Adhesive layer forming composition, laminate, method for manufacturing laminate and treating method for laminate

Abstract

The present invention provides a composition for forming an adhesive layer that is easy to peel off from the adherend by 355nm laser irradiation and has good adhesion and solvent resistance to the adhesive layer. This invention relates to a composition for forming an adhesive layer, which is used to form an adhesive layer that "bonds a support to an adherend, and the support to the adherend can be separated by light irradiation". The composition comprises (A) a polymeric compound containing unsaturated groups, (B) an ultraviolet absorber, and (F) a solvent; the content of the ultraviolet absorber (B) is 10% by mass or more and 80% by mass or less relative to the total mass of the solid components.

Description

[Technical Field]

[0001] This invention relates to a composition for forming an adhesive layer, a laminate, a method for manufacturing the laminate, and a method for processing the laminate. [Previous Technology]

[0002] (Regarding the prior art disclosed in section 1)

[0002] In recent years, with the increasing functionality of digital machines, the flexible displays and semiconductor chips that are mounted on them are becoming thinner. However, it is difficult to transport the flexible displays and semiconductor chips, which have reduced strength due to thinning, using conventional automated transport methods.

[0003] Therefore, a method for safely and easily transporting thinned flexible displays and semiconductor wafers has been studied. For example, a laminate on which a flexible display and semiconductor wafer are fixed is formed by passing an adhesive layer through a light-transmitting support such as a glass substrate, and a method for transporting the entire laminate, namely the aforementioned flexible display and semiconductor wafer, has been studied. In this case, the adhesive layer is sometimes made of a composition that deteriorates or decomposes when exposed to light, resulting in reduced adhesion. If the aforementioned adhesive layer is used, after transport, the adhered material can be separated (peeled off) from the support by irradiating the adhesive layer from the support side, and transferred to, for example, other substrates (laser stripping process, hereinafter also referred to as "LLO process").

[0004] Regarding the composition of the adhesive used to enable the LLO process, Patent Document 1 describes a composition in which a curable resin with a 9,9'-diphenyl tannin (Cardo structure) structure and unsaturated groups is dissolved in a solvent. Patent Document 1 describes an adhesive layer formed by applying this composition to a glass support and heating it; the glass support can be easily peeled off from the substrate by irradiation with a laser having a wavelength of 308 nm. Furthermore, Patent Document 1 describes an adhesive layer formed by applying a composition in which a resin with a benzotriazole structure is dissolved in a solvent to a glass support and heating it; the glass support can be easily peeled off from the substrate by irradiation with a laser having a wavelength of 355 nm.

[0005] Furthermore, regarding the composition of the adhesive described above, Patent Document 2 discloses a photosensitive composition comprising: a curable resin containing a Cardo structure and unsaturated groups, a photopolymerizable monomer, and a light absorber (carbon black). Patent Document 2 also discloses that the photosensitive composition, when coated onto a glass support and heated to form a hardened film, exhibits excellent adhesion to the substrate.

[0006] (Regarding the prior art disclosed in section 2)

[0006] Furthermore, in imaging devices such as digital cameras and mobile phones with cameras, solid-state imaging elements such as CCD (charge-coupled device) image sensors or CMOS (complementary metal-oxide semiconductor) image sensors are already incorporated. These image sensors, designed to improve light concentration, have fine condensing lenses (microlenses). In recent years, there has been a demand for high pixel density, high sensitivity, and miniaturization in these image sensors, and materials for microlenses corresponding to these requirements have been developed.

[0007] For example, Patent Document 3 discloses a resin composition used for forming microlens patterns, which includes an alkali-soluble resin with a glass transition temperature (Tg) of 70°C or lower and a photosensitizer. According to Patent Document 3, the above-mentioned resin composition can form fine dot patterns even by using a low-temperature (60 to 100°C) heat flow. Patent Document 3 also describes that the above-mentioned resin composition can form microlens patterns by removing the positive pattern of the exposed portion.

[0008] Furthermore, Patent Document 4 discloses a silicone resin composition comprising a silicone resin, metal-containing particles, and a polymeric compound having ethylene-unsaturated double bonds. According to Patent Document 4, the silicone resin composition maintains a high refractive index in its cured form and improves lightfastness by setting the ratio of Ti to Zr in the metal-containing particles within a specific range. Patent Document 4 also describes how the silicone resin composition can form a microlens pattern by removing a negative pattern from the unexposed areas.

[0008] [Previous Technical Documents]

[0008] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2012-106486

[0009] [Patent Document 2] Japanese Patent Application Publication No. 2018-001604

[0009] [Patent Document 3] Japanese Patent Application Publication No. 2020-100793

[0009] [Patent Document 4] Japanese Patent Application Publication No. 2019-173016

[0010] (Topic 1)

[0010] Previously, the development of adhesives used in LLO processes focused on compositions capable of producing the peeling of adherends using high-energy, high-processability short-wavelength lasers (wavelengths such as 248nm and 266nm). However, processing with lasers at these wavelengths requires the use of supports made of expensive materials such as quartz glass or sapphire substrates with high transmittance in the short-wavelength region. Therefore, conventional LLO processes suffer from increased operating costs. Thus, in order to allow the use of cheaper transparent glass, there is a demand for the development of an adhesive layer capable of peeling off adherends using longer-wavelength lasers (e.g., 355nm).

[0011] However, conventionally known adhesive compositions have high transmittance at 355 nm, making it difficult to peel off the adhered body by laser irradiation. Furthermore, although Patent Document 1 describes a composition that can peel off the adhered body by irradiation with a 355 nm laser, according to the inventors' knowledge, such compositions have problems such as low adhesion strength of the adhered body to the adhesive layer or low solvent resistance of the hardened film.

[0012] The invention disclosed in the first part of this specification is constructed in view of the following points, and aims to provide an adhesive layer forming composition that is easy to peel off the adherend by 355nm laser irradiation and has good adhesion and solvent resistance of the adherend to the adhesive layer; a laminate formed by bonding a support and an adherend using the adhesive layer forming composition; and a method for manufacturing and processing the laminate.

[0013] One aspect of the present invention for solving the problem disclosed in the first paragraph above relates to an adhesive layer forming composition for forming an adhesive layer that "adheres a support and an adherend, and the support and the adherend can be separated by light irradiation". The composition comprises (A) a polymeric compound containing an unsaturated group, (B) an ultraviolet absorber, and (F) a solvent, wherein the content of the ultraviolet absorber (B) is 10% by mass or more and 80% by mass or less relative to the total mass of the solid components.

[0014] Another aspect of the present invention for solving the problem disclosed in the first paragraph above relates to a laminate having a support, an adhesive body, and an adhesive layer comprising a hardened composition for forming an adhesive layer disposed between the support and the adhesive body.

[0015] Another aspect of the present invention for solving the problem disclosed in the first paragraph above relates to a method for manufacturing a laminate, which includes the following steps: applying an adhesive layer to the surface of at least one of a support and an adherend to form an adhesive layer by applying the aforementioned adhesive layer forming composition, and passing the aforementioned support and the aforementioned adherend through the aforementioned formed adhesive layer.

[0016] Another aspect of the present invention for solving the problem disclosed in the first paragraph above relates to a method for processing a laminate, which includes the following steps: preparing the laminate and irradiating the adhesive layer with light to separate the support from the adhered body.

[0017] Another aspect of the present invention for solving the problem disclosed in the second paragraph above relates to a solid-state imaging element having the microlens described above.

[0018] Another aspect of the present invention for solving the problem disclosed in the second paragraph above relates to an imaging device having the solid-state imaging element described above.

[0019] According to the invention disclosed in the first part of this specification, it is possible to provide an adhesive layer forming composition that is easy to peel off by irradiation with a 355nm laser, and has good adhesion and solvent resistance to the adhesive layer; a laminate formed by bonding a support and an adhesive layer using the adhesive layer forming composition; and a method for manufacturing and processing the laminate.

[0020] According to the invention disclosed in section 2 of this specification, a microlens forming composition with a limited amount of resin that is easy to use and does not easily produce residue during development can be provided, a method for manufacturing a microlens using the composition, a hardened film formed by hardening the composition, a solid image element having the microlens, and an imaging device having the solid image element.

Implementation Method

[0021] Hereinafter, although embodiments of the present invention are described, the present invention is not limited to these embodiments. Furthermore, in the present invention, when the first decimal place of the content of each component is 0, the decimal point and subsequent fractions may be omitted. Also, unless otherwise specified, in the examples exemplified herein, only one type of compound, functional group, or structure may be used, or multiple types may be used together.

[0022] The first disclosure in this specification, which addresses the aforementioned problem 1, relates to a curable adhesive layer forming composition comprising:

[0022] (A) Polymer compounds containing unsaturated groups,

[0022] (B) Ultraviolet absorber, and

[0022] (F) Solvent,

[0022] Among them, relative to the total mass of the solid components, (B) the content of the ultraviolet absorber is more than 10% by mass and less than 80% by mass.

[0023] Furthermore, the second disclosure in this specification, which addresses the second issue described below, relates to a composition for forming a microlens, comprising:

[0023] (A1) Belongs to the category of alkali-soluble resins containing unsaturated groups and polymeric compounds.

[0023] (A2) Polymer compounds containing unsaturated groups that do not contain alkali-soluble groups.

[0023] (B) Ultraviolet absorber,

[0023] (C) Epoxy compounds having two or more epoxy groups,

[0023] (D) Photopolymerization initiator, and

[0023] (F) Solvent,

[0023] Among them, relative to the total mass of the solid components, the content of (B) ultraviolet absorber is more than 3% by mass and less than 20% by mass.

[0024] Since these components use common materials, the materials used will be described first, and then the preferred form of each component using the materials will be described.

[0025] 1. Materials

[0025] 1-1.(A) Polymers containing unsaturated groups

[0025] (A) A polymeric compound containing an unsaturated group (hereinafter referred to only as "(A) component") is a compound that has a polymeric unsaturated group and undergoes a polymerization reaction and hardening by stimulation such as heat and light.

[0026] (A) The components improve the adhesion and solvent resistance of the hardened film formed by hardening the individual components to the adherend or substrate.

[0027] (A) The component can be any component that can ensure adhesion to the adherend or substrate and solvent resistance. It can be a known polymeric compound containing unsaturated groups, such as an alkali-soluble resin or an acrylic resin.

[0028] (A) The components are broadly classified into (A1) components belonging to alkali-soluble resins and (A2) components belonging to other polymeric compounds containing unsaturated groups that do not have alkali-soluble groups.

[0029] The alkali-soluble resin belonging to component (A1) preferably has a polymerizable unsaturated group (preferably (meth)acrylic acid group) and an acidic group (alkali-soluble group) for exhibiting alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. There are no particular limitations as long as the resin is as described above, and it can be widely used. Because the above-mentioned alkali-soluble resin has both a polymerizable unsaturated group and a carboxyl group, when patterning individual components, it not only imparts excellent photocuring properties but also good developability and patterning characteristics.

[0030] Regarding the alkali-soluble resin belonging to component (A1) of this embodiment, it is preferably an alkali-soluble resin containing polymerizable unsaturated groups obtained by reacting an epoxy compound having two or more epoxy groups with a reactant of (meth)acrylic acid and then with a polyprotic acid carboxylic acid or its anhydride. When manufacturing the above-mentioned alkali-soluble resin, a polyester is generated by reacting hydroxyl groups with a polyprotic acid carboxylic acid, but a low molecular weight with an average degree of polymerization of approximately 2 to 500 is preferred. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth)acrylyl" is a general term for acrylyl and methacrylyl, meaning one or both of these.

[0031] Preferably, the above-mentioned epoxy compound is an epoxy compound having two or more epoxy groups. Examples of such epoxy compounds include: bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fusiform type epoxy compounds, phenolic varnish type epoxy compounds, cresol phenolic varnish type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenolic aryl alkyl type epoxy compounds, phenolic varnish compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Co., Ltd.), naphthol aryl alkyl type epoxy compounds, phenolic methane type epoxy compounds, tetraphenolic ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of monomers containing (meth)acrylic acid groups as units, represented by copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide). 2021P: manufactured by DAICL Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., Epolead GT401: manufactured by DAICL Corporation), epoxy compounds with epoxy cyclohexyl groups, represented by HiREM-1 manufactured by Shikoku Chemical Industry Co., Ltd., multifunctional epoxy compounds with a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-epoxyethoxy)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by DAICL Corporation), epoxidized polybutadiene (e.g., NISSO-PB‧JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds with a polysiloxane skeleton, etc.

[0032] The alkali-soluble resin belonging to component (A1) is preferably an acrylic copolymer.

[0033] In the example of acrylic copolymers, there are copolymers of (meth)acrylic acid, (meth)acrylate, etc., and include resins having (meth)acrylic acid groups and carboxyl groups. In the above-mentioned resin examples, there are: copolymers obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent, and alkali-soluble resins containing polymerizable unsaturated groups obtained by reacting (meth)acrylic acid with an anhydride of dicarboxylic acid or tricarboxylic acid. The copolymers mentioned above can be referenced to the copolymers shown in Japanese Patent Application Publication No. 2014-111722, which are composed of 20 to 90 mol% repeating units derived from glycerol ester, with the hydroxyl groups at both ends esterified by (meth)acrylic acid, and 10 to 80 mol% repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized therewith, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g; and the alkali-soluble resin containing polymerizable unsaturated groups shown in Japanese Patent Application Publication No. 2018-141968, which is a polymer containing units derived from (meth)acrylic acid compounds and units having (meth)acrylic acid groups and di or tricarboxylic acid residues, having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mg / KOH.

[0034] From the viewpoint of further improving the heat resistance, solvent resistance and adhesion to the adherend or substrate of the hardened film, component (A1) is preferably a resin having a plurality of aromatic rings, more preferably a alkali-soluble resin having repeating units containing fluorene structures, and even more preferably a alkali-soluble resin having repeating units containing a diaryl fluorene skeleton. For example, component (A1) is preferably a resin represented by the following general formula (1).

[0035]

[0036] In formula (1), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and a portion of the hydrogen atom constituting Ar may be substituted by an alkyl group with 1 to 10 carbon atoms, an aryl or arylalkyl group with 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group with 3 to 10 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, or a halogen group. R1 is an alkyl group with 2 to 4 carbon atoms. l is a number with 0 to 3. G is a (meth)acrylyl group, or a substituent shown in general formula (2) or general formula (3) below. Y is a tetravalent carboxylic acid residue. Z is a hydrogen atom or a substituent shown in general formula (4) below, and at least one of Z is a substituent shown in general formula (4) below. n is a number with an average value of 1 to 20.

