substrate. Furthermore, in step Sc of the manufacturing method according to the third embodiment described later, after removing the second unexposed layer composed of the second developable composition containing a colorant, the first unexposed layer composed of the first developable composition that does not contain a colorant can be removed, thus suppressing the residue of colorant between patterns during development. For these reasons, the substrate laminate L1 can suppress the adhesion of foreign matter derived from colorants.

[0045] [Configuration of substrate stack L1] The following describes an example of the configuration of the substrate laminate L1, with reference to the drawings as appropriate. Figure 1 is a cross-sectional view showing an example of the substrate laminate L1. The substrate laminate 10 shown in Figure 1 has a first substrate 11, a second substrate 12, and a cured material layer 13 interposed between the first substrate 11 and the second substrate 12. The cured material layer 13 is patterned and has, from the first substrate 11 side, a first layer 14 composed of cured material of the first developable composition, and a second layer 15 composed of cured material of the second developable composition, in that order. The first developable composition is a developable composition that includes a polymerizable first curable compound and a first photopolymerization initiator, but does not contain a colorant. The second developable composition is a developable composition that includes a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0046] Furthermore, the substrate laminate 10 further includes an adhesive layer 16 that bonds the cured material layer 13 to the second substrate 12. In the example shown in Figure 1, the second layer 15 and the second substrate 12 are bonded together by the adhesive layer 16. The substrate laminate 10 having the adhesive layer 16 can suppress the intrusion of foreign matter into the hollow portion Z surrounded by the first substrate 11, the second substrate 12, the cured material layer 13, and the adhesive layer 16. The reason for this is presumed to be as follows.

[0047] When manufacturing the substrate laminate 10, in step Sd1 described later, the semi-cured first developable composition and the semi-cured second developable composition are further cured, and then the cured coating film (cured coating film) can be bonded to the second substrate 12 with an adhesive. The cured coating film has lower tackiness than the semi-cured coating film, and foreign matter is relatively less likely to adhere to it. Therefore, when bonding the first substrate 11 and the second substrate 12 in the substrate laminate 10, the incorporation of foreign matter into the hollow portion Z can be suppressed.

[0048] In the substrate laminate 10, the second layer 15 is composed of a cured product of a second developable composition containing a colorant. Therefore, the second layer 15 can be used, for example, as a light-shielding barrier to suppress flare and ghosting. When the second layer 15 is used as a light-shielding barrier, for example, the cured product layer 13 and the adhesive layer 16 are provided so as to surround a light-receiving element (not shown) provided on the second substrate 12.

[0049] The interface between the first layer 14 and the second layer 15 may or may not be clearly identifiable. If the interface between the first layer 14 and the second layer 15 cannot be clearly identified, an intermediate layer (not shown) containing a mixture of cured material from the first developable composition and cured material from the second developable composition may exist between the first layer 14 and the second layer 15. In that case, the cured material layer 13 is composed of the first layer 14, the intermediate layer, and the second layer 15.

[0050] In the substrate laminate 10, the hollow portion Z may be a sealed space. When the substrate laminate 10 constitutes an image sensor and the hollow portion Z is a sealed space, the cured material layer 13 and the adhesive layer 16 function as partitions to prevent moisture and dust from entering the effective pixel area. In the substrate laminate 10 shown in Figure 1, the width of the cured material layer 13 (length in the left-right direction in Figure 1) and the width of the adhesive layer 16 are approximately the same, but in the present invention, the width of the cured material layer and the width of the adhesive layer may be different.

[0051] As an indicator of the light-shielding properties of the second layer 15, the light transmittance of the second layer 15 can be used. From the viewpoint of flare suppression, when the thickness of the second layer 15 is 50 μm, the maximum transmittance of light with a wavelength of 300 to 400 nm in the second layer 15 is preferably 15% or less, more preferably 10% or less, and even more preferably 0.1% or less. Similarly, from the viewpoint of flare suppression, when the thickness of the second layer 15 is 50 μm, the optical density (OD) of the second layer 15 is preferably 0.8 or more, more preferably 1.0 or more, and even more preferably 3.0 or more. The maximum transmittance of light with a wavelength of 300 to 400 nm in the second layer 15 and the optical density of the second layer 15 can be adjusted, for example, by changing the amount of colorant in the second layer 15.

[0052] [Elements of substrate laminate L1] Next, we will explain the elements of the substrate stack L1.

[0053] (First substrate 11 and second substrate 12) Examples of the first substrate 11 and the second substrate 12 include silicon wafers, glass substrates, resin substrates (such as transparent resin substrates), ceramic substrates, and semiconductor device substrates. Examples of semiconductor device substrates include sensor substrates (more specifically, image sensor substrates). The first substrate 11 and the second substrate 12 may be of the same type or may be of different types. When either the first substrate 11 or the second substrate 12 is a transparent substrate (more specifically, a glass substrate, a transparent resin substrate, etc.), the substrate laminate L1 can be applied to a component of an optical component. In particular, a substrate laminate L1 in which one of the first substrate 11 and the second substrate 12 is a transparent substrate and the other is a semiconductor device substrate is suitable for an image sensor.

[0054] Using a glass substrate as the first substrate 11 can suppress the adhesion of foreign matter derived from colorants to the glass substrate. As a result, when the substrate laminate L1 is applied to an image sensor, the reflection of foreign matter during imaging can be suppressed.

[0055] The thicknesses of the first substrate 11 and the second substrate 12 are, for example, 50 μm or more and 2000 μm or less, respectively. If one of the first substrate 11 and the second substrate 12 is a semiconductor device substrate, the thickness of the semiconductor device substrate is, for example, 50 μm or more and 800 μm or less. The thicknesses of the first substrate 11 and the second substrate 12 may be the same or different.

[0056] (1st layer 14) The first layer 14 is composed of a cured product of the first developable composition. Details of the first developable composition that forms the first layer 14 will be described later. The thickness (height) of the first layer 14 is, for example, 0.001 μm or more and 100 μm or less. In order to further suppress the adhesion of foreign matter derived from the colorant, the thickness of the first layer 14 is preferably 0.005 μm or more, more preferably 0.01 μm or more, even more preferably 0.1 μm or more, even more preferably 1 μm or more, and particularly preferably 2 μm or more. Furthermore, in order to effectively suppress flare and ghosting by using the second layer 15 as a light-shielding barrier, the thickness of the first layer 14 is preferably 50 μm or less, more preferably 10 μm or less, even more preferably 9 μm or less, even more preferably 8 μm or less, particularly preferably 7 μm or less, and may also be 6 μm or less or 5 μm or less.

[0057] The width of the first layer 14 is, for example, 10 μm or more and 500 μm or less, preferably 10 μm or more and 200 μm or less, and more preferably 20 μm or more and 150 μm or less.

[0058] (2nd layer 15) The second layer 15 is composed of a cured product of the second developable composition. Details of the second developable composition that forms the second layer 15 will be described later. The thickness (height) of the second layer 15 is, for example, 0.01 μm or more and 100 μm or less. In order to effectively suppress flare and ghosting by using the second layer 15 as a light-shielding barrier, the thickness of the second layer 15 is preferably 0.1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, even more preferably 15 μm or more, and particularly preferably 20 μm or more. From the viewpoint of ease of patterning the second layer 15, the thickness of the second layer 15 is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less. The second developable composition that forms the second layer 15 contains a coloring agent, but when the thickness of the second layer 15 is 50 μm or less, the second layer 15 can be formed without hindering patterning.

[0059] The width of the second layer 15 is, for example, 10 μm or more and 500 μm or less, preferably 10 μm or more and 200 μm or less, and more preferably 20 μm or more and 150 μm or less.

[0060] (Adhesive layer 16) The adhesive layer 16 is composed of cured adhesive. Examples of adhesives used as materials for the adhesive layer 16 include thermosetting adhesives (more specifically, epoxy adhesives, etc.) and ultraviolet curing adhesives (more specifically, acrylic adhesives, etc.). Note that "acrylic adhesive" refers to an adhesive whose main component is (meth)acrylic acid or its derivatives (more specifically, (meth)acrylic acid esters, etc.), or polymers of (meth)acrylic acid or its derivatives.

[0061] To obtain a substrate laminate L1 with superior adhesion between substrates, an epoxy adhesive is preferred as the adhesive material for the adhesive layer 16. When using an epoxy adhesive as the adhesive material for the adhesive layer 16, in order to obtain a substrate laminate L1 with superior adhesion between substrates, an aromatic epoxy compound having two or more epoxy groups is preferred as the main component of the epoxy adhesive, a bisphenol-based diglycidyl ether (more specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, etc.) is more preferred, and bisphenol A diglycidyl ether is even more preferred.

[0062] When using an epoxy adhesive as the adhesive material for the adhesive layer 16, an imidazole-based curing agent is preferred as the curing agent for the epoxy adhesive in order to obtain a substrate laminate L1 with superior adhesion between substrates.

[0063] To obtain a substrate laminate L1 with even better adhesion between substrates, the adhesive material for the adhesive layer 16 is preferably an epoxy adhesive containing bisphenol diglycidyl ether as the main component and an imidazole curing agent as the curing agent, and more preferably an epoxy adhesive containing bisphenol A diglycidyl ether as the main component and an imidazole curing agent as the curing agent. In this case, the mass ratio of the main component to the curing agent (main component / curing agent) in the epoxy adhesive is, for example, 100 / 1 or more and 100 / 10 or less.

[0064] To obtain a substrate laminate L1 that exhibits excellent adhesion between substrates and superior reliability as evaluated by thermal shock tests, the thickness (height) of the adhesive layer 16 is preferably 0.01 μm or more and 200 μm or less, more preferably 0.1 μm or more and 150 μm or less, and even more preferably 1 μm or more and 120 μm or less. The width of the adhesive layer 16 can be appropriately changed according to the width of the second layer 15, but for example, it is 10 μm or more and 500 μm or less, preferably 10 μm or more and 20 μm or more and more preferably 20 μm or more and 150 μm or less. To obtain a substrate laminate L1 with superior reliability as evaluated by thermal shock tests, the width of the adhesive layer 16 when the width of the second layer 15 is taken as 100% is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and may be 100% or more, 110% or more, or 120% or more.

[0065] [First developing composition] Next, the first developable composition that forms the material for the first layer 14 will be described. The first developable composition is a developable composition that contains a polymerizable first curable compound and a first photopolymerization initiator, and does not contain a colorant. The first developable composition may also contain components other than the first curable compound and the first photopolymerization initiator (other components). However, in order to form a first layer 14 with excellent heat resistance and obtain a substrate laminate L1 with excellent adhesion between substrates, the total content of the first curable compound and the first photopolymerization initiator is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more and 100% by mass or less, based on the total solid content of the first developable composition.

[0066] Other components mentioned above include reactive diluents, crosslinking agents, basic compounds, sensitizers, adhesion modifiers, thermoplastic resins, fillers, antioxidants, radical inhibitors, polymer dispersants, mold release agents, flame retardants, flame retardant aids, surfactants, defoamers, emulsifiers, leveling agents, anti-repellent agents, ion trapping agents (such as antimony-bismuth), thixotropic agents, tackifiers, storage stability modifiers, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, thermal stabilizers, conductivity modifiers, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, metal deactivators, thermal conductivity modifiers, property modifiers, solvents, and the like.

[0067] The first curable compound, for example, has cationic polymerizability and / or radical polymerizability. That is, the first curable compound has one or more groups selected from the group consisting of cationic polymerizable groups and radical polymerizable groups (hereinafter sometimes referred to as "polymerizable groups"). In order to obtain a substrate laminate L1 with excellent adhesion between substrates, it is preferable that the first curable compound has a cationic polymerizable group, and more preferably that it has both a cationic polymerizable group and a radical polymerizable group.

[0068] The first curable compound preferably has multiple polymerizable groups in one molecule. When the first curable compound has multiple polymerizable groups in one molecule, a first layer 14 with a high crosslink density is obtained, and as a result, the heat resistance of the first layer 14 tends to improve. The multiple polymerizable groups may be of the same type or two or more different functional groups. Furthermore, the first developable composition may contain only one type of first curable compound or may contain multiple types of first curable compounds.

[0069] Furthermore, the first developable composition may contain both a first curable compound having a cationic polymerizable group and a first curable compound having a radical polymerizable group.

