(METH)acrylic copolymer, composition for forming adhesive layer, laminate, method for producing adhesive layer, method for producing laminate, and method for treating laminate

Abstract

To provide a (meth)acrylic copolymer that favorably absorbs laser light at both wavelengths of 266 nm and 355 nm.SOLUTION: A (meth)acrylic copolymer comprises a structural unit derived from a polymerizable monomer containing an ultraviolet-absorbing moiety represented by general formula (6), and a structural unit different from the structural unit.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a (meth)acrylic copolymer, a composition for forming an adhesive layer, a laminate, a method for producing an adhesive layer, a method for producing a laminate, and a method for treating a laminate. [Background technology]

[0002] Resin materials have the advantage of being easier to process than inorganic materials, and have been used in various semiconductor components in recent years.

[0003] One application of resin materials is as an adhesive layer used for safely and easily transporting thinned flexible displays, semiconductor chips, and the like. For example, to facilitate transport of flexible displays and semiconductor chips, whose strength has been reduced due to thinning, a method has been considered in which a laminate is created by fixing an adherend, such as a flexible display and a semiconductor chip, to a light-transmitting support such as a glass substrate via an adhesive layer, and then transporting the flexible display and semiconductor chip together with the laminate. In this case, the adhesive layer may be made of a composition that changes or decomposes upon exposure to light, thereby reducing its adhesive strength. When using the adhesive layer, after transport, the adherend can be separated (peeled) from the support by irradiating the adhesive layer from the support side, allowing it to be transferred to, for example, another substrate (laser lift-off process, hereinafter also referred to simply as the "LLO process").

[0004] Patent Document 1 describes a composition for an adhesive that enables the LLO process, in which a curable resin having a 9,9'-diphenylfluorene (cardo) structure and an unsaturated group is dissolved in a solvent. Patent Document 1 also describes that when this composition is applied to a glass support and heated to form an adhesive layer, the glass support can be easily peeled from the adherend by irradiating it with a laser having a wavelength of 308 nm. Patent Document 1 also describes that when a composition in which a resin having a benzotriazole structure is dissolved in a solvent is applied to a glass support and heated to form an adhesive layer, the glass support can be easily peeled from the adherend by irradiating it with a laser having a wavelength of 355 nm.

[0005] Furthermore, Patent Document 2 describes a photosensitive composition containing a curable resin containing a cardo structure and an unsaturated group, a photopolymerizable monomer, and a light absorber (carbon black) as a composition for the adhesive. Patent Document 2 also describes that this photosensitive composition was applied to a glass support and heated to form a cured film, which had excellent adhesion to the adherend. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-106486 [Patent Document 2] Japanese Patent Application Publication No. 2018-001604 Summary of the Invention [Problem to be solved by the invention]

[0007] For example, when a resin material is used as an adhesive layer for the LLO process (hereinafter also referred to as an "adhesive layer for the LLO process"), research has been conducted into adhesive layers that can absorb high-energy, highly processable short-wavelength lasers (wavelengths of 248 nm and 266 nm, etc.) well and enable peeling of adherends using short-wavelength lasers.

[0008] However, in order to process with lasers of these wavelengths, it is necessary to use a support that has high transmittance in the short wavelength region, and in some cases, for example, a support that has low transmittance in the short wavelength region may be used. Therefore, there is a demand for the development of an adhesive layer that absorbs not only short wavelength lasers but also long wavelength lasers (e.g., 355 nm) well, and that can peel the adherend with lasers of either wavelength.

[0009] In addition, there are cases where resin materials that can absorb not only short-wavelength lasers but also long-wavelength lasers well are required, and there is a demand for the development of resin materials that can absorb lasers with both wavelengths of 266 nm and 355 nm well.

[0010] However, according to the findings of the present inventors, when the compositions described in Patent Documents 1 and 2 were used as adhesive layers for LLO processes, it was not possible to form adhesives that absorbed lasers of either wavelengths of 266 nm or 355 nm well, and it was not possible to form adhesive layers that could be peeled off from adherends when irradiated with lasers of either wavelengths of 266 nm or 355 nm.

[0011] The present invention has been made in view of the above points, and aims to provide a (meth)acrylic copolymer that exhibits good absorption of lasers with wavelengths of both 266 nm and 355 nm, a composition for forming an adhesive layer using the (meth)acrylic copolymer, a laminate obtained by bonding a support and an adherend using the composition for forming an adhesive layer, methods for producing the adhesive layer and the laminate, and a method for treating the laminate. [Means for solving the problem]

[0012] One aspect of the present invention for solving the above problems relates to a (meth)acrylic copolymer described in the following [1] to [6].

[0013] [1] A structural unit derived from a polymerizable monomer having an ultraviolet absorbing moiety represented by the following general formula (1), A structural unit different from the structural unit; A (meth)acrylic copolymer comprising:

[0014] [ka]

[0015] In general formula (1), Z is a sulfur atom or an oxygen atom. R1 and R2 may be bonded to any substitutable carbon of the naphthalene ring. R1 independently represents a (meth)acryloyloxyalkyl group or a (meth)acryloyloxy group which may contain a heteroatom. R2 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a vinyl group, a styryl group, an allyl group, a (meth)acryloyloxyalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. In general formula (1), a is an integer of 1 to 6, and b is an integer of 0 to 6.

[0016] [2] A structural unit containing an ultraviolet absorbing moiety represented by the following general formula (2): A structural unit represented by the following general formula (3), A (meth)acrylic copolymer comprising:

[0017] [ka]

[0018] In general formula (2), Z is a sulfur atom or an oxygen atom. R4 and R5 may be bonded to any substitutable carbon atom of the naphthalene ring. In general formula (2), R3 independently represents a hydrogen atom or a methyl group. R4 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. R5 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. Furthermore, c is an integer of 0 to 6. * indicates the bonding site to other structural units.

[0019] [ka]

[0020] In general formula (3), R6 independently represents a hydrogen atom or a methyl group. R7 represents an alkyl group having 1 to 10 carbon atoms, which may contain a heteroatom and may have a cyclic structure or an aromatic ring. Note that * indicates a bonding site to other structural units.

[0021] [3] A structural unit containing an ultraviolet absorbing moiety represented by the following general formula (2): a structural unit containing a polymerizable unsaturated group represented by the following general formula (4), A structural unit containing a carboxy group represented by the following general formula (5), A (meth)acrylic copolymer comprising:

[0022] [ka]

[0023] In general formula (2), Z is a sulfur atom or an oxygen atom. R4 and R5 may be bonded to any substitutable carbon atom of the naphthalene ring. In general formula (2), R3 independently represents a hydrogen atom or a methyl group. R4 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. R5 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. c is an integer of 0 to 6. * indicates the bonding site to another structural unit.

[0024] [ka]

[0025] [ka]

[0026] In the general formula (4) and the general formula (5), R, R 11 and R 12 R9 to R10 each independently represent a hydrogen atom or a methyl group. 10 and R 13 ~R 14each independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond. d and e each independently represent 0, 1, or 2. X1 and X2 each independently represent an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. Note that * indicates a bonding site with other structural units.

[0027] [4] The weight average molecular weight is 1,000 to 100,000. The (meth)acrylic copolymer according to any one of [1] to [3].

[0028] [5] The acid value is 20 mg KOH / g to 200 mg KOH / g. The (meth)acrylic copolymer according to [3].

[0029] [6] In the following general formula (6), the content mass X1 (g) of only the dinaphthothiophene moiety calculated from the content mass Y1 (g) of the structural unit including the dinaphthothiophene moiety in which Z is a sulfur atom using the following formula (I), In the following general formula (6), the content mass X2 (g) of only the dinaphthofuran moiety calculated from the content mass Y2 (g) of the structural unit including the dinaphthofuran moiety in which Z is an oxygen atom using the following formula (II), The total mass X1+X2 (g) is 10% by mass to 60% by mass with respect to the total mass TM (g) of all structural units constituting the (meth)acrylic copolymer. The (meth)acrylic copolymer according to any one of [1] to [5]. Formula (I) X1(g) = Y1(g) × M X1 (g / mol) / M Y1 (g / mol) Formula (II) X2(g)=Y2(g)×M X2 (g / mol) / M Y2 (g / mol)

[0030] During the ceremony, X1(g): Mass of the dinaphthothiophene moiety alone Y1(g): the mass of the structural unit containing the dinaphthothiophene moiety M X1 (g / mol): Molar mass of the dinaphthothiophene moiety alone M Y1 (g / mol): Molar mass of the structural unit containing the dinaphthothiophene moiety X2 (g): Mass of the dinaphthofuran moiety alone Y2(g): Mass of the structural unit containing the dinaphthofuran moiety M X2 (g / mol): Molar mass of the dinaphthofuran moiety alone M Y2 (g / mol): Molar mass of the structural unit containing the dinaphthofuran moiety Shows.

[0031] [ka]

[0032] In the general formula (6), Z is a sulfur atom or an oxygen atom.

[0033] One aspect of the present invention for solving the above problems relates to a composition for forming an adhesive layer as described in the following items [7] to

[10] .

[0034] [7] A composition for forming an adhesive layer for forming an adhesive layer that bonds a support and an adherend and enables the support and the adherend to be separated by irradiation with light, (A) the (meth)acrylic copolymer according to any one of [1] to [6]; (B) an unsaturated group-containing polymerizable compound having neither a dinaphthothiophene moiety nor a dinaphthofuran moiety; (C) a solvent; Including, The content by mass of the component (A) is 10% by mass or more relative to the total mass of the solid content of the adhesive layer-forming composition. Composition for forming adhesive layer.

[0035] [8] The (B) unsaturated group-containing polymerizable compound contains (B1) an alkali-soluble resin, The weight average molecular weight of the component (B1) is 1,000 to 40,000. The adhesive layer-forming composition according to [7].

[0036] [9] The alkali-soluble resin (B1) is a resin represented by the following general formula (B1-1): The adhesive layer-forming composition according to [7] or [8]. [ka]

[0037] In formula (B1-1), Ar independently represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. 31 are independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (B1-2) or the following general formula (B1-3). Y is a tetravalent carboxylic acid residue. Z2 is independently a hydrogen atom or a substituent represented by the following general formula (B1-4), and at least one Z2 is a substituent represented by the following general formula (B1-4). n is a number with an average value of 1 to 20.

[0038] [ka]

[0039] [ka]

[0040] In formulas (B1-2) and (B1-3), R 32is a hydrogen atom or a methyl group, and R 33 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R 34 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 or more and 10 or less. * indicates a bonding site.

[0041] [ka]

[0042] In formula (B1-4), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0043]

[10] The (B) unsaturated group-containing polymerizable compound includes (B2) an unsaturated group-containing polymerizable compound having no alkali-soluble group. The adhesive layer-forming composition according to any one of [7] to [9].

[0044] One aspect of the present invention for solving the above problem relates to a laminate described in

[11] below.

[0045]

[11] a support; An adherend; an adhesive layer comprising a cured product of the adhesive layer-forming composition according to any one of [7] to

[10] , which is disposed between the support and the adherend; A laminate having:

[0046] One aspect of the present invention for solving the above problem relates to a method for producing an adhesive layer as described in

[12] below.

[0047]

[12] A step of applying the adhesive layer-forming composition according to any one of [7] to

[10] to the surface of at least one of the support and the adherend to form an adhesive layer; exposing the adhesive layer to light through a photomask; developing the exposed adhesive layer; A method for producing an adhesive layer comprising the steps of:

[0048] One aspect of the present invention for solving the above problem relates to a method for producing a laminate described in

[13] below.