[0037]

[0038]

[0039] In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is an alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, R4 is a saturated or unsaturated hydrocarbon group with 2 to 20 carbon atoms, and p is a value of 0 to 10.

[0040]

[0041] In formula (4), W refers to a divalent or trivalent carboxylic acid residue, and m refers to a value of 1 or 2.

[0042] The resin system shown in general formula (1) can be synthesized by the following method.

[0043] First, an epoxy compound (a-1) (hereinafter also referred to as "epoxide compound (a-1)") having some alkyl epoxide modification groups in one molecule and having a diaryl epoxide skeleton, as shown in general formula (5) below, is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative shown in general formula (6) below, and a (meth)acrylic acid derivative shown in general formula (7) below to obtain a diol compound belonging to the epoxy group (meth)acrylic acid ester. Furthermore, the diaryl epoxide skeleton is preferably a bis(naphthol) epoxide skeleton or a bisphenol epoxide skeleton.

[0044]

[0045] In formula (5), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and a portion of the hydrogen atom constituting Ar can be substituted by an alkyl group with 1 to 10 carbon atoms, an aryl or arylalkyl group with 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group with 3 to 10 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, or a halogen group. R1 is an alkyl group with 2 to 4 carbon atoms. l is a number with 0 to 3.

[0046]

[0047]

[0048] In formulas (6) and (7), R2 is a hydrogen atom or a methyl group, R3 is an alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, R4 is a saturated or unsaturated hydrocarbon group with 2 to 20 carbon atoms, and p is a number with 0 to 10.

[0049] The reaction of the above-mentioned epoxy compound (a-1) with (meth)acrylic acid or its derivatives can be carried out using known methods. For example, Japanese Patent Application Publication No. 4-355450 discloses that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid relative to 1 mole of an epoxy compound having 2 epoxy groups. In this embodiment, the compound obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group as shown in the following general formula (8) (hereinafter, it is also referred to as "diol (d)").

[0050]

[0051] In formula (8), each of the Ar groups is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the hydrogen atom constituting Ar can be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each of the G groups is independently (meth)acrylyl, a substituent shown in general formula (2) or general formula (3), and each of the R1 groups is independently an alkyl group having 2 to 4 carbon atoms. Each of the l groups is independently a number of 0 to 3.

[0052]

[0053]

[0054] In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is an alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, R4 is a saturated or unsaturated hydrocarbon group with 2 to 20 carbon atoms, and p is a number with 0 to 10.

[0055] Next, by reacting the diol (d), dicarboxylic acid or tricarboxylic acid or its anhydride (b), and tetracarboxylic acid or its dianhydride (c) obtained above, a curable resin containing unsaturated groups having a carboxyl group and a polymerizable unsaturated group in one molecule of the general formula (1) can be obtained.

[0056] The above-mentioned acid component is a polyacid component that can react with the hydroxyl group in the diol (d) molecule. In order to obtain the resin shown in general formula (1), it is necessary to use a dicarboxylic acid or tricarboxylic acid or its equivalent anhydride (b) and a tetracarboxylic acid or its equivalent dianhydride (c). The carboxylic acid residues of the above-mentioned acid component can be either saturated hydrocarbon groups or unsaturated hydrocarbon groups. Furthermore, these carboxylic acid residues can contain heteroelement bonds such as -O-, -S-, and carbonyl groups.

[0057] In the above examples of dicarboxylic acids or tricarboxylic acids or their anhydrides (b), there are chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, and such anhydrides.

[0058] In the above examples of chain-type dicarboxylic acids or tricarboxylic acids, there are succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxyglutaric acid, pimelic acid, sebacic acid, octanoic acid, and diethylene glycol, as well as such dicarboxylic acids or tricarboxylic acids introduced with any substituent.

[0059] In the above examples of alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, they include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-terminated methylenetetrahydrophthalic acid, chlorobridged acid, hexahydrotriphenylcarboxylic acid and norbornene dicarboxylic acid, as well as such dicarboxylic acids or tricarboxylic acids introduced with any substituent.

[0060] In the above examples of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, as well as such dicarboxylic acids or tricarboxylic acids introduced with any substituent.

[0061] Of the dicarboxylic acids or tricarboxylic acids mentioned above, succinic acid, itconic acid, tetrahydrophthalic acid, hexahydrotriphenylcarboxylic acid, phthalic acid and trimellitic acid are preferred, and succinic acid, itconic acid and tetrahydrophthalic acid are even more preferred.

[0062] The dicarboxylic acid or tricarboxylic acid mentioned above is preferably an anhydride thereof.

[0063] The above examples of tetracarboxylic acids or their dianhydrides (c) include chain-type hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and their dianhydrides.

[0064] In the above-mentioned examples of chain-type tetracarboxylic acids, there are butanetetracarboxylic acids, pentanetetracarboxylic acids, hexanetetracarboxylic acids, and chain-type tetracarboxylic acids that have been introduced with substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups.

[0065] The above examples of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norcamphene tetracarboxylic acid, as well as alicyclic tetracarboxylic acids that have been introduced with substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups.

[0066] In the above-mentioned example of aromatic hydrocarbon tetracarboxylic acid, it includes pyromellitic tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl tannic acid tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid, etc.

[0067] Among the above-mentioned tetracarboxylic acids, biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are preferred, with biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid being even more preferred.

[0068] The above-mentioned tetracarboxylic acid preferably uses its dianhydride.

[0069] Alternatively, aryl esters of dipyridine tricarboxylic anhydride may be used to replace the above-mentioned tetracarboxylic acid or its dianhydride (c). The so-called aryl esters of dipyridine tricarboxylic anhydride are, for example, compounds produced by the method described in International Publication No. 2010 / 074065, and are dianhydrides in the form of ester bonds formed by reacting two hydroxyl groups of an aromatic diol (naphthalene glycol, biphenol, and triphenyl diol, etc.) with the carboxyl groups of two molecules of dipyridine tricarboxylic anhydride respectively.

[0070] There are no particular limitations on the reaction method of diol (d) with acid components (b) and (c), and known methods may be used. For example, Japanese Patent Application Publication No. 9-325494 describes a method for reacting epoxy (meth)acrylate with tetracarboxylic acid dianhydride at a reaction temperature of 90 to 140°C.

[0071] In this case, it is preferable that the compound is terminally carboxylated, and the reaction is carried out in a molar ratio of epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or the like of an anhydride (b), and tetracarboxylic acid dianhydride (c) such that (d):(b):(c) = 1.0:0.01 to 1.0:0.2 to 1.0.

[0072] For example, when using acid monohydric anhydride (b) and acid dianhydride (c), it is preferable to react them in such a way that the molar ratio of the amount of acid component [(b) / 2+(c)] to diol (d) [[(b) / 2+(c)] / (d)] is greater than 0.5 and less than 1.0. If the molar ratio is less than 1.0, the end of the curing resin containing unsaturated groups as shown in general formula (1) will not become an anhydride, thus suppressing the increase in the content of unreacted acid dianhydride and improving the time-dependent stability of each component. Furthermore, if the molar ratio is greater than 0.5, the increase in the residual amount of unreacted components in diol (d) containing polymerizable unsaturated groups can be suppressed, thereby improving the time-dependent stability of each component. Furthermore, based on the purpose of adjusting the acid value and molecular weight of the curing resin containing unsaturated groups as shown in general formula (1), the molar ratios of each component in (b), (c) and (d) can be arbitrarily changed within the above-mentioned range.

[0073] Furthermore, the synthesis of diol (d) and the subsequent reaction of polycarboxylic acids or their anhydrides are usually carried out in a solvent using a catalyst as needed.

[0074] In the examples of the solvents described above, the solvents include celestine-based solvents such as ethyl celestine acetate and butyl celestine acetate, high-boiling-point ether or ester-based solvents such as dimethyl ether diglyceride, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Furthermore, there are no particular restrictions on the reaction conditions of the solvents, catalysts, etc., used; however, for example, it is preferable to use a solvent without hydroxyl groups that has a boiling point higher than the reaction temperature as the reaction solvent.

[0075] Furthermore, the reaction between the epoxy group and the carboxyl or hydroxyl group is preferably carried out using a catalyst. Regarding the aforementioned catalyst, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and phosphine derivatives such as tris(2,6-dimethoxyphenyl)phosphine have been disclosed in Japanese Patent Application Publication No. 9-325494.

[0076] The curing resin containing unsaturated groups shown in general formula (1) preferably has an acid value of 50 mg KOH / g or higher to 200 mg KOH / g, and more preferably 60 mg KOH / g or higher to 150 mg KOH / g. If the acid value is 50 mg KOH / g or higher, residue is less likely to remain during alkaline development. If it is 200 mg KOH / g or lower, the alkaline developer will not penetrate too early, thus inhibiting stripping development. Furthermore, the acid value is obtained by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0077] (A1) The weight-average molecular weight (Mw) of the polystyrene obtained by gel permeation chromatography (GPC) of the alkali-soluble resin of component (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) is preferably between 1,000 and 40,000, more preferably between 1,500 and 30,000, and even more preferably between 2,000 and 15,000. If the weight-average molecular weight (Mw) is 1,000 or higher, the adhesion between the support and the substrate can be improved. Furthermore, if the weight-average molecular weight (Mw) is 40,000 or lower, it is easier to adjust the solution viscosity of the composition suitable for coating, the coating time on the surface of the support or the substrate will not be excessive, and the adhesion to the substrate is easier to improve. When adhesion strength is important, a weight-average molecular weight (Mw) of 1,000 to 4,500 is preferred.

[0078] Other polymeric compounds containing unsaturated groups belonging to component (A2) (hereinafter also referred to as "(A2) component") are compounds that have two or more polymeric unsaturated groups and undergo polymerization reactions by stimulation such as heat and light, and do not have base-soluble groups.

[0079] In addition to improving the adhesion strength and solvent resistance of the hardened film formed by curing the individual components to the adherend or substrate, component (A2) can also improve exposure sensitivity and developability. Component (A2) only needs to have at least two polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups present in component (A1) or other polymerizable unsaturated groups present in the molecules of component (A2). Preferably, the polymerizable unsaturated groups are functional groups that are the same as those present in component (A1) when used in combination with component (A1). Specifically, (meth)acrylic acid group is preferred. Furthermore, component (A2) can be a monomer, an oligomer, or a polymer. When used in combination with component (A1), component (A2) is preferably a monomer or an oligomer.

[0080] In the example of ingredient (A2), it includes:

[0080] (Meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;

[0080] Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyltetrol di(meth)acrylate, neopentyltetrol tri(meth)acrylate, neopentyltetrol tetra(meth)acrylate, dinepentyltetrol tetra(meth)acrylate, dinepentyltetrol penta(meth)acrylate, dinepentyltetrol hexa(meth)acrylate (meth)acrylates;

[0080] Neopentyl tetraacrylate toluene diisocyanate aminocarbamate prepolymer, neopentyl tetraacrylate hexamethylene diisocyanate aminocarbamate prepolymer, neopentyl tetraacrylate isoflavone diisocyanate aminocarbamate prepolymer, and dinepentyl tetraacrylate hexamethylene diisocyanate aminocarbamate prepolymer, etc., aminocarbamate acrylate monomers;

[0080] Epoxy (meth)acrylates of bisphenol A type, bisphenol F type, bisphenol fusiform type, diphenylfusiform type, phenolic varnish type, cresol phenolic varnish type, phenolic alkyl type, etc.; and

[0080] Dental polymers, etc., that have (meth)acrylic acid groups as compounds having ethylene double bonds.

[0081] (A2) It is preferable that the component has two or more (meth)acrylic groups, and even more preferably it has three or more (meth)acrylic groups. By having two or more (meth)acrylic groups in the above-mentioned (A2) component, the crosslinking density is increased and the solvent resistance of the hardened film is improved.

[0082] 1-2.(B) Ultraviolet absorber

[0082] [(B) Component]

[0082] (B) The component is an ultraviolet absorber.

[0083] Furthermore, in this specification, the term "ultraviolet absorber" refers to a compound that has a distinct absorption peak in the ultraviolet region, specifically an organic compound. Carbon black and the like, which exhibit broad absorption, are not included among the ultraviolet absorbers in this specification. Because the aforementioned ultraviolet absorbers do not absorb light in the visible light region, they are less likely to produce coloring residue. Furthermore, the aforementioned ultraviolet absorbers are readily soluble in alkaline stripping solutions and are easy to wash off after stripping.

[0084] (B) The component is a compound that has an absorption peak between 250 nm and 450 nm, preferably between 300 nm and 450 nm.

[0085] In the example of component (B), it includes compounds with the following structures: benzotriazole structure, benzophenone structure, tri-structure, salicylic acid structure, benzoic acid ester structure, cinnamic acid derivative structure, naphthalene derivative structure, anthracene-based structure, a structure having a dinaphthalene structure, and a phenophylline structure. Among these, compounds with the benzotriazole structure, benzophenone structure, and tri-structure are preferred because they can efficiently absorb ultraviolet light at 355 nm.

[0086] In examples of compounds having a benzotriazole structure, the compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole. 2-Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-terpentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-{2'-hydroxy-3'-(3”,4”,5”,6”-tetrahydrophthalimidemethyl)-5'-methylphenyl}benzotriazole, C7-C9-alkyl-3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionic ether, etc.

[0087] Examples of compounds having a benzophenone structure include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, hydroxytridecylbenzophenone, etc.

[0088] In the example of a compound having a tri-structure, it includes 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-tris, 2-[4((2-hydroxy-3-tetrazyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris, 2-[4-((2-hydroxy-3-tetrazyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris, etc.

[0089] 1-3.(C) Epoxy compounds having two or more epoxy groups

[0089] (C) Epoxy compounds having two or more epoxy groups form a fully cross-linked structure, thereby improving the chemical resistance of the hardened film.

[0090] In the example of component (C), it includes bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol epoxide type epoxy compound, bisnaphthol epoxide type epoxy compound, diphenyl epoxide type epoxy compound, phenolic varnish type epoxy compound, cresol phenolic varnish type epoxy compound, phenolic alkyl type epoxy compound, phenolic varnish compound containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), and biphenyl type epoxy compound (e.g., jER). YX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the same company), naphthol aralkyl type epoxy compounds, phenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of monomers containing (meth)acrylic acid groups as units, including (meth)acrylic acid glycidyl esters represented by copolymers of methacrylic acid and glycidyl methacrylic acid, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane esters (e.g., Celloxide 2021P: manufactured by DAICEL Co., Ltd., "Celloxide" is a registered trademark of the same company), tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone of butanetetracarboxylic acid (e.g., Epolead). GT401: manufactured by DAICL Corporation ("Epolead" is a registered trademark of the same company), epoxy compounds with an epoxy group of cyclohexyl (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), multifunctional epoxy compounds with a dicyclopentadiene backbone (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by DAICL Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd. ("NISSO-PB" is a registered trademark of the same company), epoxy compounds with a polysiloxane backbone, etc. Furthermore, these compounds may be used in combination with only one type of compound or with two or more types.

