Manufacturing method for substrate stacks for solid-state image sensors

Abstract

In an inspection during the manufacturing process of a substrate laminate, when a defect in a precursor laminate including a first board and a second board is found, by peeling (reworking) the first substrate and the second substrate, a method for manufacturing a substrate laminate for a solid-state imaging device is provided in which the first board and / or the second board can be reused. 1 base In the manufacturing method of a substrate laminate for a solid-state imaging device, which includes forming a patterned resin film on one main surface of a first substrate, 2 bases manufacturing a precursor laminate in which the first substrate and the second substrate are temporarily fixed by bonding the second substrate to the patterned resin film on the first substrate, 1 base inspecting the precursor laminate, and 2 bases in the manufacturing method of a substrate laminate for a solid-state imaging device, the die shear strength between the resin film and the second substrate in the precursor laminate is set to 0.8 kgf / mm or more at 23°C, 0.005 kgf / mm or more and 0.1 kgf / mm or less at 100°C, and the resin film is configured to be curable by heating above 150°C. manufacturing a precursor laminate in which the first substrate and the second substrate are temporarily fixed by bonding the second substrate to the patterned resin film on the first substrate, inspecting the precursor laminate, and in the manufacturing method of a substrate laminate for a solid-state imaging device, the die shear strength between the resin film and the second substrate in the precursor laminate is set to 0.8 kgf / mm or more at 23°C, 2 0.005 kgf / mm or more and 0.1 kgf / mm or less at 100°C, and the resin film is configured to be curable by heating above 150°C. 2 0.005 kgf / mm or more and 0.1 kgf / mm or less at 100°C, and the resin film is configured to be curable by heating above 150°C. 2 0.005 kgf / mm or more and 0.1 kgf / mm or less at 100°C, and the resin film is configured to be curable by heating above 150°C.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a substrate laminate for a solid-state imaging device.

Background Art

[0002] Image sensors such as CMOS sensors and CCD sensors are used in various devices such as digital cameras and smartphones. In recent years, with the spread of surveillance cameras in automobiles, factories, etc., the usage amount of image sensors has increased, and miniaturization and high definition of image sensors have been progressing more and more.

[0003] The substrate laminate constituting the image sensor has, for example, a hollow structure in which a semiconductor element substrate having a light-receiving element and a glass substrate are bonded together with an adhesive. Here, the semiconductor element substrate is a substrate on which semiconductor elements are mounted.

[0004] The substrate laminate having a hollow structure is manufactured, for example, by the following method. First, a liquid adhesive containing a resin component such as an epoxy resin or an acrylic resin is applied to the periphery of the adhesive surface of the semiconductor element substrate. Next, a glass substrate, which is a sealing substrate, is placed on the adhesive surface of the semiconductor element substrate. Then, by curing the liquid adhesive by heating, a substrate laminate in which the semiconductor element substrate and the glass substrate are fixed via the cured adhesive is manufactured.

[0005] Also, a method using a photosensitive composition instead of the liquid adhesive has been studied for the purpose of improving pattern accuracy.

[0006] For example, in Patent Document 1, a step of forming a coating film by applying a photosensitive composition on a first substrate such as a glass substrate, a step of patterning the obtained coating film, a step of forming a laminate by laminating the first substrate and a second substrate such as a semiconductor element substrate through the patterned coating film, a step of heating the obtained laminate to bond the first substrate and the second substrate, A method for manufacturing a substrate laminate comprising the above is described. Furthermore, a coating film of a patterned photosensitive composition may be referred to as a "patterned film" below.

[0007] Furthermore, Patent Document 1 describes that the photosensitive composition includes a cationic polymerizable compound and a photoacid generator (photocationic polymerization initiator), and that in the process of patterning the coating film, the exposed parts of the coating film are made semi-cured by irradiating the coating film with light through a photomask, and then developed and heat-cured to form a patterned film. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2019-62048 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] When producing substrate stacks used in image sensors and the like, errors such as faulty stacking between substrates can occur. From this perspective, image sensors and the like are classified as "acceptable" or "unacceptable" based on inspection results. "Unacceptable" products are usually discarded. However, due to the increasing performance of semiconductor elements, the cost of materials used in image sensors and the like has skyrocketed. Therefore, yield has a significant impact on costs in the production of image sensors and the like. For these reasons, there is a strong desire to reduce material costs by reusing circuit boards after delaminating (reworking) them in "rejected products."

[0010] However, in the method described in Patent Document 1, the photosensitive composition hardens due to heating during the lamination process, and the substrate and the hardened material adhere firmly, making rework difficult.

[0011] The present invention has been made in view of the above problems, and aims to provide a method for manufacturing a substrate laminate for a solid-state image sensor, wherein if a defect in the precursor laminate including the first substrate and the second substrate is found during inspection in the manufacturing process of the substrate laminate, the first substrate and / or the second substrate can be reused by peeling off (reworking) the first substrate and the second substrate. [Means for solving the problem]

[0012] In view of the above circumstances, the inventors of this invention have conducted diligent studies and found that the above problems can be solved by the following method, and have completed the present invention. Specifically, the present invention provides the following 1) to 7).

[0013] (1) A method for manufacturing a substrate laminate for a solid-state image sensor, The above manufacturing method involves the formation of a patterned resin film on one main surface of the first substrate, Manufacturing a preliminary laminate in which the first substrate and the second substrate are temporarily fixed by bonding the second substrate to a patterned resin film on the first substrate, Inspection of the precursor laminate, Includes, The die shear strength between the resin film and the second substrate in the precursor laminate is 0.8 kgf / mm² at 23°C. 2 The above is the result, and at 100℃, it is 0.005 kgf / mm 2 The above is 0.1 kgf / mm². 2 The following: In the precursor laminate, the die-shear strength between the resin film and the second substrate is as follows: 1)~3): 1) To obtain a laminate consisting of an unpatterned resin film made of the same material as the patterned resin film, with dimensions of 2 mm in length, 2 mm in width, and 50 μm in thickness, and a first substrate with dimensions of 2 mm in length, 2 mm in width, and 2 mm in thickness. 2) With the unpatterned resin film from the laminate obtained in 1) in contact with the second substrate heated to 80°C, a 2kg weight is placed on the second substrate for 30 seconds, and the first substrate is bonded to the second substrate via the unpatterned resin film to obtain a precursor laminate for die shear strength measurement. 3) In the prototype laminate for die shear strength measurement obtained at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the unpatterned resin film in the prototype laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force when the first substrate and the second substrate delaminate is measured as the die shear strength. Measured by a method including, The resin film can be cured by heating at temperatures exceeding 150°C. If the inspection result is satisfactory, the precursor laminate is heated to harden the resin film, thereby manufacturing a substrate laminate in which the first substrate and the second substrate are fixed together. A manufacturing method in which, if the inspection result is unsatisfactory and at least one of the first substrate and the second substrate is reusable, the first substrate and the second substrate are recovered by heating the precursor laminate to a temperature of 50°C to 150°C to peel the second substrate from the resin film, and at least one of the recovered first substrate and the second substrate is reused in the manufacture of the precursor laminate. (2) A method for manufacturing a substrate laminate according to (1), wherein the resin film is made of an exposed photosensitive composition. (3) A method for producing a substrate laminate according to (2), wherein the photosensitive composition comprises a radical polymerizable compound, a cationic polymerizable compound, and a photoradical polymerization initiator. (4) The first substrate is a glass substrate, A method for manufacturing a substrate laminate according to any one of (1) to (3), wherein the second substrate is a substrate on which semiconductor elements are mounted. (5) The method for manufacturing a substrate laminate according to (4), wherein the second substrate is a ceramic substrate on which semiconductor elements are mounted. (6) If the test result is satisfactory, A method for manufacturing a substrate laminate according to any one of (1) to (5), wherein the substrate laminate is heated to 180°C or higher to cure the resin film, thereby fixing the first substrate and the second substrate together. (7) In a substrate laminate in which the first substrate and the second substrate are fixed together, the die shear strength between the cured resin film and the second substrate is 1.5 kgf / mm at 23°C. 2 The above is the result, and at 100°C, it is 1.2 kgf / mm². 2 That's all. The die shear strength between the cured resin film and the second substrate is as follows: I) and II): I) To obtain a die-shear strength measurement precursor laminate containing a cured resin film by heating the die-shear strength measurement precursor laminate used for measuring die-shear strength between the resin film and the second substrate at 200°C for 2 hours to cure the resin film, and II) In the precursor laminate for die shear strength measurement, which includes a resin film cured at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the cured resin film in the precursor laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force when the first substrate and the second substrate delaminate is measured as the die shear strength. A method for manufacturing a substrate laminate according to any one of (1) to (6), which is measured by a method including the following: [Effects of the Invention]