[0049]

[13] A method for manufacturing an adhesive layer comprising the steps of: bonding the support and the adherend via an adhesive layer manufactured by the method for manufacturing an adhesive layer according to

[12] . A method for manufacturing a laminate.

[0050] One aspect of the present invention for solving the above problem relates to a method for treating a laminate described in

[14] below.

[0051]

[14] A step of preparing a laminate according to

[11] ; a step of irradiating the adhesive layer of the laminate with light to separate the support and the adherend; A method for treating a laminate, comprising: [Effects of the Invention]

[0052] According to the present invention, there are provided a (meth)acrylic copolymer that exhibits good absorption of lasers with wavelengths of both 266 nm and 355 nm, a composition for forming an adhesive layer using the (meth)acrylic copolymer, a laminate obtained by bonding a support and an adherend using the composition for forming an adhesive layer, methods for producing the adhesive layer and the laminate, and a method for treating the laminate. [Brief explanation of the drawings]

[0053] [Figure 1] Fig. 1A is a schematic diagram showing a process of transferring an adherend from an original substrate to a holding substrate by irradiating light to alter and decompose the resin holding the adherend, and Fig. 1B is a schematic diagram showing a process of capturing the adherend peeled from the original substrate with an adhesive layer applied to the surface of the holding substrate to obtain a laminate including an adhesive layer to which multiple adherends are bonded. [Figure 2]Fig. 2A is a schematic diagram showing a process of peeling an adherend from an adhesive layer by irradiation with light (or laser) and transferring the adherend from the holding substrate to another substrate, and Fig. 2B is a schematic diagram showing a process of catching the adherend peeled from the holding substrate with an adhesive layer applied to the surface of another substrate to obtain an adhesive layer bonding multiple adherends. DETAILED DESCRIPTION OF THE INVENTION

[0054] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In this specification, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted. Furthermore, unless otherwise specified, only one type of the exemplified compounds, functional groups, or structures may be used, or multiple types may be used in combination.

[0055] In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic, and "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and means one or both of them.

[0056] 1. (A) (Meth)acrylic copolymer The (meth)acrylic copolymer (A) according to the present embodiment (hereinafter also simply referred to as "component (A)") is a (meth)acrylic copolymer containing a structural unit derived from a polymerizable monomer containing a dinaphthothiophene moiety or a dinaphthofuran moiety, as represented by the following general formula (6), and a structural unit different from the structural unit derived from the polymerizable monomer:

[0057] [ka]

[0058] In the general formula (6), Z is a sulfur atom or an oxygen atom.

[0059] Because component (A) contains structural units derived from a polymerizable monomer containing a dinaphthothiophene moiety or a dinaphthofuran moiety, it readily absorbs ultraviolet light at wavelengths of 266 nm and 355 nm. Therefore, when used in an adhesive layer for an LLO process, laser irradiation at either 266 nm or 355 nm accelerates the degradation or decomposition of the cured product. This facilitates laser peeling of the adherend. Furthermore, by including structural units different from those derived from the polymerizable monomer containing the dinaphthothiophene moiety or the dinaphthofuran moiety, it is possible to enhance solubility in solvents and facilitate blending with other additives when formulated into a composition. Therefore, for example, when used in an adhesive layer for an LLO process, facilitating blending with unsaturated group-containing polymerizable compounds can enhance the adhesive strength and solvent resistance of the adhesive layer. Furthermore, since monomers containing a (meth)acryloyl group can be easily copolymerized with various known methacrylate compounds, forming a (meth)acrylic copolymer can facilitate adjustment of desired physical properties.

[0060] In addition, in general formula (6), a copolymer in which Z is a sulfur atom refers to a dinaphthothiophene moiety, and a copolymer in which Z is an oxygen atom refers to a dinaphthofuran moiety. From the viewpoint of easily absorbing light with a wavelength of 266 nm and easily improving heat resistance, the (meth)acrylic copolymer (A) preferably contains a structural unit derived from a polymerizable monomer containing a dinaphthothiophene moiety in general formula (6), where Z is a sulfur atom. On the other hand, from the viewpoint of easily absorbing light with a wavelength of 355 nm and easily improving solubility in solvents, the (meth)acrylic copolymer (A) preferably contains a structural unit derived from a polymerizable monomer containing a dinaphthofuran moiety in general formula (6), where Z is an oxygen atom. Furthermore, the component (A) may contain both a structural unit derived from a polymerizable monomer containing a dinaphthothiophene moiety and a structural unit derived from a polymerizable monomer containing a dinaphthothiophene moiety. In this embodiment, it becomes easier to adjust the absorbance of light with a wavelength of 266 nm and light with a wavelength of 355 nm, and it becomes easier to adjust the light absorbance of the component (A).

[0061] The component (A) is preferably, for example, a (meth)acrylic copolymer containing the structural unit (AA) of the following structural units (AA) to (AE) and at least one structural unit of the structural units (AB) to (AE). (AA) a structural unit containing a dinaphthothiophene moiety or a dinaphthofuran moiety represented by the above general formula (6) (AB) a structural unit having a polymerizable unsaturated group and no carboxy group (AC) a structural unit having a carboxy group and no polymerizable unsaturated group (AD) Structural unit having a polymerizable unsaturated group and a carboxy group (AE) a structural unit represented by general formula (6) that does not have any of an ultraviolet absorbing moiety, a polymerizable unsaturated group, and a carboxy group

[0062] The structural unit (AA) is a structural unit having a dinaphthothiophene moiety or a dinaphthofuran moiety represented by the above general formula (6). The structural unit (AA) may have the dinaphthothiophene moiety or the dinaphthofuran moiety in the main chain or in the side chain of the (meth)acrylic copolymer, but from the viewpoint of ease of production of the (meth)acrylic copolymer, it is preferable that the dinaphthothiophene moiety or the dinaphthofuran moiety be in the side chain. Furthermore, when the dinaphthothiophene moiety or the dinaphthofuran moiety is in the side chain, the dinaphthothiophene moiety or the dinaphthofuran moiety may be a functional group derived from a monomer, or may be grafted to the side chain of the structural unit (AA). In other words, the dinaphthothiophene moiety or the dinaphthofuran moiety may be bonded to the side chain of the structural unit (AA) via a linking group or linking structure generated during grafting.

[0063] Examples of the linking group or linking structure include an ester bond, a urethane bond, an epoxy acrylate residue, etc. For example, after forming the skeleton of the structural unit (AE) by copolymerizing a monomer having an isocyanate group, a monomer having a dinaphthothiophene moiety or a dinaphthofuran moiety and a hydroxyl group is reacted to graft the dinaphthothiophene moiety or the dinaphthofuran moiety by forming a urethane bond.

[0064] Of these, the dinaphthothiophene moiety or the dinaphthofuran moiety is preferably a functional group derived from the monomer that is the material of the structural unit (AA) because of ease of synthesis.

[0065] The structural unit (AB) is a structural unit having a polymerizable unsaturated group. However, in this specification, a structural unit having both a polymerizable unsaturated group and a carboxy group is a structural unit (AD) and is not included in the structural unit (AB). It is preferable that the structural unit (AB) does not have either a dinaphthothiophene moiety or a dinaphthofuran moiety.

[0066] Examples of the polymerizable unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyl group, among which a (meth)acryloyl group is preferred.

[0067] The polymerizable unsaturated group is preferably grafted to a side chain of the structural unit (AB). In other words, the polymerizable unsaturated group is preferably bonded to a side chain of the structural unit (AB) via a linking group or linking structure generated during grafting. Examples of the linking group or linking structure include an ester bond, a urethane bond, and an epoxy acrylate residue. Among these, the polymerizable unsaturated group is preferably grafted to a side chain via a urethane bond or an epoxy acrylate residue, because grafting is easy. From the viewpoint of easily increasing the solubility of the (meth)acrylic copolymer in a solvent and facilitating mixing with other additives when prepared as a composition, the polymerizable unsaturated group is preferably grafted to a side chain via a urethane bond. From the viewpoint of more easily adjusting the development rate, the polymerizable unsaturated group is preferably grafted to a side chain via an epoxy acrylate residue.

[0068] The structural unit (AC) is a structural unit having a carboxy group. However, in this specification, a structural unit having both a carboxy group and a polymerizable unsaturated group is a structural unit (AD) and is not included in the structural unit (AC). It is preferable that the structural unit (AC) does not have either a dinaphthothiophene moiety or a dinaphthofuran moiety.

[0069] The carboxy group may be a functional group derived from a monomer (such as (meth)acrylic acid) that is a material for the structural unit (AC), or may be grafted to a side chain in the structural unit (AC). In other words, the carboxy group may be bonded to a side chain in the structural unit (AC) via a linking group or linking structure generated during grafting. Examples of the linking group or linking structure include an ester bond, a urethane bond, and an epoxy acrylate residue. Of these, the carboxy group is preferably a functional group derived from a monomer (such as (meth)acrylic acid) that is a material for the structural unit (AC) because of ease of synthesis.

[0070] The structural unit (AD) is a structural unit having a polymerizable unsaturated group and a carboxy group. The polymerizable unsaturated group in the structural unit (AD) is the same as the polymerizable unsaturated group in the structural unit (AB). It is preferable that the structural unit (AD) does not have either a dinaphthothiophene moiety or a dinaphthofuran moiety.

[0071] Both the polymerizable unsaturated group and the carboxy group are preferably grafted to the side chain of the structural unit (AD). In other words, the polymerizable unsaturated group is preferably bonded to the side chain of the structural unit (AD) via a linking group or linking structure generated during grafting. Examples of the linking group or linking structure include an ester bond, a urethane bond, and an epoxy acrylate residue. For example, the skeleton of the structural unit (AD) is formed by copolymerizing a monomer having a glycidyl group or an alicyclic epoxy group, and then a monomer having a polymerizable unsaturated group and a carboxy group is reacted to form an epoxy acrylate, thereby grafting the polymerizable unsaturated group. Furthermore, the structural unit (AD) can be formed by reacting a polycarboxylic acid or its anhydride with the hydroxyl group generated by the formation of the epoxy acrylate to graft a carboxy group. The structural unit (AD) thus formed has the polymerizable unsaturated group and the carboxy group grafted to the side chain via an epoxy acrylate residue, and the carboxy group is grafted to the side chain via an ester bond. Grafting via ester bonds and urethane bonds can also be carried out by known methods.

[0072] The structural unit (AE) is a structural unit that is optionally introduced to impart desired properties (for example, to facilitate increasing solubility in a solvent or to facilitate mixing with other additives when prepared as a composition). Note that the structural unit (AE) does not have either a dinaphthothiophene moiety or a dinaphthofuran moiety.

[0073] The structural unit (AE) may be a structural unit derived from a monomer that does not have any of the above functional groups, and may be a structural unit to which a functional group different from the above functional groups has been grafted in order to adjust the physical properties of the (meth)acrylic copolymer.

[0074] Each of the structural units described above may be modified with an alkylene oxide or a lactone.

[0075] The (meth)acrylic copolymer preferably has the following embodiments i) to iii). i) A copolymer containing the structural unit (AA) and the structural unit (AE) as essential structural units and optionally containing the structural unit (AB), the structural unit (AC), and the structural unit (AD). ii) A copolymer containing the structural unit (AA), the structural unit (AB) and the structural unit (AC) as essential structural units, and optionally containing the structural unit (AD) and the structural unit (AE). iii) A copolymer containing the structural unit (AA) and the structural unit (AD) as essential structural units and optionally containing the structural unit (AB), the structural unit (AC), and the structural unit (AE).