[0070] Examples of the cationic polymerizable groups mentioned above include epoxy groups, vinyl ether groups, oxetanyl groups, and alkoxysilyl groups. From the viewpoint of storage stability of the first developable composition, it is preferable that the cationic polymerizable group be one or more selected from the group consisting of glycidyl groups, alicyclic epoxy groups, and oxetanyl groups, and more preferably one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups. Among these, alicyclic epoxy groups are particularly preferred because they have excellent photocationic polymerization properties.

[0071] When the first developable composition contains a first curable compound having one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups, it is preferable that the first substrate 11 described above is a glass substrate. Since both glycidyl groups and alicyclic epoxy groups have good bonding properties to the surface of a glass substrate, when the first developable composition contains a first curable compound having one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups, and the first substrate 11 is a glass substrate, a substrate laminate L1 with superior adhesion between substrates can be obtained.

[0072] Furthermore, if the first developable composition contains a first curable compound having one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups, it is preferable to use an epoxy adhesive as the adhesive material for the adhesive layer 16 in order to obtain a substrate laminate L1 with superior adhesion between substrates.

[0073] The above-mentioned first curable compound having a cationic polymerizable group includes a polysiloxane compound having a cationic polymerizable group, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolacphenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, and 1,2-cyclopropanedicarbon Examples include bisglycidyl acid esters, triglycidyl isocyanurates, monoallyl diglycidyl isocyanurates, diallyl monoglycidyl isocyanurates, 3-ethyl-3-(phenoxymethyl)oxetane, 4,5-epoxycyclohexane-1,2-dicarboxylate di2-ethylhexyl (Shin Nippon Rika Co., Ltd. "Sensor® E-PS"), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Corporation "Celoxide® 2021P"), ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Corporation "Celoxide® 2081"), etc.

[0074] If a curable compound having one cationic polymerizable group per molecule (for example, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di2-ethylhexyl) is used as the first curable compound, the crosslinking density decreases, and as a result, the flexibility of the first layer 14 increases. Therefore, in order to obtain a substrate laminate L1 with excellent reliability as evaluated by thermal shock tests, it is preferable that the first developable composition contains a curable compound having one cationic polymerizable group per molecule as the first curable compound, and more preferably contains a curable compound having one alicyclic epoxy group per molecule.

[0075] Examples of the radical polymerizable groups mentioned above include acryloyl groups and methacryloyl groups. The first curable compound may have only one of the radical polymerizable groups, an acryloyl group or a methacryloyl group, or it may have both. Among these, the acryloyl group is particularly preferred because it exhibits excellent photoradical polymerizability.

[0076] The first curable compound having the radical polymerizable group mentioned above includes polysiloxane compounds having a radical polymerizable group, isoamyl acrylate, lauryl acrylate, octyl acrylate, decyl acrylate, isostearyl acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Examples include acrylates, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (more specifically, polypropylene glycol #700 diacrylate, etc.), 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc.

[0077] The first developable composition contains one or more compounds selected from the group consisting of compounds having alkali-soluble groups and compounds soluble in organic solvents. Examples of compounds having alkali-soluble groups include polysiloxane compounds having alkali-soluble groups, resins having phenolic hydroxyl groups (e.g., novolac resins having phenolic hydroxyl groups), resins having carboxyl groups (e.g., copolymers of (meth)acrylic acid and (meth)acrylic acid esters), and epoxy acrylate compounds having acidic groups. The compounds soluble in organic solvents are not particularly limited, but include component (A) described later. When patterning, using an alkaline developer tends to result in better patterning performance than using an organic solvent developer; therefore, it is preferable that the first developable composition contains a compound having alkali-soluble groups. The first developable composition may be both alkali-soluble and organic solvent-soluble.

[0078] In order to improve the heat resistance of the first layer 14 while maintaining excellent patternability, and to enhance adhesion between substrates and reliability in thermal shock tests, it is preferable that the first developable composition contains a polysiloxane compound having polymerizable groups and alkali-soluble groups in one molecule (hereinafter sometimes referred to as "component (A)") as the first curable compound.

[0079] Component (A) is not particularly limited as long as it is a polysiloxane compound having polymerizable groups (one or more groups selected from the group consisting of cationic polymerizable groups and radical polymerizable groups) and alkali-soluble groups in one molecule. It is preferable that component (A) has multiple polymerizable groups in one molecule. When component (A) has multiple polymerizable groups in one molecule, a first layer 14 with a high crosslink density is obtained, and as a result, the heat resistance of the first layer 14 tends to be further improved. The multiple polymerizable groups may be of the same type or two or more different functional groups. It is also preferable that component (A) has multiple alkali-soluble groups in one molecule. When component (A) has multiple alkali-soluble groups in one molecule, the removal of unexposed areas during development is improved, and thus the developability tends to be further improved. The multiple alkali-soluble groups may be of the same type or two or more different functional groups.

[0080] Component (A) may have a linear polysiloxane structure or a cyclic polysiloxane structure. To form the first layer 14 which has superior heat resistance, it is preferable that component (A) has a cyclic polysiloxane structure. Furthermore, when component (A) has a cyclic polysiloxane structure, the film-forming and developability of the first developable composition tend to be improved.

[0081] Component (A) may have a polysiloxane structure in its main chain or in its side chains. To form a first layer 14 with superior heat resistance, it is preferable that component (A) has a polysiloxane structure in its main chain. To form a first layer 14 with even superior heat resistance, it is preferable that component (A) has a cyclic polysiloxane structure in its main chain.

[0082] The cyclic polysiloxane structure may be monocyclic or polycyclic. The polycyclic structure may also be polyhedral. Among the siloxane units that make up the ring, the T unit (XSiO 3 / 2 ) or Q unit (SiO 4 / 2 The higher the content of (X3SiO), the harder and more heat-resistant the resulting first layer 14 tends to be. 1 / 2 ) or D unit (X2SiO2 / 2 The higher the content of ), the more flexible the resulting first layer 14 tends to be, and the more residual stress can be reduced.

[0083] When component (A) is a polymer having a polysiloxane structure in its main chain, the weight-average molecular weight of the polymer is preferably 10,000 to 50,000, and more preferably 20,000 to 40,000. When the weight-average molecular weight is 10,000 or more, the heat resistance of the resulting first layer 14 tends to be improved. On the other hand, when the weight-average molecular weight is 50,000 or less, the developability tends to be improved.

[0084] Examples of polymerizable groups possessed by component (A) are the same as those listed above as polymerizable groups possessed by the first curable compound (in detail, examples of cationic polymerizable groups and examples of radical polymerizable groups), and the same applies to preferred examples.

[0085] The alkali-soluble group of component (A) is preferably one or more selected from the group consisting of a monovalent organic group represented by the following chemical formula (X1) (hereinafter sometimes referred to as "X1 group"), a divalent organic group represented by the following chemical formula (X2) (hereinafter sometimes referred to as "X2 group"), a phenolic hydroxyl group, and a carboxyl group. The X1 group is a monovalent organic group derived from N-monosubstituted isocyanuric acid. The X2 group is a divalent organic group derived from N,N'-disubstituted isocyanuric acid.

[0086] [ka]

[0087] In order to form a first layer 14 with superior heat resistance, it is preferable that the alkali-soluble group of component (A) be one or more selected from the group consisting of X1 groups and X2 groups.

[0088] The method for introducing polymerizable groups into a polysiloxane compound is not particularly limited, but a method using a hydrosilylation reaction is preferred because polymerizable groups can be introduced into the polysiloxane compound via chemically stable silicon-carbon bonds (Si-C bonds). In other words, component (A) is preferably a polysiloxane compound that has been organically modified by a hydrosilylation reaction and into which polymerizable groups have been introduced via silicon-carbon bonds. It is also preferable that alkali-soluble groups are introduced into the polysiloxane compound via a hydrosilylation reaction and silicon-carbon bonds.

[0089] Component (A) can be obtained, for example, by a hydrosilylation reaction using the following compounds (α), (β), and (γ) as starting materials. • Compound (α): A polysiloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule. • Compound (β): A compound having a carbon-carbon double bond that is reactive with a SiH group and a polymerizable group in one molecule. • Compound (γ): A compound having a carbon-carbon double bond that is reactive with a SiH group and an alkali-soluble group in one molecule.

[0090] (Compound (α)) Compound (α) is a polysiloxane compound having at least two SiH groups in one molecule. For example, a compound described in International Publication No. 96 / 15194, which has at least two SiH groups in one molecule, can be used. Specific examples of compound (α) include hydrosilyl group-containing polysiloxanes having a linear structure, polysiloxanes having hydrosilyl groups at the molecular ends, and cyclic polysiloxanes having hydrosilyl groups (hereinafter sometimes simply referred to as "cyclic polysiloxanes"). Cyclic polysiloxanes may have a polycyclic structure, and the polycyclic structure may be a polyhedral structure. In order to form the first layer 14 with high heat resistance and mechanical strength, it is preferable to use a cyclic polysiloxane having at least two SiH groups in one molecule as compound (α). Compound (α) is preferably a cyclic polysiloxane having three or more SiH groups in one molecule. From the viewpoint of heat resistance and light resistance, it is preferable that the group present on the Si atom is either a hydrogen atom or a methyl group.

[0091] Examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers of diphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers of methylphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; and polysiloxanes whose ends are sealed by dimethylhydrogensilyl groups.

[0092] Polysiloxanes having hydrosilyl groups at their molecular ends include polysiloxanes whose ends are sealed by dimethylhydrogensilyl groups, and dimethylhydrogensiloxane units (H(CH3)2SiO 1 / 2 (units), and SiO2 units, SiO 3 / 2 Examples include polysiloxanes, which consist of one or more siloxane units selected from the group consisting of units and SiO units.

[0093] The cyclic polysiloxane is represented by, for example, the following general formula (I).

[0094] [Chemical Formula]

[0095] In the general formula (I), 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 or more and 10 or more, and n represents an integer of 0 or more and 10 or less. In order to easily carry out the hydrosilylation reaction, it is preferable that m is 3 or more. In order to easily carry out the hydrosilylation reaction, it is preferable that m + n is 3 or more and 12 or less. In order to more easily carry out the hydrosilylation reaction, it is preferable that n is 0.

[0096] R 1 , R 2 and R 3 are preferably organic groups composed of elements selected from the group consisting of C, H, and O. Examples of R 1 , R 2 and R 3 include an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an oxyalkyl group, an aryl group, etc. Among them, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group; a cyclic alkyl group such as a cyclohexyl group, a norbornyl group; or a phenyl group is preferable. From the viewpoint of the availability of the cyclic polysiloxane, R 1 , R 2 and R 3 are preferably a linear alkyl group having 1 to 6 carbon atoms or a phenyl group. In order to easily carry out the hydrosilylation reaction, R 1 , R 2 and R 3 are preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

[0097] Examples of cyclic polysiloxanes represented by general formula (I) 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. In particular, from the viewpoint of availability and the reactivity of the SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in general formula (I), m=4, n=0, R 1 Compounds in which the group is a methyl group are preferred.

[0098] Compound (α) can be obtained by known synthesis methods. For example, a cyclic polysiloxane represented by general formula (I) can be synthesized by the method described in International Publication No. 96 / 15194, etc. Cyclic polysiloxanes having a polyhedral skeleton can be synthesized by the method described in, for example, Japanese Patent Publication No. 2004-359933, Japanese Patent Publication No. 2004-143449, Japanese Patent Publication No. 2006-269402, etc. Alternatively, a commercially available polysiloxane compound may be used as compound (α).

[0099] In order to improve the developability of the first developable composition and form a first layer 14 with superior heat resistance, the content of structural units derived from compound (α) in component (A) is preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 45% by mass or less, based on 100% by mass of component (A).

[0100] (Compound (β)) Compound (β) is a compound having a carbon-carbon double bond that reacts with a SiH group (hydrosilyl group) and a polymerizable group in one molecule, and is a compound for introducing a polymerizable group into a polysiloxane compound. The polymerizable group in compound (β) is the same as the polymerizable group in component (A) described above, and the preferred embodiment is also the same.