[0014] According to the present invention, if a defect in the precursor laminate including the first substrate and the second substrate is found during inspection in the manufacturing process of the substrate laminate, the first substrate and / or the second substrate can be reused by peeling off (reworking) the first substrate and the second substrate. [Modes for carrying out the invention]

[0015] ≪Manufacturing method for substrate laminates≫ A substrate stack for a solid-state image sensor is manufactured by the substrate stack manufacturing method described below. The method for manufacturing a substrate laminate is: Formation of a patterned resin film on one main surface of the first substrate, Manufacturing a preliminary laminate in which the first substrate and the second substrate are temporarily fixed by bonding the second substrate to a patterned resin film on the first substrate, Inspection of the precursor laminate, Includes. The die shear strength between the resin film and the second substrate in the precursor laminate is 0.8 kgf / mm² at 23°C. 2 The above is the result, and at 100℃, it is 0.005 kgf / mm 2 The above is 0.1 kgf / mm². 2 The following applies: The die-shear strength between the resin film and the second substrate in the precursor laminate is measured by the following methods, including 1) to 3). 1) To obtain a laminate consisting of an unpatterned resin film made of the same material as the patterned resin film, with dimensions of 2 mm in length, 2 mm in width, and 50 μm in thickness, and a first substrate with dimensions of 2 mm in length, 2 mm in width, and 2 mm in thickness. 2) With the unpatterned resin film from the laminate obtained in 1) in contact with the second substrate heated to 80°C, a 2kg weight is placed on the second substrate for 30 seconds, and the first substrate is bonded to the second substrate via the unpatterned resin film to obtain a precursor laminate for die shear strength measurement. 3) In the precursor laminate for die shear strength measurement obtained at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the unpatterned resin film in the precursor laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force when the first substrate and the second substrate delaminate is measured as the die shear strength. More specifically, the die shear strength between the resin film and the second substrate is measured by the method described later in the examples. The above resin film can be cured by heating at temperatures exceeding 150°C. If the above inspection is successful, the precursor laminate is heated to cure the resin film, thereby manufacturing a substrate laminate in which the first substrate and the second substrate are fixed together. If the above inspection is unsuccessful and at least one of the first substrate and the second substrate is reusable, the first substrate and the second substrate are recovered by heating the precursor laminate to a temperature of 50°C to 150°C to peel the second substrate from the resin film, and at least one of the recovered first substrate and the second substrate is reused in the manufacture of the precursor laminate.

[0016] According to the above method, if a defect in the precursor laminate, including the first and second substrates, is discovered during inspection in the manufacturing process of the substrate laminate, the first and / or second substrates can be reused by peeling off (reworking) them.

[0017] The following describes the manufacturing of the precursor laminate, its inspection, and the procedures taken in response to the inspection results. Furthermore, the present invention is not limited in any way to the embodiments described below.

[0018] <Formation of patterned resin film> A patterned resin film is formed on one of the main surfaces of the first substrate. The method for forming the patterned resin film will be described below.

[0019] [First substrate] Examples of the first substrate 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, examples of semiconductor device substrates include image sensor substrates. The thickness of the first substrate is preferably, for example, 50 μm or more and 2000 μm or less.

[0020] As the semiconductor element mounted on the image sensor substrate, a light receiving element having a photodiode is preferable. Typically, such a light receiving element includes a microlens that condenses light onto the light receiving element, and a color filter that is located between the microlens and the photodiode and selects the wavelength of the light beam incident on the photodiode.

[0021] Among the above substrates, a glass substrate is preferable as the first substrate.

[0022] The precursor laminate described below is a laminate in which a second substrate is temporarily fixed to a first substrate, obtained by bonding the second substrate to a patterned resin film on the first substrate.

[0023] The die shear strength between the resin film and the second substrate in the precursor laminate is 0.8 kgf / mm 2 or more at 23°C, and 0.005 kgf / mm 2 or more and 0.1 kgf / mm 2 or less at 100°C. The die shear strength at 23°C is preferably, for example, 2 kgf / mm 2 or less, and more preferably 1.5 kgf / mm 2 or less. The above die shear strength is preferably 0.9 kgf / mm 2 or more at 23°C, and more preferably 1 kgf / mm 2 or more. The above die shear strength is preferably 0.005 kgf / mm 2 or more and 0.5 kgf / mm 2 or less at 100°C, more preferably 0.005 kgf / mm 2 or more and 0.1 kgf / mm 2 or less, and even more preferably 0.005 kgf / mm 2 or more and 0.02 kgf / mm 2 or less.

[0024] In other words, the tackiness of the resin film is relatively high at room temperature and low at temperatures around 100°C. Specifically, the tackiness of the resin film decreases as the temperature rises from around room temperature to around 100°C. This is because the resin components contained in the resin film soften when heated. As a result, by heating the precursor laminate, in which the first substrate and the second substrate are temporarily fixed, to a temperature of approximately 50°C to 150°C, the second substrate can be peeled off from the resin film.

[0025] [Resin film] As mentioned above, the die shear strength between the resin film and the second substrate is 0.8 kgf / mm² at 23°C. 2 The above is the result, and at 100℃, it is 0.005 kgf / mm 2 The above is 0.1 kgf / mm². 2 The following applies: Furthermore, the resin film can be cured by heating at temperatures exceeding 150°C. For good and rapid curing of the resin film, it is preferable to heat the precursor laminate containing the patterned resin film at a temperature of 180°C or higher.

[0026] Furthermore, the resin film is patterned. The method for forming the patterned resin film is not particularly limited. Examples of methods for forming the patterned resin film include printing methods such as inkjet printing and photolithography using a photosensitive composition. Photolithography using a photosensitive composition is preferred as a method for forming the patterned resin film because it can form a finely patterned resin film with high precision.

[0027] Because it exhibits the above die-shear strength and facilitates the formation of a resin film that can be cured by heating above 150°C, an exposed photosensitive composition is preferred as the resin film.

[0028] As mentioned above, the patterned resin film is ultimately cured by heating, becoming a patterned cured film. Therefore, in the substrate laminate, there is a void between the first substrate and the second substrate, partitioned by the first substrate, the second substrate, and the patterned cured film. This void may be sealed, or it may have an opening in at least a part of it, but it is preferable that it be sealed. The thickness of the patterned cured film is preferably, for example, 0.01 μm to 200 μm, more preferably 0.1 μm to 150 μm, and even more preferably 5 μm to 150 μm.

[0029] When the resin film consists of an exposed photosensitive composition, a patterned resin film is formed using a photosensitive composition containing a compound that can polymerize upon exposure. In such a photosensitive composition, the compound that can polymerize upon exposure becomes insoluble in the developer upon exposure due to polymerization. Such a photosensitive composition is a so-called negative-type photosensitive composition. The photosensitive composition may or may not contain a resin. If the photosensitive resin composition does not contain a resin, the polymer of a compound that can be polymerized by exposure in the exposed photosensitive composition that constitutes the resin film corresponds to the resin component.

[0030] Specifically, first, a photosensitive composition is applied to one main surface of the first substrate to form a coating film. Methods for applying the photosensitive composition to the first substrate include spin coating, roll coating, printing, and bar coating. The application method is not limited to these methods. The thickness of the coating film is, for example, 0.01 μm to 200 μm, preferably 0.1 μm to 150 μm, and more preferably 5 μm to 150 μm.