[0076] A (meth)acrylic copolymer having the structural unit (AA) and the structural unit (AE) as essential structural units can be applied to applications that do not require pattern formation, is easy to synthesize, and facilitates low production costs. Furthermore, a (meth)acrylic copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units is easy to synthesize because it does not require a step for introducing the structural unit (AD). A (meth)acrylic copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units can easily adjust the amount of each functional group imparted by the structural unit (AD), thereby facilitating adjustment of the development speed, etc.

[0077] The (meth)acrylic copolymer preferably has a weight-average molecular weight (Mw) of 1,000 to 100,000, more preferably 5,000 to 70,000, and even more preferably 10,000 to 50,000. A weight-average molecular weight (Mw) of 1,000 or more can suppress volatilization of the copolymer during the heating process during molding, which can facilitate improved adhesion when used in an adhesive layer for an LLO process. Furthermore, a weight-average molecular weight (Mw) of 100,000 or less can easily adjust the solution viscosity to a level suitable for application, allowing for application in a short period of time. This facilitates improved adhesion when used in an adhesive layer for an LLO process. The weight-average molecular weight (Mw) of the (meth)acrylic copolymer can be expressed as a polystyrene-equivalent value measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation).

[0078] (AA) The total mass X1+X2(g) of the mass X1(g) of only the dinaphthothiophene moiety calculated from the mass Y1(g) of the structural unit containing the dinaphthothiophene moiety where Z is a sulfur atom in the above general formula (6) and the mass X2(g) of only the dinaphthofuran moiety calculated from the mass Y2(g) of the structural unit containing the dinaphthofuran moiety where Z is an oxygen atom in the above general formula (6) is preferably 10% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass, relative to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer. By setting the content of the structural unit (AA) to 10% by mass or more, light of both 266 nm and 355 nm wavelengths is easily absorbed, and when used in an adhesive layer for an LLO process, irradiation with a laser of either 266 nm or 355 nm wavelength is likely to promote deterioration or decomposition of the cured product. By setting the proportion of the structural unit (A) to 60% by mass or less, it is possible to increase solubility in solvents and facilitate mixing with other additives when formed into a composition. Formula (I) X1(g) = Y1(g) × M X1 (g / mol) / M Y1 (g / mol) Formula (II) X2(g)=Y2(g)×M X2 (g / mol) / M Y2 (g / mol) During the ceremony, X1(g): Mass of the dinaphthothiophene moiety alone Y1(g): the mass of the structural unit containing the dinaphthothiophene moiety M X1 (g / mol): Molar mass of the dinaphthothiophene moiety alone M Y1 (g / mol): Molar mass of the structural unit containing the dinaphthothiophene moiety X2 (g): Mass of the dinaphthofuran moiety alone Y2(g): Mass of the structural unit containing the dinaphthofuran moiety M X2 (g / mol): Molar mass of the dinaphthofuran moiety alone M Y2 (g / mol): Molar mass of the structural unit containing the dinaphthofuran moiety and M of the dinaphthothiophene moiety. X is 284.38 g / mol, and the M of the dinaphthofuran moiety X is 268.32 g / mol.

[0079] The monomer that is the source of the structural unit (AA) is preferably a structural unit derived from a monomer having an absorbance of 0.06 or more at 266 nm and an absorbance of 0.06 or more at 355 nm. Furthermore, it is more preferably a structural unit derived from a monomer having an absorbance of 0.10 to 1.00 at 266 nm and an absorbance of 0.10 to 1.00 at 355 nm. The structural unit derived from a monomer having an absorbance of 0.10 or more at 266 nm and an absorbance of 0.10 or more at 355 nm facilitates absorption of light at both 266 nm and 355 nm wavelengths. When used in an adhesive layer for an LLO process, irradiation with a laser at either 266 nm or 355 nm facilitates deterioration or decomposition of the cured product. When the absorbance at 266 nm is 1.00 or less and the absorbance at 355 nm is 1.00 or less, the exposure sensitivity is likely to be increased, and when used for pattern formation, the pattern formability is likely to be improved. The above absorbance is a value measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) in a quartz cell with an optical path length of 1 cm for the absorbance of a 0.001 wt% acetonitrile solution. If the compound is not soluble in acetonitrile, the value is calculated by measuring it in a PGMEA solution.

[0080] Furthermore, the molar absorption coefficient of component (A) at wavelengths of 266 nm and 355 nm is preferably 3000 L / (mol·cm) to 90,000 L / (mol·cm), more preferably 4000 L / (mol·cm) to 80,000 L / (mol·cm), and even more preferably 5000 L / (mol·cm) to 50,000 L / (mol·cm). A molar absorption coefficient of 3000 L / (mol·cm) or higher facilitates absorption of light at both 266 nm and 355 nm wavelengths. When used in adhesive layers for LLO processes, irradiation with lasers at both 266 nm and 355 nm wavelengths can promote deterioration or decomposition of the cured product. A molar absorption coefficient of 90,000 L / (mol·cm) or lower facilitates increased exposure sensitivity, which, when used in pattern formation, can facilitate improved pattern formability. The molar extinction coefficient absorbance is a value calculated by measuring the absorbance of a 0.001 wt% acetonitrile solution in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), and then dividing the value by the molar concentration. If the compound is not soluble in acetonitrile, it is measured in a PGMEA solution and the calculated value is used.

[0081] In the case of a (meth)acrylic copolymer containing the structural unit (AC) and / or the structural unit (AD) (for example, ii) a (meth)acrylic copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units, or iii) a (meth)acrylic copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units), the acid value is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 30 mgKOH / g to 180 mgKOH / g, and even more preferably 40 mgKOH / g to 150 mgKOH / g. By adjusting the acid value to 20 mgKOH / g or more, when used for pattern formation, it is possible to reduce the residue remaining during alkaline development. By adjusting the acid value to 200 mgKOH / g or less, when used for pattern formation, it is possible to appropriately adjust the penetration of an alkaline developer into the composition, thereby suppressing peeling development due to rapid penetration of the alkaline developer. The acid value can be determined by titration with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0082] Furthermore, in the case of a (meth)acrylic copolymer containing the structural unit (AC) and / or the structural unit (AD), the proportion of structural units having a carboxy group (the proportion of the total amount of the structural units (AC) and the structural units (AD)) is preferably 3 mol % to 50 mol %, more preferably 5 mol % to 45 mol %, and even more preferably 7 mol % to 40 mol %, relative to 100 mol % of all structural units. When the proportion of structural units having a carboxy group is 3 mol % or more, residues are less likely to remain during alkaline development when used for pattern formation. When the proportion of structural units having a carboxy group is 50 mol % or less, penetration of an alkaline developer into the composition can be appropriately adjusted when used for pattern formation, and peeling development due to rapid penetration of the alkaline developer can be suppressed.

[0083] In the case of a (meth)acrylic copolymer containing the structural unit (AB) and / or the structural unit (AD) (for example, ii) a (meth)acrylic copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units, or iii) a (meth)acrylic copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units), the (meth)acrylic copolymer preferably has an acrylic equivalent of 300 g / eq to 3000 g / eq, more preferably 350 g / eq to 2500 g / eq, and even more preferably 400 g / eq to 2000 g / eq. By setting the acrylic equivalent to 300 g / eq or more, sufficient introduction of the structural unit (AA) is possible, which facilitates ultraviolet absorption. By setting the acrylic equivalent to 3000 g / eq or less, photocuring proceeds easily even at low exposure doses, which facilitates increased curability, and when used for pattern formation, this facilitates the formation of a developed pattern.

[0084] Furthermore, in the case of a (meth)acrylic copolymer containing the structural unit (AB) and / or the structural unit (AD), the proportion of structural units having a polymerizable unsaturated group (the proportion of the total amount of the structural units (AB) and the structural units (AD)) is preferably 5 mol% to 50 mol%, and more preferably 15 mol% to 40 mol%, relative to 100 mol% of all structural units. When the proportion of structural units having a polymerizable unsaturated group is 5 mol% or more, photocuring proceeds easily even at low exposure doses, and curability is easily improved, making it easier to form a developed pattern when used for pattern formation. When the proportion of structural units having a polymerizable unsaturated group is 50 mol% or less, sufficient structural units (AA) can be introduced, making it easier to absorb ultraviolet light.

[0085] Four preferred embodiments of the component (A) are exemplified below, but the (meth)acrylic copolymer according to this embodiment is not limited to the following embodiments.

[0086] 1-1. First aspect of component (A) A first preferred embodiment of the component (A) is a (meth)acrylic copolymer containing a structural unit derived from a polymerizable monomer containing an ultraviolet absorbing moiety represented by the following general formula (1) and a structural unit different from the structural unit:

[0087] In the (meth)acrylic copolymer, the structural unit derived from a polymerizable monomer containing an ultraviolet absorbing moiety represented by the following general formula (1) is included in the structural unit (AA).

[0088] [ka]

[0089] In the general formula (1), Z is a sulfur atom or an oxygen atom. R1 and R2 may be bonded to any substitutable carbon atom of the naphthalene ring. R1 independently represents a (meth)acryloyloxyalkyl group or a (meth)acryloyloxy group which may contain a heteroatom. R2 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a vinyl group, a styryl group, an allyl group, a (meth)acryloyloxyalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. In the above general formula (1), a is an integer of 1 to 6, and b is an integer of 0 to 6.

[0090] Examples of the (meth)acryloyloxyalkyl group represented by R1 include a (meth)acryloyloxymethyl group and a (meth)acryloyloxyethyl group, and the (meth)acryloyloxymethyl group and the (meth)acryloyloxyethyl group are preferred.

[0091] Furthermore, a is preferably an integer of 1 to 2, and a is more preferably 1.

[0092] The alkyl group having 1 to 15 carbon atoms and optionally containing a heteroatom, represented by R2, may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a methoxy group, an ethoxy group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0093] The cycloalkyl group having 3 to 15 carbon atoms and optionally containing a heteroatom, represented by R2, may have either a monocyclic structure or a polycyclic structure. Examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

[0094] The aryl group having 6 to 15 carbon atoms and optionally containing a heteroatom, represented by R2, may have a monocyclic structure or a fused ring structure. Examples of such an aryl group include a phenyl group, a naphthyl group, and a pyridyl group.

[0095] Examples of the aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, represented by R2, include a benzyl group and a phenethyl group.

[0096] Examples of the (meth)acryloyloxyalkyl group having 4 to 15 carbon atoms which may contain a heteroatom and which is represented by R2 include a (meth)acryloyloxymethyl group and a (meth)acryloyloxyethyl group.

[0097] Examples of the hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom and is represented by R2 include a hydroxymethyl group, a hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group.

[0098] Examples of the hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, represented by R2, include a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, and a 2,3-dihydroxypropoxy group.

[0099] Examples of the glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom and which is represented by R2 include a glycidylmethyl group, a glycidylethyl group, a 1-glycidylpropyl group, a 2-glycidylpropyl group, a 3-glycidylpropyl group, a 1-glycidylbutyl group, a 2-glycidylbutyl group, and a 3-glycidylbutyl group.

[0100] Examples of the glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, represented by R2, include a 2-glycidylethoxy group and a 2-glycidylpropoxy group.

[0101] Furthermore, b is preferably an integer of 0 to 2, and more preferably 0.

[0102] Examples of polymerizable monomers containing an ultraviolet absorbing moiety represented by the above general formula (1) include 6-methyl methacrylate-dinaphtho[2,1-b:1',2'-d]thiophene, 6-methyl acrylate-dinaphtho[2,1-b:1',2'-d]thiophene, 5-ethyl methacrylate-dinaphtho[2,1-b:1',2'-d]furan, and 5-ethyl acrylate-dinaphtho[2,1-b:1',2'-d]furan.