[0091] (C) Among the components, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fumonisin type epoxy compound, bisnaphthol fumonisin type epoxy compound, phenolic varnish type epoxy compound, cresol phenolic varnish type epoxy compound, and biphenyl type epoxy compound are preferred, with biphenyl type epoxy compound being even more preferred. By using biphenyl type epoxy compounds, the mechanical strength or chemical resistance of the cured material that meets the required characteristics can be combined with the patternability of the composition for microlens forming during photocuring, and the degree of freedom in designing the composition for microlens forming can be increased.

[0092] (C) The epoxy equivalent of the epoxy compound is preferably 100 g / eq or more and 300 g / eq or less, more preferably 100 g / eq or more and 250 g / eq or less. Furthermore, the number average molecular weight (Mn) of the epoxy compound in (C) is preferably 100 or more and 5000 or less. If the epoxy equivalent is 100 g / eq or more, and the number average molecular weight (Mn) of the epoxy compound is 100 or more, a hardened film with good solvent resistance can be formed. If the epoxy equivalent is 300 g / eq or less, and the number average molecular weight (Mn) is 5000 or less, sufficient alkali resistance can be maintained when using alkaline solutions in subsequent steps.

[0093] Furthermore, the epoxy equivalent of component (C) can be obtained by titration with 1 / 10 N-perchloric acid solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). Furthermore, the number average molecular weight (Mn) of the aforementioned epoxy compound can be obtained, for example, using the aforementioned gel permeation chromatography (GPC) method "HLC-8220GPC" (manufactured by TOSOH Co., Ltd.).

[0094] When using component (C), a hardener and a hardening accelerator may also be used together.

[0095] In the above-mentioned examples of hardeners, there are amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, and Lewis acid complexes, etc.

[0096] In the examples of the above-mentioned curing accelerators, they include tertiary amines, quaternary ammonium salts, tertiary phosphine, quaternary phosphonium salts, borate esters, Lewis acid, organometallic compounds, and imidazoles, which help promote the curing of epoxy resins. In the examples of the above-mentioned thermal polymerization inhibitors and antioxidants, they include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenoxythiocyanates, and phenol-inhibiting compounds, etc. In the examples of the above-mentioned plasticizers, they include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, etc. In the examples of the above-mentioned fillers, they include glass fiber, silicon dioxide, mica, and alumina, etc. In the examples of the above-mentioned defoamers and leveling agents, they include polysiloxane, fluorine, and acrylic compounds, etc. In the examples of the above-mentioned surfactants, they include fluorine surfactants and polysiloxane surfactants, etc. Examples of the coupling agents mentioned above include 3-(glycidoxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, and 3-ureopropyltriethoxysilane.

[0097] 1-4.(D) Photopolymerization initiator

[0097] (D) The photopolymerization initiator system can fully carry out the reaction of the part exposed to light and reduce the solubility of the hardened part during development to form the desired fine pattern.

[0098] In the example of component (D), it comprises 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane, 2-(o-chlorophenyl)-4,5-phenylbisimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)bisimidazole, 2-(o-fluorophenyl)-4,5-diphenylbisimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbisimidazole, 2,4,5-triarylbisimidazole, 2,2 Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-bisimidazole and other bisimidazole compounds; halomethylthiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-diazole, 2-trichloromethyl-5-(p-cyanostyl)-1,3,4-diazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-diazole; 2,4,6-trichloromethyl-1,3,5-tri... 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-tris, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-tris, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-tris, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tris, 2-(4-methoxystyrene) Halomethyl-s-triterpenoids such as 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tritri, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-tritri, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triterpenoids; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime) (Irgacure OXE01, manufactured by BASF Japan, "Irgacure" is a registered trademark of the same company), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate,2-Diketone-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]- Tetrahydrofuranylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-benzoate, 1-[ 9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecane ester, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-adamantane carboxylate, 1-[4-(phenylhydrothio)phenyl]octane-1,2-dione=2-O -Benzyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]acetophenone-O-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-en-2-yl)-acetyloxime, acetophenone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-en- O-acetylated compounds such as [-2-yl]-1-(o-acetylated oxime), acetone, 1-(-9,9-dibutyl-7-nitro-9H-furo-2-yl)-1-O-acetylated oxime, acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetylated oxime) (Irgacure OXE02); benzyl dimethyl acetal; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,Anthraquinones such as 3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide. Furthermore, these photopolymerization initiators can be used alone or in combination of two or more.

[0099] Of these, component (D) is preferably a acetooxime-based (including ketoxime) photopolymerization initiator. Acrytooxime-based photopolymerization initiators have high sensitivity, thus they can significantly improve the photosensitivity of the curable resin composition and significantly improve the developability (resolution) of the resin curable film.

[0100] In the example of a acetooxime photopolymerization initiator, it comprises an O-acetooxime photopolymerization initiator represented by general formula (9) or general formula (10).

[0101]

[0102] In formula (9), R5 and R6 independently represent alkyl groups having 1 to 15 carbon atoms, aryl groups having 6 to 18 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or heterocyclic groups having 4 to 12 carbon atoms, respectively. R7 represents alkyl groups having 1 to 15 carbon atoms, aryl groups having 6 to 18 carbon atoms, or arylalkyl groups having 7 to 20 carbon atoms. Here, alkyl and aryl groups can be substituted with alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, or halogens. The extended alkyl part can contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group can be any of the following: straight-chain, branched, or cyclic alkyl groups.

[0103]

[0104] (In formula (10), R8 and R9 are each independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group that can be substituted with an alkyl group having 1 to 6 carbon atoms. R10 are each independently a straight-chain or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein one portion of the -CH2- group in the alkyl or alkenyl group can be substituted with an -O- group. Furthermore, one portion of the hydrogen atom in these R8 to R10 groups can be substituted with a halogen atom.)

[0105] In this specification, the molar absorptivity of the photopolymerization initiator is a value obtained by measuring the absorbance of a 0.001% by weight acetonitrile solution in a quartz cell with an optical path length of 1 cm using a UV-Vis-IR spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.).

[0106] 1-5. (E) Sensitizer

[0106] (E) The sensitizer system can control the hardening reaction carried out with (D) photopolymerization initiator with greater precision.

[0107] In the example of ingredient (E), it includes triethanolamine, triisopropanolamine, benzophenone, and 4,4'-bis(dimethylamino)benzophenone (Michler's ketone). Benzyl ketones, including 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; acetophenones, including 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyl dimethyl acetal; benzoin ethers, including benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy)ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and 2,4-diethylthionyl anthracene. The benzophenone family includes ketones such as 2,4-diisopropylthioxanthraphenone, 4-benzoyl-4'-methyl-diphenyl sulfide, benzophenone acrylic acid, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthraphenone, 2-chlorothioxanthraphenone, 2-methylthioxanthraphenone, 2-isopropylthioxanthraphenone, 4-isopropylthioxanthraphenone, 2,4-dimethylthioxanthraphenone, 2,4-diethylthioxanthraphenone, 2,4-dichlorothioxanthraphenone, 1-chloro-4-propoxythioxanthraphenone, 4,4'-bis(diethylamino)benzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthroquinone, camphorquinone, etc. Furthermore, these sensitizers can be used alone or in combination with two or more.

[0108] 1-6. (F) Solvent

[0108] (F) Solvent (hereinafter also referred to as "(F) component") is used to dissolve or disperse the components contained in each component and to improve the coatability of each component.

[0109] In the example of component (F), it includes alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ceroxysulfonyl, methyl ceroxysulfonyl, ethyl ceroxysulfonyl, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol, etc. Glycol monomethyl ethers, propylene glycol monoethyl ethers, dipropylene glycol monomethyl ethers, dipropylene glycol monoethyl ethers, triethylene glycol monomethyl ethers, and triethylene glycol monoethyl ethers; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxy-butyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, ceroxose acetate, ethyl ceroxose acetate, butyl ceroxose acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By using these substances to dissolve and mix them, the individual components can be formed into a homogeneous solution.

[0110] 1-7. Other ingredients

[0110] Each component system may be formulated with thermal polymerization inhibitors, antioxidants, chain transfer agents, plasticizers, fillers, leveling agents, defoamers, surfactants, and coupling agents as needed.

[0110] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenoxythiazolinone, and phenolic compounds.

[0110] In the example of chain transfer agents, there are thiol compounds including 2-hydrothiobenzimidazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzothiazole, β-hydrothiopropionic acid, 2-ethylhexyl-3-hydrothiopropionate, n-octyl-3-hydrothiopropionate, methoxybutyl-3-hydrothiopropionate, stearyl-3-hydrothiopropionate, trimethylolpropane-3-hydrothiopropionate, trimethylolpropane-3-hydrothiopropionate, trimethylolpropane-3-[(3-hydrothiopropoxy)-ethyl]-triisocyanate, neopentyltetraethylene ...

[0110] In the case of plasticizers, it includes dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. In the case of fillers, it includes glass fiber, silicon dioxide, mica, alumina, etc.

[0110] In the case of defoamers or leveling agents, they include polysiloxane, fluorine, and acrylic compounds.

[0110] In the case of surfactants, there are fluorinated surfactants, polysiloxane surfactants, etc.

[0110] In the case of coupling agents, it includes 3-(glycidoxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, 3-ureopropyltriethoxysilane, etc.

[0111] 2. First revelation

[0111] 2-1. Composition

[0111] The first disclosure in this specification relates to a curable adhesive layer forming composition, which comprises

[0111] (A) Polymers containing unsaturated groups

[0111] (B) Ultraviolet absorbers, and

[0111] (F) Solvent,

[0111] Wherein, relative to the total mass of the solid components, the content of (B) ultraviolet absorber is 10% by mass or more and 80% by mass or less. The above-mentioned adhesive layer forming composition system may, as needed, include (C) an epoxy compound having two or more epoxy groups, (D) a photopolymerization initiator, (E) a sensitizer, etc.

[0112] According to the composition for forming the adhesive layer disclosed in the first paragraph above, the adhesive can be easily peeled off by irradiation with a 355nm laser, and the adhesion of the adhesive layer to the adhesive layer and the solvent resistance are good.

[0113] Furthermore, the composition system for forming the adhesive layer may contain only component (A1), or only component (A2), or both components (A1) and (A2) may be used together.

[0114] 2-1-1. Suitable for the compound disclosed in Part 1

[0114] [(A2) Ingredients]

[0114] When using (A2), from the viewpoint of further improving the adhesion of the hardened film to the substrate, component (A2) is preferably a compound modified with an epoxy alkane or a lactone. It is believed that such modifiers improve the contact area (adhesion area) by increasing the fluidity of the adhesive layer forming composition at the interface with the substrate and burying the tiny gaps between the substrate and the adhesive layer forming composition, thereby further improving the adhesion of the hardened film to the substrate. In particular, when component (B) is a high molecular weight compound, component (A2), which is a modified compound, compensates for the decrease in fluidity of the adhesive layer forming composition obtained with component (B), thus significantly improving the adhesion.

[0115] The above-mentioned epoxy alkyl modified compound is preferably a compound having an epoxy alkyl group with 2 to 6 carbon atoms, more preferably a compound having an epoxy alkyl group with 2 to 4 carbon atoms, and even more preferably a compound having an epoxy alkyl group with 2 to 3 carbon atoms.

[0116] The above-mentioned lactone modified compound is preferably a compound having a lactone ring-opening structure with 2 to 6 carbons (-C(=O)-(CH2)kO-, where k is a number one less than the number of carbons of the lactone), more preferably a compound having a lactone ring-opening structure with 4 to 6 carbons, and even more preferably a compound having a lactone ring-opening structure with 6 carbons.

[0117] The above-mentioned epoxy alkyl group and lactone can exist alone in the molecule after ring opening, or two or more but less than six of the above-mentioned epoxy alkyl group or lactone can be linked together, but it is preferred that they exist alone or two of the above-mentioned epoxy alkyl group or lactone can be linked together.

[0118] The above-mentioned modified system may be, for example, a compound represented by the following general formula (11).

[0119]

[0120] In formula (11), V is a group that independently has an epoxy alkyl or lactone ring-opening structure. a to e are independently integers from 0 to 6, but at least one of a to e is an integer from 1 to 6. a to e is preferably 1 or 2. R11 to R15 are independently (meth)acrylic or hydroxyl, but at least two of R11 to R15 are (meth)acrylic. R5 to R9 are preferably all (meth)acrylic. T is a group of substituted or unsubstituted 1 to 4 valent hydrocarbon groups, selected from the group consisting of -O- and -S-, preferably substituted or unsubstituted 2 valent hydrocarbon groups, -O- and -S-, and more preferably -O-. q is independently 0 or 1, preferably 0. r is an integer of the same valence as Z, from 1 to 4, preferably 2.

[0121] In the example of the modified product shown in general formula (11), it includes ethylene oxide modified dinepentylenetetroxide hexaacrylate, dinepentylenetetroxide dicaprolactone hexaacrylate, dinepentylenetetroxide tricaprolactone hexaacrylate, dinepentylenetetroxide hexacaprolactone hexaacrylate, dinepentylenetetroxide polycaprolactone hexaacrylate (any of which is manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide modified triacrylate, and trimethylolpropane ethylene oxide modified triacrylate (any of which is manufactured by Toa Synthetic Co., Ltd.).

[0122] Among the above-mentioned modified compounds other than those shown in general formula (9), there are bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, ethylene isocyanate modified di and triacrylate, diglycerol ethylene oxide modified acrylate (any of which is manufactured by East Asia Synthetic Co., Ltd.), and phosphazene ethylene oxide modified hexa(meth)acrylate, etc.

[0123] [(A) component (common to (A1) component / (A2) component)]

[0123] (A) Component may be a resin whose cured product obtained by polymerization of polymeric unsaturated groups absorbs a suitable amount of electromagnetic waves (preferably electromagnetic waves with wavelengths in the ultraviolet region) and undergoes deterioration or decomposition. For example, component (A) may be a compound in which the cured product obtained above has a repeating structure of a resin containing polymeric unsaturated groups and conjugated π electron systems such as benzene rings, condensed rings, and heterocycles within the molecule. Furthermore, the aforementioned benzene rings, condensed rings, and heterocycles may be substituted. For example, component (A) may be a compound in which a resin containing repeating units of a benzophenone structure can be obtained, or a compound in which a resin having a benzophenone structure, a diphenyl sulfone structure, a diphenyl sulfone structure, a diphenyl structure, a diphenylamine structure, and a benzotriazole structure in the side chain can be obtained.