[0031] The coating film formed in this manner may be dried by pre-baking. Pre-baking is performed at a temperature at which the resin film does not harden. Pre-baking is typically performed at a temperature between 60°C and 150°C.

[0032] By the method described above, the coating film formed on the first substrate is exposed to light through a mask corresponding to the pattern shape of the patterned resin film. In the exposed areas of the coating film, components contained in the photosensitive composition polymerize, causing the film to become poorly soluble in the developer and enter a semi-cured state. The wavelength of the light irradiated during exposure is preferably in the range of 200 nm to 450 nm. Examples of light sources 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 cumulative exposure dose in the exposure area is preferably 1 mJ / cm². 2 More than 50000mJ / cm 2 The following, more preferably 1 mJ / cm² to 20,000 mJ / cm² 2 The following applies:

[0033] After exposure, a patterned resin film is obtained by removing the unexposed areas of the coating film using an appropriate developer according to the type of photosensitive composition. For example, if a photosensitive composition contains an alkali-soluble component, the unexposed areas can be removed using an alkaline developer. Furthermore, if a sufficiently large difference in solubility in an organic solvent occurs between the exposed and unexposed areas of the photosensitive composition after exposure, an organic solvent can be used as the developer. Development methods include immersion, paddle, and spray methods.

[0034] From the perspective of achieving high contrast during development, it is preferable that the photosensitive composition contains alkali-soluble components and the developer is an alkaline developer. Examples of alkaline developers include aqueous solutions containing one or more organic bases such as tetramethylammonium hydroxide (TMAH) and choline; and inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate. From the viewpoint of increasing the contrast between exposed and unexposed areas, the concentration of the alkaline component in the alkaline developer is preferably 25% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0035] The patterned resin film formed as described above is washed with pure water or an organic solvent as needed.

[0036] A photosensitive composition containing a cationic polymerizable compound (A), a radical polymerizable compound (B), and a photoradical polymerization initiator (C) is preferred as a material for forming a resin film that satisfies the above conditions. Such a photosensitive composition yields a semi-cured, patterned resin film by patterning at a temperature lower than the polymerization temperature of the cationic polymerizable compound (A). The semi-cured, patterned resin film yields a cured film by heating at a temperature above 150°C.

[0037] (Cationically polymerizable compound (A)) Cationic polymerizable compound (A) is a compound having one or more cationic polymerizable groups in one molecule. Preferably, the cationic polymerizable compound has one or more cationic polymerizable groups and one or more alkali-soluble groups in one molecule.

[0038] When the cationic polymerizable compound (A) has one or more cationic polymerizable groups and one or more alkali-soluble groups in one molecule, a photosensitive composition with excellent curability and patternability by photolithography can be obtained.

[0039] The cationic polymerizable compound (A) preferably has two or more cationic polymerizable groups in one molecule. When the cationic polymerizable compound (A) has two or more cationic polymerizable groups in one molecule, a cured film with a high crosslink density can be formed. As a result, the cured film has excellent heat resistance. The two or more cationic polymerizable groups may consist of only one type of group, or a combination of two or more groups.

[0040] The cationic polymerizable compound (A) preferably has two or more alkali-soluble groups in one molecule. When the cationic polymerizable compound (A) has two or more alkali-soluble groups in one molecule, it is easier to remove unexposed areas during development, and it is easier to form patterned resin films by photolithography. The two or more alkali-soluble groups may consist of only one type of group, or a combination of two or more types of groups.

[0041] Examples of cationic polymerizable groups include epoxy groups, vinyl ether groups, oxetane groups, and alkoxysilyl groups. From the viewpoint of storage stability of the photosensitive composition, one or more cationic polymerizable groups selected from the group consisting of alicyclic epoxy groups, glycidyl groups, and oxetanyl groups are preferred, with alicyclic epoxy groups and / or glycidyl groups being more preferred. Among these, alicyclic epoxy groups are particularly preferred because they have relatively high reactivity during curing and can suppress curing shrinkage of the cured layer.

[0042] Examples of alkali-soluble groups in the cationic polymerizable compound (A) include a monovalent organic group represented by the following formula (X1), a divalent organic group represented by the following formula (X2), a phenolic hydroxyl group, and a carboxyl group. Among these, one or more groups selected from the group consisting of a monovalent organic group represented by the following formula (X1), a divalent organic group represented by the following formula (X2), and a phenolic hydroxyl group are preferred. Hereafter, a monovalent organic group represented by formula (X1) may be referred to as an "X1 group." Similarly, a divalent organic group represented by formula (X2) may be referred to as an "X2 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.

[0043] [ka]

[0044] To maintain the semi-cured state of the patterned resin film more stably, the alkali-soluble group of the cationic polymerizable compound (A) is preferably one or more selected from the group consisting of X1 groups, X2 groups, and phenolic hydroxyl groups, more preferably X1 groups and / or X2 groups, and particularly preferably X2 groups.

[0045] The acidity of both the X1 and X2 groups is relatively low. Therefore, even if the first substrate or precursor laminate, which has a semi-cured patterned resin film, is stored for a relatively long period of time, cationic polymerization in the resin film is less likely to proceed.

[0046] From the viewpoint of the heat resistance of the cured product of the photosensitive composition, it is preferable that the cationic polymerizable compound (A) contains a polymer backbone structure. Examples of polymer backbone structures include the main chain structures of polymers such as polyacrylic, polyphenol, polyamide, polyacid anhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazene, polysiloxane, polysilane, polystyrene, polysulfide, polysulfone, polyurethane, polyurea, and polyvinyl.

[0047] From the viewpoint of higher heat resistance of the cured product of the photosensitive composition, the cationic polymerizable compound (A) is preferably having a polysiloxane structure, more preferably a polymer having a polysiloxane structure in its main chain, and even more preferably a polymer having a cyclic polysiloxane structure in its main chain.

[0048] 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 higher the hardness and heat resistance of the cured layer of the photosensitive composition tends to be. On the other hand, the higher the content of (X3SiO), the higher the hardness and heat resistance of the cured layer of the photosensitive composition. 1 / 2 ), or D unit (X2SiO 2 / 2The higher the content of ), the more flexible the cured product of the photosensitive composition tends to be, and the lower the residual stress tends to be.

[0049] When the cationic polymerizable compound (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, more preferably 20,000 to 40,000, and even more preferably 25,000 to 35,000. When the weight-average molecular weight is 10,000 or more, the cured product of the photosensitive composition tends to have excellent heat resistance. On the other hand, when the weight-average molecular weight is 50,000 or less, the unexposed areas in the coating film of the photosensitive composition tend to be easily removed during development, and the patternability of the photosensitive rough material tends to be good.

[0050] A cationic polymerizable compound (A) having a polysiloxane structure can be obtained, for example, by a hydrosilylation reaction using the following compounds (α), (β), and (γ). Compounds (α), (β), and (γ) all have a SiH group (hydrosilyl group) or an ethylenically unsaturated double bond.

[0051] • Compound (α): A polysiloxane compound having at least two SiH groups in one molecule. • Compound (β): A compound having an ethylenically unsaturated double bond and a cationic polymerizable group in one molecule. • Compound (γ): A compound having an ethylenically unsaturated double bond and an alkali-soluble group in one molecule.

[0052] ·Compound (α) Compound (α) is a polysiloxane compound having at least two SiH groups in one molecule. For example, compound (α) can be a compound described in International Publication No. 96 / 15194 that has at least two SiH groups in one molecule. 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. Cyclic polysiloxanes having hydrosilyl groups may have a polycyclic structure. The polycyclic structure may also be a polyhedral structure. To form a cured product 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 of the cured product of the photosensitive composition, it is preferable that the group present on the Si atom is either a hydrogen atom or a methyl group.

[0053] 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.

[0054] Polysiloxanes having hydrosilyl groups at the molecular ends include polysiloxanes whose ends are sealed by dimethylhydrogensilyl groups, and dimethylhydrogensiloxane units (H(CH3)2SiO 1 / 2 (Units) and SiO 4 / 2 Unit, SiO 3 / 2 Units, and SiO 2 / 2 Examples include polysiloxanes, which consist of one or more siloxane units selected from a group of units.