[0103] The monomer that serves as the material for the structural unit other than the structural unit derived from the polymerizable monomer containing the UV-absorbing moiety represented by general formula (1) above is preferably a monomer that serves as the material for structural unit (AC) or structural unit (AE), or a monomer having a hydroxyl group, an isocyanate group, a glycidyl group, or an alicyclic epoxy group. From the viewpoint of easily increasing alkali solubility, it is preferable to copolymerize with the monomer that serves as the material for structural unit (AC). From the viewpoint of easily increasing solubility in solvents and facilitating mixing with other additives when prepared as a composition, it is preferable to copolymerize with the monomer that serves as the material for structural unit (AE). The monomer having a hydroxyl group, an isocyanate group, a glycidyl group, or an alicyclic epoxy group is a monomer that introduces a carboxyl group or a polymerizable unsaturated group into the side chain of the (meth)acrylic copolymer by grafting to form the structural units (AA) to (AD). Among these, a monomer having a hydroxyl group is preferred from the viewpoint of ease of synthesis.

[0104] Examples of monomers that can be used to form the structural unit (AC) include (meth)acrylic acid, succinic acid mono(2-(meth)acryloyloxyethyl), hexahydrophthalic acid (2-(meth)acryloyloxyethyl), phthalic acid (2-(meth)acryloyloxyethyl), maleic acid (2-(meth)acryloyloxyethyl), fumaric acid (2-acryloyloxyethyl) (2-(meth)acryloyloxyethyl), itaconic acid (2-(meth)acryloyloxyethyl), hydroxyethyl), citraconic acid (2-(meth)acryloyloxyethyl), carboxyethyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, mono-n-butyl maleate (2-(meth)acryloyloxyethyl), mono-n-butyl fumarate (2-(meth)acryloyloxyethyl), and mono-n-butyl itaconate (2-(meth)acryloyloxyethyl). Of these, (meth)acrylic acid is preferred from the viewpoint of easily increasing solubility in a developer and easily improving developability.

[0105] Examples of monomers that can be used to make structural units (AE) include: (meth)acrylates having an alkyl chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylates having an alkyl chain having 1 to 10 carbon atoms modified with alkylene oxide, such as methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, and butoxydiethylene glycol (meth)acrylate; (meth)acrylates having an alicyclic hydrocarbon having 3 to 30 carbon atoms, such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantan-1-yl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate; (meth)acrylates having aromatic hydrocarbons having 3 to 30 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-biphenyl (meth)acrylate, and 2-naphthyl (meth)acrylate; (meth)acrylates having alkylene oxide-modified aromatic hydrocarbons having 3 to 30 carbon atoms, such as neopentyl glycol-acrylic acid-benzoic acid ester, phenoxyethylene glycol methacrylate, and ethoxylated-O-phenylphenol (meth)acrylate; (Meth)acrylates having a hydrocarbon group having 1 to 30 carbon atoms which may have one or two heteroatoms, such as phthalimide (meth)acrylate, maleimide (meth)acrylate, benzophenone (meth)acrylate, 2-hydroxy-4-(meth)acryloyloxybenzophenone, and hydroxy-4-(2-(meth)acryloyloxy)ethoxybenzophenone Among these, methyl (meth)acrylate is preferred from the viewpoints of reducing steric hindrance when grafting functional groups without impairing other physical properties and facilitating an increase in the reaction rate of the grafting reaction.

[0106] Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and ethyl-α-hydroxymethyl acrylate. Among these, 2-hydroxyethyl (meth)acrylate is preferred from the viewpoints of reducing steric hindrance when grafting a functional group, increasing the introduction rate of functional groups such as acrylate moieties, and facilitating adjustment of the introduction rate of the functional group.

[0107] Examples of the monomer having an isocyanate group include (2-(meth)acryloyloxyethyl)isocyanate.

[0108] Examples of the monomer having a glycidyl group or an alicyclic epoxy group include glycidyl (meth)acrylate, β-propylglycidyl (meth)acrylate, β-methylglycidyl-α-ethyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0109] 1-2. Second aspect of component (A) A second preferred embodiment of the component (A) is a (meth)acrylic copolymer containing a structural unit having an ultraviolet absorbing moiety represented by the following general formula (2) and a structural unit represented by the following general formula (3):

[0110] The second aspect is included in the (meth)acrylic copolymer having the aforementioned i) structural unit (AA) and structural unit (AE) as essential structural units, in which the structural unit (AA) contains a structural unit having an ultraviolet absorbing moiety represented by the following general formula (2), and the structural unit (AE) contains a structural unit represented by the following general formula (3).

[0111] [ka]

[0112] In the above general formula (2), Z is a sulfur atom or an oxygen atom. R4 and R5 may be bonded to any substitutable carbon of the naphthalene ring. In the above general formula (2), R3 independently represents a hydrogen atom or a methyl group. R4 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. R5 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. Furthermore, c is an integer of 0 to 6. * indicates the bonding site to other structural units.

[0113] [ka]

[0114] In the general formula (3), R6 independently represents a hydrogen atom or a methyl group. R7 represents an alkyl group having 1 to 10 carbon atoms, which may contain a heteroatom, a cyclic structure, or an aromatic ring. Note that * indicates a bonding site to other structural units.

[0115] Examples of the alkylene group having 1 to 10 carbon atoms represented by R4 include: linear or branched divalent alkylene groups including methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups; divalent hydrocarbon groups having an alicyclic structure, including a cyclohexylene group, a methylcyclohexylene group, an ethylcyclohexylene group, a dimethylcyclohexylene group, a diethylcyclohexylene group, a methylethylcyclohexylene group, a propylcyclohexylene group, and a methylpropylcyclohexylene group; Divalent hydrocarbon groups having an aromatic group, including phenylene, methylphenylene, ethylphenylene, dimethylphenylene, methylethylphenylene, and naphthylene groups Among these, a methylene group and an ethylene group are preferred, and a methylene group is more preferred.

[0116] The alkyl group having 1 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a methoxy group, an ethoxy group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0117] The cycloalkyl group having 3 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may have a monocyclic structure or a polycyclic structure. Examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

[0118] The aryl group having 6 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may have a monocyclic structure or a fused ring structure. Examples of such an aryl group include a phenyl group, a naphthyl group, and a pyridyl group.

[0119] Examples of the aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a benzyl group and a phenethyl group.

[0120] Examples of the hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom and is represented by R5 include a hydroxymethyl group, a hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group.

[0121] Examples of the hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, and a 2,3-dihydroxypropoxy group.

[0122] Examples of the glycidylalkyl group having 4 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, include a glycidylmethyl group, a glycidylethyl group, a 1-glycidylpropyl group, a 2-glycidylpropyl group, a 3-glycidylpropyl group, a 1-glycidylbutyl group, a 2-glycidylbutyl group, and a 3-glycidylbutyl group.

[0123] Examples of the glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a 2-glycidylethoxy group and a 2-glycidylpropoxy group.

[0124] Furthermore, c is preferably an integer of 0 to 2, and c is more preferably 0.

[0125] Examples of the alkyl group having 1 to 10 carbon atoms, which may contain a heteroatom and which may contain a cyclic structure or an aromatic ring, represented by R7, include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the cycloalkyl group having 3 to 30 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m-, and p-tolyl groups, a xylyl group, o-, m-, and p-cumenyl groups, a mesityl group, a pentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, a quaternaphthalenyl group, a heptalenyl group, a biphenylenyl group, an indacenyl group, and a fluoranthenyl group. Examples of the alkyl group include an acenaphthylenyl group, an aceanthrylenyl group, a phenalenyl group, a fluorenyl group, an anthryl group, a bianthracenyl group, a teranthracenyl group, a quaternanthracenyl group, an anthraquinolyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a pleiadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, and a pyrantrenyl group. Among these, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0126] A preferred range of the content ratio of the total mass X1+X2(g), which is the mass content X1(g) of only the dinaphthothiophene moiety calculated by formula (I) from the mass content of the structural unit represented by general formula (2), and the mass content X2(g) of only the dinaphthofuran moiety calculated by formula (II) from the mass content of the structural unit represented by general formula (2), to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer, is the same as the preferred range of the content ratio of the total mass X1+X2(g) of X1(g) and X2(g), which is calculated by formulas (I) and (II) from the mass content of the structural unit (AA) described above, to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer.

[0127] The molar proportion of the structural unit represented by general formula (3) is preferably 45 mol% to 95 mol%, and more preferably 55 mol% to 85 mol%, relative to 100 mol% of all structural units in the (meth)acrylic copolymer. A proportion of 45 mol% or more can facilitate increased solubility in solvents and easier mixing with other additives when formulated into a composition. A proportion of 95 mol% or less can facilitate absorption of ultraviolet light with wavelengths of 266 nm and 355 nm. Therefore, for example, when used in an adhesive layer for an LLO process, irradiation with a laser with either a 266 nm or a 355 nm wavelength can promote alteration or decomposition of the cured product. This facilitates peeling of the adherend by laser irradiation.

[0128] 1-3. Third aspect of component (A) A third preferred embodiment of the component (A) is a (meth)acrylic copolymer containing a structural unit containing an ultraviolet absorbing moiety represented by the following general formula (2), a structural unit containing a polymerizable unsaturated group represented by the following general formula (4), and a structural unit containing a carboxy group represented by the following general formula (5).

[0129] The third aspect is included in the above-mentioned ii) (meth)acrylic copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units, in which the structural unit (AA) contains a structural unit having an ultraviolet absorbing moiety represented by the following general formula (2), the structural unit (AB) contains a structural unit represented by the following general formula (4), and the structural unit (AC) contains a structural unit represented by the following general formula (5).

[0130] [ka]

[0131] In the above general formula (2), Z is a sulfur atom or an oxygen atom. R4 and R5 may be bonded to any substitutable carbon of the naphthalene ring. In the above general formula (2), R3 independently represents a hydrogen atom or a methyl group. R4 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. R5 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. Furthermore, c is an integer of 0 to 6. * indicates the bonding site to other structural units.

[0132] [ka]

[0133] [ka]

[0134] In the general formula (4) and the general formula (5), R, R 11 and R 12 R9 to R10 each independently represent a hydrogen atom or a methyl group. 10 and R 13 ~R 14are each independently a hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond. d and e are 0, 1, or 2. X1 and X2 are each independently an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. * indicates a bonding site with other structural units.

[0135] Examples of the alkylene group having 1 to 10 carbon atoms represented by R4 include: linear or branched divalent alkylene groups including methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups; divalent hydrocarbon groups having an alicyclic structure, including a cyclohexylene group, a methylcyclohexylene group, an ethylcyclohexylene group, a dimethylcyclohexylene group, a diethylcyclohexylene group, a methylethylcyclohexylene group, a propylcyclohexylene group, and a methylpropylcyclohexylene group; Divalent hydrocarbon groups having an aromatic group, including phenylene, methylphenylene, ethylphenylene, dimethylphenylene, methylethylphenylene, and naphthylene groups Among these, a methylene group and an ethylene group are preferred, and a methylene group is more preferred.

[0136] The alkyl group having 1 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a methoxy group, an ethoxy group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0137] The cycloalkyl group having 3 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may have a monocyclic structure or a polycyclic structure. Examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

[0138] The aryl group having 6 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, may have a monocyclic structure or a fused ring structure. Examples of such an aryl group include a phenyl group, a naphthyl group, and a pyridyl group.

[0139] Examples of the aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a benzyl group and a phenethyl group.

[0140] Examples of the hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom and is represented by R5 include a hydroxymethyl group, a hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group.

[0141] Examples of the hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, and a 2,3-dihydroxypropoxy group.