[0101] Groups containing a carbon-carbon double bond that are reactive with the SiH group (hereinafter sometimes simply referred to as "alkenyl group") include, for example, vinyl group, allyl group, methallyl group, allyloxy group (-O-CH2-CH=CH2), 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2-(allyloxy)phenyl group, 3-(allyloxy)phenyl group, 4-(allyloxy)phenyl group, 2-(allyloxy)ethyl group, 2,2-bis(allyloxymethyl)butyl group, 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, vinyl ether group, etc. From the viewpoint of reactivity with the SiH group, compound (β) preferably has one or more alkenyl groups selected from the group consisting of vinyl group, allyl group, and allyloxy group, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl group and allyl group.

[0102] Specific examples of compound (β) for introducing cationic polymerizable groups include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, allyl oxetanyl ether, diallyl monoglycidyl isocyanurate, and monoallyl diglycidyl isocyanurate. From the viewpoint of reactivity in cationic polymerization, compound (β) is preferably a compound having one or more functional groups selected from the group consisting of alicyclic epoxy groups and glycidyl groups, and a compound having an alicyclic epoxy group is more preferred. To further enhance the reactivity in cationic polymerization, compound (β) is preferably one or more compounds selected from the group consisting of allyl glycidyl ether and 1-vinyl-3,4-epoxycyclohexane, and 1-vinyl-3,4-epoxycyclohexane is more preferred.

[0103] Specific examples of compound (β) for introducing radical polymerizable groups include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, 2-butenyl acrylate, and 2-butenyl methacrylate. From the viewpoint of reactivity in radical polymerization, compound (β) is preferably one or more selected from the group consisting of vinyl acrylate and allyl acrylate, with allyl acrylate being more preferred.

[0104] In order to improve the developability of the first developable composition and form a first layer 14 with superior heat resistance, the content of structural units derived from compound (β) in component (A) is preferably 20% by mass or more and 50% by mass or less, and more preferably 22% by mass or more and 45% by mass or less, based on 100% by mass of component (A).

[0105] (Compound (γ)) Compound (γ) is a compound having a carbon-carbon double bond that is reactive with a SiH group and an alkali-soluble group in one molecule, and is a compound for introducing an alkali-soluble group to a polysiloxane compound. The alkali-soluble group in compound (γ) is the same as the alkali-soluble group in component (A) mentioned above, and the preferred embodiment is also the same.

[0106] Compound (γ) has a group (alkenyl group) containing a carbon-carbon double bond that is reactive with a SiH group. Examples of the alkenyl group of compound (γ) include the same alkenyl group as exemplified for compound (β) above, and the preferred embodiments are also the same. That is, compound (γ) preferably has one or more alkenyl groups selected from the group consisting of vinyl groups, allyl groups, and allyloxy groups, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl groups and allyl groups.

[0107] Compound (γ) may have two or more alkenyl groups in one molecule. When compound (γ) contains multiple alkenyl groups in one molecule, multiple compounds (α) can be crosslinked by the hydrosilylation reaction, which tends to increase the crosslinking density of the resulting cured product and improve its heat resistance.

[0108] Specific examples of compound (γ) include diallyl isocyanurate, monoallyl isocyanurate, 2,2'-diallylbisphenol A, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, and undecylenic acid.

[0109] To obtain a first developable composition with superior developability, compound (γ) is preferably one or more selected from the group consisting of diallyl isocyanurate, monoallyl isocyanurate, and 2,2'-diallylbisphenol A, and more preferably one or more selected from the group consisting of diallyl isocyanurate and monoallyl isocyanurate. When monoallyl isocyanurate is used as compound (γ), component (A) having X1 group as an alkali-soluble group is obtained. Furthermore, when diallyl isocyanurate is used as compound (γ), component (A) having X2 group as an alkali-soluble group is obtained.

[0110] To obtain a first developable composition with superior developability, the content of structural units derived from compound (γ) in component (A) is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, based on 100% by mass of component (A).

[0111] (Other starting materials) In the hydrosilylation reaction, other starting materials may be used in addition to the above-mentioned compounds (α), (β), and (γ). For example, other starting materials may include alkenyl group-containing compounds different from those described above as compounds (β) and (γ) (hereinafter sometimes referred to as "other alkenyl group-containing compounds").

[0112] To obtain a first layer 14 with superior heat resistance, it is preferable to use a compound having two or more alkenyl groups in one molecule (hereinafter sometimes referred to as "compound (δ)") as the other alkenyl group-containing compound. When compound (δ) is used, the number of crosslinking sites increases during the hydrosilylation reaction, which tends to further improve the heat resistance of the resulting first layer 14.

[0113] Specific examples of compound (δ) 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-decadien, diallyl ether, and their oligomers.

[0114] To further improve the heat resistance of the resulting first layer 14, one or more compounds selected from the group consisting of triallyl isocyanurate and diallyl monomethyl isocyanurate are preferred as compound (δ), with diallyl monomethyl isocyanurate being more preferred.

[0115] In order to further improve the heat resistance of the resulting first layer 14 while enhancing its alkali developability, the content of structural units derived from compound (δ) in component (A) is preferably 5% by mass or more and 30% by mass or less, and more preferably 8% by mass or more and 20% by mass or less, based on 100% by mass of component (A).

[0116] (Hydrosilylation reaction) The sequence and method of the hydrosilylation reaction to obtain component (A) are not particularly limited. For example, component (A) can be obtained by a hydrosilylation reaction using the above-mentioned compound (α), compound (β), compound (γ), and other optional starting materials in accordance with the method described in International Publication No. 2009 / 075233. Component (A) obtained using the above-mentioned compound (α), compound (β), compound (γ), and other optional starting materials is, for example, a polymer having multiple polymerizable groups and multiple alkali-soluble groups in one molecule, and having a polysiloxane structure in the main chain.

[0117] The proportions of each compound in the hydrosilylation reaction are not particularly limited, but it is preferable that the total amount of alkenyl groups A and the total amount of SiH groups B of the starting material satisfy 1 ≤ B / A ≤ 30, and more preferably 1 ≤ B / A ≤ 10.

[0118] Hydrosilylation catalysts such as chloroplatinic acid, platinum-olefin complexes, and platinum-vinylsiloxane complexes may be used in the hydrosilylation reaction. A hydrosilylation catalyst and a co-catalyst may also be used in combination. The amount (substance) of hydrosilylation catalyst added is not particularly limited, but preferably 10 times the total amount of alkenyl groups contained in the starting material. -8 more than 10 times -1 More than double, more advanced 10 -6 more than 10 times -2 It is less than double.

[0119] The reaction temperature for hydrosilylation can be set appropriately, preferably between 30°C and 200°C, and more preferably between 50°C and 150°C. The oxygen concentration in the gas phase during the hydrosilylation reaction is preferably 3% by volume or less. From the viewpoint of promoting the hydrosilylation reaction, the gas phase may contain 0.1% to 3% by volume of oxygen.

[0120] A solvent may be used in the hydrosilylation reaction. The solvent can be a single solvent or a mixed solvent of two or more solvents. Suitable solvents 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, or chloroform are preferred because they are easily removed after the reaction. A gelation inhibitor may be used in the hydrosilylation reaction as needed.

[0121] To obtain a substrate laminate L1 with superior adhesion between substrates, it is preferable that the content of the first curable compound in the first developable composition is 20% by mass or more and 99% by mass or less, based on the total amount of solids in the first developable composition.

[0122] Next, the first photopolymerization initiator will be described. The first photopolymerization initiator can be appropriately selected depending on the polymerizable groups of the first curable compound. That is, if the first curable compound has cationic polymerizability, a photocationic polymerization initiator is used as the first photopolymerization initiator, and if the first curable compound has radical polymerizability, a photoradical polymerization initiator is used as the first photopolymerization initiator.

[0123] Examples of the above-mentioned photocationic polymerization initiators include photocationic polymerization initiators having one or more structures selected from the group consisting of a naphthalimide structure and an oxime sulfonate structure, carboxylic acid ester compounds, onium salt compounds, and the like. From the viewpoint of ease of patterning, a photocationic polymerization initiator having one or more structures selected from the group consisting of a naphthalimide structure and an oxime sulfonate structure is preferred, and a photocationic polymerization initiator having a naphthalimide structure is more preferred.

[0124] From the viewpoint of photosensitivity, the naphthalimide structure is preferably represented by the following general formula (II). Furthermore, from the viewpoint of photosensitivity, the photocationic polymerization initiator having a naphthalimide structure is preferably represented by the following general formula (II).

[0125] [ka]

[0126] In general formula (II), R 11 ~R 16 Each independently represents a hydrogen atom; an alkyl group having 1 to 14 carbon atoms which may be substituted with a halogen atom; a cycloalkyl group having 3 to 12 carbon atoms which may be substituted with a halogen atom; or an alkoxy group having 4 to 18 carbon atoms which may be substituted with a halogen atom or a heterocyclic group having 3 to 20 carbon atoms, R 17 This represents an alkyl group having 1 to 18 carbon atoms, which may be substituted with a halogen atom; an aryl group having 6 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms; or a cycloalkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.

[0127] In order to increase solubility in the solvent while increasing the rate of acid generation during active energy ray irradiation, R 11 ~R 16 The number of carbon atoms in the substituent represented by is preferably 1 to 14, and more preferably 3 to 8.

[0128] Specific examples of photocationic polymerization initiators having a naphthalimide structure represented by general formula (II) include, but are not limited to, ADEKA's SP-082, SP-606, SP-601, SP-613, and SP-103.

[0129] From the viewpoint of photosensitivity, the oxime sulfonate structure is preferably the structure represented by the following general formula (III). Furthermore, from the viewpoint of photosensitivity, the photocationic polymerization initiator having an oxime sulfonate structure is preferably the compound represented by the following general formula (III).

[0130] [ka]

[0131] In general formula (III), R 21 and R 22 Each independently represents a hydrogen atom; a cyano group; a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms that may be substituted with a halogen atom; an alkyl group having 1 to 14 carbon atoms that may be substituted with a halogen atom; a cycloalkyl group having 3 to 12 carbon atoms; an alkoxy group having 4 to 18 carbon atoms that may be substituted with a halogen atom or a heterocyclic group having 3 to 20 carbon atoms; or an alkylthio group having 4 to 18 carbon atoms that may be substituted with a halogen atom, a cycloalkyl group having 3 to 12 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. 21 and R 22 These may bond to each other to form a heterocycle with 2 to 8 carbon atoms, R 23This represents an alkyl group having 1 to 20 carbon atoms, which may be substituted with a halogen atom; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a halogen atom; a cycloalkyl group having 3 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms; a cycloalkenyl group having 3 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms; or an aryl group having 6 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group having 1 to 14 carbon atoms, or a halogenated alkyl group having 1 to 14 carbon atoms.

[0132] R in general formula (III) 21 and R 22 If one of the components is a substituted aryl group, the photocationic polymerization initiator having the structure represented by general formula (III) may have two substructures other than the "substituted aryl group" in general formula (III). In this case, the photocationic polymerization initiator has a structure in which the two substructures are linked by a divalent organic group containing an aromatic ring.

[0133] Specific examples of photocationic polymerization initiators having an oxime sulfonate structure represented by general formula (III) include, but are not limited to, BASF's Irgacure® PAG103, Irgacure® PAG121, Irgacure® PAG203, CGI725, and CGI1907.

[0134] Examples of the above-mentioned onium salt compounds include sulfonium salt compounds and iodonium salt compounds.

[0135] If we arrange the photocationic polymerization initiators in order from the strongest acid produced, we get SbF6. - A compound containing B(C6F5)4 as an anion. - A compound containing PF6 as an anion. - Compounds containing as anions, such as CF3SO3 - A compound containing HSO4 as an anion. - This results in a compound containing as an anion. When a photocationic polymerization initiator with a strong acid strength is used, the residual film rate tends to be high. The pKa of the acid generated from the photocationic polymerization initiator is preferably less than 3, more preferably less than 1.

[0136] Examples of cations found in sulfonium salt compounds include the cation represented by the following chemical formula (IV).

[0137] [ka]

[0138] Examples of commercially available sulfonium salt compounds (sulfonium salt photocationic polymerization initiators) include a photocationic polymerization initiator containing a fluoroalkyl fluorophosphate (anion) and a cation represented by chemical formula (IV) (SunApro's "CPI-210S").