[0055] A cyclic polysiloxane can be represented, for example, by the following formula (1). [ka]

[0056] In formula (1), R 1 , R 2 , and R 3 Each of these independently represents a monovalent organic group having 1 to 20 carbon atoms. m represents an integer from 2 to 10. n represents an integer from 0 to 10. In terms of ease of hydrosilylation reaction, m is preferably 3 or greater. In terms of ease of hydrosilylation reaction, m+n is preferably 3 to 12. In terms of even easier hydrosilylation reaction, n is preferably 0.

[0057] R 1 , R 2 , and R 3 As such, an organic group composed of elements selected from the group consisting of C, H, and O is preferred. 1 , R 2 , and R 3 Examples of organic groups include alkyl groups, cycloalkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, and -(R 01 -O)xR 02 Examples include the group represented by R, and aryl groups. 01 R is an alkylene group having 2 to 3 carbon atoms. 02 x is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. x is an integer of 2 or more, preferably 2 to 10.

[0058] R 1 , R 2 , and R 3 Preferred organic groups include chain alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, decyl, and dodecyl groups, cycloalkyl groups such as cyclohexyl and norbornyl groups, and phenyl groups. From the perspective of the availability of cyclic polysiloxanes, R 1 , R2 , and R 3 Preferred organic groups include linear alkyl groups having 1 to 6 carbon atoms, and phenyl groups. In terms of ease of hydrosilylation reaction, 1 , R 2 , and R 3 As for the organic group, a chain-like alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred.

[0059] Examples of cyclic polysiloxanes represented by formula (1) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Among these, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is preferred from the viewpoint of availability and the reactivity of the SiH group.

[0060] Compound (α) can be obtained by known synthesis methods. For example, a cyclic polysiloxane represented by formula (1) 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 methods described in, for example, Japanese Patent Publication No. 2004-359933, Japanese Patent Publication No. 2004-143449, and Japanese Patent Publication No. 2006-269402, etc. Alternatively, a commercially available polysiloxane compound may be used as compound (α).

[0061] ·Compound (β) Compound (β) is a compound having an ethylenically unsaturated double bond and a cationic polymerizable group in one molecule. The cationic polymerizable group is the same as the cationic polymerizable group described above for cationic polymerizable compound (A). That is, compound (β) preferably has an epoxy group as the cationic polymerizable group, more preferably an alicyclic epoxy group and / or a glycidyl group, and even more preferably an alicyclic epoxy group.

[0062] Compound (β) preferably has an ethylenically unsaturated alkenyl group. Suitable examples of alkenyl groups or alkenyl group-containing groups that compound (β) may have include vinyl group, allyl group, methallyl group, 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, and vinyl ether group. From the viewpoint of reactivity with SiH groups, compound (β) preferably has a vinyl group and / or an allyl group as the alkenyl group.

[0063] Specific examples of compound (β) include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, and monoallyl diglycidyl isocyanurate. From the viewpoint of cationic polymerizability, compounds having an alicyclic epoxy group are preferred as compound (β), and 1-vinyl-3,4-epoxycyclohexane is particularly preferred.

[0064] ·Compound (γ) Compound (γ) is a compound having an ethylenically unsaturated double bond and an alkali-soluble group in one molecule. The alkali-soluble group in compound (γ) is the same as the alkali-soluble group described above for cationic polymerizable compound (A). That is, compound (γ) preferably has one or more alkali-soluble groups selected from the group consisting of X1 groups, X2 groups, and phenolic hydroxyl groups, more preferably has X1 groups and / or X2 groups, and even more preferably has X2 groups.

[0065] Compound (γ) has an ethylenically unsaturated double bond. It is preferable that compound (γ) has an ethylenically unsaturated double bond as an alkenyl group. Examples of alkenyl groups are the same as those described above for compound (β). That is, it is preferable that compound (γ) has a vinyl group and / or an allyl group as the alkenyl group.

[0066] Specific examples of compound (γ) include diallyl isocyanurate, monoallyl isocyanurate, 2,2'-diallylbisphenol A, vinylphenol, and allylphenol. In terms of being able to more stably maintain the semi-cured state of the patterned resin film, the compound (γ) is preferably diallyl isocyanurate, monoallyl isocyanurate, and 2,2'-diallylbisphenol A, more preferably diallyl isocyanurate and monoallyl isocyanurate, and even more preferably diallyl isocyanurate.

[0067] • Other compounds In the hydrosilylation reaction, other compounds may be used in addition to the above-mentioned compounds (α), (β), and (γ). For example, other compounds that contain an alkenyl group, other than those described above (β) and (γ), may be used.

[0068] To obtain a cured product with excellent heat resistance, it is preferable to use a compound having two or more alkenyl groups in one molecule as the other compound mentioned above. Hereinafter, a compound having two or more alkenyl groups in one molecule will also be referred to as "compound (δ)". When compound (δ) is used, the number of crosslinking sites formed by the hydrosilylation reaction increases, which tends to improve the heat resistance of the cured product of the photosensitive composition.

[0069] 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.

[0070] In terms of heat resistance of the cured product of the photosensitive composition, diallyl monomethyl isocyanurate is preferred as compound (δ).

[0071] In order to suppress excessive reduction in the thickness of the resin film during development, it is preferable to use compound (ε), which is a compound having an alkenyl group and a (meth)acryloyl group in one molecule, as another compound. When compound (ε) is used, the (meth)acryloyl group is introduced into the cationic polymerizable compound (A), resulting in a relatively large number of reaction sites for radical polymerization. For this reason, the exposed, semi-cured resin film has high alkali resistance.

[0072] Specific examples of compound (ε) include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, 2-butenyl acrylate, and 2-butenyl methacrylate. Vinyl acrylate and / or allyl acrylate are preferred as compound (ε) because they are particularly effective in suppressing excessive reduction in the thickness of the resin film during development. Allyl acrylate is more preferred.

[0073] • Hydrosilylation reaction The method for carrying out the hydrosilylation reaction to obtain the cationic polymerizable compound (A) is not particularly limited. For example, a cationic polymerizable compound (A) having a polysiloxane structure can be obtained by carrying out the hydrosilylation reaction using the above-mentioned compound (α), compound (β), compound (γ), and other optional components in a manner consistent with the method described in International Publication No. 2009 / 075233. The cationic polymerizable compound (A) obtained using the above-mentioned compound (α), compound (β), compound (γ), and other optional components is, for example, a polymer having multiple cationic polymerizable groups and multiple alkali-soluble groups in one molecule, and having a polysiloxane structure in the main chain.

[0074] The proportions of each compound in the hydrosilylation reaction are not particularly limited, but it is preferable that the total number of moles A of ethylenically unsaturated double bonds in the compounds subjected to the hydrosilylation reaction and the total number of moles B of SiH groups in the compounds subjected to the hydrosilylation reaction satisfy 1 ≤ B / A ≤ 30, and more preferably 1 ≤ B / A ≤ 10.

[0075] In order to maintain a stable semi-cured state of the patterned resin film while improving the heat resistance of the cured product of the photosensitive composition, the charging ratio of compound (β) to compound (α) in the hydrosilylation reaction (mass of compound (β) / mass of compound (α)) is preferably 0.1 or more and 1.0 or less, and more preferably 0.2 or more and 0.9 or less.

[0076] To obtain a photosensitive composition with excellent patterning properties, the ratio of the amount of compound (γ) to the amount of compound (α) in the hydrosilylation reaction (mass of compound (γ) / mass of compound (α)) is preferably 0.1 or more and 0.9 or less, and more preferably 0.2 or more and 0.8 or less.

[0077] When compound (δ) is used, in terms of the high heat resistance of the cured photosensitive composition and the good patternability of the photosensitive composition, the ratio of the amount of compound (δ) to the amount of compound (α) in the hydrosilylation reaction (mass of compound (δ) / mass of compound (α)) is preferably 0.01 or more and 0.5 or less, and more preferably 0.05 or more and 0.4 or less.