[0142] Examples of the glycidylalkyl group having 4 to 15 carbon atoms and optionally containing a heteroatom, represented by R5, include a glycidylmethyl group, a glycidylethyl group, a 1-glycidylpropyl group, a 2-glycidylpropyl group, a 3-glycidylpropyl group, a 1-glycidylbutyl group, a 2-glycidylbutyl group, and a 3-glycidylbutyl group.

[0143] Examples of the glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, represented by R5, include a 2-glycidylethoxy group and a 2-glycidylpropoxy group.

[0144] Furthermore, c is preferably an integer of 0 to 2, and c is more preferably 0.

[0145] R9~R 10 and R 13 ~R 14 Examples of the hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond, are: linear or branched divalent alkylene groups including methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups; divalent hydrocarbon groups having an alicyclic structure, including a cyclohexylene group, a methylcyclohexylene group, an ethylcyclohexylene group, a dimethylcyclohexylene group, a diethylcyclohexylene group, a methylethylcyclohexylene group, a propylcyclohexylene group, and a methylpropylcyclohexylene group; divalent hydrocarbon groups having an aromatic group, such as a phenylene group, a methylphenylene group, an ethylphenylene group, a dimethylphenylene group, a methylethylphenylene group, and a naphthylene group; Among these, a methylene group and / or an ethylene group are preferred, and R9 to R 10 is more preferably an ethylene group, and R 13 ~R 14 is more preferably a methylene group.

[0146] d and e are 0, 1 or 2, and are preferably 0.

[0147] X1 and X2 are preferably urethane bonds.

[0148] A preferred range of the content ratio of the total mass X1+X2(g), which is the mass content X1(g) of only the dinaphthothiophene moiety calculated by formula (I) from the mass content of the structural unit represented by general formula (2), and the mass content X2(g) of only the dinaphthofuran moiety calculated by formula (II) from the mass content of the structural unit represented by general formula (2), to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer, is the same as the preferred range of the content ratio of the total mass X1+X2(g) of X1(g) and X2(g), which is calculated by formulas (I) and (II) from the mass content of the structural unit (AA) described above, to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer.

[0149] The proportion of the structural unit represented by general formula (4) relative to 100 mol% of all structural units is the same as the preferred range of the proportion of structural units having a polymerizable unsaturated group described above (proportion of the total amount of structural units (AB) and structural units (AD)).

[0150] The proportion of the structural unit represented by general formula (5) relative to 100 mol% of all structural units is the same as the preferred range of the proportion of structural units having a carboxy group described above (proportion of the total amount of structural units (AC) and structural units (AD)).

[0151] 1-4. Fourth aspect of component (A) A fourth preferred embodiment of the component (A) is a (meth)acrylic copolymer containing a structural unit having an ultraviolet absorbing moiety represented by the following general formula (2) and a structural unit having a polymerizable unsaturated group and a carboxy group represented by the following general formula (7):

[0152] The fourth aspect is included in the (meth)acrylic copolymer having the above-mentioned iii) structural unit (AA) and structural unit (AD) as essential structural units, in which the structural unit (AA) contains a structural unit having an ultraviolet absorbing moiety represented by the following general formula (2), and the structural unit (AD) contains a structural unit represented by the following general formula (7).

[0153] [ka]

[0154] In the above general formula (2), Z is a sulfur atom or an oxygen atom. R4 and R5 may be bonded to any substitutable carbon of the naphthalene ring. In the above general formula (2), R3 independently represents a hydrogen atom or a methyl group. R4 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. R5 independently represents a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. Furthermore, c is an integer of 0 to 6. * indicates a bonding site to another structural unit.

[0155] [ka]

[0156] In the above general formula (7), R 15 and R 18 R each independently represents a hydrogen atom or a methyl group. 16 ~R 17 R each independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond. 19 are independently a hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond.

[0157] R16 ~R 17 Examples of hydrocarbon groups having 1 to 10 carbon atoms are: linear or branched divalent alkylene groups including methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups; divalent hydrocarbon groups having an alicyclic structure, including a cyclohexylene group, a methylcyclohexylene group, an ethylcyclohexylene group, a dimethylcyclohexylene group, a diethylcyclohexylene group, a methylethylcyclohexylene group, a propylcyclohexylene group, and a methylpropylcyclohexylene group; Divalent hydrocarbon groups having an aromatic group, including phenylene, methylphenylene, ethylphenylene, dimethylphenylene, methylethylphenylene, and naphthylene groups Among these, a methylene group and an ethylene group are preferred, and a methylene group is more preferred.

[0158] R 19 An example of this is R 16 ~R 17 and cycloalkene groups having 3 to 10 carbon atoms such as a cyclopropene group, a cyclobutene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, and a cyclooctene group. Among these, an ethylene group and a propylene group are preferred, and an ethylene group is more preferred.

[0159] A preferred range of the content ratio of the total mass X1+X2(g), which is the mass content X1(g) of only the dinaphthothiophene moiety calculated by formula (I) from the mass content of the structural unit represented by general formula (2), and the mass content X2(g) of only the dinaphthofuran moiety calculated by formula (II) from the mass content of the structural unit represented by general formula (2), to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer, is the same as the preferred range of the content ratio of the total mass X1+X2(g) of X1(g) and X2(g), which is calculated by formulas (I) and (II) from the mass content of the structural unit (AA) described above, to the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer.

[0160] The proportion of the structural unit represented by general formula (7) is preferably 5 mol % to 50 mol %, and more preferably 10 mol % to 45 mol %, relative to 100 mol % of all structural units. When the proportion of the structural unit represented by general formula (7) is 5 mol % or more, photocuring proceeds easily even at low exposure doses. Furthermore, when used for pattern formation, residues are less likely to remain during alkaline development, which improves pattern formability. When the proportion of the structural unit represented by general formula (7) is 50 mol % or less, penetration of an alkaline developer into the composition can be appropriately adjusted, and peeling development due to rapid penetration of the alkaline developer can be suppressed when used for pattern formation.

[0161] 1-5. Method for synthesizing component (A) The (meth)acrylic copolymer may be synthesized by copolymerizing an appropriate combination of the following monomers, or may be synthesized by a method in which a polymer obtained by copolymerizing an appropriate combination of the following monomers is reacted with compounds (Ay1a) to (Ay3) and compound (Az3) to the side chains of structural units derived from monomers (Ax1) to (Ax3) to graft a dinaphthothiophene moiety or dinaphthofuran moiety, a polymerizable unsaturated group, or a carboxy group.

[0162] (Aa) A monomer having a (meth)acryloyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety (Ac) A monomer having a (meth)acryloyl group and a carboxy group (Ae) A monomer having a (meth)acryloyl group and having neither a dinaphthothiophene moiety nor a dinaphthofuran moiety carboxy group (Ax1) A monomer having a (meth)acryloyl group and a hydroxyl group (Ax2) A monomer having a (meth)acryloyl group and an isocyanate group (Ax3) A monomer having a (meth)acryloyl group and a glycidyl group or an alicyclic epoxy group (Ay1a) Compound having an isocyanate group and a polymerizable unsaturated group (Ay1b) Dicarboxylic acid or its monoanhydride (Ay2) Compound having a hydroxyl group and a polymerizable unsaturated group (Aw2) Compounds having a hydroxyl group and a dinaphthothiophene or dinaphthofuran moiety (Ay3) Compound having a carboxy group and a polymerizable unsaturated group (Az3) Polycarboxylic acids or their anhydrides

[0163] The monomer (Aa) is a monomer for introducing a dinaphthothiophene moiety or a dinaphthofuran moiety into the (meth)acrylic copolymer.

[0164] Examples of the monomer (Aa) include 6-methyl methacrylate-dinaphtho[2,1-b:1',2'-d]thiophene, 6-methyl acrylate-dinaphtho[2,1-b:1',2'-d]thiophene, 5-ethyl methacrylate-dinaphtho[2,1-b:1',2'-d]furan, 5-ethyl acrylate-dinaphtho[2,1-b:1',2'-d]furan, and the like.

[0165] The monomer (Ac) is a monomer for introducing a carboxy group into the (meth)acrylic copolymer. The monomer (Ac) is preferably a monomer that does not have either the dinaphthothiophene moiety or the dinaphthofuran moiety described above. The monomer (Ac) is also preferably a monomer that has an absorbance of less than 0.06 at a wavelength of 266 nm and at a wavelength of 355 nm. The absorbance is a value measured by the same method as described above.

[0166] Examples of the monomer (Ac) include (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, (2-(meth)acryloyloxyethyl) hexahydrophthalate, (2-(meth)acryloyloxyethyl) phthalate, (2-(meth)acryloyloxyethyl) maleate, (2-acryloyloxyethyl) fumarate, (2-(meth)acryloyloxyethyl) itaconic acid, , citraconic acid (2-(meth)acryloyloxyethyl), carboxyethyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, mono-n-butyl maleate (2-(meth)acryloyloxyethyl), mono-n-butyl fumarate (2-(meth)acryloyloxyethyl), and mono-n-butyl itaconate (2-(meth)acryloyloxyethyl).

[0167] The monomer (Ae) is a monomer that facilitates increasing the solubility in a solvent and facilitating mixing with other additives when prepared into a composition. As described above, the monomer (Ae) is a monomer that does not have the above-mentioned carboxy group, dinaphthothiophene moiety, or dinaphthofuran moiety. Furthermore, the monomer (Ae) is preferably a monomer whose absorbance at a wavelength of 266 nm and absorbance at a wavelength of 355 nm are both less than 0.06. The absorbance is a value measured by the same method as described above.

[0168] Examples of monomers (Ae) include: (meth)acrylates having an alkyl chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylates having an alkyl chain having 1 to 10 carbon atoms modified with alkylene oxide, such as methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, and butoxydiethylene glycol (meth)acrylate; (meth)acrylates having an alicyclic hydrocarbon having 3 to 30 carbon atoms, such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantan-1-yl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate; (meth)acrylates having aromatic hydrocarbons having 3 to 30 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-biphenyl (meth)acrylate, and 2-naphthyl (meth)acrylate; (meth)acrylates having alkylene oxide-modified aromatic hydrocarbons having 3 to 30 carbon atoms, such as neopentyl glycol-acrylic acid-benzoic acid ester, phenoxyethylene glycol methacrylate, and ethoxylated-O-phenylphenol (meth)acrylate; (Meth)acrylates having a hydrocarbon group having 1 to 30 carbon atoms which may have one or two heteroatoms, such as phthalimide (meth)acrylate, maleimide (meth)acrylate, benzophenone (meth)acrylate, 2-hydroxy-4-(meth)acryloyloxybenzophenone, and hydroxy-4-(2-(meth)acryloyloxy)ethoxybenzophenone These include:

[0169] The monomers (Ax1) to (Ax3) are monomers for introducing the above-mentioned functional groups into the side chains of the (meth)acrylic copolymer by grafting.

[0170] The monomers (Ax1) to (Ax3) are preferably monomers that do not have the above-mentioned dinaphthothiophene moiety. The monomers (Ax1) to (Ax3) are preferably monomers that have an absorbance at a wavelength of 266 nm and an absorbance at a wavelength of 355 nm that are both less than 0.06. The monomers (Ax1) to (Ax3) are preferably monomers that do not have a carboxy group. The absorbance is a value measured by the same method as described above.

[0171] For example, the monomer (Ax1) having a hydroxyl group can be copolymerized with other monomers, and then reacted with a compound (Ay1a) having an isocyanate group and a polymerizable unsaturated group to introduce the polymerizable unsaturated group into the (meth)acrylic copolymer via a urethane bond.