[0124] [(B) Component]

[0124] In the first disclosure, component (B) (ultraviolet absorber) effectively absorbs laser light and generates heat in the hardened film formed by curing the adhesive layer with the composition. Subsequently, the heat causes component (A) to deteriorate, thereby causing the hardened film to peel off.

[0125] Component (B) is any compound that has an absorption peak in the wavelength range of 250 nm to 450 nm, preferably 300 nm to 450 nm. However, from the viewpoint of forming an adhesive layer that can be peeled off from the adhered body by a longer wavelength laser (e.g., 355 nm), component (B) preferably has an absorbance of 0.10 or higher at a wavelength of 355 nm, more preferably 0.12 or higher, and even more preferably 0.15 or higher. The above absorbance is measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.), which can be set to measure the absorbance of a 0.001% by weight acetonitrile solution in a quartz cell with an optical path length of 1 cm. Furthermore, if component (B) is not easily soluble in acetonitrile, the absorbance of a solution dissolved in propylene glycol monomethyl ether acetate can be measured instead.

[0126] Furthermore, when using an alkali-soluble resin having repeating units containing a benzotriazole structure as the (A1) component, since the compatibility with the (A1) component is good and it is difficult to increase the haze value of the hardened film and difficult to reduce the solvent resistance of the hardened film, it is preferable to use a compound having a benzotriazole structure and a benzophenone structure, and even more preferable to use a compound having a benzotriazole structure (hydroxyphenylbenzotriazole structure).

[0127] Furthermore, when the adhesive is cured, from the viewpoint of suppressing the exudation of component (B) from the cured film, component (B) is preferably a high-molecular-weight ultraviolet absorber with a weight average molecular weight (Mw) of 1000 or more. The aforementioned high-molecular-weight ultraviolet absorber may be a homopolymer of a compound having the above-mentioned structure (particularly preferably a benzotriazole structure) and polymerizable unsaturated groups, or a copolymer of the compound with other monomers.

[0128] Furthermore, according to the inventors' knowledge, while polymeric ultraviolet absorbers improve the heat resistance of the hardened film, they tend to reduce the adhesion (flowability) of the adhesive layer forming composition to the adherend or the solvent resistance of the hardened film. In contrast, in this embodiment, since the adhesion to the adherend and solvent resistance are ensured by hardening with component (A), the aforementioned problems of reduced adhesion and solvent resistance are less likely to occur. The aforementioned effects on adhesion and solvent resistance are significantly effective when component (A) is a cross-linking compound and a cross-linked structure is formed during hardening. Furthermore, as mentioned above, if component (A2) is a modified product modified with epoxy alkyl or lactone, such modified products compensate for the reduction in flowability of the adhesive layer forming composition caused by the polymeric ultraviolet absorber, thus significantly improving the adhesion of the hardened film to the adherend.

[0129] From the viewpoint of more fully obtaining the above-mentioned improvement in heat resistance, the weight average molecular weight (Mw) of the (B) component of the high-molecular-weight ultraviolet absorber is preferably 1,000 to 100,000, more preferably 5,000 to 90,000, and even more preferably 10,000 to 80,000.

[0130] Furthermore, the aforementioned weight-average molecular weight can be set as the value obtained by gel permeation chromatography (GPC) and conversion to polystyrene. For example, the above GPC can be performed using an HLC-8220 GPC (manufactured by TOSOH Corporation) with one or more of the following columns: HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH Corporation). The precipitate can be THF (tetrahydrofuran).

[0131] 2-1-2. Mixing Quantity

[0131] In the composition for forming the adhesive layer, the content of component (A) relative to the total mass of the solid components is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and when adhesion strength is important, 40% by mass or more and 80% by mass or less is even more preferred. If the above-mentioned content of component (A) is 10% by mass or more, the adhesion of the hardened film to the substrate increases, and the hardened film will absorb the irradiated laser (e.g., ultraviolet light) and is prone to deterioration or decomposition, thus making it easier for the support to separate from the substrate. Furthermore, if it is 90% by mass or less, the hardness (crosslinking density) of the hardened adhesive layer is not high enough, so it is easy to erode when irradiated with light and is not easy to generate residue.

[0132] When components (A1) and (A2) are used together, the content of component (A2) in the composition forming the adhesive layer is preferably 5 to 1000 parts by mass, more preferably 10 to 600 parts by mass, and even more preferably 20 to 300 parts by mass. If the content of component (A2) is 5 parts by mass or more, sufficient polymerizable unsaturated groups are present in the resin, resulting in a sufficient cross-linking structure and thus improved chemical resistance. Furthermore, if it is 1000 parts by mass or less, sufficient cross-linking density of the cured adhesive layer makes it easier to erode and less likely to produce residue when exposed to light.

[0133] When light processability and heat resistance are required, it is preferable that the content of component (A2) be more than 20 parts by mass and less than 100 parts by mass when the total mass of component (A1) is taken as 100 parts by mass.

[0134] When the adhesion at room temperature is required, it is preferable to use component (A2) alone, or to use component (A2) in combination with 100 to 1000 parts by mass when the total mass of component (A1) is taken as 100 parts by mass.

[0135] The content of component (B) relative to the total mass of the solid component is 10% by mass or more and 80% by mass or less. The higher the content, the greater the effect of component (B) in improving peelability due to ultraviolet absorption. On the other hand, the lower the content, the less likely it is to cause problems with the exudation of component (B) at high temperatures or the decrease in solvent resistance of the hardened film. From the point of view of achieving such a balance, the content of component (B) relative to the total mass of the solid component is preferably 20% by mass or more and 65% by mass or less. When more emphasis is placed on adhesive strength, it is preferably 20% by mass or more and 45% by mass or less. When more emphasis is placed on peelability, it is preferably 35% by mass or more and 65% by mass or less.

[0136] The content of component (C) relative to the total mass of the solid components is preferably 0 parts by mass to 60 parts by mass, and more preferably 5 parts by mass to 50 parts by mass. If the content of component (C) is 5 parts by mass or more, a sufficient cross-linking structure can be formed, thereby improving the chemical resistance. Furthermore, if the content of component (C) is 60 parts by mass or less, the cross-linking density of the adhesive layer after curing will not be too high, so it is easy to erode when exposed to light and less likely to produce residue.

[0137] When the content of component (D) is based on the total mass of component (A) as 100 parts by mass, it is preferable to be 0.1 parts by mass to 30 parts by mass, and even more preferable to be 0.3 parts by mass to 20 parts by mass. If the above-mentioned content of component (D) is 0.1 parts by mass or more, it can promote photopolymerization and accelerate the photopolymerization speed. Furthermore, if the above-mentioned content of component (D) is 30 parts by mass or less, it can suppress excessive increase in sensitivity, and when etched by light, it is less likely to produce scorching, peeling residue, etc. Furthermore, when the composition for forming the adhesive layer is preferably formed by photoetching, it is preferable to contain component (D), but when not forming a pattern, or when forming a pattern by a method other than photoetching, it may not contain component (D).

[0138] Furthermore, in this disclosure, when patterning the adhesive layer, the (D) component preferably has a molar absorptivity of 10000 L / mol‧cm or higher at 365 nm. Because such a photopolymerization initiator has high sensitivity, even in curing resin compositions containing a relatively large acrylic equivalent (A2) component, sufficient photosensitivity can be ensured, and the developability (resolution) of the curing resin composition can be significantly improved. Examples of such photopolymerization initiators include Omnirad 1312 (manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the same company) and ADEKA ARKLS NCI-831 (manufactured by ADEKA Corporation, "ADEKA ARKLS" is a registered trademark of the same company).

[0139] When the total mass of component (D) is taken as 100 parts by mass, the content of component (E) is preferably 0.5 parts by mass to 400 parts by mass, and more preferably 1 part by mass to 300 parts by mass. If the above-mentioned content of component (E) is 0.5 parts by mass or more, the sensitivity of component (D) can be improved, thereby accelerating the photopolymerization speed. Furthermore, if the above-mentioned content of component (E) is 400 parts by mass or less, excessive increase in sensitivity can be suppressed, and when etched by light, it is less likely to produce scorching, peeling residue, etc.

[0140] (F) Although the content of the component varies depending on the viscosity and other properties of the target curing component, it is preferable to be 50% by mass or more and 90% by mass or less relative to the total mass of the curing component.

[0141] 2-2. Manufacturing method of laminated bodies

[0141] The method for manufacturing a laminate according to other embodiments disclosed in the first paragraph includes (1) forming an adhesive layer by applying the adhesive layer forming composition to the surface of at least one of the support and the adherend; and (2) bonding the support and the adherend through the formed adhesive layer. The steps are described below.

[0142] [Steps for forming the adhesive layer]

[0142] The adhesive layer forming step is a step of forming an adhesive layer comprising the above-described adhesive layer forming composition on the surface of at least one of the support and the adhered body.

[0143] (Support)

[0143] The type of support is not limited as long as an adhesive layer can be formed on its surface.

[0144] In this embodiment, the support system is preferably one with laser transmittance. In particular, the support is more preferably able to allow light (laser) with wavelengths of 10 nm to 450 nm to pass through, even more preferably, it allows light (laser) with wavelengths of 100 nm to 450 nm to pass through, and especially preferably, it allows light (laser) with wavelengths of 350 nm to 450 nm to pass through. Examples of supports with the above-mentioned laser transmittance include glass substrates, acrylic substrates, sapphire substrates, and quartz glass substrates. However, for glass substrates and acrylic substrates, it is necessary to use substrates with sufficient transmittance of the wavelength of light used. Among the above supports, glass substrates are preferred from a cost-effectiveness perspective.

[0145] Preferably, the support described above has a transmittance of 70% or more for light with wavelengths between 350 nm and 450 nm across the entire wavelength range. A support with such transmittance allows long-wavelength lasers (e.g., 355 nm) irradiated from the support side to penetrate sufficiently and reach the adhesive layer.

[0146] The above transmittance can be measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.), with atmospheric transmittance as the baseline.

[0147] (Adhered body)

[0147] In the case of the adhered body, it includes semiconductor wafers, semiconductor chips, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers, etc.

[0148] (Adhesive layer)

[0148] The adhesive layer is formed by applying an adhesive layer forming composition to the surface of at least one of the aforementioned support and the aforementioned adherend. The hardened film of the adhesive layer forming composition after curing will sufficiently absorb long-wavelength laser light (e.g., 355 nm). Therefore, even under irradiation by long-wavelength laser light, it can be sufficiently etched and the adherend can be easily peeled off (excellent laser processability).

[0149] In the above examples of adhesive application methods, known methods include solution impregnation, spin coating, inkjet coating, spray coating, and methods using roller coaters, land coaters, slot coaters, and spin coaters.

[0150] After the adhesive is applied by the above method, an adhesive layer is formed by drying the solvent (pre-baking). The pre-baking is performed by heating in an oven, heating plate, or the like. The heating temperature and heating time during pre-baking are appropriately selected according to the solvent used, for example, at a temperature of 60 to 110°C for 1 to 10 minutes.

[0151] The thickness of the adhesive layer can be arbitrarily selected. In this embodiment, a thickness of 0.1 μm to 50 μm is preferred, and 0.5 μm to 30 μm is even more preferred. If the thickness of the adhesive layer is 0.1 μm or more, the adhesive layer can have sufficient holding force to adhere to the substrate. Furthermore, if it is 50 μm or less, the adhesive layer can be sufficiently cured by light or heat curing.

[0152] Furthermore, in this step, after the adhesive is applied to the surface of either or both of the aforementioned support and the aforementioned adherend, an exposure step and a development step for patterning the adhesive layer may be included. By patterning the adhesive layer, the adhesive layer can be formed only on the portion where the adherend is attached, and poor peeling or displacement of the adherend during the step of separating the support from the adherend (described later) can be suppressed.

[0153] Examples of light used in the exposure step include visible light, ultraviolet light, far-ultraviolet light, electron beams, X-rays, etc. Ultraviolet light (wavelength 250 to 400 nm) is preferred. Furthermore, a developer suitable for alkaline development is used in the development step. Examples of such developers include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected to suit the characteristics of the resin layer, but surfactants can be added as needed. A development temperature of 20°C to 35°C is preferred, allowing for precise formation of fine images using commercially available developing machines or ultrasonic cleaners. After alkaline development, the product is usually washed with water. Regarding the development method, shower development, spray development, immersion development, and paddle (liquid-filled) development methods are applicable.

[0154] [Steps for attaching the support and the adhered object]

[0154] The step of bonding the support and the adhered body is the step of bonding the support and the adhered body through the adhesive layer mentioned above.

[0155] In an example of the method for bonding the support to the adherend described above, the method includes: applying pressure while heating by contacting the adherend (with adhesive applied to the surface in contact with the adhesive layer) with the surface of the adhesive layer formed on the surface of the support. Furthermore, the bonding conditions between the support and the adherend are as follows: the temperature during pressure application is preferably between room temperature and 200°C, and more preferably between 30°C and 150°C. The bonding pressure is preferably between 0.01 MPa and 20 MPa, and more preferably between 0.03 MPa and 15 MPa. Additionally, if necessary, after the pressurized hot-pressing is completed, the adhesive layer may be thermally hardened at a temperature between 120°C and 250°C. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support through the adhesive layer.

[0156] Furthermore, in the above-described bonding step, the support and the substrate can be bonded by photocuring. An example of a method for photocuring the adhesive layer is irradiation using a high-pressure mercury lamp. Also, the bonding conditions for the support and the substrate are preferably such that the wavelength of the irradiating light is between 200 nm and 500 nm. The exposure intensity of the irradiating light is preferably between 25 mJ / cm² and 3000 mJ / cm², and more preferably between 50 mJ / cm² and 2000 mJ / cm².

[0157] In this manner, a laminate is formed, the laminate system having a support, an adhesive body, and an adhesive layer of a hardened material containing the aforementioned adhesive layer forming composition disposed between the support and the adhesive body.

[0158] 2-3. Methods for handling laminated bodies

[0158] A processing method for a laminate according to one embodiment of the present invention includes: (1) a step of preparing the laminate, and (2) a step of irradiating the laminate with light to separate the support from the adhered body. Hereinafter, each step will be described.

[0159] [Steps for preparing a laminated body]

[0159] The steps for preparing a laminate are as described above, which are steps for preparing to form a laminate, or for a laminate that has already been formed.