[0078] When compound (ε) is used, in terms of good adhesion of the cured film formed by heating the patterned resin film and suppression of excessive reduction in the thickness of the resin film during development, the ratio of the amount of compound (ε) to the amount of compound (α) in the hydrosilylation reaction (mass of compound (ε) / mass of compound (α)) is preferably 0.1 or more and 0.5 or less, and more preferably 0.2 or more and 0.4 or less.

[0079] 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 (in moles) of hydrosilylation catalyst added is not particularly limited, but is preferably 10 / 8 to 10 / 1 times, and more preferably 10 / 6 to 10 / 2 times, relative to the number of moles of ethylenically unsaturated double bonds contained in the unsaturated compound subjected to the hydrosilylation reaction.

[0080] The reaction temperature for hydrosilylation can be set as appropriate. The reaction temperature is preferably 30°C to 200°C, and more preferably 50°C to 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.

[0081] A solvent may be used in the hydrosilylation reaction. The solvent may be used alone or in combination of two or more. Examples of 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, and chloroform are preferred because they are easily removed by distillation after the reaction.

[0082] In the hydrosilylation reaction, a gelation inhibitor may be used as needed.

[0083] (Radical polymerizable compound (B)) The radical polymerizable compound (B) is not particularly limited as long as it is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated double bond, and more preferably a (meth)acryloyl group. The (meth)acryloyl group is a general term for acryloyl groups and methacryloyl groups.

[0084] As described above, compounds having a (meth)acryloyl group are preferred as the radical polymerizable compound (B). Radical polymerizable compounds (B) having a (meth)acryloyl group are compounds having at least one of an acryloyl group and a methacryloyl group in one molecule.

[0085] Compounds having an acryloyl group are preferred as radical polymerizable compounds (B) because they exhibit high alkali resistance in the semi-cured exposed resin film and easily suppress excessive reduction in the film thickness of the resin film during development.

[0086] As the radical polymerizable compound (B), a compound having two or more (meth)acryloyl groups in one molecule is preferred, a compound having three or more (meth)acryloyl groups in one molecule is more preferred, and a compound having four or more (meth)acryloyl groups in one molecule is even more preferred.

[0087] In terms of suppressing excessive reduction in the thickness of the resin film during development, the radical polymerizable compound (B) is preferably a compound having two or more acryloyl groups in one molecule, more preferably a compound having three or more acryloyl groups in one molecule, and even more preferably a compound having four or more acryloyl groups in one molecule.

[0088] In terms of good adhesion of the cured film obtained by heating the patterned resin film, the number of (meth)acryloyl groups in one molecule of the radical polymerizable compound (B) is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less.

[0089] Examples of radical polymerizable compounds (B) having one (meth)acryloyl group in one molecule include 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, and tetrahydrofurfuryl (meth)acrylate.

[0090] Examples of radical polymerizable compounds (B) having two (meth)acryloyl groups in one molecule include triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. Specific examples of polypropylene glycol di(meth)acrylate include polypropylene glycol #700 diacrylate.

[0091] Examples of radical polymerizable compounds (B) having three (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin propoxy tri(meth)acrylate.

[0092] Examples of radical polymerizable compounds (B) having four (meth)acryloyl groups in one molecule include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate.

[0093] The radical polymerizable compound (B) may have cationic polymerizable groups. Furthermore, the radical polymerizable compound (B) may have alkali-soluble groups. However, in order to improve patternability and more stably maintain the semi-cured state of the patterned resin film, it is preferable that the photosensitive composition does not contain a compound having cationic polymerizable groups and alkali-soluble groups in a single molecule as the radical polymerizable compound (B). In other words, it is preferable that the radical polymerizable compound (B) is not a compound that has a cationic polymerizable group and an alkali-soluble group in one molecule.

[0094] The radical polymerizable compound (B) is preferably a compound having an isocyanuric ring and a (meth)acryloyl group in one molecule. When such a compound is used, the cohesive force of the patterned resin film is improved, and it is easier to suppress the cohesive failure of the patterned resin film during rework. By suppressing the cohesive failure of the patterned film, no residue remains on the second substrate, making it easier to reuse the second substrate.

[0095] (Photoradical polymerization initiator (C)) Component (C) is a photoradical polymerization initiator. In order to more stably maintain the semi-cured state of the patterned resin film made of the exposed photosensitive resin composition, the photoradical polymerization initiator (C) is preferably a compound that does not generate cations during the heat treatment until the semi-cured patterned resin film is formed, and more preferably a compound that does not generate cations even when heat-treated at a temperature of 200°C or less and for a heating time of 60 minutes or less.

[0096] Specific examples of photoradical polymerization initiators (C) 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. In order to more effectively suppress excessive reduction in the thickness of the resin film during development, it is preferable that the photoradical polymerization initiator (C) be one or more selected from the group consisting of acetophenone compounds, benzophenone compounds, and oxime ester compounds.

[0097] Examples of acetophenone compounds include 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4'-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2'-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-(4'-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4'-morpholinophenyl)butan-1-one, 1-hydroxycyclohexylphenyl ketone, and the like.

[0098] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0099] 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).

[0100] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0101] Examples of benzophenone compounds include benzyldimethyl ketone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0102] Examples of α-diketone compounds include methylbenzoylformate.

[0103] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'- Tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl 2,2'-Bimidazole, 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-Tetrakis(4-ethoxycarbonylphenyl)-1,2'-Bimidazole, 2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-Tetraphenyl-1,2'-Bimidazole, 2,2'-Bis(2,4,6-trichlorophenyl)-4,4',5,5'- Examples include tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0104] Examples of polynuclear quinone compounds include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1,4-naphthoquinone.

[0105] Examples of xanthone compounds include xanthone, thioxanthone, and 2-chlorothioxanthone.

[0106] Examples of triazine compounds include 1,3,5-tris(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-methoxyphenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, and 2-(2'-furylethylidene)-4,6-bis(trichloromethyl) Examples include 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(2'-thiophenylethylidene)-4,6-bis(trichloromethyl)-s-triazine.

[0107] In order to suppress an excessive reduction in the thickness of the resin film during development, the amount of the photoradical polymerization initiator (C) is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more, per 100 parts by mass of the radical polymerizable compound (B). Furthermore, in terms of good adhesion of the cured film obtained by heating the patterned resin film, the amount of photoradical polymerization initiator (C) is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the radical polymerizable compound (B).

[0108] (solvent) The photosensitive composition may contain a solvent. For example, a photosensitive composition can be obtained by dissolving or dispersing a cationic polymerizable compound (A), a radical polymerizable compound (B), a photoradical polymerization initiator (C), and other components as described later, in a solvent.

[0109] 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; and halogen solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. From the viewpoint of the coatability of the photosensitive composition, glycol solvents are preferred as solvents, and propylene glycol-1-monomethyl ether-2-acetate is more preferred.

[0110] From the viewpoint of the coatability of the photosensitive composition, the amount of solvent is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the cationic polymerizable compound (A).

[0111] (Other ingredients) The photosensitive composition may contain other components besides the cationic polymerizable compound (A), the radical polymerizable compound (B), and the photoradical polymerization initiator (C), as long as they do not impair the objectives and effects of the present invention.

[0112] However, in order to suppress an excessive decrease in the thickness of the resin film during development and to maintain a more stable semi-cured state of the patterned resin film, the total amount of the cationic polymerizable compound (A), the radical polymerizable compound (B), and the photoradical polymerization initiator (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more and 100% by mass or less, based on the total solid content of the photosensitive composition.

[0113] Other components include thermal cationic polymerization initiators, radical scavengers, colorants, sensitizers, fillers, adhesion modifiers, coupling agents such as silane coupling agents, degradation inhibitors, mold release agents, flame retardants, flame retardant aids, surfactants, defoamers, emulsifiers, leveling agents, anti-repellent agents, thixotropic agents, tackifiers, storage stability modifiers, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, thermal stabilizers, conductivity modifiers, antistatic agents, radiation shielding agents, nucleating agents, lubricants, metal deactivators, and thermal conductivity modifiers.