[0172] Alternatively, the monomer (Ax1) having a hydroxyl group can be copolymerized with another monomer, and then reacted with (Ay1b) a dicarboxylic acid or its monoanhydride to introduce a carboxyl group into the (meth)acrylic copolymer via an ester bond.

[0173] Examples of such monomers (Ax1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and ethyl-α-hydroxymethyl acrylate.

[0174] Examples of the compound (Ay1a) having an isocyanate group and a polymerizable unsaturated group, which is used together with the monomer (Ax1), include 2-isocyanatoethyl (meth)acrylate.

[0175] Examples of the dicarboxylic acid (Ay1b) or the acid monoanhydride thereof used together with the monomer (Ax1) include a chain hydrocarbon dicarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid, an aromatic hydrocarbon dicarboxylic acid, and the acid monoanhydrides thereof.

[0176] Examples of the above-mentioned chain hydrocarbon dicarboxylic acid and tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, as well as these dicarboxylic acids having any substituent introduced therein.

[0177] Examples of the alicyclic hydrocarbon dicarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-endomethylenetetrahydrophthalic acid, chlorendic acid, and norbornanedicarboxylic acid, as well as dicarboxylic acids having any substituent introduced therein.

[0178] Examples of the aromatic hydrocarbon dicarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, as well as these dicarboxylic acids having any substituent introduced therein.

[0179] Of these, the dicarboxylic acids are preferably succinic acid, itaconic acid, tetrahydrophthalic acid, and phthalic acid, and more preferably succinic acid, itaconic acid, and tetrahydrophthalic acid.

[0180] The dicarboxylic acid is preferably used as its monoanhydride.

[0181] Instead of the compound (Ay1a) having an isocyanate group and a polymerizable unsaturated group, a compound having an isocyanate group and a dinaphthothiophene moiety or a dinaphthofuran moiety, or a compound having an isocyanate group and a carboxy group may be used to introduce the dinaphthothiophene moiety, the dinaphthofuran moiety, or the carboxy group into the side chain of the structural unit derived from the monomer (Ax1) via a urethane bond.

[0182] Alternatively, instead of (Ay1b) dicarboxylic acid or its monoanhydride, a compound having a carboxy group and a dinaphthothiophene moiety or a dinaphthofuran moiety, or a compound having a carboxy group and a polymerizable unsaturated group may be used to introduce the dinaphthothiophene moiety, the dinaphthofuran moiety, or the polymerizable unsaturated group into the side chain of the structural unit derived from the monomer (Ax1) via a urethane bond.

[0183] Furthermore, the monomer (Ax2) having an isocyanate group can be used for copolymerizing with other monomers, and then reacting the isocyanate group with a compound (Ay2) having a hydroxyl group and a polymerizable unsaturated group to introduce a polymerizable unsaturated group into the (meth)acrylic copolymer via a urethane bond.

[0184] Examples of such a monomer (Ax2) include the compounds exemplified above as compounds having an isocyanate group and a polymerizable unsaturated group.

[0185] Examples of the compound (Ay2) having a hydroxyl group and a polymerizable unsaturated group, which is used together with the monomer (Ax2), include the compounds exemplified as the monomer (Ax1).

[0186] Instead of the compound (Ay2) having a hydroxyl group and a polymerizable unsaturated group, a compound (Aw2) having a hydroxyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety, or a compound having a hydroxyl group and a carboxyl group may be used to introduce the dinaphthothiophene moiety, the dinaphthofuran moiety, or the carboxyl group into the side chain of the structural unit derived from the monomer (Ax2) via a urethane bond.

[0187] Examples of the compound (Aw2) having a hydroxyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety, which is used together with the monomer (Ax2), include 5-hydroxymethyldinaphthothiophene, 5-hydroxyethyldinaphthothiophene, 6-hydroxymethyldinaphthothiophene, 6-hydroxyethyldinaphthothiophene, 5-hydroxymethyldinaphthofuran, 5-hydroxyethyldinaphthofuran, 6-hydroxymethyldinaphthofuran, and 6-hydroxyethyldinaphthofuran.

[0188] Furthermore, the monomer (Ax3) having a glycidyl group or an alicyclic epoxy group can be copolymerized with another monomer, and then reacted with a compound (Ay3) having a carboxy group and a polymerizable unsaturated group to introduce a polymerizable unsaturated group into the (meth)acrylic copolymer via an epoxy acrylate residue.

[0189] Examples of such monomers (Ax3) include glycidyl (meth)acrylate, β-propylglycidyl (meth)acrylate, β-methylglycidyl-α-ethyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0190] Examples of the compound (Ay3) having a carboxy group and a polymerizable unsaturated group, which is used together with the monomer (Ax3), include the compounds exemplified as the monomer (Ac).

[0191] The epoxy acrylate residue generated from the monomer (Ax3) may be further reacted with a polycarboxylic acid (Az3) or an anhydride thereof to introduce a carboxy group into the (meth)acrylic copolymer via the epoxy acrylate residue.

[0192] Examples of polycarboxylic acids to be reacted with the epoxy acrylate residue include the dicarboxylic acids or their monoanhydrides exemplified as the monomer (Ay1b), as well as tricarboxylic acids or their monoanhydrides and tetracarboxylic acids or their dianhydrides.

[0193] Examples of the tricarboxylic acid include trimellitic acid and hexahydrotrimellitic acid.

[0194] Examples of the tetracarboxylic acid include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, and aromatic tetracarboxylic acids.

[0195] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0196] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein.

[0197] Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0198] The tetracarboxylic acid is preferably an acid dianhydride thereof.

[0199] For example, the above i) A copolymer having the structural unit (AA) and the structural unit (AE) as essential structural units. ii) A copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units. iii) Copolymers containing the structural unit (AA) and the structural unit (AD) as essential structural units can be synthesized by the following steps.

[0200] 1-5-1. Step (1) i) Method for synthesizing a copolymer having structural units (AA) and (AE) as essential structural units [Process (1)] (Aa) a monomer having a (meth)acryloyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety; (Ae) a monomer having a (meth)acryloyl group and having no dinaphthothiophene moiety, no dinaphthofuran moiety, and no carboxy group; A step of copolymerizing the above to obtain a copolymer.

[0201] The copolymerization in step (1) can be carried out by mixing the monomers to be copolymerized together with a thermal polymerization initiator in a solvent and reacting them. The reaction temperature depends on the type of thermal polymerization initiator used, but it is preferable to carry out the reaction in a solvent at a temperature range of 60 to 100°C for 2 to 12 hours.

[0202] The thermal polymerization initiator may be any general thermal radical polymerization initiator, and is preferably an azo compound or a peroxide, more preferably an azo compound from the viewpoint of producing a linear polymer.

[0203] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(isobutyrate) dimethyl, etc. Among these, 2,2'-azobisisobutyronitrile is preferred from the viewpoint of reaction temperature.

[0204] The solvent can be appropriately selected from those used in resin compositions. Examples of solvents that can be used include alcohols, glycols, aliphatic cyclic ketones, and acetate esters. Of these, it is preferable to use a solvent other than alcohols.

[0205] Examples of glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0206] Examples of the aliphatic cyclic ketones include cyclohexanone, ortho-methylcyclohexanone, meta-methylcyclohexanone, para-methylcyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.

[0207] Examples of acetate esters include ethyl acetate, n-propyl acetate, and n-butyl acetate.

[0208] In addition to these, saturated hydrocarbon solvents such as solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone, n-octane, and isooctane, as well as ethyl cellosolve and butyl cellosolve may also be used.

[0209] Among these, in terms of easily increasing the solubility of the monomer that is the material of the structural unit (AA), when a dinaphthothiophene moiety is contained, N-methyl-2-pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred. When a dinaphthofuran moiety is contained, propylene glycol monomethyl ether acetate and N-methyl-2-pyrrolidone are preferred. In particular, when the monomer that is the material of the structural unit (AA) is a compound containing an acrylate moiety and a dinaphthofuran moiety (e.g., 5-ethylacrylatedinaphtho[2,1-b:1',2'-d]furan), N-methyl-2-pyrrolidone is more preferred.

[0210] The amount of the solvent is preferably 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the total of the monomers to be copolymerized mixed in the above range.

[0211] 1-5-2. Step (2) ii) Method for synthesizing copolymers having structural units (AA), (AB), and (AC) as essential structural units [Process (2)-1] (Aa) a monomer having a (meth)acryloyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety; (Ac) a monomer having a (meth)acryloyl group and a carboxy group; (Ax1) a monomer having a (meth)acryloyl group and a hydroxyl group; A step of copolymerizing the above to obtain a copolymer.

[0212] [Process (2)-2] a step of reacting the copolymer obtained in step (2)-1 with a compound (Ay1a) having an isocyanate group and a polymerizable unsaturated group to form a urethane bond between the hydroxyl group derived from the monomer (Ax1) and the isocyanate group of the compound (Ay1a), thereby grafting the polymerizable unsaturated group onto the copolymer;

[0213] The copolymerization in step (2)-1 can be carried out in the same manner as the copolymerization in step (1) described above. The reaction temperature depends on the type of thermal polymerization initiator used, but it is preferable to carry out the reaction in a solvent at a temperature in the range of 60 to 100°C for 2 to 12 hours.

[0214] The thermal polymerization initiator may be any general thermal radical polymerization initiator, and is preferably an azo compound or a peroxide, more preferably an azo compound from the viewpoint of producing a linear polymer.

[0215] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(isobutyrate) dimethyl, etc. Among these, 2,2'-azobisisobutyronitrile is preferred from the viewpoint of reaction temperature.

[0216] The solvent can be appropriately selected from those used in resin compositions. Examples of solvents that can be used include alcohols, glycols, aliphatic cyclic ketones, and acetate esters. Of these, it is preferable to use a solvent other than alcohols.

[0217] Examples of glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0218] Examples of the aliphatic cyclic ketones include cyclohexanone, ortho-methylcyclohexanone, meta-methylcyclohexanone, para-methylcyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.

[0219] Examples of acetate esters include ethyl acetate, n-propyl acetate, and n-butyl acetate.

[0220] In addition to these, saturated hydrocarbon solvents such as solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone, n-octane, and isooctane, as well as ethyl cellosolve and butyl cellosolve may also be used.

[0221] In this case, it is preferable not to use a solvent containing a hydroxyl group, such as isopropyl alcohol (IPA) or propylene glycol monomethyl ether (PGME), etc. This avoids the reaction of the isocyanate group of the compound having an isocyanate group and a polymerizable unsaturated group (Ay1a) with the hydroxyl group of the solvent in the next step, and allows the reaction to form a urethane bond to proceed reliably and sufficiently.

[0222] Among these, in terms of easily increasing the solubility of the monomer that is the material of the structural unit (AA), when a dinaphthothiophene moiety is contained, N-methyl-2-pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred. When a dinaphthofuran moiety is contained, the commonly used propylene glycol monomethyl ether acetate and N-methyl-2-pyrrolidone are preferred. In particular, when the monomer that is the material of the structural unit (AA) is a compound containing an acrylate moiety and a dinaphthofuran moiety (e.g., 5-ethylacrylatedinaphtho[2,1-b:1',2'-d]furan), N-methyl-2-pyrrolidone is more preferred.

[0223] The amount of the solvent is preferably 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the total of the monomers to be copolymerized mixed in the above range.

[0224] In the reaction of step (2)-2, it is preferable to mix the monomer (Ay1a), a compound having an isocyanate group and a polymerizable unsaturated group, with the reaction solution obtained in the above-mentioned step (2)-1, and then react them in a solvent at a temperature in the range of 40°C to 100°C for 2 to 12 hours.