[0160] [Steps for separating the support from the adhered object]

[0160] The step of separating the support from the adhesive is a step of separating the support from the adhesive by irradiating the adhesive layer with light.

[0161] The irradiated light is not particularly limited as long as it can separate the support and the adherend. In this embodiment, ultraviolet light is preferred. The wavelength of the light is more preferably 10 nm to 450 nm, more preferably 100 nm to 450 nm, and particularly preferably 350 nm to 450 nm. If the wavelength of the light is 10 nm or more, the polymer components of the adhesive layer will absorb the light and deteriorate or decompose, reducing the strength and adhesion, thus making it easier to separate the support and the adherend. Furthermore, if the wavelength of the light is 450 nm or less, the adhesive layer of the processing section will absorb the light, thus suppressing the generation of residue in the hardened film. Furthermore, if the wavelength of the ultraviolet light is 350 nm or more, inexpensive glass substrates and acrylic substrates can be used, especially glass substrates, thus reducing operating costs.

[0162] In the above examples of light sources, there are low-mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and far-ultraviolet laser light sources. Among the above light sources, laser light sources that irradiate lasers are preferred.

[0163] The above-described examples of lasers include solid-state lasers, liquid lasers, and gas lasers. Furthermore, the above-described examples of solid-state lasers include semiconductor-excited lasers, etc. The examples of liquid lasers include pigment lasers, etc. The examples of gas lasers include excimer lasers, etc. Among these, semiconductor-excited lasers are preferred.

[0164] Examples of semiconductor-excited lasers include Nd:YAG lasers, Nd:YLF lasers, Nd:glass lasers, Nd:YVO4 lasers, Yb:YAG lasers, Yb-doped fiber lasers, Er:YAG lasers, and Tm:YAG lasers. Examples of excimer lasers include KrF lasers, XeCl lasers, ArF lasers, and F2 lasers. Among these, Nd:YAG lasers are preferred.

[0165] Furthermore, the output and cumulative light intensity of the light irradiating the adhesive layer vary depending on the type of light source, etc. However, when the irradiating light is a laser, the output can be between 0.1mW and 200W. Also, the cumulative light intensity is preferably between 1mJ / cm² and 50J / cm². If the cumulative light intensity is 0.1mJ / cm² or higher, it is less likely to produce scorching, peeling residue, etc., that occur during etching. If it is 50J / cm² or lower, the etching rate can be appropriately controlled for proper processing.

[0166] When irradiating the adhesive layer with light (laser), it is preferable to irradiate the adhesive layer from the support side with a laser. There is no particular limitation on the method of irradiation, and it can be carried out by a known method.

[0167] This embodiment may include a step of processing the prepared laminate before the step of separating the support from the adhered body.

[0168] The method for processing the above-mentioned multilayer includes thin film formation of the substrate such as slicing and back-side grinding, photosensitive etching, semiconductor wafer stacking, mounting of various components, resin encapsulation, etc.

[0169] Furthermore, this embodiment may include the following steps: moving the processed laminate from one device to another. The method of moving the laminate may include a method using a robotic arm, etc.

[0170] The laminate of this embodiment is processed in such a manner.

[0171] 3. Second revelation

[0171] (Topic 2)

[0171] As described in Patent Documents 3 and 4, the resin composition for forming microlenses is either a resin composition known to form positive patterns or a resin composition known to form negative patterns.

[0172] However, according to the present inventors, the conventional resin compositions described in Patent Document 3 or Patent Document 4, etc., are prone to producing residues during development. Furthermore, when the inter-lens distance is narrow, these residues can sometimes cause the microlenses to connect with each other. On the other hand, the resin composition used for forming microlenses is also required to produce microlens patterns with good adhesion to the substrate.

[0173] The invention disclosed in relation to the second part of this specification is constructed in view of the following points, with the aim of providing a microlens forming composition that has a limited range of usable resins, does not easily produce residues during development, and can form microlens patterns with good adhesion to a substrate; a method for manufacturing a microlens using the composition; a hardened film formed by hardening the composition; a solid-state imaging element having the microlens; and an imaging device having the solid-state imaging element.

[0174] 3-1. Composition

[0174] The second disclosure in this specification, which addresses the second problem described above, relates to a composition for forming a microlens, which comprises...

[0174] (A1) Belongs to the category of alkali-soluble resins containing unsaturated groups and polymeric compounds.

[0174] (A2) Polymers containing unsaturated groups that do not have base-soluble groups.

[0174] (B) Ultraviolet absorber,

[0174] (C) Epoxy compounds having two or more epoxy groups,

[0174] (D) Photopolymerization initiator, and

[0174] (F) Solvent,

[0174] (B) The content of ultraviolet absorber is more than 3% by mass and less than 20% by mass relative to the total mass of the solid components.

[0175] According to the composition for forming microlenses disclosed in the second paragraph above, the limitations of the resin that can be used are small, and it is not easy to generate residues during development, and it can form microlens patterns with good adhesion to the substrate.

[0175] 3-1-1. Suitable for the compound disclosed in the second paragraph.

[0175] [(B) Ingredients]

[0175] In conventional microlens manufacturing, when forming a negative pattern, sometimes after reaching the substrate interface, the composition hardens at the interface with the substrate in areas where no radiation is irradiated due to the radiation rays extending along the interface. It is believed that the resin hardened along the substrate interface expands, and this expanded resin becomes residue. In contrast, in the second disclosure, component (B) (ultraviolet absorber) absorbs the irradiated radiation and suppresses the expansion of excess radiation along the substrate interface. Therefore, it is believed that by including component (B) in the composition for forming the microlens, the occurrence of residue specific to the formation of a negative pattern can be suppressed. Furthermore, it is believed that by suppressing residue, the connection between microlenses caused by narrow inter-lens distances can also be suppressed.

[0176] (B) The component is preferably a benzotriazole compound, a benzophenone compound, or a triazole compound. These ultraviolet absorbers can efficiently absorb the energy of radiation (e.g., ultraviolet light) and can inhibit the spread of excess radiation along the substrate interface, thereby reducing the residue at the ends of the pattern after development.

[0177] Furthermore, component (B) is preferably a compound with a photosensitive functional group, and benzotriazole compounds, benzophenone compounds, and tri-compounds with photosensitive functional groups are even more preferred. From the viewpoint of improving the reactivity of components (A1) and (A2), the aforementioned photosensitive functional group is preferably an vinyl unsaturated group. Examples of the aforementioned vinyl unsaturated groups include acrylonitrile, methacrylonitrile, vinyl, allyl, styrene, etc. Among these, acrylonitrile and methacrylonitrile, which have high reactivity with components (A1) and (A2), are preferred. By using an ultraviolet absorber with an vinyl unsaturated group, the photosensitive reactive group of the ultraviolet absorber reacts with component (A1) or component (A2), and the ultraviolet absorber can be absorbed into the resin. Therefore, from the viewpoint of reducing heat damage to the substrate, for example, when the composition is hardened at a low temperature such as 140°C, the exudation of ultraviolet absorbers into the solvent can be suppressed, thereby improving the chemical resistance of the hardened product. Furthermore, it can also suppress coloring caused by the precipitation of ultraviolet absorbers or sublimation during baking.

[0178] In the examples of benzotriazole compounds, benzophenone compounds and tri-compounds having an ethylene unsaturated group, 2-[2-hydroxy-5-(methacryloxyethyl)phenyl]-2H-benzotriazole, etc.

[0179] Furthermore, among the commercially available examples of the aforementioned ultraviolet absorbers, there are products such as RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0180] 3-1-2. Mixing Quantity

[0180] The content of component (A1) is preferably 10% by mass or more and 90% by mass or less relative to the total mass of the solid component, and even better is 30% by mass or more and 80% by mass or less. By setting the content of component (A1) to 10% by mass or more, even for fine patterns, the adhesion of the developed area is excellent and the peeling of the pattern can be suppressed. By setting it to 90% by mass or less, good photocuring properties can be exhibited, the contrast between the exposed and unexposed areas during development is excellent, and sufficient photoetching properties are obtained.

[0181] The content of component (A2) is preferably 1 to 200 parts by mass relative to 100 parts by mass of component (A1), more preferably 4 to 100 parts by mass, and even more preferably 10 to 70 parts by mass. When the content of component (A2) is 1 part by mass or more relative to 100 parts by mass of component (A1), the enhancement effect of exposure sensitivity and developability produced by component (A2) can be fully utilized. Furthermore, when the content of component (A2) is 200 parts by mass or less relative to 100 parts by mass of component (A1), the concentration of acidic functional groups is very high, which can obtain good solubility for alkaline developer in the exposure section, thus forming the desired pattern.

[0182] The content of component (B) relative to the total mass of the solid components is preferably 3% by mass to 20% by mass, and more preferably 4% by mass to 20% by mass, and even more preferably 6% by mass to 18% by mass. By setting the content of component (B) to 3% by mass or more, the amount of radiation rays extending along the substrate interface can be reduced, and the residue at the pattern ends generated after development can be reduced. By setting the content of component (B) to 20% by mass or less, the reaction of the portion exposed to radiation rays can be sufficiently carried out, thus allowing the composition for microlens formation to be sufficiently hardened.

[0183] The content of component (C) relative to the total mass of the solid components is preferably 1 part by mass to 30 parts by mass, and more preferably 3 parts by mass to 20 parts by mass. By setting the content of epoxy compound in component (C) to 1 part by mass or more, the chemical resistance can be further improved, and by setting the content of epoxy compound in component (C) to 30 parts by mass or less, the adhesion to the substrate can be fully ensured.

[0184] Compared to the combined mass of components (A1) and (A2) of 100 parts by mass, the content of component (D) is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 0.3 parts by mass to 20 parts by mass. When the content of component (D) is 0.1 parts by mass or more, photopolymerization can be more fully carried out, especially on the surface of the composition (the side exposed to radiation). Furthermore, when the content of component (D) is 30 parts by mass or less, the curing reaction is difficult to proceed to the depth of the coating, and lens shapes are easily formed by heat flow.

[0185] The content of component (E) is preferably 0.5 to 200 parts by mass relative to the total of 100 parts by mass of component (D), and more preferably 1 to 100 parts by mass. By setting the content of component (E) to 0.5 parts by mass or more, the photopolymerization initiator can be fully activated by light irradiation, and by setting it to 200 parts by mass or less, the hardening reaction generated by the photopolymerization initiator can be controlled more precisely.

[0186] The content of component (F) is preferably 40% by mass or more and 80% by mass or less relative to the total mass of the composition for forming microlenses. If the content of component (F) is 40% by mass or more, the viscosity of the composition for forming microlenses can be formed to make it easy to coat the substrate. If it is 80% by mass or less, a coating with excellent film thickness uniformity can be obtained.

[0187] 2-2. Manufacturing method of components for microlenses

[0187] The following describes the manufacturing methods (1) to (3) of the components for microlenses disclosed in the second disclosure.

[0188] [Manufacturing Method of Microlenses (1)]

[0188] A method for manufacturing a microlens component according to one embodiment of the present invention includes: (i) a coating layer forming step, wherein the microlens forming component is coated and dried to form a coating of the microlens forming component; (ii) an exposure step, wherein a portion of the coating is irradiated with radiation through a photomask; (iii) a developing step, wherein the irradiated coating is developed and the unexposed portion is removed; and (iv) a heat flow step, wherein heat flow is applied to the exposed portion after development to process the exposed portion into a microlens shape, and heat hardening is performed simultaneously. The steps are described below.

[0189] [Coating Layer Formation Steps]

[0189] The coating layer forming step is a step of applying the above-mentioned microlens forming composition to a substrate and drying it to form a coating layer.

[0190] The aforementioned substrate can be any known material. Examples of substrates include glass substrates, silicon wafers, plastic substrates, and substrates on which color resists, coatings, anti-reflective films, and various metal films are formed. Examples of plastic substrates include resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide. Light-receiving elements such as photodiodes, light-emitting elements such as organic light-emitting elements, and pigmented elements such as color filters can also be provided on the substrate.

[0191] The coating method for the composition for forming microlenses can be any known coating method. Examples of the coating methods described above include known methods such as solution immersion coating, spray coating, roller coating, land coater, slot coater, or rotary coating. By these methods, the composition for forming microlenses can be coated to the desired thickness.

[0192] The drying method for the microlens forming composition coated by the above method can be any known drying method. The drying method can be performed by heating from an oven, a hot air blower, a heating plate, an infrared heater, vacuum drying, or a combination thereof. The heating temperature and heating time of the resin film can be appropriately selected according to the solvent used. For example, the heating temperature and heating time are preferably performed at 80 to 120°C for 1 to 10 minutes.

[0193] [Exposure Steps]

[0193] The exposure step is a step in which a portion of the above-mentioned coating layer is irradiated with radiation through a photomask, and a portion of the above-mentioned coating (a component for forming microlenses) is photocured.

[0194] The aforementioned photomask can be any known type. In examples of photomasks, multi-tone masks such as halftone masks and grayscale masks are included. A grayscale mask has a light-shielding portion and a diffraction grating formed on a light-transmitting substrate. The spacing between the light-transmitting areas of the slits, dots, and meshes of the diffraction grating is below the resolution limit of the light used for exposure, thereby controlling the light transmittance. A halftone mask has a light-shielding portion and a semi-transparent portion formed on a light-transmitting substrate. The transmittance of the light used for exposure is controlled by the semi-transparent portion.

[0195] The radiation irradiated includes visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these, ultraviolet light is preferred. Furthermore, the irradiation apparatus can be a known exposure device (ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, far ultraviolet lamp, etc.). Also, the wavelength of the radiation used for irradiation is preferably between 250 nm and 400 nm. The exposure dose of the radiation is preferably between 25 mJ / cm² and 3000 mJ / cm², and more preferably between 50 mJ / cm² and 2000 mJ / cm².

[0196] [Developing Steps]

[0196] The developing step is a step of developing the coating film exposed to radiation with alkali and removing the coating film from the unexposed areas.

[0197] Examples of coating development methods include shower development, spray development, dip development, and paddle (liquid-filled) development. Furthermore, the above development methods can be performed using commercially available developing machines or ultrasonic cleaners.

[0198] Furthermore, examples of suitable developing solutions include aqueous solutions containing alkalis (alkaline compounds) such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diacrylbicyclo[5.4.0]-7-undecene, and 1,5-diacrylbicyclo[4.3.0]-5-nonane. The developing conditions vary depending on the composition used for microlens formation, but it is preferable to develop at a temperature of 20 to 30°C for 10 to 120 seconds.