[0114] • Thermal cation polymerization initiator When a photosensitive composition contains a thermal cationic polymerization initiator as another component, the curing of the semi-cured patterned resin film by heating can be performed at a lower temperature than when the photosensitive composition does not contain a thermal cationic polymerization initiator. As a result, for example, degradation of the substrate due to heating can be suppressed. As a thermal cationic polymerization initiator, a compound exhibiting a thermal decomposition temperature higher than the bake temperature when forming a semi-cured patterned resin film or the heating temperature when performing rework after inspection is preferred, and a compound exhibiting a thermal decomposition temperature 5°C or more higher than the bake temperature when forming a semi-cured patterned resin film or the heating temperature when performing rework after inspection is more preferred.

[0115] However, in order to more stably maintain the semi-cured state of the patterned resin film, it is preferable that the photosensitive composition according to the embodiment does not contain a thermal cationic polymerization initiator. Even if the photosensitive composition according to the embodiment does not contain a thermal cationic polymerization initiator, cations are generated from, for example, alkali-soluble groups of component (A) by heating during the C-stage formation, so thermal curing of the patterned film is possible. Note that "thermal decomposition temperature" refers to the temperature at which the weight loss due to thermal decomposition of the thermal cationic polymerization initiator begins when the thermal gravimetric analysis of the thermal cationic polymerization initiator is performed using a differential thermogravimetric analyzer.

[0116] • Radical scavengers When a photosensitive composition contains a radical scavenger as another component, the diffusion of active radicals generated by light irradiation to unexposed areas is suppressed when the photosensitive composition is exposed to light. As a result, polymerization of the radical polymerizable compound (B) in the unexposed areas is suppressed, thereby reducing the generation of residue after development.

[0117] Examples of radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl, and bis-(2,2,6,6-tetramethylpiperidine-1-oxyl)-sebacate. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is preferred as a radical scavenger because it easily suppresses the generation of residue after development.

[0118] In order to suppress excessive reduction in the thickness of the resin film during development and to further suppress the generation of residue after development, the amount of radical scavenger is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.03 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of radical polymerizable compound (B).

[0119] • Colorants If the photosensitive composition contains a coloring agent as another component, the cured film made from the cured product of the photosensitive composition can be used, for example, as a light-shielding barrier to suppress flare and ghosting.

[0120] Examples of colorants include organic pigments, inorganic pigments, and dyes. From the viewpoint of heat resistance and colorability, it is preferable to use pigments as colorants. When forming a black colored pattern on a light-shielding partition or the like, it is preferable to use black pigment as the colorant. In addition to black patterns, other colored patterns include red patterns, yellow patterns, and blue patterns.

[0121] As pigments, those that absorb a wide range of wavelengths in the visible light region are preferred. Among pigments that absorb a wide range of wavelengths in the visible light region, examples of black organic pigments include anthraquinone-based black pigments, perylene-based black pigments, azo-based black pigments, and lactam-based black pigments. Among these, perylene-based black pigments and lactam-based black pigments are preferred due to their excellent light-shielding properties. Examples of black inorganic pigments include carbon black and black lower-order titanium oxynitride. Examples of other inorganic pigments include composite metal oxide pigments, titanium dioxide, 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, and magnesium carbonate. Examples of dyes include azo compounds, anthraquinone compounds, perylene compounds, perinone compounds, phthalocyanine compounds, carbonium compounds, and indigoid compounds.

[0122] Pigments used to obtain coloring patterns other than black include red, orange, yellow, green, and blue. Chromatic pigments such as purple, cyanine, or magenta can be used. Two or more of these pigments may be used in combination.

[0123] To further suppress flare and ghosting, black inorganic pigments are preferred as colorants, and carbon black is more preferred.

[0124] In order to obtain a photosensitive composition with excellent photopolymerization properties while suppressing the generation of residue, flare, and ghosting after development, the amount of colorant is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 7 parts by mass or less, and even more preferably 0.3 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of cationic polymerizable compound (A).

[0125] In order to suppress excessive reduction in the thickness of the resin film during development, to maintain a more stable semi-cured state of the pattern film, and to improve the adhesion of the cured film to the first and second substrates, the photosensitive composition preferably satisfies the following condition 1, more preferably satisfies the following condition 2, even more preferably satisfies the following condition 3, and even more preferably satisfies the following condition 4.

[0126] Condition 1: The cationic polymerizable compound (A) has a polysiloxane structure, and the amount of the radical polymerizable compound (B) is 10 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the cationic polymerizable compound (A). Condition 2: The above condition 1 is satisfied, and the cationic polymerizable compound (A) has an alicyclic epoxy group as a cationic polymerizable group. Condition 3: The above condition 2 is satisfied, and the cationic polymerizable compound (A) has X2 groups as alkali-soluble groups. Condition 4: The above condition 3 is satisfied, and the radical polymerizable compound (B) is a compound having two or more acryloyl groups in one molecule.

[0127] <Manufacturing of Pre-Laminates> By bonding the second substrate to a patterned resin film on the first substrate, a precursor laminate in which the first substrate and the second substrate are temporarily fixed is manufactured. When bonding the second substrate to the patterned resin film on the first substrate, a load in the range of 0.1 kg to 5 kg may be applied. Furthermore, the second substrate may be bonded to the patterned resin film on the first substrate while heating at a temperature within the range where the patterned resin film does not harden. The heating temperature is, for example, 60°C to 150°C.

[0128] <Test> The resulting precursor laminate is then inspected for various defects. During the inspection, for example, it is checked for misalignment of the first and second substrates in the precursor laminate, as well as for the presence of foreign matter or scratches on the first and second substrates. Based on the above inspection, the precursor laminates are sorted into acceptable and unacceptable products.

[0129] The approved prototype laminate is heated to cure the resin film. The curing of the resin film produces a substrate laminate in which the first substrate and the second substrate are firmly bonded together. The temperature at which the precursor laminate containing the resin film is heated is preferably above 150°C, and more preferably above 180°C. The upper limit of the heating temperature is preferably 300°C or less, and more preferably 250°C or less.

[0130] In a substrate laminate in which the first substrate and the second substrate are fixed together, the die shear strength between the cured resin film and the second substrate is 1.5 kgf / mm² at 23°C. 2 The above is the result, and at 100°C, it is 1.2 kgf / mm². 2 That's all. The die shear strength between the cured resin film and the second substrate is measured by the methods including I) and II) below. I) To obtain a die-shear strength measurement precursor laminate containing a cured resin film by heating the die-shear strength measurement precursor laminate used for measuring die-shear strength between the resin film and the second substrate at 200°C for 2 hours to cure the resin film, and II) In the precursor laminate for die shear strength measurement, which includes a resin film cured at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the cured resin film in the precursor laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force when the first substrate and the second substrate delaminate is measured as the die shear strength. More specifically, the die-shear strength between the cured resin film and the second substrate is measured by the method described later in the examples.

[0131] There is no particular upper limit to the die shear strength at 23°C, but for example, 15.0 kgf / mm². 2 The following is preferable: 12.0 kgf / mm² 2 The following are preferable. There is no particular upper limit to the die shear strength at 100°C, but for example, 15.0 kgf / mm² 2 The following is preferable: 10.0 kgf / mm 2 The following are preferable. The die shear strength at 23°C is 1.7 kgf / mm². 2 The above is preferable, 2 kgf / mm 2 The above is more preferable. The die shear strength at 100°C is 1.4 kgf / mm². 2 The above is preferable, and 1.6 kgf / mm 2 The above is preferable.

[0132] The rejected precursor laminates are heated to a temperature of 50°C to 150°C. The heating temperature is preferably 50°C to 140°C, more preferably 50°C to 120°C, and even more preferably 50°C to 100°C. Heating softens the patterned resin film, reducing the die-shear strength between the resin film and the second substrate. As a result, the second substrate can be easily peeled off from the resin film.

[0133] The second substrate, recovered after delamination, is washed with pure water or organic solvents as needed, and then reused in the manufacture of substrate laminates.