[0225] The solvent can be appropriately selected from those mentioned above. The reaction can be carried out by adding a catalyst, if necessary. Examples of the catalyst include tin compounds, titanium compounds, and amine compounds. Specific examples of the catalyst include dibutyltin laurate, tetra-n-butoxytitanium, and triethylamine. Among these, tin compounds are preferred because the reaction is easily controlled. The amount of catalyst added is preferably 0.01 to 10 parts by weight per 100 parts by weight of the total of the monomer (Ay1a) containing an isocyanate group and a polymerizable unsaturated group. In this case, it is preferable not to polymerize the (meth)acryloyl group of the monomer (Ay1a) containing an isocyanate group and a polymerizable unsaturated group, and for this purpose, a polymerization inhibitor or the like may be added.

[0226] The compound having an isocyanate group and a polymerizable unsaturated group in the monomer (Ay1a) is preferably reacted with the isocyanate group in a molar amount equal to or less than the hydroxyl group in the monomer (Ax1). Specifically, the molar amount of the isocyanate group in the monomer (Ay1a) is more preferably 98 to 100% of the hydroxyl group in the monomer (Ax1).

[0227] The materials used may be changed as appropriate depending on the constitution of each structural unit contained in the resulting polymer.

[0228] 1-5-3. Step (3) iii) Method for synthesizing copolymers having structural units (AA) and (AD) as essential structural units [Process (3)-1] (Aa) a monomer having a (meth)acryloyl group and a dinaphthothiophene moiety or a dinaphthofuran moiety; (Ax3) a monomer having a (meth)acryloyl group and a glycidyl group or an alicyclic epoxy group; A step of copolymerizing the above to obtain a copolymer.

[0229] [Process (3)-2] a step of reacting the copolymer obtained in step (3)-1 with a compound (Ay3) having a carboxy group and a polymerizable unsaturated group to form an epoxy acrylate residue by reaction between the glycidyl group or alicyclic epoxy group derived from the monomer (Ax3) and the carboxy group of the compound (Ay3), thereby grafting the polymerizable unsaturated group onto the copolymer;

[0230] [Process (3)-3] a step of reacting (Az3) a polycarboxylic acid or anhydride thereof with the copolymer to which the polymerizable unsaturated groups have been grafted in step (3)-2, thereby further grafting a carboxy group onto the copolymer by a reaction between a hydroxyl group derived from the monomer (Ax1) or an epoxy acrylate residue formed by the reaction of the monomer (Ax3) with the monomer (Ay3) and a carboxy group or a carboxylic acid anhydride group possessed by the compound (Az3).

[0231] The copolymerization in step (3)-1 can be carried out in the same manner as the copolymerization in step (1) described above. The reaction temperature depends on the type of thermal polymerization initiator used, but it is preferable to carry out the reaction in a solvent at a temperature in the range of 60 to 100°C for 2 to 12 hours.

[0232] The thermal polymerization initiator may be any general thermal radical polymerization initiator, and is preferably an azo compound or a peroxide, more preferably an azo compound from the viewpoint of producing a linear polymer.

[0233] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(isobutyrate) dimethyl, etc. Among these, 2,2'-azobisisobutyronitrile is preferred from the viewpoint of reaction temperature.

[0234] The solvent can be appropriately selected from those used in resin compositions. Examples of solvents that can be used include alcohols, glycols, aliphatic cyclic ketones, and acetate esters. Of these, it is preferable to use a solvent other than alcohols.

[0235] Examples of glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0236] Examples of the aliphatic cyclic ketones include cyclohexanone, ortho-methylcyclohexanone, meta-methylcyclohexanone, para-methylcyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.

[0237] Examples of acetate esters include ethyl acetate, n-propyl acetate, and n-butyl acetate.

[0238] In addition to these, saturated hydrocarbon solvents such as solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone, n-octane, and isooctane, as well as ethyl cellosolve and butyl cellosolve may also be used.

[0239] In this step, by not using a solvent containing a hydroxyl group, such as isopropyl alcohol (IPA) or propylene glycol monomethyl ether (PGME), it is possible to avoid a reaction between the acid anhydride group of the polycarboxylic acid (Az3) or its anhydride and the hydroxyl group of the solvent in the next step, and to ensure that the reaction to form an ester bond can be carried out reliably and sufficiently.

[0240] Among these, in terms of facilitating increasing the solubility of the monomer that is the material of the structural unit (AA), when a dinaphthothiophene moiety is contained, N-methyl-2-pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred. When a dinaphthofuran moiety is contained, the commonly used propylene glycol monomethyl ether acetate and N-methyl-2-pyrrolidone are preferred. In particular, when the monomer that is the material of the structural unit (AA) is a compound containing an acrylate moiety and a dinaphthofuran moiety (e.g., 5-ethylacrylatedinaphtho[2,1-b:1',2'-d]furan), N-methyl-2-pyrrolidone is more preferred.

[0241] The amount of the solvent is preferably 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the total of the monomers to be copolymerized mixed in the above range.

[0242] The reaction in step (3)-2 can be carried out in a solvent at a temperature ranging from 80 to 130°C for 5 to 18 hours. The reaction can be carried out more efficiently by adding a base catalyst. Examples of the base catalyst include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0243] The reaction in step (3)-3 can be carried out at a reaction temperature in the range of 80 to 130° C. for 5 to 48 hours in a solvent to form the compound.

[0244] Alternatively, in step (3)-1, a monomer (Ax1) having a (meth)acryloyl group and a hydroxyl group may be copolymerized, and in step (3)-3, an ester bond may be formed between the hydroxyl group derived from the monomer (Ax1) and the carboxyl group or carboxylic anhydride group of the compound (Az3), thereby grafting the carboxyl group onto the copolymer. The reaction conditions in this case may be the same as those in step (3)-3.

[0245] It goes without saying that the monomers and compounds exemplified in the above synthesis method are merely examples, and other monomers and compounds having similar functional groups can also be used.

[0246] 1-6. (A) Use of ingredients Because component (A) easily absorbs ultraviolet light at both 266 nm and 355 nm wavelengths, it is preferably used as an optical material such as a light transmission control film. Component (A) is also preferably used as a paint, varnish, ink, and a material for three-dimensional modeling using light.

[0247] 2. Composition for forming adhesive layer The adhesive layer-forming composition according to this embodiment (hereinafter also simply referred to as the "composition") is The aforementioned component (A), (B) an unsaturated group-containing polymerizable compound having neither a dinaphthothiophene moiety nor a dinaphthofuran moiety (hereinafter also referred to simply as "component (B)"); (C) a solvent (hereinafter also referred to simply as "component (C)"), Including, The content by mass of the component (A) is 10% by mass or more relative to the total mass of the solid content of the adhesive layer-forming composition. It is preferably a composition for forming an adhesive layer.

[0248] The component (B) is broadly divided into a component (B1), which is a polymerizable alkali-soluble resin containing an unsaturated group, and a component (B2), which is an unsaturated group-containing polymerizable compound that does not have an alkali-soluble group. The composition may contain only the component (B1), only the component (B2), or both the component (B1) and the component (B2).

[0249] Furthermore, the composition may contain, as necessary, an epoxy compound (D) (hereinafter also simply referred to as component (D)), a photopolymerization initiator (E) (hereinafter also simply referred to as component (E)), and other components.

[0250] Specifically, for example, when pattern formation is not required, a) a composition comprising, as component (A), i) a copolymer having structural units (AA) and (AE) as essential structural units, component (B2), and component (C); (ii) a composition containing, as the component (A), ii) a copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units and / or iii) a copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units, a component (B2), and a component (C); c) A composition containing, as component (A), ii) a copolymer having the structural unit (AA), the structural unit (AB), and the structural unit (AC) as essential structural units and / or iii) a copolymer having the structural unit (AA) and the structural unit (AD) as essential structural units, and components (B1), (B2), and (C). Among these, from the viewpoint of easily increasing heat resistance, the compositions described in (b) or (c) above are preferred, and from the viewpoint of easily increasing adhesive strength, the composition described in (c) above is more preferred.

[0251] Also, for example, when pattern formation is required, d) a composition containing, as the component (A), i) a copolymer having the structural unit (AA) and the structural unit (AE) as essential structural units, a component (B1), a component (B2), a component (C), and a component (E); e) a composition comprising, as component (A), ii) a copolymer having structural units (AA), (AB), and (AC) as essential structural units and / or iii) a copolymer having structural units (AA) and (AD) as essential structural units, component (B2), component (C), and component (E); f) a composition comprising, as component (A), ii) a copolymer having structural units (AA), (AB), and (AC) as essential structural units and / or iii) a copolymer having structural units (AA) and (AD) as essential structural units, and components (B1), (B2), (C), and (E); Among these, the composition described in (f) above is preferred from the viewpoint of easily increasing adhesive strength and solvent resistance while maintaining pattern formability.

[0252] The content by mass of component (A) is preferably 10% by mass or more, more preferably 10% by mass to 90% by mass, even more preferably 20% by mass to 80% by mass, even more preferably 25% by mass to 60% by mass, even more preferably 35% by mass to 60% by mass, and most preferably 45% by mass to 60% by mass, based on the total mass of solids in the adhesive layer-forming composition. When the content by mass of component (A) is 10% by mass or more, the adhesive layer is more likely to absorb ultraviolet light, and the alteration or decomposition of the cured product is more likely to be promoted by irradiation with a laser having a wavelength of either 266 nm or 355 nm. When the content by mass of component (A) is 20% by mass or more, the adhesive layer is more likely to absorb ultraviolet light, and the alteration or decomposition of the cured product is more likely to be promoted by irradiation with a laser having a wavelength of either 266 nm or 355 nm. When the content of component (A) is 35% by mass or more, the adhesive layer is more likely to absorb ultraviolet light, and irradiation with a laser having a wavelength of either 266 nm or 355 nm is more likely to accelerate the deterioration or decomposition of the cured product. When the content of component (A) is 90% by mass or less, the adhesive layer's properties, such as adhesive strength, pattern formability, and solvent resistance, can be improved. When the content of component (A) is 60% by mass or less, the proportion of component (B) can be increased, making it easier to improve curability, and when used for pattern formation, pattern formability is more likely to be improved.

[0253] Hereinafter, each component other than the aforementioned component (A) that may be contained in the composition will be described.

[0254] 2-1. (B) Unsaturated group-containing polymerizable compound having neither a dinaphthothiophene moiety nor a dinaphthofuran moiety Component (B) is a compound that has a polymerizable unsaturated group and that undergoes a polymerization reaction and hardens when stimulated by heat, light, etc. Component (B) does not have a dinaphthothiophene moiety or a dinaphthofuran moiety in the molecule.

[0255] The component (B) facilitates improving the adhesiveness to the adherend and solvent resistance of the adhesive layer obtained by curing the composition.

[0256] The component (B) may be any compound that can ensure adhesion to the adherend and solvent resistance, and may be a known unsaturated group-containing polymerizable compound such as an alkali-soluble resin or an acrylic resin.

[0257] 2-1-1. (B1) Component (B) having an alkali-soluble group The component (B1) preferably has a polymerizable unsaturated group and an acidic group (alkali-soluble group) for exhibiting alkali solubility in one molecule, and more preferably contains both a (meth)acryloyl group and a carboxy group. Any of the above resins can be used without particular limitations. Because the alkali-soluble resin has both a polymerizable unsaturated group and an alkali-soluble group, it not only provides excellent photocurability when patterning of the adhesive layer-forming composition is required, but also provides good developability and patterning properties, and further enhances the adhesion of the adhesive layer to the substrate.