[0199] [Heat Flow Step]

[0199] The hot flow step involves applying hot flow to the exposed section (coating) after development, causing it to melt and flow, processing the exposed section into a microlens shape, and simultaneously performing a heat curing step.

[0200] The method for heat flow in the exposure section after development can be performed by known methods (heating by oven, hot air blower, heating plate, infrared heater, etc., vacuum drying, or a combination thereof). The temperature of the heat flow is not particularly limited as long as it is the temperature at which the coating melts and flows. It is preferable to heat flow at a temperature of 140 to 250°C for 10 to 120 minutes, and even more preferable to heat flow at a temperature of 180 to 230°C for 30 to 90 minutes.

[0201] By using the microlens forming composition of the present invention, even when a microlens pattern is formed by a negative photolithography method as in manufacturing method (1), the spread of radiation lines along the substrate interface can be suppressed, and the residue at the end of the pattern after development can be reduced. Therefore, the connection between microlenses can be suppressed, and a microlens pattern with a better shape can be formed.

[0202] [Manufacturing Method of Microlenses (2)]

[0202] The composition system for forming microlenses of the present invention can fully exert the residue suppression effect in the above manufacturing method (1), but it is also suitable for use in the formation of microlenses by the following manufacturing methods (2) or manufacturing methods (3).

[0203] A method for manufacturing a microlens composition according to one embodiment of the present invention includes: (i) a resin layer forming step, wherein the microlens composition is coated, irradiated with radiation, and dried to form a resin layer of the microlens composition; (ii) a step of forming an etch resist layer on the surface of the resin layer; (iii) an exposure step, wherein a portion of the etch resist layer is irradiated with radiation through a photomask; (iv) a development step, wherein the etch resist layer irradiated with radiation is developed; (v) a heat flow step, wherein the exposed portion after development is heat flowed to process the exposed portion into a microlens shape; and (vi) a transfer step, wherein the exposed portion after heat flow is used as a mask layer to dry etch the resin layer, and the shape of the mask layer is transferred to the resin layer.

[0204] [Resin Layer Formation Steps]

[0204] The resin layer formation step involves coating the above-mentioned microlens forming composition onto the surface of a substrate, irradiating it with radiation, and drying it to form a resin layer of the microlens forming composition. In the above step, before coating the microlens forming composition, a transparent resin is coated onto the unevenness of the substrate surface using a spin coater and embedded to planarize it. Then, after coating the microlens forming composition onto the planarized substrate surface, it is irradiated with radiation (e.g., ultraviolet light) to thermally harden it and form a resin layer. Furthermore, the method of coating the microlens forming composition and the method of irradiating the coated microlens forming composition with radiation can be performed by the same method as that used in the manufacturing method (1) described above. The above thermal hardening can be performed by a general method of thermally hardening (post-baking) the composition containing alkali-soluble resin and epoxy resin.

[0205] [Steps for forming the etch resist layer]

[0205] The step of forming the etching resist layer is the step of forming the etching resist layer on the surface of the above-mentioned resin layer.

[0206] The composition of the etching resist is only required to transfer its shape to the resin layer as a mask layer in the transfer step described later, and there are no particular restrictions. The etching resist can be a positive resist or a negative resist. Furthermore, the method for forming the etching resist layer on the surface of the resin layer can be a known method.

[0207] [Exposure Steps]

[0207] The exposure step is a step in which a portion of the etch resist layer is irradiated with radiation through a photomask, and the portion of the etch resist layer is photocured. Furthermore, the method for exposing the etch resist layer is the same as the method used in the manufacturing method (1) described above, but the appropriate conditions such as temperature can be changed according to the type of etch resist.

[0208] [Developing Steps]

[0208] The development step is a step of alkaline development of the etch resist layer that has been exposed to radiation. When the etch resist is positive, the exposed areas are removed; when the etch resist is negative, the unexposed areas are removed. The alkaline development method can be appropriately selected from known methods as long as it is suitable for the type of etch resist.

[0209] [Heat Flow Step]

[0209] The hot flow step involves applying hot flow to the exposed portion of the etch resist layer after development, causing it to melt and flow, thereby processing the exposed portion of the etch resist layer into a microlens shape. Furthermore, the hot flow step is the same method used in the manufacturing method (1) described above, but the appropriate temperature and other conditions can be changed to suit the type of etch resist.

[0210] [Transfer Steps]

[0210] The transfer step is a step of dry etching the resin layer by using the exposed portion of the etch resist layer after heat flow as a mask layer, and transferring the shape of the mask layer onto the resin layer.

[0211] The above-described dry etching system can use known methods. Examples of dry etching methods include plasma etching, ion etching, reactive ion etching, sputtering etching, etc. Furthermore, known apparatus can be used in the dry etching system. Examples of gases that can be used in dry etching include fluorine gases such as CHF3, CF4, C2F6, C3F8, and SF6; chlorine gases such as Cl2 and BCl3; oxygen gases such as O2 and O3; reducing gases such as H2, NH3, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8, HF, HI, HBr, HCl, NO, NH3, and BCl3; and inert gases such as He, N2, and Ar. These gas systems can be mixed and used.

[0212] [Manufacturing Method of Microlenses (3)]

[0212] A method for manufacturing a microlens composition according to one embodiment of the present invention includes (i) a coating forming step, in which the microlens composition is coated on a lens material layer and dried to form a coating of the microlens composition; (ii) an exposure step, in which a portion of the coating is irradiated with radiation through a photomask; (iii) a development step, in which the irradiated coating is developed and the unexposed portion is removed; (iv) a mask layer forming step, in which the developed coating is subjected to heat flow to process the coating into a microlens shape and is simultaneously heated and hardened to form a mask layer having a microlens pattern; and (v) a transfer step, in which the lens material layer and the aforementioned mask layer are dry etched and the shape of the coating layer is transferred to the lens material layer.

[0213] [Coating Formation Steps]

[0213] The coating formation step involves coating the aforementioned microlens forming composition onto the lens material layer and drying it to form a coating film of the microlens forming composition. At this time, the surface of the lens material layer is planarized using the same method as described in the microlens manufacturing method (2). Furthermore, the method of coating the microlens forming composition and the method of drying the coated microlens forming composition can be performed using the same method as used in the manufacturing method (1) described above.

[0214] The lens material layer can be any layer obtained from a known lens material.

[0215] [Exposure and Development Steps]

[0215] The above-mentioned exposure step (ii) and development step (iii) can be performed by the same method as described in the microlens manufacturing method (1).

[0216] [Mask Layer Formation Steps]

[0216] The mask layer forming step involves subjecting the developed coating to heat flow, causing it to melt and flow, processing the coating into a microlens shape while simultaneously heating and hardening it to form a mask layer with a microlens pattern. The heat flow of the coating can be performed using the same method as that used in the manufacturing method (1) described above.

[0217] [Transfer Steps]

[0217] The transfer step can be performed using the same dry etching method as the manufacturing method (2) described above.

[0218] By using the microlens forming composition of the present invention, such as in the manufacturing method (3), even in a method where the microlens forming composition is used as a resist material, the propagation of radiation lines along the interface between the lens layer and the etched resist layer can be suppressed, and the occurrence of residue at the ends of the resist pattern can be suppressed. Therefore, if the hardened form of the microlens forming composition of the present invention is used as a mask, the lens layer can be etched with high precision, and a microlens pattern with a better shape can be formed.

[0219] 2-3. Solid-state imaging elements

[0219] The solid-state imaging element disclosed in the second part has the microlens described above. Because the solid-state imaging element of the present invention has the microlens described above, high pixel count and high sensitivity are possible.

[0220] 2-4. Imaging Device

[0220] The imaging device disclosed in the second disclosure has the aforementioned solid-state imaging element. The imaging device of the present invention can obtain high-quality images using the aforementioned solid-state imaging element.

[0221] 2-5. Example of the second state

[0221] Regarding the second state based on the above-mentioned technical concept, the following can be exemplified.

[0221] [1] A composition for forming a microlens, which is a composition for forming a microlens pattern, and includes

[0221] (A1) Belongs to the category of alkali-soluble resins containing unsaturated groups and polymeric compounds.

[0221] (A2) Polymer compounds containing unsaturated groups that do not have alkali-soluble groups;

[0221] (B) Ultraviolet absorber,

[0221] (C) Epoxy compounds having two or more epoxy groups,

[0221] (D) Photopolymerization initiator, and

[0221] (F) Solvent;

[0221] Wherein, relative to the total mass of the solid components, the content of the aforementioned (B) ultraviolet absorber is more than 3% by mass and less than 20% by mass.

[0222] [2] The microlens forming composition as described in [1], wherein the aforementioned (A1) is a polymeric compound containing unsaturated groups of an alkali-soluble resin and is a resin represented by the following general formula (1).

[0222]

[0222] (In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atom may be substituted by a group consisting of a straight-chain or branched alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R1 is an alkyl group having 2 to 4 carbon atoms, and l is a number from 0 to 3. G is a (meth)acrylonitrile group, a substituent of formula (2) or formula (3) below, and Y is a tetravalent carboxylic acid residue. Z is a hydrogen atom or a substituent of formula (4) below, and more than one is a substituent of formula (4) below. n is a number with an average value from 1 to 20.)

[0222]

[0222]

[0222] (In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkyl group or an alkylaryl group with 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group with 2 to 20 carbon atoms, and p is a value from 0 to 10.)

[0222]

[0222] (In formula (4), W represents a divalent or trivalent carboxylic acid residue, and m represents a value of 1 or 2.)

[0223] [3] The microlens forming composition as described in [1] or [2], wherein the aforementioned (B) ultraviolet absorber is selected from the group consisting of benzotriazole compounds, benzophenone compounds and tri compounds.

[0224] [4] A microlens forming composition as described in any one of [1] to [3], wherein the aforementioned (B) ultraviolet absorber has an ethylene unsaturated group.

[0225] [5] The microlens forming composition as described in any one of [1] to [4], wherein the aforementioned (A1) is a polymeric compound containing unsaturated groups of an alkali-soluble resin with a weight average molecular weight of 1,000 or more and 40,000 or less, and an acid value of 50 mg KOH / g or more and 200 mg KOH / g or less.

[0226] [6] The microlens forming composition as described in any one of [1] to [5] contains a sensitizer as component (E).

[0227] [7] A method for manufacturing a microlens, comprising:

[0227] The coating layer forming step involves coating the microlens forming composition described in any one of [1] to [6] and drying it to form a coating of the microlens forming composition;

[0227] The exposure step involves irradiating a portion of the aforementioned coating with radiation through a photomask;

[0227] The developing step involves developing the coating that has been irradiated with the aforementioned radiation and removing the unexposed areas;

[0227] The hot flow step involves hot flow to the exposure section after the aforementioned development, processing the aforementioned exposure section into a microlens shape, and simultaneously heating and hardening it.

[0228] [8] A method for manufacturing a microlens includes:

[0228] The resin layer forming step involves coating the microlens forming composition described in any one of [1] to [6], irradiating it with radiation, and drying it to form a resin layer of the microlens forming composition;

[0228] The step of forming an etching resist layer on the surface of the aforementioned resin layer;

[0228] The exposure step involves irradiating a portion of the aforementioned etch resist layer with radiation through a photomask;

[0228] The development step involves developing the etch resist layer that has been irradiated by the aforementioned radiation.

[0228] The hot flow step involves performing hot flow on the exposure section after the aforementioned development, thereby processing the aforementioned exposure section into a microlens shape;

[0228] The transfer step involves using the previously exposed portion after the heat flow as a mask layer to dry-etch the resin layer, and transferring the shape of the mask layer to the resin layer.

[0229] [9] A method for manufacturing a microlens includes

[0229] The coating forming step involves coating the microlens forming composition described in any one of [1] to [6] onto a lens material layer and drying it to form a coating film of the microlens forming composition;

[0229] The exposure step involves irradiating a portion of the aforementioned coating with radiation through a photomask;

[0229] The developing step involves developing the coating that has been irradiated with the aforementioned radiation and removing the unexposed areas;

[0229] The mask layer forming step involves applying heat to the aforementioned developed coating film to process the coating film into a microlens shape while simultaneously heating and hardening it to form a mask layer with a microlens pattern.

[0229] The transfer step involves dry etching the aforementioned lens material layer and the aforementioned mask layer, and transferring the shape of the aforementioned coating layer to the aforementioned lens material layer.

[0230]

[10] A hardened film is formed by hardening the microlens forming composition described in any one of [1] to [6].

[0231]

[11] A microlens comprising the hardened film described in

[10] .

[0232]

[12] A solid-state imaging element having the microlens described in

[11] .

[0233]

[13] An imaging device having the solid-state imaging element described in

[12] .

[0233] [Example]

[0234] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto.

[0235] First, we will explain the synthesis examples of alkali-soluble resins containing unsaturated groups belonging to component (A1). Unless otherwise specified, the evaluation of the resins in these synthesis examples will be carried out as follows.

[0236] Furthermore, when using the same type of measuring machine, the name of the machine manufacturer is omitted from point 2. Also, in the embodiments, the glass substrates used in the fabrication of the substrate with the measuring hardened film are all subjected to the same treatment. Also, when the first decimal place of the content of each component is 0, the notation below the decimal point is sometimes omitted.

[0237] [Solid component concentration]

[0237] The weight of 1g of the resin solution obtained in the synthesis example after being immersed in a glass filter [weight: W0(g)] and weighed [W1(g)] and heated at 160°C for 2 hours [W2(g)] is calculated according to the following formula.

[0237] Solid component concentration (weight %) = 100 × (W2 - W0) / (W1 - W0)

[0238] [Acid Value]

[0238] The resin solution was dissolved in diane and titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0239] [Molecular Weight]

[0239] The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using a "HLC-8220GPC" (manufactured by TOSOH Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by TOSOH Corporation), temperature: 40°C, speed: 0.6 ml / min). The value was converted to the standard polystyrene (manufactured by TOSOH Corporation, PS-oligomer kit) to obtain the molecular weight.

[0240] The abbreviations recorded in the synthetic examples are as follows.