[0134] The first substrate, recovered after peeling, still has the patterned resin film on it. When reusing the first substrate, it may be possible to reuse the first substrate with the patterned resin film, but it is preferable to remove the patterned resin film from the first substrate. The patterned resin film is removed from the first substrate by, for example, a treatment using an organic solvent or a basic or acidic chemical solution. [Examples]

[0135] The following describes embodiments of the present invention. The present invention is not limited to the following embodiments.

[0136] <Synthesis of cationic polymerizable compounds> The synthesis methods for cationic polymerizable compounds A1 and A2 are described below. The weight-average molecular weights of cationic polymerizable compounds A1 and A2 were calculated from chromatograms obtained using Tosoh Corporation's "HLC-8420GPC" (columns: Shodex GPC KD-G 4A (1) and Shodex GPC KD-806M (1)) with N,N-dimethylformamide as the solvent at a flow rate of 1.0 mL / min, and converted to standard polystyrene equivalents.

[0137] [Synthesis of cationic polymerizable compound A1] To a mixture of 40 g of diallyl isocyanurate, 29 g of diallyl monomethyl isocyanurate, and 264 g of 1,4-dioxane, 143 μL of a xylene solution of platinum vinylsiloxane complex (Pt-VTSC-3X, manufactured by Yumicore Precious Metals Japan, containing 3% by mass of platinum) was added to obtain solution S1. In addition, 88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 176 g of toluene to obtain solution S2.

[0138] Then, under a nitrogen atmosphere containing 3% by volume of oxygen, solution S1 was added dropwise over 3 hours to solution S2, which had been heated to 105°C. After the dropwise addition was complete, the reaction mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S3. Note that the alkenyl groups of the compounds contained in the obtained solution S3 1 The reaction rate, as determined by measurement using 1H-NMR, was over 95%.

[0139] In addition, solution S4 was obtained by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene.

[0140] 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 reaction mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S5. Note that the alkenyl groups of the compounds contained in the obtained solution S5 1 The reaction rate, as determined by measurement using 1H-NMR, was over 95%.

[0141] Next, the solvent was removed from solution S5 under reduced pressure to obtain a solid residue. Then, propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was added to the obtained solid to obtain solution SA1 containing cationic polymerizable compound A1. The concentration of cationic polymerizable compound A1 in solution SA1 was 70% by mass. Cationic polymerizable compound A1 was a polymer having multiple cationic polymerizable groups and multiple alkali-soluble groups in one molecule, and having a cyclic polysiloxane structure in its main chain. Specifically, the cationic polymerizable groups were alicyclic epoxy groups, namely 3,4-epoxycyclohexyl groups. The alkali-soluble groups were the aforementioned X2 groups. The weight-average molecular weight of the polymer having a cyclic polysiloxane structure was 30,000. Furthermore, the cationic polymerizable compound A1 was alkali-soluble and organic solvent-soluble.

[0142] [Synthesis of cationic polymerizable compound A2] Solution SA2 containing cationic polymerizable compound A2 was obtained by the same method as the synthesis of cationic polymerizable compound A1, except that solution S4 was obtained by dissolving 31 g of 1-vinyl-3,4-epoxycyclohexane and 28 g of allyl acrylate in 59 g of toluene. The concentration of cationic polymerizable compound A2 in solution SA1 was 70% by mass. Cationic polymerizable compound A2 was a polymer having multiple cationic polymerizable groups, multiple alkali-soluble groups, and multiple radical polymerizable groups in one molecule, and having a cyclic polysiloxane structure in its main chain. Specifically, the cationic polymerizable group was the alicyclic epoxy group 3,4-epoxycyclohexyl group. The alkali-soluble group was the aforementioned X2 group. The radical polymerizable group was the acryloyl group. The weight-average molecular weight of the polymer having the cyclic polysiloxane structure was 30,000. Furthermore, the cationic polymerizable compound A2 was alkali-soluble and organic solvent-soluble.

[0143] <Preparing other materials> In addition to the above-mentioned solutions SA1 and SA2, the following materials were prepared as materials for the photosensitive composition. Furthermore, all of the photoradical polymerization initiators described below were compounds that did not generate cations when heat-treated in the <formation of patterned resin films> described later.

[0144] (Cationically polymerizable compound (A)) jER1001: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) Ceroxide (registered trademark) 2021P: 3',4'-Epoxycyclohexylmethyl-3,4-Epoxycyclohexanecarboxylate (manufactured by Daicel Corporation)

[0145] (Radical polymerizable compound (B)) AD-TMP: Ditrimethylolpropanetetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) A9300: Tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Ebecryl 8402:2 Functional Aliphatic Urethane Acrylate (manufactured by Daicel Ornex Co., Ltd.)

[0146] (Photoradical polymerization initiator (C)) Omnirad® 651: Benzophenone compound (manufactured by BASF)

[0147] (Photocationic polymerization initiator) CPI-210S: Aromatic sulfonium salt compound (manufactured by Sunapro Co., Ltd.)

[0148] (Radical scavenger) H-TEMPO:4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Evonik)

[0149] <Preparation of photosensitive composition> Each material listed in Table 1 was mixed in the amounts specified in Table 1 to obtain the photosensitive compositions used in Examples 1-4 and Comparative Examples 1-3.

[0150] <Formation of patterned resin film> Each photosensitive composition listed in Table 1 was applied to a glass plate, which served as a glass substrate, using a spin coater, so that the thickness of the coating after pre-baking was 50 μm. The glass substrate was pre-baked by heating it on a hot plate at 85°C for 10 minutes, followed by heating it at 120°C for 10 minutes, to obtain a glass substrate with a coating.

[0151] 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 3000 mJ / cm². 2 The coating film on the glass substrate was exposed under the following conditions.

[0152] The exposed coating was left for 1 minute in an atmosphere at 25°C, and then immersed for 60 seconds in an aqueous TMAH solution (TMAH concentration: 2.38% by mass) as an alkaline developer. Next, the coating film, which had been immersed in an alkaline developer, was washed with water for 30 seconds, and then the surface moisture was removed with compressed air to obtain a glass substrate with a semi-cured, patterned resin film.

[0153] Using the glass substrate equipped with the obtained patterned resin film, the reworkability and bonding properties were evaluated according to the method described later.

[0154] <Measurement of die shear strength> • Die shear strength of a semi-cured resin film First, a 50 μm thick semi-cured resin film was fabricated on a 0.5 mm thick glass substrate (first substrate) using the same method as for forming the patterned resin film described above, except that a photomask was not used and development was not performed. The semi-cured resin film covered the entire surface of one main surface of the glass substrate. Subsequently, a 2mm x 2mm test piece was cut from a glass substrate having a semi-cured resin film on one of its main surfaces. Next, while heating the alumina ceramic substrate (second substrate) to 80°C, a 2 kg weight was placed on the alumina ceramic substrate for 30 seconds, and the glass substrate was attached to the alumina ceramic substrate via a semi-cured resin film to obtain a precursor laminate for die shear strength measurement.

[0155] Using the obtained precursor laminate, the die shear strength of the alumina ceramic substrate against the semi-cured resin film was measured at 23°C and 100°C under the following conditions. Shear force was applied to the interface between the alumina ceramic substrate and the semi-cured resin film in the precursor laminate by sliding the glass substrate at a constant speed along the planar direction of the substrate. Measurement device: Bond tester (DAGE, 4000Plus) Share speed: 0.1 μm / sec

[0156] • Die shear strength against hardened film A precursor laminate for measuring the die shear strength of a semi-cured resin film was heated in a 200°C oven for 2 hours to cure the resin film, thereby obtaining a laminate in which the glass substrate and the alumina ceramic substrate were fixed via the cured film. Using the obtained laminate, the die shear strength of the patterned cured film was measured in the same manner as when measuring the die shear strength of a semi-cured resin film.

[0157] The measured die shear strengths obtained are shown in Table 1.