[0139] Specific examples of the above-mentioned photoradical polymerization initiators include acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, α-diketone compounds, biimidazole compounds, polynuclear quinone compounds, triazine compounds, oxime ester compounds, titanocene compounds, xanthone compounds, thioxanthone compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, and fluoroamine compounds. To suppress film thinning during development, it is preferable that the photoradical polymerization initiator be one or more selected from the group consisting of acetophenone compounds, benzophenone compounds, and oxime ester compounds, with oxime ester compounds being more preferable.

[0140] Examples of oxime ester compounds include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)] and ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0141] There are no particular restrictions on the content of the first photopolymerization initiator in the first developable composition. From the viewpoint of the curing speed and the balance of physical properties of the cured product, the content of the first photopolymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the first curable compound.

[0142] Next, other components that the first developable composition may contain (components other than the first curable compound and the first photopolymerization initiator) will be described.

[0143] (solvent) The first developable composition may contain a solvent. For example, the first developable composition can be obtained by dissolving or dispersing the above-mentioned first curable compound and first photopolymerization initiator, as well as other components described later and used as needed, in a solvent.

[0144] Specific examples of solvents include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; 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; ester solvents such as isobutyl isobutyrate; and halogen solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. From the viewpoint of the coatability (film-forming stability) of the first developable composition, glycol solvents are preferred as solvents, and propylene glycol 1-monomethyl ether 2-acetate is more preferred.

[0145] From the viewpoint of the coatability (film-forming stability) of the first developable composition, the amount of solvent is preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 20 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the first curable compound.

[0146] (Sensitizer) The first developable composition may contain a sensitizer. The use of a sensitizer improves patternability. Anthracene compounds are preferred as sensitizers. Specific examples of anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 2,6-di-t-butylanthracene, and 9,10-diphenyl-2,6-di-t-butylanthracene. Among these, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene are preferred from the viewpoint of compatibility with the first developable composition.

[0147] The content of the sensitizer in the first developable composition is not particularly limited, but from the viewpoint of balance between curability and the physical properties of the cured product, it is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the first curable compound.

[0148] [Second developing composition] Next, the second developable composition, which is the material for the second layer 15, will be described. The second developable composition is a developable composition comprising a polymerizable second curable compound, a second photopolymerization initiator, and a colorant. As the second curable compound, the curable compounds listed above as examples of the first curable compound can be used. As the second photopolymerization initiator, the photopolymerization initiators listed above as examples of the first photopolymerization initiator can be used. The second curable compound and the second photopolymerization initiator of the second developable composition may be the same as the first curable compound and the first photopolymerization initiator of the first developable composition, respectively, or they may be of different types. Furthermore, the content of the second curable compound and the content of the second photopolymerization initiator in the second developable composition may be the same as the content of the first curable compound and the content of the first photopolymerization initiator in the first developable composition, respectively, or they may be different from each other.

[0149] (Coloring agent) The second developable composition contains a coloring agent. The inclusion of a coloring agent in the second developable composition results in a colored second layer 15. Examples of coloring agents include organic pigments, inorganic pigments, and dyes. From the viewpoint of heat resistance and colorability, pigments are preferred as coloring agents. When forming a black colored pattern such as a light-shielding black partition (black rib material), it is preferable to use a black pigment as the coloring agent, but the method is not limited to this. In addition, colored patterns other than black, such as red patterns, yellow patterns, and blue patterns, can be used depending on the application.

[0150] Examples of black organic pigments that broadly absorb wavelengths in the visible light region include anthraquinone-based black pigments, perylene-based black pigments (perylene black), azo-based black pigments, and lactam-based black pigments (lactam black). Mixed organic pigments may also be used, which are prepared by blending two or more chromatic pigments such that the resulting mixture is black, i.e., absorbs light of wavelengths in the visible light region. To efficiently reduce light transmittance, it is preferable that the mixed organic pigment contains one or more pigments selected from the group consisting of blue pigments and purple pigments.

[0151] Examples of inorganic pigments include composite metal oxide pigments, carbon black, black lower oxynitride titanium, titanium oxide (more specifically, titanium black, etc.), barium sulfate, lead sulfate, yellow lead, red iron oxide, ultramarine, Prussian blue, chromium oxide, antimony white, zinc sulfide, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate, etc. Examples of dyes include azo compounds, anthraquinone compounds, perylene compounds, perinone compounds, phthalocyanine compounds, carbonium compounds, indigoid compounds, etc.

[0152] Pigments other than black can be used to obtain colored patterns, including chromatic pigments such as red, orange, yellow, green, blue, purple, cyanine, and magenta.

[0153] To further enhance the heat resistance of the second layer 15, it is preferable to use an inorganic pigment as a coloring agent, and more preferably to use carbon black. Inorganic pigments have excellent heat resistance and are less prone to decomposition by heating. To obtain a second layer 15 with even better heat resistance, it is preferable that the proportion of inorganic pigment in the coloring agent be 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more.

[0154] In order to obtain a second developable composition that can form a second layer 15 that is superior in light shielding and heat resistance while also having excellent developability, it is preferable that the amount of colorant is 0.005% by mass or more and 80% by mass or less, more preferably 0.01% by mass or more and 80% by mass or less, even more preferably 0.1% by mass or more and 50% by mass or less, and even more preferably 0.1% by mass or more and 10% by mass or less, based on the total solid content of the second developable composition. Furthermore, if the amount of colorant is 0.1% by mass or more and 10% by mass or less, based on the total solid content of the second developable composition, it is possible to further suppress the adhesion of foreign matter derived from the colorant while improving light shielding and adhesive strength between substrates.

[0155] Other aspects of the second developer composition (other than those described above) are the same as those described in the section on the [first developer composition] above.

[0156] [Other configuration examples of substrate stack L1] Next, other configuration examples of the substrate laminate L1 will be described with reference to Figures 2 to 6. Figures 2 to 6 are all cross-sectional views showing other configuration examples of the substrate laminate L1.

[0157] In the substrate laminate 20 shown in Figure 2, the second layer 15 is directly bonded to the second substrate 12. In other words, the substrate laminate 20 does not have the adhesive layer 16 (see Figure 1) described above. Other aspects of the substrate laminate 20 are the same as those of the substrate laminate 10 described above. Since the substrate laminate 20 does not require the step of providing the adhesive layer 16, the manufacturing process can be simplified.

[0158] In the substrate laminate 30 shown in Figure 3, the second substrate 12 has a semiconductor element substrate 31 and a frame material 32. The frame material 32 and the first substrate 11 are bonded via a cured material layer 13 and an adhesive layer 16. In other words, in the substrate laminate 30, the first substrate 11, cured material layer 13, adhesive layer 16, frame material 32, and semiconductor element substrate 31 are laminated in this order. The frame material 32 can be made of epoxy resin, ceramic, or the like. The thickness (height) of the frame material 32 is, for example, 30 μm or more and 30,000 μm or less. Using the frame material 32 widens the hollow portion Z, so that, for example, an interposer (not shown) can be easily placed in the hollow portion Z. The frame material 32 may be pre-bonded to the semiconductor element substrate 31 with an adhesive, or it may be molded on the semiconductor element substrate 31 by molding or the like. Other aspects of the substrate laminate 30 are the same as those of the substrate laminate 10 described above.

[0159] In the substrate stack 40 shown in Figure 4, the frame material 32 is a concave structure. The semiconductor element substrate 31 is in contact with the concave part of the frame material 32, and the semiconductor element substrate 31 and the frame material 32 are integrated together. Other aspects of the substrate stack 40 are the same as those of the substrate stack 30 described above.

[0160] In the substrate laminate 50 shown in Figure 5, a portion of the adhesive layer 16 is positioned between the first substrate 11 and the frame material 32. Other aspects of the substrate laminate 50 are the same as those of the substrate laminate 30 described above.

[0161] In the substrate laminate 60 shown in Figure 6, the cured layer 13 has, from the first substrate 11 side, a first layer 14, a second layer 15, and a third layer 61 composed of a cured product of the third developable composition, in this order. In the substrate laminate 60, the third layer 61 and the second substrate 12 are bonded together via an adhesive layer 16. The thickness (height) of the third layer 61 is, for example, 0.01 μm or more and 100 μm or less. The third developable composition is a developable composition that contains a polymerizable third curable compound and a third photopolymerization initiator, but does not contain a colorant. Furthermore, "the third developable composition does not contain a colorant" means that the amount of colorant in the third layer 61, which is made up of the cured product of the third developable composition, is less than 0.1 parts by mass (preferably less than 0.01 parts by mass, more preferably less than 0.001 parts by mass, and even more preferably less than 0.0001 parts by mass) per 100 parts by mass of colorant in the second layer 15, which is made up of the cured product of the second developable composition.

[0162] As the third curable compound, any of the curable compounds listed above as examples of the first curable compound can be used. Furthermore, as the third photopolymerization initiator, any of the photopolymerization initiators listed above as examples of the first photopolymerization initiator can be used. The third curable compound and the third photopolymerization initiator in the third developable composition may be the same as, or different from, the first curable compound and the first photopolymerization initiator in the first developable composition. Also, the content of the third curable compound and the third photopolymerization initiator in the third developable composition may be the same as, or different from, the content of the first curable compound and the first photopolymerization initiator in the first developable composition. Other aspects of the third developable composition (other than those described above) are the same as those described in the section on [First Developable Composition] above.

[0163] Since the third developable composition, which is a component of the third layer 61, does not contain a colorant, the patternability when forming the third layer 61 is better than that when forming the second layer 15. Therefore, the thickness of the third layer 61 can be increased relatively easily. Thus, in the substrate laminate 60, since the cured material layer 13 has the third layer 61, the thickness of the cured material layer 13 can be increased relatively easily. When the thickness of the cured material layer 13 is large, for example, a sealing resin layer (not shown) can be easily formed around the cured material layer 13.

[0164] Other aspects of the substrate laminate 60 are the same as those of the substrate laminate 10 described above.

[0165] <Second Embodiment: Substrate Laminate> Next, a substrate laminate according to a second embodiment of the present invention will be described. The substrate laminate according to the second embodiment of the present invention (hereinafter sometimes referred to as "substrate laminate L2") has a first substrate, a second substrate, an adhesive layer for bonding the first substrate and the second substrate, and a cured material layer disposed on the side of the first substrate opposite to the second substrate side. The cured material layer is patterned and has, in order from the first substrate side, a first layer composed of a cured material of a first developable composition and a second layer composed of a cured material of a second developable composition. The first developable composition is a developable composition that includes a polymerizable first curable compound and a first photopolymerization initiator, but does not contain a colorant. The second developable composition is a developable composition that includes a polymerizable second curable compound, a second photopolymerization initiator, and a colorant. The details of the first developable composition and the second developable composition in the second embodiment are the same as the details of the first developable composition and the second developable composition in the first embodiment described above, so their description will be omitted. Furthermore, the details of the first substrate, second substrate, adhesive layer, cured material layer, first layer, and second layer of the substrate laminate L2 are the same as those of the first substrate, second substrate, adhesive layer, cured material layer, first layer, and second layer of the substrate laminate L1 described above, so their explanations are omitted.

[0166] The substrate laminate L2 can be manufactured by the manufacturing method according to the fourth embodiment described later. Therefore, when manufacturing the substrate laminate L2, a first film composed of a first developable composition that does not contain a colorant can be formed on the first substrate, and then a second film composed of a second developable composition that contains a colorant can be formed on this first film. This suppresses contact between the second developable composition containing a colorant and the first substrate. Furthermore, in step Sc of the manufacturing method according to the fourth embodiment described later, after removing the second unexposed layer composed of the second developable composition containing a colorant, the first unexposed layer composed of the first developable composition that does not contain a colorant can be removed, thus suppressing the residue of colorant between patterns during development. For these reasons, the substrate laminate L2 can suppress the adhesion of foreign matter derived from colorants.

[0167] [Configuration of substrate laminate L2] The following describes an example of the configuration of the substrate laminate L2, with reference to the drawings as appropriate. Figure 7 is a cross-sectional view showing an example of the substrate laminate L2. The substrate laminate 70 shown in Figure 7 has a first substrate 11, a second substrate 12, an adhesive layer 16 that bonds the first substrate 11 and the second substrate 12, and a cured material layer 13 located on the side of the first substrate 11 opposite to the second substrate 12. The cured material layer 13 is patterned and has a first layer 14 and a second layer 15 in that order from the first substrate 11 side. When the substrate laminate 70 is applied to an image sensor, the adhesive layer 16 is provided so as to surround a light-receiving element (not shown) provided on the second substrate 12.