[0240] BPFE: Bisphenol A epoxy resin (in general formula (5), Ar is a benzene ring, l is an epoxy resin with 0, and epoxy equivalent 256 g / eq)

[0240] BNFE: Bisnaphthol-type epoxy resin (the epoxy resin in general formula (1) where Ar is a naphthalene ring, l is 0, and the epoxy equivalent is 281 g / eq)

[0240] BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride

[0240] THPA: 1,2,3,6-Tetrahydrophthalic anhydride

[0240] TPP: Triphenylphosphine

[0240] AA: Acrylic Acid

[0240] PGMEA: Propylene glycol monomethyl ether acetate

[0240] DCPMA: Dicyclopentyl Methacrylate

[0240] GMA: Glycidyl methacrylate

[0240] St: Styrene

[0240] AIBN: Azobisisobutyronitrile

[0240] TDMAMP: Trimethylaminomethylphenol

[0240] HQ: Hydroquinone

[0240] SA: Succinic anhydride

[0240] TEA: Triethylamine

[0241] [Synthesis Example 1]

[0241] In a 250 mL four-necked flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g) were packed and stirred at 100 to 105 °C for 12 hours to obtain the reaction product. Afterward, PGMEA (25.00 g) was packed to adjust the solid content to 50% by mass.

[0242] Then, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were loaded into the obtained reaction product, and the mixture was stirred at 115 to 120 °C for 6 hours to obtain a curable resin (A1)-1 containing unsaturated groups. The solid content of the obtained resin solution was 57.0% by mass, and the acid value (converted to solid content) was 96 mg KOH / g. The Mw obtained by GPC analysis was 3600.

[0243] [Synthesis Example 2]

[0243] In a 250 mL four-necked flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g) were packed and stirred at 100 to 105 °C for 12 hours to obtain the reaction product. Afterward, PGMEA (25.00 g) was packed to adjust the solid content to 50% by mass.

[0244] Then, BPDA (10.06 g, 0.03 mol) and THPA (11.89 g, 0.08 mol) were loaded into the obtained reaction product, and the mixture was stirred at 115 to 120 °C for 6 hours to obtain a curable resin (A1)-2 containing unsaturated groups. The solid content of the obtained resin solution was 57.0% by mass, and the acid value (converted to solid content) was 98 mg KOH / g. The Mw obtained by GPC analysis was 2300.

[0245] [Synthesis Example 3]

[0245] In a 250 mL four-necked flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g) were packed and stirred at 100 to 105 °C for 12 hours to obtain the reaction product. Afterward, PGMEA (25.00 g) was packed to adjust the solid content to 50% by mass.

[0246] Then, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were loaded into the obtained reaction product, and the mixture was stirred at 115 to 120 °C for 6 hours to obtain a curable resin (A1)-3 containing unsaturated groups. The solid content of the obtained resin solution was 56.3% by mass, and the acid value (converted to solid content) was 97 mg KOH / g. The Mw obtained by GPC analysis was 4700.

[0247] [Synthesis Example 4]

[0247] In a 250 mL four-necked flask equipped with a reflux condenser, BPFE (50.00 g, 0.09 mol), AA (12.82 g, 0.20 mol), TPP (0.23 g), and PGMEA (40.00 g) were packed and stirred at 100 to 105 °C for 12 hours to obtain the reaction product. Subsequently, PGMEA (25.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0248] Then, BPDA (13.09 g, 0.04 mol) and THPA (6.77 g, 0.04 mol) were loaded into the obtained reaction product, and the mixture was stirred at 115 to 120 °C for 6 hours to obtain a curable resin (A1)-4 containing unsaturated groups. The solid content of the obtained resin solution was 56.1% by mass, and the acid value (converted to solid content) was 91 mg KOH / g. The Mw obtained by GPC analysis was 3500.

[0249] [Synthesis Example 5]

[0249] In a 1L four-necked flask equipped with a reflux condenser, 300g of PGMEA was placed in the flask and nitrogen-substituted within the flask system. The temperature was then raised to 120°C. A mixture consisting of 10g of AIBN dissolved in a monomer mixture (DCPMA (77.1g, 0.35mol), GMA (49.8g, 0.35mol), St (31.2g, 0.30mol)) was added dropwise over 2 hours through a dropping funnel in the flask. The mixture was then stirred at 120°C for 2 hours to obtain a copolymer solution.

[0250] Then, after replacing the flask system with air, AA (24.0 g, 95% glycidyl group), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups. SA (30.0 g, 90% of the added mole of AA) and TEA (0.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 120°C for 4 hours to obtain a curable resin (A1)-5 containing unsaturated groups. The solids content of the resin solution was 46.0% by mass, and the acid value (converted to solids content) was 76 mg KOH / g. The Mw obtained by GPC analysis was 5300.

[0251] 1. Embodiments / Comparative Examples Disclosed in Section 1

[0251] The composition for forming the adhesive layer is prepared according to the mixing amounts (in mass%) listed in Tables 1 to 3. The mixing components used in Tables 1 to 3 are as follows.

[0252] (Polymerizable compounds containing unsaturated groups)

[0252] (A1)-1: The resin solution obtained in Synthesis Example 1 (solid content concentration 57.0% by mass).

[0252] (A1)-2: The resin solution obtained in Synthesis Example 2 (solid content concentration 57.0% by mass).

[0252] (A1)-3: The resin solution obtained in Synthesis Example 3 (solid content concentration 56.3% by mass)

[0252] (A1)-5: The resin solution obtained in Synthesis Example 5 (solid content concentration 46.0% by mass)

[0252] (A2)-1: A mixture of dinepentylenetetroxide pentaacrylate and hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is a registered trademark of the same company)

[0252] (A2)-2: Ethylene oxide 6-molar adduct of trimethylolpropane triacrylate (ARONIX M-360, manufactured by Dong-A Synthetic Co., Ltd.)

[0252] (A2)-3: Ethylene oxide 12-molar adduct of dinepentylenetetramethylol hexaacrylate (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.)

[0252] (A2)-4: ε-caprolactone 6-molar adduct of dinepentyltetramethylol hexaacrylate (KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)

[0253] (UV absorber)

[0253] (B)-1: RUVA-93 (2-(2'-hydroxy-5'-methylpropenylated ethylphenyl)-2-H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd., molecular weight: 323.35, absorbance at 355 nm: 0.25)

[0253] (B)-2: Tinuvin 477 (hydroxyphenyl tri-type ultraviolet absorber, manufactured by BASF, solid content 80.0% by mass, molecular weight: 1100, absorbance at 355nm: 0.28)

[0253] (B)-3: UVA-5080 (3-2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenylethyl = copolymer of methacrylate and methyl methacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., solid content concentration 41.0% by mass, molecular weight: 40,000 to 60,000, absorbance at 355 nm wavelength: 0.16)

[0253] (B)-4: UVA-935LH (benzophenone-based polymer, manufactured by BASF, solid content concentration 30.0% by mass, absorbance at 355nm wavelength: 0.04)

[0253] (B)'-5: Carbon black concentration 25.0% by mass, polymeric dispersant concentration 4.0% by mass, and PGMEA dispersion of the dispersing resin (alkali-soluble resin (A1)-1 (solid content 9.0% by mass) in the synthesis example (solid content 38.0% by mass)

[0254] Furthermore, the above absorbance was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.) in a quartz cell with an optical path length of 1 cm, measuring the absorbance of a 0.001% by weight acetonitrile solution. Also, when component (B) is not readily soluble in acetonitrile, the absorbance of a solution dissolved in propylene glycol monomethyl ether acetate (PGMEA) was measured instead.

[0255] (solvent)

[0255] (F): Propylene glycol monomethyl ether acetate (PGMEA)

[0256] [Table 1]

[0257] [Table 2]

[0258] [Table 3]

[0259] [Evaluation]

[0259] The hardened film formed by hardening the above-described adhesive layer composition is evaluated as follows.

[0260] [Fabrication of substrates with hardened films for transmittance / laser processability evaluation]

[0260] The adhesive layer forming compositions shown in Tables 1 to 3 were applied using a spin coater to a 125mm × 125mm synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") that had been pre-treated with ultraviolet light at a wavelength of 254nm and an illuminance of 1000mJ / cm² by a low-pressure mercury lamp and then cleaned. The resulting film thickness was 1.0μm after heat curing. A dry film was then pre-baked at 90°C for 3 minutes using a hot air dryer. Finally, a substrate with a cured film (coating) was obtained by formal curing (post-baking) at 250°C for 30 minutes. Furthermore, the transmittance of the synthetic quartz glass substrate at wavelengths between 350nm and 450nm is 90% or more across the entire wavelength range described above.

[0261] Furthermore, the above transmittance was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.), with the transmittance of a single quartz glass monomer as the baseline.

[0262] [Penetration Rate Assessment]

[0262] The transmittance of the substrate with the hardened film after formal hardening was measured at wavelengths of 355nm and 400nm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.).

[0263] [Laser Processability (Peelability) Assessment]

[0263] (Evaluation Method)

[0263] For the hardened film after formal curing, a flash-excited Nd:YAG Q-SW laser oscillator "Callisto" (manufactured by V Technology Co., Ltd.) was used to irradiate the quartz glass substrate side with laser (laser wavelength: 355nm). The hardened film was processed (coating removal) with a laser energy of 100 to 600 mJ / cm2, and the processed hardened film was observed with an optical microscope. Furthermore, a value of Δ or higher is considered acceptable.

[0264] (Evaluation Basis)

[0264] ◎:No coating residue in the laser irradiation area when the coating strength is below 400mJ / cm2.

[0264] ○: No coating residue in the laser irradiation area when the value exceeds 400 mJ / cm2 but is below 500 mJ / cm2.

[0264] △: No coating residue in the laser irradiation area when the value exceeds 500 mJ / cm2 but is below 600 mJ / cm2.

[0264] ×: Coating residue is present in the laser irradiation area when the concentration exceeds 600 mJ / cm2.

[0265] [Next, the fabrication of the substrate with the hardened film used for strength evaluation]

[0265] The adhesive layer formation compositions shown in Tables 1 to 3 were coated onto a glass substrate "#1737" with a film thickness of 5.0 μm after heat curing using a spin coater. A dry film was prepared by pre-baking at 90°C for 3 minutes using a heated plate. Then, a glass substrate "#1737" cut into 2 mm × 2 mm pieces was placed on the dry film and heated on a heated plate at 110°C for 1 minute for temporary bonding. After this, a formal curing (post-baking) was performed at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured film.

[0266] [Evaluation of Adhesion Strength (Shear Strength)]

[0266] (Evaluation Method)

[0266] For a 2mm × 2mm glass substrate "#1737" bonded to the hardened film, the bonding strength was tested using a wafer shear strength tester (manufactured by ARC TECH). A value of △ or higher was considered acceptable.

[0267] (Evaluation Basis)

[0267] ◎:The bonding strength is above 10MPa

[0267] ○: The strength is above 8MPa but below 10MPa

[0267] △: The strength is above 5MPa but below 8MPa

[0267] ×: The strength was less than 5MPa.

[0268] [Preparation of hardened films for heat resistance evaluation / compatibility evaluation / chemical resistance evaluation / detergency evaluation]

[0268] Adhesive layer forming compositions shown in Tables 1 to 3 were coated onto a glass substrate "#1737" with a film thickness of 5.0 μm after heat curing using a spin coater. A dry film was then pre-baked at 90°C for 3 minutes using a heated plate. Subsequently, a substrate with a cured film was obtained by formal curing (post-baking) at 230°C using a hot air dryer for 30 minutes. Furthermore, during heat resistance evaluation, the obtained cured film was cut out for TG-DTA measurement.

[0269] [Heat Resistance Assessment]

[0269] (Evaluation Method)

[0269] Using a TG-DTA apparatus "TG / DTA6200" (manufactured by SEIKO INSTRUMENTS Co., Ltd.), the powder of the obtained hardened film was heated from 30°C to 400°C in air at a heating rate of 5°C / min, and the temperature at which the weight of the sample decreased by 5% was measured. Furthermore, a value of △ or higher is considered acceptable.

[0270] (Evaluation Basis)

[0270] ○: The temperature at which 5% weight is reduced is above 280℃.

[0270] △: The temperature at which a 5% weight reduction occurs is above 250℃ but below 280℃.

[0270] ×: The temperature at which 5% weight is reduced is 250℃

[0271] [Compatibility Assessment]

[0271] (Evaluation Method)

[0271] The haze value of the hardened film (coating) on ​​the substrate with the hardened film was measured using a turbidimeter "NDH5000" (manufactured by Nippon Denshoku Kogyo Co., Ltd.). A value of △ or higher is considered acceptable.

[0272] (Evaluation Criteria)

[0272] ○: The haze value of the substrate with the resin curing film is 10 or less.

[0272] △: The haze value of the substrate with the resin curing film is greater than 10 and less than 50.

[0272] ×: The haze value of the substrate with the resin curing film exceeds 50.

[0273] [Solvent Resistance Assessment]

[0273] (Evaluation Method)

[0273] The hardened film (coating) of the substrate with the hardened film was immersed in N-methylpyrrolidone for 10 minutes, and then washed / dried. After that, the film thickness of the hardened film (coating) after the test was measured using a stylus-type step shape measuring device "P-17" (manufactured by KLA TENCOR Co., Ltd.). A thickness of △ or above is considered acceptable.

[0274] The residual film rate in the drug resistance assessment is calculated by taking the film thickness before the test as L1 and the film thickness after the test as L2, and using the following formula.

[0274] Residual film rate (%) = L2 / L1 × 100

[0275] (Evaluation Basis)

[0275] ○: Residual film rate is over 90%.

[0275] △: Residual film rate is above 80% but below 90%.

[0275] ×: Residual film rate not reaching 80%

[0276] [Cleanliness Assessment]

[0276] (Evaluation Method)

[0276] The hardened film (coating) of the substrate with the hardened film was immersed in the cleaning solution "NK poleve 480" (manufactured by Nippon Kayaku Co., Ltd.) at room temperature for 10 minutes to clean the hardened film (coating). After this, the glass substrate was cleaned and dried, and the absence of residue on the glass substrate was checked using an optical microscope. A value of △ or higher is considered acceptable.

[0277] (Evaluation Basis)

[0277] ○: No residue is visible on the glass substrate.

[0277] △: Residue can be seen on a portion of the glass substrate.

[0277] ×: Residue is visible throughout the glass substrate.

[0278] The evaluation results are presented in Tables 4 to 6.

[0279] [Table 4]

[0280] [Table 5]

[0281] [Table 6]

[0282] As shown in Tables 4 to 6, it can be seen that the above-mentioned adhesive layer forming composition, when used in an adhesive layer laminate, exhibits excellent processability (peelability) under laser processing at a wavelength of 355 nm. This is believed to be because the addition of component (B) allows light of that wavelength to be efficiently absorbed by the adhesive layer, causing the adhesive layer to deteriorate and decompose.

[0283] Furthermore, it is known that setting the amount of component (B) relative to the total mass of the solid components to 10% by mass or more and 80% by mass or less ensures good laser processability (peelability) while obtaining a hardened film with excellent adhesion strength and chemical resistance. This is believed to be because the unsaturated groups of components (A1) and (A2) polymerize and are thermo-cured, which can improve the strength of the hardened film and inhibit solvent dissolution.