[0158] (Evaluation of reworkability) Following the aforementioned method for forming a patterned resin film, a lattice-like, semi-cured resin film with a thickness of 50 μm (vertical direction: line / space = 50 μm / 50 μm, horizontal direction: line / space = 100 μm / 100 μm) was formed on a glass substrate measuring 10 mm in length, 10 mm in width, and 0.5 mm in thickness. Next, an alumina ceramic substrate measuring 50 mm in length, 50 mm in width, and 2 mm in thickness was heated to 80°C, and a 2 kg weight was placed on the alumina ceramic substrate for 30 seconds. A glass substrate was then attached to the alumina ceramic substrate via a semi-cured resin film to obtain a precursor laminate. The resulting pre-laminate was heated on a 100°C hot plate for 30 seconds, and its reworkability was evaluated using a spatula, a jig to rotate the glass substrate, and a jig to slide the glass substrate. In Example 1, Example 3, and Comparative Example 2, evaluation was performed only using the spatula method.

[0159] In the method using a spatula, while fixing the precursor laminate, the spatula was inserted between the glass substrate and the alumina ceramic substrate from the side parallel to the vertical pattern of the resin film in the precursor laminate, thereby peeling the alumina ceramic substrate from the resin film. In a method of rotating a glass substrate with a jig, the glass substrate was rotated while the alumina ceramic substrate was fixed, such that the axis of rotation was a straight line passing through the center of gravity of the main surface of the precursor laminate and perpendicular to the surface direction of the main surface of the precursor laminate, thereby peeling the alumina ceramic substrate from the resin film. In the method of sliding the glass substrate with a jig, the alumina ceramic substrate was separated from the resin film by fixing the glass substrate in place and moving the jig along the edges parallel to the vertical pattern of the resin film and in a direction aligned with the surface of the substrate.

[0160] The evaluation criteria for reworkability are as follows. A and B are considered acceptable. The results of the reworkability evaluation are shown in Table 1. Note that, as will be explained later, the glass substrate and the alumina ceramic substrate could not be properly bonded, so reworkability was not evaluated for Comparative Example 3. A: The alumina ceramic substrate can be peeled off the resin film, and the resin film does not adhere to the alumina ceramic substrate. B: The alumina ceramic substrate can be peeled off the resin film, and a small amount of the resin film adheres to the alumina ceramic substrate. C: The alumina ceramic substrate cannot be peeled from the resin film, or the alumina ceramic substrate can be peeled from the resin film, but a large amount of the resin film adheres to the alumina ceramic substrate.

[0161] (Evaluation of bonding properties) A precursor laminate was obtained using the same method as for evaluating reworkability. The obtained precursor laminate was visually inspected, and the adhesion between the alumina ceramic substrate and the resin film was evaluated according to the following criteria. A and B are considered acceptable. The results of the bonding evaluation are shown in Table 1. A: There is no delamination across the entire outer periphery of the precursor laminate, and the alumina ceramic substrate and the resin film are well bonded together. B: Some delamination is observed on the outer periphery of the precursor laminate, but the alumina ceramic substrate and the resin film are bonded together without any problems. C: Delamination is observed in most of the outer periphery of the precursor laminate, or the alumina ceramic substrate and the resin film are not bonded together.

[0162] [Table 1]

[0163] According to Examples 1-4, Formation of a patterned resin film on one main surface of a glass substrate as the first substrate, The manufacturing of a precursor laminate in which the first substrate and the second substrate are temporarily fixed by bonding an alumina ceramic substrate as the second substrate to a patterned resin film on the first substrate, Inspection of the aforementioned precursor laminate, In a method including, The die shear strength between the resin film and the second substrate in the precursor laminate is 0.8 kgf / mm² at 23°C. 2 The above is the result, and at 100℃, it is 0.005 kgf / mm 2 The above is 0.1 kgf / mm². 2 The following conditions indicate that by heating the precursor laminate to a temperature between 50°C and 150°C, the second substrate can be easily peeled from the resin film, enabling successful rework. Furthermore, in Examples 1 to 4, since the resin film can be cured by heating at temperatures above 150°C, the patterned resin film hardens, and the first substrate and the second substrate are firmly bonded together by the cured film.

[0164] According to Comparative Examples 1-3, the die shear strength between the resin film and the second substrate was 0.8 kgf / mm² at 23°C. 2 The above is the result, and at 100℃, it is 0.005 kgf / mm 2 The above is 0.1 kgf / mm². 2 If the following conditions are not met, it will be found that the second substrate cannot be properly peeled off from the resin film even if the precursor laminate is heated to a temperature between 50°C and 150°C.

Claims

1. A method for manufacturing a substrate laminate for a solid-state image sensor, The manufacturing method involves forming a patterned resin film on one main surface of the first substrate, Manufacturing a preliminary laminate in which the first substrate and the second substrate are temporarily fixed by bonding the second substrate to the patterned resin film on the first substrate, Inspection of the aforementioned precursor laminate, Includes, The die shear strength between the resin film and the second substrate in the aforementioned precursor laminate is 0.8 kgf / mm at 23°C. ２ The above is true, and at 100°C, the reading is 0.005 kgf / mm². ２ The above is 0.1 kgf / mm². ２ The following: The die shear strength between the resin film and the second substrate is as follows: 1) to 3) 1) To obtain a laminate consisting of an unpatterned resin film made of the same material as the patterned resin film, with dimensions of 2 mm in length, 2 mm in width, and 50 μm in thickness, and a first substrate with dimensions of 2 mm in length, 2 mm in width, and 2) With the unpatterned resin film obtained in 1) in contact with the second substrate heated to 80°C, a 2 kg weight is placed on the second substrate for 30 seconds, thereby bonding the first substrate to the second substrate via the unpatterned resin film to obtain a precursor laminate for die shear strength measurement, and 3) In the precursor laminate for die shear strength measurement obtained at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the unpatterned resin film in the precursor laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force when the first substrate and the second substrate delaminate is measured as the die shear strength. Measured by a method including, The aforementioned resin film can be cured by heating at temperatures exceeding 150°C. If the inspection is successful, the precursor laminate is heated to cure the resin film, thereby manufacturing the substrate laminate in which the first substrate and the second substrate are fixed together. A manufacturing method comprising: if the result of the inspection is unsatisfactory and at least one of the first substrate and the second substrate is reusable, heating the precursor laminate to a temperature of 50°C to 150°C to peel the second substrate from the resin film, thereby recovering the first substrate and the second substrate, and reusing at least one of the recovered first substrate and the second substrate in the manufacture of the precursor laminate.

2. The method for manufacturing a substrate laminate according to claim 1, wherein the resin film is made of an exposed photosensitive composition.

3. The method for producing a substrate laminate according to claim 2, wherein the photosensitive composition comprises a radical polymerizable compound, a cationic polymerizable compound, and a photoradical polymerization initiator.

4. The first substrate described above is a glass substrate, The method for manufacturing a substrate laminate according to any one of claims 1 to 3, wherein the second substrate is a substrate on which semiconductor elements are mounted.

5. The method for manufacturing a substrate laminate according to claim 4, wherein the second substrate is a ceramic substrate on which semiconductor elements are mounted.

6. If the result of the aforementioned inspection is satisfactory, A method for manufacturing a substrate laminate according to any one of claims 1 to 3, wherein the substrate laminate is heated to 180°C or higher to cure the resin film, thereby fixing the first substrate and the second substrate together.

7. In the substrate laminate in which the first substrate and the second substrate are fixed together, the die shear strength between the cured resin film and the second substrate is 1.5 kgf / mm at 23°C. ２ The above is the result, and at 100°C, it is 1.2 kgf / mm². ２ That's all. The die shear strength between the cured resin film and the second substrate is as follows: I) and II): I) To obtain a die-shear strength measurement precursor laminate containing the cured resin film, which was used to measure the die-shear strength between the resin film and the second substrate, by heating the precursor laminate for die-shear strength measurement at 200°C for 2 hours to cure the resin film, and II) In the precursor laminate for die shear strength measurement, which includes the resin film cured at 23°C and 100°C, a shear force is applied to the interface between the second substrate and the cured resin film in the precursor laminate for die shear strength measurement by shifting the first substrate along the planar direction of the first substrate at a constant speed of 0.1 μm / second, and the shear force at which the first substrate and the second substrate delaminate is measured as the die shear strength. A method for manufacturing a substrate laminate according to any one of claims 1 to 3, which is measured by a method including the following:

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