[0168] In the substrate laminate 70, the second layer 15 is composed of a cured product of a second developable composition containing a coloring agent. Therefore, the second layer 15 can be used, for example, as a light-shielding film to suppress flare and ghosting. When the substrate laminate 70 is applied to an image sensor, for example, when the substrate laminate 70 is viewed from the first substrate 11 (e.g., a glass substrate) side, the cured product layer 13 is provided so as to surround a light-receiving element (not shown) provided on the second substrate 12.

[0169] [Other configuration examples of substrate stack L2] Next, other configuration examples of the substrate laminate L2 will be described with reference to Figure 8. In the substrate laminate 80 shown in Figure 8, the cured layer 13 has, from the first substrate 11 side, a first layer 14, a second layer 15, and a third layer 61 composed of the cured product of the third developable composition, in this order. The thickness (height) of the third layer 61 is, for example, 0.01 μm or more and 100 μm or less. The third developable composition is a developable composition that contains a polymerizable third curable compound and a third photopolymerization initiator, but does not contain a colorant. Note that "the third developable composition does not contain a colorant" means that the amount of colorant in the third layer 61 composed of the cured product of the third developable composition is less than 0.1 parts by mass (preferably less than 0.01 parts by mass, more preferably less than 0.001 parts by mass, and even more preferably less than 0.0001 parts by mass) per 100 parts by mass of colorant in the second layer 15 composed of the cured product of the second developable composition.

[0170] As the third curable compound, the curable compound listed as an example of the first curable compound in the first embodiment described above can be used. Furthermore, as the third photopolymerization initiator, the photopolymerization initiator listed as an example of the first photopolymerization initiator in the first embodiment described above can be used. The third curable compound and the third photopolymerization initiator of the third developable composition may be of the same type as the first curable compound and the first photopolymerization initiator of the first developable composition, which are constituent materials of the first layer 14, or they may be of different types. Also, the content of the third curable compound and the content of the third photopolymerization initiator in the third developable composition may be the same as the content of the first curable compound and the first photopolymerization initiator in the first developable composition, which are constituent materials of the first layer 14, or they may be different. Other aspects of the third developable composition (points other than those described above) are the same as those described in the [First Developable Composition] section of the first embodiment described above.

[0171] Since the third developable composition, which is a component of the third layer 61, does not contain a colorant, the patternability when forming the third layer 61 is better than that when forming the second layer 15. Therefore, the thickness of the third layer 61 can be increased relatively easily. Thus, in the substrate laminate 80, since the cured material layer 13 has the third layer 61, the thickness of the cured material layer 13 can be increased relatively easily. When the thickness of the cured material layer 13 is large, for example, a sealing resin layer (not shown) can be easily formed around the cured material layer 13. Other aspects of the substrate laminate 80 are the same as those of the substrate laminate 70 described above.

[0172] Other aspects of the substrate laminate L2 (points other than those described above) are the same as those described in the section <First Embodiment: Substrate Laminate> above.

[0173] <Applications of substrate laminate L1 and substrate laminate L2> The substrate stack L1 and substrate stack L2 are used, for example, as components constituting a MEMS (Micro Electro Mechanical Systems). Preferably, the substrate stack L1 and substrate stack L2 are used as components constituting sensors such as image sensors, acceleration sensors, and pressure sensors.

[0174] When substrate stack L1 or substrate stack L2 is applied to an image sensor, the image sensor having substrate stack L1 or substrate stack L2 can suppress the adhesion of foreign matter derived from colorants, thereby suppressing the occurrence of imaging errors such as reflections during imaging. In an image sensor having substrate stack L1 or substrate stack L2, for example, one of the first substrate 11 and the second substrate 12 is a transparent substrate, and the other is a semiconductor element substrate (image sensor substrate).

[0175] <Third Embodiment: Method for Manufacturing a Substrate Laminate> Next, a method for manufacturing a substrate laminate according to the third embodiment of the present invention (hereinafter sometimes referred to as "manufacturing method M1") will be described with reference to the drawings as appropriate. Manufacturing method M1 is a preferred method for manufacturing the substrate laminate (substrate laminate L1) according to the first embodiment described above. In the following description, explanations of content that overlaps with the first embodiment may be omitted.

[0176] Manufacturing method M1 comprises steps Sa, Sb, Sc, and Sd1. In step Sa, a coating film is formed on a first substrate. In step Sb, exposed areas and unexposed areas are formed on the first substrate by irradiating the coating film with active energy rays through a photomask. In step Sc, a patterned coating film (hereinafter sometimes referred to as "patterned film") is formed on the first substrate by removing the unexposed areas from the first substrate with a developer. In step Sd1, the first substrate and the second substrate are bonded together via the patterned film. The patterned film in step Sd1 includes two types of films: a patterned coating film in a semi-cured state and a film obtained after further curing of the patterned coating film in a semi-cured state (a cured layer composed of cured material of the patterned coating film).

[0177] The semi-cured exposed area formed in step Sb has, from the first substrate side, a first semi-cured layer composed of a semi-cured first developable composition, and a second semi-cured layer composed of a semi-cured second developable composition, in that order. The first developable composition is a developable composition that contains a polymerizable first curable compound and a first photopolymerization initiator, but does not contain a colorant. The second developable composition is a developable composition that contains a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0178] In manufacturing method M1, a first film composed of a first developable composition that does not contain a colorant can be formed on a first substrate, and then a second film composed of a second developable composition that contains a colorant can be formed on this first film. This suppresses contact between the second developable composition containing the colorant and the first substrate. Furthermore, in step Sc, after removing the second unexposed layer composed of the second developable composition containing the colorant, the first unexposed layer composed of the first developable composition that does not contain a colorant can be removed, thus suppressing the residue of colorant between patterns during development. For these reasons, manufacturing method M1 can suppress the adhesion of foreign matter derived from colorants.

[0179] The following describes each step of an example of manufacturing method M1, with reference to the drawings as appropriate. Figure 9 is a plan view showing an example of the first substrate after the cured layer has been formed when manufacturing a substrate laminate by manufacturing method M1. Figure 10 is a plan view showing an example of the first substrate after the cured layer has been formed and after it has been separated into individual pieces when manufacturing a substrate laminate by manufacturing method M1. Figures 11A-C, 12A-C, and 13A-C are cross-sectional views showing each step of an example of manufacturing method M1.

[0180] In one example of manufacturing method M1, a cured material layer 13 is first formed on a large first substrate 11 in a patterned manner of a rectangular tube (Figure 9). The pattern of the cured material layer 13 is not limited to the pattern shown in Figure 9, and can be designed to suit the desired shape, for example, a grid pattern. The number of patterns in the cured material layer 13 is not particularly limited, and it is sufficient that at least one pattern is formed. The patterned cured material layer 13 shown in Figure 9 can be formed by the process described in detail below.

[0181] [Process Sa] The first method of step Sa is described below. In the first method, a first developable composition is applied to one side of a large first substrate 11 to form a first film 201 made of the first developable composition on one side of the first substrate 11 (Figure 11A). The application method is not particularly limited, and general application methods such as spin coating, slit coating, roll coating, printing, and bar coating can be used. In the first method, the first film 201 may be heated to remove at least a portion of the solvent in the first film 201. The heating temperature of the first film 201 can be set as appropriate, but is preferably 60°C to 200°C, and more preferably 80°C to 150°C.

[0182] The thickness of the first film 201 (or the thickness of the first film 201 after heating, if a heating step is provided) is, for example, 0.001 μm or more and 100 μm or less. In order to further suppress the adhesion of foreign matter derived from the coloring agent, the thickness of the first film 201 is preferably 0.005 μm or more, more preferably 0.01 μm or more, even more preferably 0.1 μm or more, even more preferably 1 μm or more, and particularly preferably 2 μm or more. Furthermore, in order to effectively suppress flare and ghosting by using the above-mentioned second layer 15 as a light-shielding barrier, the thickness of the first film 201 is preferably 50 μm or less, more preferably 10 μm or less, even more preferably 9 μm or less, even more preferably 8 μm or less, particularly preferably 7 μm or less, and may also be 6 μm or less or 5 μm or less.

[0183] Next, the second developable composition is applied onto the first film 201 to form a second film 202 made of the second developable composition on the first film 201 (Figure 11B). This forms a coating film 200 including the first film 201 and the second film 202, as shown in Figure 11B. The application method for the second developable composition is not particularly limited, and general application methods such as spin coating, slit coating, roll coating, printing, and bar coating can be used. In the first method, the second film 202 may be heated to remove at least a portion of the solvent in the second film 202. The heating temperature of the second film 202 can be set as appropriate, but is preferably 60°C to 200°C, and more preferably 80°C to 150°C.

[0184] The thickness of the second film 202 (or the thickness of the second film 202 after heating, if a heating step is provided) is, for example, 0.01 μm or more and 100 μm or less. In order to effectively suppress flare and ghosting by using the above-described second layer 15 as a light-shielding barrier, the thickness of the second film 202 is preferably 0.1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, even more preferably 15 μm or more, and particularly preferably 20 μm or more. From the viewpoint of ease of patterning the second film 202, the thickness of the second film 202 is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0185] In order to further suppress the adhesion of foreign matter to the first substrate 11, it is preferable that almost the entire area on the first substrate 11 where the second film 202 is formed is covered with the first film 201, and it is more preferable that the entire area on the first substrate 11 where the second film 202 is formed is covered with the first film 201. "Almost the entire area is covered with the first film 201" means that 90% or more (preferably 95% or more, more preferably 98% or more) of the area on the first substrate 11 where the second film 202 is formed is covered with the first film 201.

[0186] The method for forming the coating film 200 in step Sa is not limited to the first method described above. For example, the second method shown below may be adopted in step Sa. In the second method, first, in step Sa, a first developable composition is applied to the first substrate 11, and the first film 201 made of this first developable composition is irradiated with active energy rays E (see Figure 11C) either through a photomask 300 (see Figure 11C) or without passing through the photomask 300. When irradiating with active energy rays E through the photomask 300, the preferred range of irradiation conditions for the active energy rays E is, for example, the same range as in step Sb described later. When irradiating with active energy rays E without passing through the photomask 300, it is preferable to irradiate with active energy rays E under irradiation conditions that allow the unexposed areas 306 (see Figure 11C) to be removed with the developer in step Sc described later. In the second method, a coating film 200 is formed by applying a second developable composition onto the first film 201 after irradiation with active energy rays E, thereby comprising the first film 201 after irradiation with active energy rays E and a second film 202 composed of the second developable composition. Other aspects of the second method (other than those described above) are the same as those of the first method described above.

[0187] [Process Sb] In step Sb, the coating film 200 is irradiated with active energy rays E through a photomask 300, thereby forming an exposed area 303 and an unexposed area 306 in the coating film 200, both composed of a semi-cured developable composition (Figure 11C). A light-transmitting region 300a is formed in the photomask 300 at the position corresponding to the exposed area 303. As a result, only the coating film 200 (exposed area 303) located below the light-transmitting region 300a is exposed, and the photocuring reaction proceeds. The semi-cured exposed area 303 has, from the first substrate 11 side, a first semi-cured layer 301 composed of a semi-cured first developable composition, and a second semi-cured layer 302 composed of a semi-cured second developable composition, in that order. The unexposed area 306 has, from the first substrate 11 side, a first unexposed layer 304 composed of a first developable composition, and a second unexposed layer 305 composed of a second developable composition, in that order. The cumulative exposure dose during exposure is not particularly limited, but is preferably 1 mJ / cm². 2 More than 50000mJ / cm 2 The following is more preferable: 1 mJ / cm² 2 More than 20000mJ / cm 2 The following applies: The wavelength of the active energy ray E irradiated in step Sb is, for example, in the range of 200 nm to 450 nm. Examples of light sources for the active energy ray E include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, xenon lamps, carbon arc lamps, and light-emitting diodes. The irradiation time for the active energy ray E is preferably 1 second to 3000 seconds, and more preferably 1 second to 1000 seconds.