[0284] Regarding component (A), by using a curable resin containing unsaturated groups as shown in general formula (1), laser peelability can be maintained while heat resistance is improved, thus ensuring sufficient process profit in the processing steps of the laminate. This is believed to be due to the excellent thermal stability of the curable resin containing unsaturated groups as shown in general formula (1), which has many aromatic rings.

[0285] Regarding component (B), it is known that by using an ultraviolet absorber with an absorbance of 0.10 or higher for light with a wavelength of 355 nm, the processing (peelability) performed by a laser with a wavelength of 355 nm is excellent. This is believed to be because component (B) absorbs light more efficiently, promoting the deterioration and decomposition of the adhesive layer.

[0286] As shown in Examples 1, 3 to 18, regarding component (B), it is known that the adhesive layer forming composition containing a UV absorber with a weight average molecular weight (Mw) of 1000 or more exhibits excellent heat resistance and solvent resistance. This is believed to be because the exudation of component (B) during heating or its dissolution in solvents can be suppressed.

[0287] As shown in Examples 14 to 16, it is evident that the adhesive layer forming composition containing an epoxy alkylate modifier or a caprolactone modifier of (meth)acrylate as component (A2) exhibits excellent adhesion strength. This is believed to be because the inclusion of a compound with high flowability upon heating as component (A2) enhances the flowability of the dried film during heat bonding and allows it to follow the adherend.

[0287] 2. Examples / Comparative Examples of the Second Disclosure

[0288] The microlens forming compositions of Examples 21 to 31 and Comparative Examples 21 to 23 were prepared using the mixing amounts (in mass %) listed in Tables 7 and 8. The mixing components used in Tables 7 and 8 are as described below.

[0289] (Polymerizable compounds containing unsaturated groups)

[0289] (A1)-1: The resin solution obtained in Synthesis Example 1 (solid content concentration 57.0% by mass).

[0289] (A1)-2: The resin solution obtained in Synthesis Example 2 (solid content concentration 57.0% by mass)

[0289] (A1)-3: The resin solution obtained in Synthesis Example 3 (solid content concentration 56.3% by mass)

[0289] (A1)-4: The resin solution obtained in Synthesis Example 4 (solid content concentration 56.1% by mass).

[0289] (A1)-5: The resin solution obtained in Synthesis Example 5 (solid content concentration 46.0% by mass)

[0289] (A2)-1: Dinepentylenetetroxide penta / hexaacrylate mixture (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is a registered trademark of the same company)

[0290] (Ultraviolet absorber)

[0290] (B)-1: RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.)

[0290] (B)-6: Tinuvin 384-2 (manufactured by BASF JAPAN, 95% by weight, "Tinuvin" is a registered trademark of the same company)

[0290] (B)-7: Tinuvin 400 (solid content concentration 85% by mass)

[0290] (B)-8: ADEKASTAB 1413 (Made by ADEKA Corporation, "ADEKASTAB" is a registered trademark of the same company)

[0291] (Epoxy compound)

[0291] (C): Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the same company, epoxy equivalent 180 to 192 g / eq)

[0292] (Photopolymerization initiator)

[0292] (D)-1: Omnirad 907 (IGM Resins, manufactured by BV, "Omnirad" is a registered trademark of the same company)

[0292] (D)-2: Irgacure OXE-01 (Made by BASF Corporation; "Irgacure" is a registered trademark of the same company)

[0293] (Sensitizer)

[0293] (E): Milchlerone

[0294] (solvent)

[0294] (F): Propylene glycol monomethyl ether acetate (PGMEA)

[0295] [Table 7]

[0296] [Table 8]

[0297] [Evaluation]

[0297] The following evaluation was performed on the hardened films formed by hardening the microlens forming composition of Examples 21 to 31 and Comparative Examples 21 to 23 shown in Tables 7 and 8.

[0298] (Fabrication of a substrate with a hardened film for refractive index measurement)

[0298] The microlens forming components shown in Tables 7 and 8 were coated on a 5-inch substrate (silicon wafer) with a heat-cured film thickness of 1.0 μm using a spin coater. A dry film was prepared by pre-baking at 100°C for 5 minutes using a heated plate. Then, the dry film was subjected to photocuring reaction (exposure) by irradiating it with ultraviolet light at 500 mJ / cm2 using an ultra-high pressure mercury lamp (wavelength 365 nm, illuminance 30 mW / cm2). Finally, it was subjected to formal curing (post-baking) at 230°C using a hot air dryer for 30 minutes to obtain a substrate with a cured film for refractive index measurement.

[0299] [Refractive Index Assessment]

[0299] The refractive index of the substrate with the hardened film after formal hardening was measured at a wavelength of 633 nm using an ellipsometry (manufactured by JAWoollam).

[0300] (Fabrication of a substrate with a hardened film for transmittance measurement)

[0300] The microlens forming components shown in Tables 7 and 8 were coated onto a 125mm × 125mm glass substrate "# 1737" (manufactured by CORNING Corporation) (hereinafter referred to as "glass substrate") using a spin coater to achieve a film thickness of 1.0 μm after heat curing. A dry film was prepared by pre-baking at 100°C for 5 minutes using a heated plate. Then, the above-mentioned dry film was subjected to a photocuring reaction (exposure) by irradiating it with ultraviolet light of 300 mJ / cm2 using an ultra-high pressure mercury lamp (wavelength 365nm, illuminance 30mW / cm2). After that, a substrate with a cured film for transmittance measurement was obtained by formally curing (post-baking) at 230°C for 30 minutes using a hot air dryer.

[0301] [Penetration Rate Assessment]

[0301] The transmittance of the substrate with the hardened film after formal hardening was measured at a wavelength of 400 nm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High Tech Science Co., Ltd.).

[0302] (Fabrication of a substrate with a hardened film for evaluating pattern adhesion and pattern end residue)

[0302] The microlens forming components shown in Tables 7 and 8 were coated on a 125mm × 125mm glass substrate with a film thickness of 2.0μm after heat curing. A dried film was prepared by pre-baking at 100°C for 5 minutes using a heated plate. Then, the dried film was subjected to photocuring reaction (exposure) by irradiating it with ultraviolet light at 300mJ / cm2 using an ultra-high pressure mercury lamp (wavelength 365nm, illuminance 30mW / cm2).

[0303] Next, the exposed dry film (exposed film) is developed for 10 seconds at 23°C using a 0.8% TMAH (tetramethylammonium hydroxide) developer at a shower pressure of 1 kgf / cm², from the time the pattern begins to appear (cut-off time = BT). Then, it is sprayed with water at 5 kgf / cm² to remove the unexposed portions of the exposed film, resulting in a dot pattern with a diameter of 5 μm on the glass substrate. Finally, the obtained dot pattern is formally cured (post-baked) at 230°C using a hot air dryer for 30 minutes to obtain a substrate with a cured film for evaluating pattern adhesion and pattern end residue.

[0304] [Pattern Adhesion Assessment]

[0304] (Evaluation Method)

[0304] Using an optical microscope, observe whether the dot pattern (hardened film) with a diameter of 5 μm on the above-mentioned substrate has peeled off. Furthermore, a value of △ or higher is considered acceptable.

[0305] (Evaluation Basis)

[0305] ○: No peeling was observed on the dot pattern.

[0305] △: Peeling was confirmed in one part of the dot pattern.

[0305] ×: All dot patterns have been removed.

[0306] [Evaluation of Residue at the End of the Pattern]

[0306] (Evaluation Method)

[0306] Using a scanning electron microscope (SEM), observe the ends of a 5μm diameter dot pattern (hardened film) on the above-mentioned substrate to check for any residue. Furthermore, a value of △ or higher is considered acceptable.

[0307] (Evaluation Basis)

[0307] ○: No residue was seen at the end of the pattern.

[0307] △: Residue was identified at one end of the pattern.

[0307] ×: The residue at the end of the pattern is significant.

[0308] (Fabrication of a substrate with a hardened film for chemical resistance evaluation)

[0308] The microlens forming components shown in Tables 7 and 8 were coated on a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A dry film was prepared by pre-baking at 100°C for 5 minutes using a heated plate. Then, the dry film was subjected to photocuring reaction (exposure) by irradiating it with ultraviolet light at 300 mJ / cm2 using an ultra-high pressure mercury lamp (wavelength 365 nm, illuminance 30 mW / cm2). After that, a formal curing (post-baking) was performed at 180°C for 1 hour using a hot air dryer, or a formal curing (post-baking) was performed at 230°C for 30 minutes to obtain a substrate with a cured film for chemical resistance evaluation.

[0309] [Solvent Resistance Assessment]

[0309] (Evaluation Method)

[0309] The film thickness (L1) of the hardened film after formal curing (post-baking) and the film thickness (L2) of the hardened film after drying, after immersion in acetone for 10 minutes and washing, are measured using a separate stylus-type step shape measuring device "P-17" (manufactured by KLA TENCOR Co., Ltd.). The residual film rate (%) is calculated from the following formula. Furthermore, a value of △ or higher is considered acceptable.

[0309] Residual film rate (%) = L2 / L1 × 100

[0310] (Evaluation Basis)

[0310] ○: Residual film rate is over 90%.

[0310] △: The residual film rate is above 80% but below 90%.

[0310] ×: Residual film rate not reaching 80%

[0311] The above assessment results are shown in Tables 9 and 10.

[0312] [Table 9]

[0313] [Table 10]

[0314] As shown in Examples 21 to 31, it can be seen that by using the resin composition for forming microlenses of the present invention, a hardened film with high refractive index and high transmittance can be formed.

[0315] As shown in Examples 21 to 31, it can be seen that by using a resin composition containing an ultraviolet absorber, the occurrence of specific residues can be suppressed during negative pattern formation. This is believed to be because the ultraviolet absorber absorbs the irradiated radiation, thus suppressing the spread of excess radiation along the substrate interface, and in areas not irradiated by radiation, it can suppress the hardening of the composition at the interface with the substrate.

[0316] Furthermore, as shown in Examples 24 to 31, it is known that by using an ultraviolet absorber having an ethylene unsaturated group, the leaching of the ultraviolet absorber into the solvent can be suppressed, and the chemical resistance of the cured material can be improved. This is believed to be because the photosensitive reactive group of the ultraviolet absorber reacts with an alkali-soluble resin or a photopolymerizable monomer containing an unsaturated group, thereby incorporating the ultraviolet absorber into the resin.

[0316] [Potential for Industrial Utilization]

[0317] According to the first disclosure of the present invention, a laminate having an adhesive that can be used in the manufacture of various articles can be provided. In particular, a laminate suitable for processing steps that are temporarily placed on a support such as a semiconductor wafer can be provided.

[0318] According to the second disclosure of the present invention, a resin composition for forming microlenses can be provided, which can be used in solid-state imaging elements that require high pixel density and high sensitivity.

Claims

1. A composition for forming an adhesive layer, wherein the adhesive layer bonds a support to an adherend, and the support and adherend can be separated by light irradiation, and the composition comprises (A) a polymeric compound containing an unsaturated group, (B) an ultraviolet absorber selected from the group consisting of benzotriazole compounds, benzophenone compounds, trichloroethylene compounds, salicylic acid compounds, and benzoic acid ester compounds, and (F) a solvent; wherein, The aforementioned (A) unsaturated polymeric compound includes (A1) an alkali-soluble resin or (A2) an unsaturated polymeric compound without an alkali-soluble group. The aforementioned (A2) unsaturated polymeric compound without an alkali-soluble group includes a compound with a (meth)acrylic group that has been modified with an epoxide or lactone. The content of the aforementioned (A) unsaturated polymeric compound is 10% by mass or more and 90% by mass or less relative to the total mass of the solid components. The content of the aforementioned (B) ultraviolet absorber is 10% by mass or more and 80% by mass or less relative to the total mass of the solid components.

2. The adhesive layer forming composition as described in claim 1, wherein, The aforementioned (A1) alkali-soluble resin is a resin with a weight average molecular weight of 1,000 to 40,000.

3. The adhesive layer forming composition as described in claim 1 or 2, wherein, The aforementioned (A1) alkali-soluble resin is a resin represented by the following general formula (1). In formula (1), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms. A portion of the hydrogen atom constituting Ar can be substituted by a substituent selected from the group consisting of alkyl with 1 to 10 carbon atoms, aryl or arylalkyl with 6 to 10 carbon atoms, cycloalkyl or cycloalkylalkyl with 3 to 10 carbon atoms, alkoxy with 1 to 5 carbon atoms, and halogen groups. R1 is an alkyl group with 2 to 4 carbon atoms. l is a number with 0 to 3. G is a (meth)acrylyl group or a substituent represented by the following general formula (2) or general formula (3). Y is a tetravalent carboxylic acid residue. Z is a hydrogen atom or a substituent represented by the following general formula (4). At least one of Z is a substituent represented by the following general formula (4). n is a number with an average value of 1 to 20. In formulas (2) and (3), R2 is a hydrogen atom or a methyl group, R3 is an alkyl group or an alkyl aryl group with 2 to 10 carbon atoms, R4 is a saturated or unsaturated hydrocarbon group with 2 to 20 carbon atoms, and p is a value of 0 to 10; In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a value of 1 or 2.

4. The adhesive layer forming composition as described in claim 1 or 2, wherein, The aforementioned (B) ultraviolet absorber has an absorbance of 0.10 or higher for light with a wavelength of 355 nm.

5. The composition for forming an adhesive layer as described in claim 1 or 2, wherein, The aforementioned (B) ultraviolet absorber is a compound with a weight average molecular weight (Mw) of 1000 or more.

6. The composition for forming an adhesive layer as described in claim 1 or 2, wherein, The aforementioned (B) ultraviolet absorber is a compound having a benzotriazole structure.

7. A laminate comprising a support, an adhesive body, and an adhesive layer, the adhesive layer being a hardened composition comprising any one of claims 1 to 6 disposed between the support and the adhesive body.

8. The stack as described in claim 7, wherein, The aforementioned support system is a support structure with a light transmittance of 70% or more for wavelengths between 350nm and 450nm.

9. A method for manufacturing a laminate, comprising: applying an adhesive layer to the surface of at least one of a support and an adherend, using an adhesive layer forming composition as described in any one of claims 1 to 6 to form an adhesive layer; and bonding the support and the adherend through the formed adhesive layer.

10. A method for processing a laminate, comprising: a step of preparing the laminate as described in claim 7 or 8; and a step of irradiating the aforementioned adhesive layer with light to separate the aforementioned support from the aforementioned adhered body.