[0188] After step Sb and before step Sc, the coating film 200 irradiated with active energy rays E may be heated. The heating temperature can be set as appropriate, but is preferably 60°C to 200°C, and more preferably 80°C to 150°C.

[0189] [Process Sc] In step Sc, the unexposed areas 306 are removed (developed) from the first substrate 11 with a developer, thereby forming a semi-cured patterned coating film (pattern film 310) on the first substrate 11 (Figure 12A). One or more types of developing solutions can be selected from the group consisting of alkaline developing solutions and organic solvent developing solutions as the developing solution used in step Sc. The developing solution used to remove the first unexposed layer 304 and the developing solution used to remove the second unexposed layer 305 may be the same type of developer or different types of developers. From the viewpoint of productivity, it is preferable that the developing solution used to remove the first unexposed layer 304 and the developing solution used to remove the second unexposed layer 305 are the same type of developer.

[0190] The alkaline developing solution is, for example, an aqueous solution containing an alkaline component. Examples of alkaline components include alkaline organic components and alkaline inorganic components. Examples of alkaline organic components include tetramethylammonium hydroxide (TMAH) and choline. Examples of alkaline inorganic components include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate. In order to enhance the contrast between the exposed area 303 and the unexposed area 306, the concentration of the alkaline component in the alkaline developing solution is preferably 25% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. The method for removing the unexposed area 306 from the first substrate 11 with an alkaline developer is not particularly limited, and examples include a method in which the alkaline developer is brought into contact with the coating film 200 by immersion, spraying, or paddle, thereby dissolving and removing the unexposed area 306.

[0191] Any organic solvent developer can be used as long as it can remove the unexposed areas 306 from the first substrate 11 and leave the patterned exposed areas 303 (pattern film 310) on the first substrate 11. Examples of organic solvent developers include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1,1,1-trichloroethane, N-methyl-2-pyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, triethylene glycol dimethyl ether, and propylene glycol 1-monomethyl ether 2-acetate. Small amounts of surfactants, defoamers, etc., may be added to the organic solvent developer, and water may be added in a range of 1% to 30% by volume for the purpose of preventing ignition. The method for removing the unexposed areas 306 from the first substrate 11 with an organic solvent developer is not particularly limited, and examples include a method in which the organic solvent developer is brought into contact with the coating film 200 by immersion, spraying, or paddle, thereby dissolving and removing the unexposed areas 306.

[0192] In step Sc, the coating film 200 may be washed with water after the reaction liquid has been brought into contact with it. When washing the coating film 200 with water, it is preferable to remove the moisture from the surface of the coating film 200 with compressed air after washing.

[0193] [Process Sd1] In step Sd1, the pattern film 310 formed in step Sc is first heated to further cure the semi-cured first developable composition and the semi-cured second developable composition, thereby obtaining a cured layer 13 (cured coating film 200) composed of cured material of the patterned coating film 200 (Figure 12B). The cured layer 13 has, from the first substrate 11 side, a first layer 14 composed of cured material of the first developable composition, and a second layer 15 composed of cured material of the second developable composition, in that order. In this way, a large number of patterned cured layers 13 are formed on the large first substrate 11 as shown in Figure 9. The temperature for heating the pattern film 310 in step Sd1 is preferably 80°C to 350°C, and more preferably 150°C to 250°C.

[0194] In step Sd1, if a method is adopted in which the semi-cured first developable composition and the semi-cured second developable composition are further cured before bonding the first substrate 11 and the second substrate 12 (hereinafter sometimes referred to as the "pre-bonding curing method"), the inclusion of foreign matter can be suppressed as described above. Therefore, with the substrate laminate L1 obtained by the pre-bonding curing method, the occurrence of cracks caused by foreign matter can be suppressed in thermal shock tests.

[0195] Furthermore, if the semi-cured first developable composition and the semi-cured second developable composition are further cured in step Sd1, the amount of outgassing released into the hollow portion Z when the first substrate 11 and the second substrate 12 are bonded can be reduced. However, if the substrate laminate L1 constitutes an image sensor, an excessive increase in the amount of outgassing released into the hollow portion Z may impair the function of the image sensor.

[0196] After obtaining a cured material layer 13 composed of patterned cured material by the above pre-adhesion curing method, the laminate of the large first substrate 11 and the cured material layer 13 is diced along the dividing line 100 in Figures 9 and 12C to obtain the individual laminates shown in Figure 10 (hereinafter sometimes referred to as "first laminate"). Next, the second layer 15 of the first laminate and the second substrate 12 are bonded together with an adhesive. Specifically, first, as shown in Figure 13A, an adhesive layer 16 is formed by applying the adhesive onto the second layer 15 with a syringe or the like. In Figure 13A, an example is shown in which the adhesive is applied to the side (end face) of the second layer 15 opposite to the first substrate 11 side, but the present invention is not limited to this, and the adhesive may be applied to the second substrate 12, or to both the second layer 15 and the second substrate 12. Furthermore, the method of applying the adhesive is not limited to applying it with a syringe, but may also be applied by, for example, a screen printing method or a stamping method.

[0197] Next, the second layer 15 and the second substrate 12 are bonded together via the adhesive layer 16 (Figure 13B). Then, the adhesive layer 16 is cured to bond the second layer 15 and the second substrate 12, thereby obtaining the substrate laminate 10 shown in Figure 13C. The method for curing the adhesive layer 16 can be appropriately selected depending on the type of adhesive that makes up the adhesive layer 16. Specific examples of methods for curing the adhesive layer 16 include curing by heating and curing by ultraviolet irradiation.

[0198] In the method described above, the first laminate and the second substrate 12 were bonded together with an adhesive, but the present invention is not limited to the above method. For example, in the process shown in Figure 12C, the laminate of the large first substrate 11 and the cured material layer 13 and the large second substrate 12 may be bonded together via an adhesive layer 16 without dicing. In this case, after bonding via the adhesive layer 16, dicing is performed to obtain a substrate laminate L1 in individual pieces.

[0199] [Other examples of manufacturing method M1] Next, as another example of manufacturing method M1, we will describe the manufacturing method for the substrate laminate 20. The manufacturing method for the substrate laminate 20 is the same as the manufacturing method described above (manufacturing method for the substrate laminate 10) up to the step shown in Figure 12A. Therefore, in the following, we will only describe the step after Figure 12A (step Sd1).

[0200] In process Sd1 of manufacturing the substrate laminate 20, first, the laminate of a large first substrate 11 and a pattern film 310, as shown in Figure 12A, is diced to obtain the individualized laminate shown in Figure 14A (hereinafter sometimes referred to as the "second laminate"). Next, the second substrate 12 is bonded to the second semi-cured layer 302 of the second laminate. This results in a laminate in which the first substrate 11 and the second substrate 12 are laminated via the pattern film 310, as shown in Figure 14B (hereinafter sometimes referred to as the "third laminate"). Next, the third laminate is heated to further cure the semi-cured pattern film 310, thereby bonding the first substrate 11 and the second substrate 12 via a cured layer 13 (patterned cured layer 13) composed of the cured pattern film 310 (Figure 14C). In the process of heating the third laminate, the third laminate may be heated while applying a load in the range of, for example, 0.05 MPa to 100 MPa. The temperature at which the third layer is heated is, for example, between 60°C and 300°C. After the above steps, the substrate laminate 20 shown in Figure 14C is obtained.

[0201] Although specific examples of manufacturing method M1 have been described above, the method for manufacturing a substrate laminate according to the present invention is not limited to the above examples. For example, in the method for manufacturing a substrate laminate according to the present invention, a second substrate having a semiconductor element substrate and a frame material may be used. In this case, in step Sd1, the first substrate and the frame material are bonded together via a pattern film to produce, for example, the substrate laminate 30 (see Figure 3), substrate laminate 40 (see Figure 4), or substrate laminate 50 (see Figure 5) described above. Furthermore, in the method for manufacturing a substrate laminate according to the present invention, a third film may be formed in step Sa by applying a third developable composition to the side of the second film opposite to the first film side. In this case, the coating film irradiated with active energy rays in step Sb has the first film, the second film, and the third film in this order from the first substrate side. The thickness of the third film is, for example, 0.01 μm or more and 100 μm or less. After forming a coating film having the first, second, and third films, the substrate laminate 60 (see Figure 6) described above can be manufactured, for example, by carrying out steps Sb, Sc, and Sd1.

[0202] <Fourth Embodiment: Method for Manufacturing a Substrate Laminate> Next, a method for manufacturing a substrate laminate according to the fourth embodiment of the present invention (hereinafter sometimes referred to as "manufacturing method M2") will be described with reference to the drawings as appropriate. Manufacturing method M2 is a preferred method for manufacturing the substrate laminate (substrate laminate L2) according to the second embodiment described above. In the following description, explanations of content that overlaps with the first, second, and third embodiments may be omitted.

[0203] Manufacturing method M2 comprises steps Sa, Sb, Sc, and Sd2. In step Sa, a coating film is formed on a first substrate. In step Sb, exposed areas and unexposed areas are formed on the first substrate by irradiating the coating film with active energy rays through a photomask. In step Sc, a patterned coating film (hereinafter sometimes referred to as "patterned film") is formed on the first substrate by removing the unexposed areas from the first substrate with a developer. In step Sd2, the side of the first substrate opposite to the side on which the patterned film is formed is bonded to the second substrate with an adhesive. The patterned film in step Sd2 includes two types of films: a patterned coating film in a semi-cured state and a film obtained after further curing of the patterned coating film in a semi-cured state (a cured layer composed of cured material of the patterned coating film).

[0204] The semi-cured exposed area formed in step Sb has, from the first substrate side, a first semi-cured layer composed of a semi-cured first developable composition, and a second semi-cured layer composed of a semi-cured second developable composition, in that order. The first developable composition is a developable composition that contains a polymerizable first curable compound and a first photopolymerization initiator, but does not contain a colorant. The second developable composition is a developable composition that contains a polymerizable second curable compound, a second photopolymerization initiator, and a colorant.

[0205] In manufacturing method M2, a first film composed of a first developable composition that does not contain a colorant can be formed on a first substrate, and then a second film composed of a second developable composition that contains a colorant can be formed on this first film. This suppresses contact between the second developable composition containing the colorant and the first substrate. Furthermore, in step Sc, after removing the second unexposed layer composed of the second developable composition containing the colorant, the first unexposed layer composed of the first developable composition that does not contain a colorant can be removed, thus suppressing the residue of colorant between patterns during development. For these reasons, manufacturing method M2 can suppress the adhesion of foreign matter derived from colorants.

[0206] The following describes each step of an example of manufacturing method M2, referring to the drawings as appropriate. Figures 15A to 15C are cross-sectional views of each step in an example of manufacturing method M2. The example of manufacturing method M2 described below is the same as the above-mentioned manufacturing method (method for manufacturing the substrate laminate 10) up to the step shown in Figure 12C. Therefore, only the steps after Figure 12C (step Sd2) will be described below.

[0207] In one example of manufacturing method M2, as shown in Figure 15A, an adhesive layer 16 is formed by applying adhesive to the second substrate 12 using a syringe or the like. Although Figure 15A shows an example of applying adhesive to the second substrate 12, the present invention is not limited to this, and the adhesive may be applied to the first substrate 11, or to both the first substrate 11 and the second substrate 12. Furthermore, the method of applying the adhesive is not limited to applying it with a syringe, but may also be applied by, for example, screen printing or stamping.

[0208] Next, the first substrate 11 and the second substrate 12 of the individualized laminate (first laminate) in Figure 12C are bonded together via the adhesive layer 16 (Figure 15B). At this time, the side of the first substrate 11 opposite to the side where the cured material layer 13 (a cured material layer composed of cured patterned coating films) is formed is bonded to the second substrate 12. Then, the adhesive layer 16 is cured to bond the first substrate 11 and the second substrate 12, thereby obtaining the substrate laminate 70 shown in Figure 15C. The method for curing the adhesive layer 16 can be appropriately selected depending on the type of adhesive that constitutes the adhesive layer 16. Specific examples of methods for curing the adhesive layer 16 include curing by heating and curing by ultraviolet irradiation.

[0209] Although specific examples of manufacturing method M2 have been described above, the method for manufacturing a substrate laminate according to the present invention is not limited to the above examples. For example, in the process shown in Figure 15A, a second substrate having a semiconductor element substrate and a frame material may be used. In this case, in step Sd2, a substrate laminate having a light-shielding film and a frame material is obtained by bonding the first substrate and the frame material using an adhesive. Alternatively, in step Sa of manufacturing method M2, a third film may be formed by applying a third developable composition to the side of the second film opposite to the first film side. In this case, the coating film irradiated with active energy rays in step Sb has the first film, the second film, and the third film in this order from the first substrate side. The thickness of the third film is, for example, 0.01 μm or more and 100 μm or less. After forming the coating film having the first film, the second film, and the third film, the substrate laminate 80 (see Figure 8) described above can be manufactured by carrying out steps Sb, Sc, and Sd2.

[0210] Other aspects of manufacturing method M2 (points other than those described above) are the same as those described in the section <Third Embodiment: Method for Manufacturing a Substrate Laminate> above.

[0211] <Preferred embodiments of manufacturing methods M1 and M2> In order to further suppress the adhesion of foreign matter derived from colorants and to further suppress flare and ghosting, it is preferable that manufacturing methods M1 and M2 satisfy the following condition 1. Furthermore, in order to obtain a substrate laminate that can further suppress the adhesion of foreign matter derived from colorants, further suppress flare and ghosting, and exhibit excellent reliability as evaluated in thermal shock tests, it is preferable that manufacturing methods M1 and M2 satisfy the following condition 2, and more preferably that they satisfy the following condition 3. Condition 1: The thickness of the first film, which is made up of the first developable composition (or the thickness of the first film after heating, if a heating step is provided), is 2 μm or more and 9 μm or less. Condition 2: The above condition 1 is satisfied, and the second developable composition comprises, as the second curable compound, a component (A) having multiple cationic polymerizable groups in one molecule, and a compound having one cationic polymerizable group in one molecule. Condition 3: The amount of the compound that satisfies Condition 2 above and has one cationic polymerizable group in one molecule is 10 parts by mass or more and 30 parts by mass or less per 100 parts by mass of component (A) having multiple cationic polymerizable groups in one molecule. [Examples]

[0212] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0213] <Synthesis of curable compounds (polysiloxane compounds)> The synthesis methods for curable compounds P1 and P2 are described below. The weight-average molecular weights of curable compounds P1 and P2 were calculated from chromatograms obtained using Tosoh Corporation's "HLC-8420GPC" (columns: Shodex GPC KD-806M (2) and TSKgel SuperAWM-H (2)) with N,N-dimethylformamide as the solvent at a flow rate of 1.0 mL / min, and converted to standard polystyrene equivalents.

[0214] [Synthesis of curable compound P1] Solution S1 was obtained by adding 143 μL of a xylene solution of a platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Yumicore Precious Metals Japan, containing 3% by mass of platinum) to a mixture of 40 g of diallyl isocyanurate, 29 g of diallyl monomethyl isocyanurate, and 264 g of 1,4-dioxane. Separately, solution S2 was obtained by dissolving 88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in 176 g of toluene.

[0215] Then, under a nitrogen atmosphere containing 3 volume% oxygen, solution S2 was heated to a temperature of 105°C, and solution S1 was added dropwise to solution S2 over 3 hours. After the dropwise addition was complete, the mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S3. The reaction rate of the alkenyl groups of the compounds contained in the obtained solution S3 was then determined. 1 When measured by 1H-NMR, the reaction rate was found to be over 95%.

[0216] In addition, solution S4 was obtained by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene.

[0217] Then, under 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 1 hour. After the dropwise addition was complete, the mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S5. The reaction rate of the alkenyl groups of the compounds contained in the obtained solution S5 was then determined. 1 When measured by 1H-NMR, the reaction rate was found to be over 95%.

[0218] Next, after cooling solution S5, the solvents (toluene, xylene, and 1,4-dioxane) were removed from solution S5 under reduced pressure to obtain a solid. Then, propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as "PGMEA") was added to the obtained solid to obtain solution SP1 containing curable compound P1 (concentration of curable compound P1: 70% by mass). Curable compound P1 was a polysiloxane compound (a polymer with a weight-average molecular weight of 30,000) having multiple cationic polymerizable groups (specifically alicyclic epoxy groups) and multiple alkali-soluble groups (specifically X2 groups) in one molecule, and having a cyclic polysiloxane structure in its main chain.

[0219] [Synthesis of curable compound P2] Solution SP2 containing curable compound P2 (concentration of curable compound P2: 70% by mass) was obtained using the same procedure as in the above [Synthesis of curable compound P1], except that 62 g of allyl acrylate was used instead of 62 g of 1-vinyl-3,4-epoxycyclohexane. Curable compound P2 was a polysiloxane compound (a polymer with a weight-average molecular weight of 28,000) having multiple radical polymerizable groups (specifically acryloyl groups) and multiple alkali-soluble groups (specifically X2 groups) in one molecule, and having a cyclic polysiloxane structure in its main chain.

[0220] <Preparing other materials> In addition to solutions SP1, SP2, and PGMEA, the following materials were prepared as materials for the developable composition. • 3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (Daicel Corporation's "Celoxide® 2021P," hereinafter referred to as "2021P"), a curable compound having two alicyclic epoxy groups in one molecule. • 4,5-Epoxycyclohexane-1,2-dicarboxylate di2-ethylhexyl (manufactured by Shin Nippon Rika Co., Ltd., "Sensor® E-PS", hereinafter referred to as "E-PS"), is a curable compound having one alicyclic epoxy group per molecule. Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A-TMPT," hereinafter referred to as "A-TMPT") is a curable compound having three acryloyl groups in one molecule. • Photocationic polymerization initiator having a naphthalimide structure (ADEKA's "SP-606", hereinafter referred to as "SP-606") • A sulfonium salt compound that acts as a photocationic polymerization initiator (SunApro Co., Ltd.'s "CPI-210S," hereinafter referred to as "CPI-210S") • The sensitizer is 9,10-dipropoxyanthracene (manufactured by Kawasaki Chemical Industries, Ltd., hereinafter referred to as "9,10-DPA"). • An epoxy acrylate compound having an acidic group (KAYARAD® CCR-1291H, manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as "1291H") • Oxime ester compounds that act as photoradical polymerization initiators (BASF Japan's "Irgacure® OXE02," hereinafter referred to as "OXE02") • The coloring agent is carbon black (Mitsubishi Chemical Corporation's "MA100," hereinafter referred to as "MA100").

[0221] <Preparation of developable composition> The materials listed in Tables 1 and 2 were blended in the amounts specified in Tables 1 and 2 to obtain developable compositions DP1 to DP15 for use in the examples and comparative examples. When curable compounds P1 and P2 were blended, they were blended as solutions SP1 and SP2, respectively. In Tables 1 and 2, the amount of PGMEA in developable compositions DP1 to DP4, DP6 to DP11, and DP13 to DP15 also includes the amount of PGMEA in solution SP1 or solution SP2. In Tables 1 and 2, "P1" and "P2" refer to curable compounds P1 and P2, respectively. In Tables 1 and 2, "-" means that the material was not blended.

[0222] [Table 1]

[0223] [Table 2]

[0224] <Fabrication of substrate laminates> The following describes the manufacturing methods for the substrate laminates (more specifically, hollow structures having sealed hollow sections) of Examples 1 to 15 and Comparative Examples 1 to 11.

[0225] [Example 1] (Preparation of Sample 1) A first laminate was obtained in which a first developable composition DP1 was applied to a glass substrate, which was a first substrate, by a spin coater, forming a first film composed of the developable composition DP1 on the glass substrate. Next, the first laminate was heated for 5 minutes on a hot plate heated to 120°C. Then, a second developable composition DP6 was applied to the heated first film by a spin coater, forming a second film composed of the developable composition DP6 on the first film. This resulted in a second laminate in which the first and second films were formed in that order on the glass substrate. Next, the second laminate was heated for 5 minutes on a hot plate heated to 120°C, forming a coating film on the glass substrate containing a first film (thickness: 4 μm) and a second film (thickness: 20 μm).

[0226] Next, using a manual exposure machine (Dai Nippon Kaken Co., Ltd. "MA-1300", lamp: high-pressure mercury lamp), the image was exposed through a photomask with a grid-like line pattern (vertical direction: line / space = 50 μm / 50 μm, horizontal direction: line / space = 100 μm / 100 μm) to achieve an integrated exposure of 10,000 mJ / cm². 2 Under these conditions, the coating film of the second laminated body was exposed (specifically, by soft contact exposure) by irradiating it with light after heating.

[0227] Next, the second laminate, after exposure, was heated for 10 minutes on a hot plate heated to 120°C. Then, the heated second laminate was left for 1 minute in an atmosphere of 25°C, and then immersed for 60 seconds in an aqueous TMAH solution (TMAH concentration: 2.38 mass%) as an alkaline developer. Next, the second laminate that had been immersed in the alkaline developer was washed with water for 30 seconds, and then the surface moisture was removed with compressed air. This formed a semi-cured coating film (pattern film) with a grid-like pattern.

[0228] Next, on a hot plate heated to 230°C, the second laminate from which moisture had been removed was heated for 30 minutes to cure the pattern film (exposed portion), thereby obtaining Sample 1 having a cured product layer (a layer in which a coating film patterned in a lattice shape was cured) patterned on a glass substrate. The cured product layer had, in this order from the glass substrate side, a first layer (thickness: 4 μm) composed of a cured product of the developable composition DP1 and a second layer (thickness: 20 μm) composed of a cured product of the developable composition DP6.

[0229] (Preparation of Sample 2) Sample 1 was cut with a dicing device to obtain Sample 2 fragmented into pieces of 12 mm × 12 mm size. Sample 2 was a sample obtained by fragmenting Sample 1.

[0230] (Preparation of Substrate Laminate) Sample 2 and a silicon wafer (size: 12 mm × 12 mm) as the second substrate were laminated via an epoxy-based adhesive to obtain a third laminate. In the lamination, the epoxy-based adhesive was laminated so as to be interposed between the cured product layer and the silicon wafer. The epoxy-based adhesive used contained bisphenol A diglycidyl ether as the main agent, an imidazole-based curing agent as the curing agent, and was a thermosetting adhesive with a mass ratio of the main agent to the curing agent (main agent / curing agent) of 100 / 3.

[0231] Next, the third laminate was heated in an oven at 200°C for 2 hours to obtain the substrate laminate of Example 1. The substrate laminate of Example 1 was a substrate laminate having a structure in which a glass substrate, a cured product layer, an adhesive layer (thickness: 100 μm) composed of a cured product of the adhesive, and a silicon wafer were laminated in this order.

[0232] [Examples 2 to 8] Substrate laminates of Examples 2 to ⑧ were obtained in the same manner as in Example 1, except that the developable compositions described in Table 3 below were used as the first developable composition and the second developable composition.

[0233] [Example 9] The substrate laminate of Example 9 was obtained using the same method as in Example 1, except that an organic solvent developer (PGMEA) was used instead of an alkaline developer.

[0234] [Example 10] A substrate laminate of Example 10 was obtained in the same manner as in Example 1, except that a third film formation step, as shown below, was performed before exposure after forming the first and second films on the glass substrate.

[0235] (Third film formation process) A developable composition DP14, which is a third developable composition, was applied to the second film using a spin coater, and a third film composed of the developable composition DP14 was formed on the second film. Next, the resulting laminate was heated for 5 minutes on a hot plate heated to 120°C, and a coating film containing a first film (thickness: 4 μm), a second film (thickness: 20 μm), and a third film (thickness: 46 μm) was formed on the glass substrate.

[0236] [Example 11] The substrate laminate of Example 11 was obtained in the same manner as in Example 10, except that developable composition DP15 was used instead of developable composition DP14.

[0237] [Examples 12-15] The substrate laminates of Examples 12 to 15 were obtained in the same manner as in Example 1, except that the amount of coating of the first developable composition was adjusted so that the thickness of the first film in the second laminate after heating and before exposure was the thickness shown in Table 4 below.

[0238] [Comparative Example 1] A substrate laminate of Comparative Example 1 was obtained in the same manner as in Example 1, except that the second film was formed directly on the glass substrate without forming the first film.

[0239] [Comparative Examples 2-8] Except for using the developable compositions described in Tables 5 and 6 below as the second developable composition, the substrate laminates of Comparative Examples 2 to 8 were obtained in the same manner as Comparative Example 1.

[0240] [Comparative Example 9] The substrate laminate of Comparative Example 9 was obtained using the same method as in Comparative Example 1, except that an organic solvent developer (PGMEA) was used instead of an alkaline developer.

[0241] [Comparative Example 10] A substrate laminate of Comparative Example 10 was obtained in the same manner as in Comparative Example 1, except that a third film formation step, as described below, was performed after forming a second film on the glass substrate and before exposure.

[0242] (Third film formation process) A developable composition DP14, which is a third developable composition, was applied to the second film using a spin coater, and a third film composed of the developable composition DP14 was formed on the second film. Next, the resulting laminate was heated for 5 minutes on a hot plate heated to 120°C, and a coating film including the second film (thickness: 20 μm) and the third film (thickness: 46 μm) was formed on the glass substrate.

[0243] [Comparative Example 11] The substrate laminate of Comparative Example 11 was obtained in the same manner as in Comparative Example 10, except that the developable composition DP15 was used instead of the developable composition DP14.

[0244] <Methods for measuring and evaluating physical properties> Next, we will explain the methods for measuring and evaluating various physical properties.

[0245] [Presence or absence of foreign objects] Using a 3D measuring laser microscope (Olympus "LEXT® OLS4000"), the spaces between patterns in the cured material layer of sample 2 were observed at a magnification of 100x to check for the presence or absence of foreign matter originating from the coloring agent in the space areas of the pattern region with a line / space ratio of 50 μm / 50 μm. The presence or absence of foreign matter was then determined according to the following criteria. If the judgment was A or B, it was evaluated as "the adhesion of foreign matter originating from the coloring agent has been suppressed." On the other hand, if the judgment was C, it was evaluated as "the adhesion of foreign matter originating from the coloring agent has not been suppressed." A: No foreign objects with a maximum diameter of 25 μm or larger were found. B: Foreign matter with a maximum diameter of 25 μm or more was confirmed, but the number of such foreign matters was 5 or less. C: Six or more foreign matters with a maximum diameter of 25 μm or more were confirmed.

[0246] [Patternability] Using a 3D measurement laser microscope (Olympus' "LEXT (registered trademark) OLS4000") and a stylus surface profiler (Veeco's "Dektak (registered trademark) 150"), the pattern shape of the pattern film of Sample 1 was observed and evaluated according to the following criteria. A: Neither residue nor peeling occurred in the pattern area with a line / space = 50 μm / 50 μm. B: Either residue or peeling occurred in the pattern area with a line / space = 50 μm / 50 μm, but neither residue nor peeling occurred in the pattern area with a line / space = 100 μm / 100 μm. C: Other than A and B above

[0247] [Optical density] Using a transmission densitometer (X-rite's "361T"), the optical density (OD) of Sample 1 was measured. In Examples 1, 2, and 5 to 15 and Comparative Examples 1, 2, and 5 to 11, the optical density was 2.7. In Examples 3 and Comparative Example 3, the optical density was 4.0. In Examples 4 and Comparative Example 4, the optical density was 0.5.

[0248] [Die shear strength] Using a die shear tester (Nordson DAGE's "SERIES4000"), a shear force (specifically, a shear force on the glass substrate and the silicon wafer) was applied to the substrate laminate, and the load when the silicon wafer peeled off from the substrate laminate was measured. Then, the maximum value of the load was taken as the die shear strength. The die shear strength was measured under the conditions in accordance with MIL STD 883, with a shear height of 50 μm and a shear speed of 80 μm / second.

[0249] [Thermal shock test 1 (thermal shock test of Sample 2)] For each example and comparative example, five samples 2 for fabricating the substrate laminate were prepared, and a thermal shock test was performed on each using a heat shock test apparatus (Hitachi Global Life Solutions, Ltd. "ES-57L"). The thermal shock test consisted of holding sample 2 in a -55°C atmosphere for 30 minutes, followed by holding it in a 125°C atmosphere for 30 minutes, with each cycle repeated 1000 times. At the end of 500 and 1000 cycles, sample 2 was observed from the glass substrate side using an optical microscope and evaluated according to the following criteria. Note that the thermal shock test of sample 2 (thermal shock test 1) allows for evaluation of reliability under more stringent conditions than the thermal shock test of the substrate laminate described later (thermal shock test 2), because the difference in thermal expansion coefficients between the glass substrate and the cured layer becomes more apparent. A: At the end of 500 cycles and 1000 cycles, no defects (at least one of cracks and delamination) were found in any of the five samples 2. B: At the end of 1000 cycles, defects (at least one of cracks and / or delamination) were found in at least one of the five Sample 2, but at the end of 500 cycles, no defects (at least one of cracks and / or delamination) were found in any of the five Sample 2. C: Other than A and B above

[0250] [Cold and Thermal Shock Test 2 (Cold and Thermal Shock Test of Substrate Laminate)] For each example and comparative example, five substrate stacks were prepared, and thermal shock tests were conducted on each using a heat shock test apparatus (Hitachi Global Life Solutions, Ltd. "ES-57L"). The thermal shock test consisted of holding the substrate stack in a -55°C atmosphere for 30 minutes, followed by holding it in a 125°C atmosphere for 30 minutes, with each cycle being repeated 2000 times. At the end of 1000 and 2000 cycles, the substrate stacks were observed from the glass substrate side using an optical microscope and evaluated according to the following criteria. A: At the end of 1000 cycles and 2000 cycles, no defects (at least one of cracks and delamination) were found in any of the five substrate stacks. B: At the end of 2000 cycles, defects (at least one of cracks and delamination) were found in one of the five substrate stacks, but at the end of 1000 cycles, no defects (at least one of cracks and delamination) were found in any of the five substrate stacks. C: Other than A and B above

[0251] [Bailing Glare Index] A camera module was fabricated using Sample 2, an image sensor substrate, and an epoxy adhesive. The epoxy adhesive used was a thermosetting adhesive containing bisphenol A diglycidyl ether as the main component and an imidazole-based curing agent as the hardening agent, with a mass ratio of 100 / 3 between the main component and the hardening agent. The resulting camera module was used as a measurement sample, and the baying glare index was measured using a baying glare evaluation device (LFM-1000, manufactured by Tsubosaka Electric Co., Ltd.). The baying glare index (unit: %) is obtained from the formula "baying glare index = 100 × luminance of blackbody / luminance of whitebody". The baying glare index of the measurement sample was normalized by setting the baying glare index obtained using the baying glare evaluation device (LFM-1000, manufactured by Tsubosaka Electric Co., Ltd.) for the reference sample shown below as 100%. The normalized value (hereinafter referred to as "normalized BG index") was used as an indicator of the performance that can suppress flare generation. The smaller the normalized BG index, the higher the performance in suppressing flare generation. The normalized BG index is preferably 95% or less, more preferably 90% or less, and even more preferably 88% or less.

[0252] (Reference sample) The camera module was prepared using the same method as the measurement sample preparation method described above, except that a glass substrate was used instead of sample 2, and this camera module was used as the reference sample.

[0253] Tables 3 to 6 show, for Examples 1 to 15 and Comparative Examples 1 to 11, the type of first developable composition, the type of second developable composition, the type of third developable composition, the thickness of the first film, the type of developer, the presence or absence of foreign matter, patterning properties, die shear strength, evaluation results of thermal shock test 1, evaluation results of thermal shock test 2, and the normalized BG index, respectively. In Tables 5 and 6, "-" in the column for the type of first developable composition means that the first film was not formed. In Tables 3 to 6, "-" in the column for the type of third developable composition means that the third film was not formed. In Tables 3 to 6, "ALK" means alkaline developer. In Tables 4 and 6, "ORG" means organic solvent developer.

[0254] [Table 3]

[0255] [Table 4]

[0256] [Table 5]

[0257] [Table 6]

[0258] In the substrate laminates of Examples 1 to 15, the cured layer consisted of a first layer made of a cured product of a developable composition without a colorant, and a second layer made of a cured product of a developable composition containing a colorant, in that order from the glass substrate side. As shown in Tables 3 and 4, the determination result for the presence or absence of foreign matter in Examples 1 to 15 was A or B. Therefore, Examples 1 to 15 were able to suppress the adhesion of foreign matter derived from the colorant.

[0259] In the substrate laminates of Comparative Examples 1 to 11, a layer consisting of a cured product of a developable composition containing a colorant was directly formed on the glass substrate. As shown in Tables 5 and 6, the result of the determination of the presence or absence of foreign matter in Comparative Examples 1 to 11 was C. Therefore, Comparative Examples 1 to 11 were unable to suppress the adhesion of foreign matter derived from the colorant.

[0260] The results above demonstrate that the present invention provides a substrate laminate that can suppress the adhesion of foreign substances derived from colorants. [Explanation of symbols]

[0261] 10, 20, 30, 40, 50, 60, 70, 80 substrate stacks 11. First circuit board 12 Second board 13 Cured material layer 14 1st layer 15 2nd layer 16 Adhesive layer 31 Semiconductor device substrate 32 Frame material 200 coating film 201 1st membrane 202 Second membrane 300 Photomasks 301 1st semi-cured layer 302 Second semi-cured layer 303 Exposure section 306 Non-exposed area

Claims

1. Step Sa of forming a coating film on the first substrate, Step Sb involves irradiating the coating film with active energy rays through a photomask to form a semi-cured exposed area and an unexposed area on the first substrate. Step Sc to form the patterned coating film on the first substrate by removing the unexposed areas from the first substrate with a developing solution, Step Sd1 involves bonding the first substrate and the second substrate via the patterned coating film. A method for manufacturing a substrate laminate comprising, The semi-cured exposure portion has, in this order from the first substrate side, a first semi-cured layer made of a first developable composition in a semi-cured state, and a second semi-cured layer made of a second developable composition in a semi-cured state. The first developable composition comprises a polymerizable first curable compound and a first photopolymerization initiator, and is a developable composition that does not contain a colorant. The aforementioned second developable composition is a developable composition comprising a polymerizable second curable compound, a second photopolymerization initiator, and a colorant. A method for manufacturing a substrate laminate, wherein the patterned coating film in step Sd1 is a patterned coating film in a semi-cured state.

2. The second substrate comprises a semiconductor element substrate and a frame material. The method for manufacturing a substrate laminate according to claim 1, wherein in step Sd1, the first substrate and the frame material are bonded together via the patterned coating film.

3. A method for manufacturing a substrate laminate according to claim 1 or 2, wherein in step Sd1, the first substrate and the second substrate are laminated via the patterned coating film in a semi-cured state to form a laminate, and then the laminate is heated to further cure the coating film, thereby bonding the first substrate and the second substrate together.

4. A method for manufacturing a substrate laminate according to claim 1, wherein in step Sa, the first developable composition is applied to the first substrate, and then the second developable composition is applied to the first film made of the first developable composition to form the coating film comprising the first film and the second film made of the second developable composition.

5. The coating film further comprises a third film composed of a third developable composition, The aforementioned third developable composition is a developable composition comprising a polymerizable third curable compound and a third photopolymerization initiator, and is free of colorants. The method for manufacturing a substrate laminate according to claim 4, wherein in step Sa, the third developable composition is applied to the side of the second film opposite to the side of the first film.

6. A method for manufacturing a substrate laminate according to claim 1, wherein in step Sa, the first developable composition is applied to the first substrate, the first film made of the first developable composition is irradiated with an active energy ray, and the second developable composition is applied to the first film after irradiation with the active energy ray to form the coating film comprising the first film and the second film made of the second developable composition.

7. The coating film further comprises a third film composed of a third developable composition, The aforementioned third developable composition is a developable composition comprising a polymerizable third curable compound and a third photopolymerization initiator, and is free of colorants. The method for manufacturing a substrate laminate according to claim 6, wherein in step Sa, the third developable composition is applied to the side of the second film opposite to the side of the first film.

8. The first developable composition and the second developable composition are alkali soluble, A method for producing a substrate laminate according to claim 1, wherein at least one of the first curable compound and the second curable compound is cationic or radically polymerizable.

9. The second photopolymerization initiator is a photocationic polymerization initiator, The method for producing a substrate laminate according to claim 1, wherein the photocationic polymerization initiator has one or more structures selected from the group consisting of a naphthalimide structure and an oximesulfonate structure.

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