[0258] The alkali-soluble resin (B1) according to the present embodiment is preferably a polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of an epoxy compound having two or more epoxy groups with (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. During the production of the alkali-soluble resin, a polyester is produced by the reaction of a hydroxy group with a polybasic carboxylic acid, and the polyester preferably has a low molecular weight with an average degree of polymerization of about 2 to 500.

[0259] The epoxy compound is preferably 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 fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000HK: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups, such as HiREM-1 manufactured by Shikoku Chemicals Corporation, multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0260] As the alkali-soluble resin of component (B1), an acrylic copolymer is also preferably used.

[0261] Examples of acrylic copolymers include copolymers of (meth)acrylic acid, (meth)acrylic acid esters, etc., and resins having a (meth)acryloyl group and a carboxy group. Examples of the resins include alkali-soluble resins containing polymerizable unsaturated groups, which are obtained by copolymerizing (meth)acrylic acid esters including glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymer include a copolymer disclosed in Japanese Patent Application Laid-Open No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and which has a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH / g; and a polymerizable unsaturated group-containing alkali-soluble resin disclosed in Japanese Patent Application Laid-Open No. 2018-141968, which is a polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, and which includes units derived from (meth)acrylic acid ester compounds and units having a (meth)acryloyl group and a di- or tricarboxylic acid residue.

[0262] From the viewpoint of further improving the heat resistance and solvent resistance of the adhesive layer and further improving the adhesion of the adhesive layer to the substrate, the component (B1) preferably has multiple aromatic rings, is more preferably an alkali-soluble resin having a repeating unit containing a fluorene structure, and is even more preferably an alkali-soluble resin having a repeating unit containing a bisarylfluorene skeleton. For example, the component (B1) is preferably a resin represented by the following general formula (B1-1):

[0263] [ka]

[0264] In formula (B1-1), Ar independently represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. 31 are independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (B1-2) or the following general formula (B1-3). Y is a tetravalent carboxylic acid residue. Z2 is independently a hydrogen atom or a substituent represented by the following general formula (B1-4), and at least one Z2 is a substituent represented by the following general formula (B1-4). n is a number with an average value of 1 to 20.

[0265] [ka]

[0266] [ka]

[0267] In formulas (B1-2) and (B1-3), R 32 is a hydrogen atom or a methyl group, and R 33 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R 34 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site.

[0268] [ka]

[0269] In formula (B1-4), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0270] The resin represented by general formula (B1-1) can be synthesized by the following method.

[0271] First, an epoxy compound (a-1) (hereinafter simply referred to as "epoxy compound (a-1)") having a bisarylfluorene skeleton represented by the following general formula (B1-5), which may have several alkylene oxide-modified groups per molecule, is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (B1-6), and a (meth)acrylic acid derivative represented by the following general formula (B1-7) to obtain a diol compound that is an epoxy (meth)acrylate. The bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

[0272] [ka]

[0273] In formula (B1-5), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. 31 are independently an alkylene group having 2 to 4 carbon atoms. 1 is independently a number from 0 to 3.

[0274] [ka]

[0275] [ka]

[0276] In formulas (B1-6) and (B1-7), R 32 is a hydrogen atom or a methyl group, and R 33is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R 34 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

[0277] The reaction of the epoxy compound (a-1) with (meth)acrylic acid or a derivative thereof can be carried out by a known method. For example, Japanese Patent Application Laid-Open 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 per mole of an epoxy compound having two epoxy groups. In this embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (B1-8) (hereinafter, also simply referred to as "diol (d)").

[0278] [ka]

[0279] In formula (B1-8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each G is independently a (meth)acryloyl group or a substituent represented by general formula (B1-2) or general formula (B1-3), and R 31 are independently an alkylene group having 2 to 4 carbon atoms. 1 is independently a number from 0 to 3.

[0280] [ka]

[0281] [ka]

[0282] In formulas (B1-2) and (B1-3), R 32 is a hydrogen atom or a methyl group, and R 33 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R 34 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

[0283] Next, the diol (d) obtained above is reacted with a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and a tetracarboxylic acid or its acid dianhydride (c), to obtain an unsaturated group-containing curable resin represented by general formula (B1-1) having a carboxy group and a polymerizable unsaturated group in one molecule.

[0284] The acid component is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule. To obtain the resin represented by general formula (B1-1), it is necessary to use a dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) in combination with a tetracarboxylic acid or its dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain a bond containing a heteroatom such as -O-, -S-, or a carbonyl group.

[0285] Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, and their acid monoanhydrides.

[0286] Examples of the above-mentioned chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0287] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0288] Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0289] Of these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid, and more preferably succinic acid, itaconic acid, or 1,2,3,6-tetrahydrophthalic acid.

[0290] The dicarboxylic acid or tricarboxylic acid is preferably used as its acid monoanhydride.

[0291] Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and acid dianhydrides thereof.

[0292] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0293] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, as well as these alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0294] Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0295] Of these, the tetracarboxylic acids are preferably 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid, and more preferably 3,3',4,4'-biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid.

[0296] The tetracarboxylic acid is preferably an acid dianhydride thereof.

[0297] Alternatively, instead of the tetracarboxylic acid or its dianhydride (c), a bis(trimellitic anhydride) aryl ester can be used. The bis(trimellitic anhydride) aryl ester is a compound produced by the method described in WO 2010 / 074065, and structurally is an acid dianhydride formed by ester bonding between two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, or terphenyldiol) and the carboxyl groups of two molecules of trimellitic anhydride.

[0298] The method for reacting the diol (d) with the acid components (b) and (c) is not particularly limited, and any known method can be used. For example, JP-A-9-325494 describes a method in which an epoxy (meth)acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0299] In this case, it is preferable to react the epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and tetracarboxylic acid dianhydride (c) in such a molar ratio that (d):(b):(c) = 1.0:0.01-1.0:0.2-1.0, so that the terminals of the compounds become carboxy groups.

[0300] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them so that the molar ratio [(b) / 2 + (c)] / (d)] of the amount of acid component relative to diol (d) [(b) / 2 + (c)] is greater than 0.5 and less than 1.0. When this molar ratio is 1.0 or less, the terminals of the unsaturated group-containing curable resin represented by general formula (B1-1) do not become acid anhydrides, thereby suppressing an increase in the content of unreacted acid dianhydrides and improving the stability of the curable composition over time. Furthermore, when this molar ratio is greater than 0.5, an increase in the amount of unreacted components remaining in diol (d) containing a polymerizable unsaturated group is suppressed, thereby improving the stability of the curable composition over time. The molar ratios of components (b), (c), and (d) can be arbitrarily changed within the above-mentioned ranges in order to adjust the acid value and molecular weight of the unsaturated group-containing curable resin represented by general formula (B1-1).

[0301] The synthesis of the diol (d) and the subsequent reaction with the polycarboxylic acid or anhydride thereof are usually carried out in a solvent, if necessary, using a catalyst.

[0302] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. While the reaction conditions, such as the solvent and catalyst used, are not particularly limited, it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent, and propylene glycol monomethyl ether acetate is particularly preferred.

[0303] The reaction between the epoxy group and the carboxy group or the hydroxy group is preferably carried out using a catalyst, and examples of the catalyst described in JP-A-9-325494 include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0304] The acid value of component (B1) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g. An acid value of 50 mgKOH / g or more reduces the likelihood of residue remaining during alkaline development, while an acid value of 200 mgKOH / g or less prevents the alkaline developer from penetrating too quickly, thereby suppressing peeling development. The acid value can be determined by titration with a 1 / 10N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0305] The polystyrene-equivalent weight-average molecular weight (Mw) of component (B1), as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. A weight-average molecular weight (Mw) of 1,000 or greater can improve adhesion between a support and an adherend. Furthermore, a weight-average molecular weight (Mw) of 40,000 facilitates adjustment of the solution viscosity of the curable composition to a level suitable for application, minimizes application time to the surface of a support or adherend, and facilitates enhanced adhesion to the adherend. When adhesive strength is important, a weight-average molecular weight (Mw) of 1,000 to 4,500 is preferred.

[0306] When pattern formation is required and component (A) does not have an alkali-soluble group (for example, the composition described in (b) above), the content of component (B1) is preferably 5 to 70% by mass, more preferably 10 to 70% by mass, even more preferably 30 to 70% by mass, and most preferably 40 to 70% by mass, based on the total mass of solids. When component (B1) is 5% by mass or more, the adhesive layer's adhesion to the adherend is enhanced and the pattern-forming properties of the adhesive layer are likely to be improved. When the content of component (B1) is 70% by mass or less, the adhesive layer does not become too hard after curing, so it is prone to ablation when irradiated with light, and is less likely to leave residue.

[0307] On the other hand, when pattern formation is not required, or when pattern formation is required but component (A) has an alkali-soluble group (for example, in the case of the compositions described in (a) and (c) to (d) above), the composition may or may not contain (B1). In particular, when pattern formation is required and component (A) has an alkali-soluble group (for example, in the case of the compositions described in (c) to (d) above), the content of component (B1) is preferably 5% to 70% by mass, more preferably 5% to 50% by mass, and even more preferably 5% to 30% by mass, based on the total mass of solids. When the content of component (B1) is 5% by mass or more, the adhesive layer tends to have improved adhesion to the adherend and improved solvent resistance. When the content of component (B1) is 70% by mass or less, the hardness of the adhesive layer after curing is not too high, so that the adhesive layer is easily ablated when irradiated with light, and is less likely to leave residue.

[0308] When the (B1) component and the (B2) component are used in combination, the content of the (B1) component in the curable composition is preferably 5 to 1,000 parts by mass, more preferably 10 to 600 parts by mass, and even more preferably 20 to 300 parts by mass, based on 100 parts by mass of the total mass of the (B2) component. When the (B1) component is 5 parts by mass or more, the resin contains a sufficient amount of polymerizable unsaturated groups, allowing for the formation of a sufficient crosslinked structure and improving chemical resistance. When the (B1) component is 1,000 parts by mass or less, the crosslink density of the cured adhesive layer is sufficient, making it prone to ablation when irradiated with light and less likely to leave residue.

[0309] The content of component (B) is preferably 5% to 89.9% by mass, more preferably 10% to 89.9% by mass, and even more preferably 15% to 89.9% by mass, based on the total mass of the solids. When the adhesive strength is important, the content of component (B) is 5% by mass or more, the adhesive layer has high adhesion to the adherend, and the adhesive layer is prone to absorbing the irradiated laser (e.g., ultraviolet light) and being altered or decomposed, making it easier to separate the support and the adherend. When the content is 89.9% by mass or less, the hardness (crosslink density) of the adhesive layer after curing is not too high, so it is prone to ablation when irradiated with light, and is less likely to leave residue.

[0310] 2-1-2. (B2) Component (B) without alkali-soluble groups Component (B2) is a compound that has a polymerizable unsaturated group, undergoes a polymerization reaction in response to stimuli such as heat and light, and does not have an alkali-soluble group. Component (B2) preferably has two or more polymerizable unsaturated groups in the molecule.

[0311] The (B2) component enhances the adhesive strength to the adherend and solvent resistance of the adhesive layer obtained by curing the curable composition. The (B2) component preferably has at least two polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups of the (B1) component, or, if the (A) component contains a polymerizable unsaturated group, with the polymerizable unsaturated groups of the (A) component. When used in combination with the (B1) component, the polymerizable unsaturated groups are preferably the same functional groups as the polymerizable unsaturated groups of the (B1) component. Specifically, the polymerizable unsaturated groups are preferably (meth)acryloyl groups. The (B2) component may be a monomer, oligomer, or polymer. When used in combination with the (B1) component, the (B2) component is preferably a monomer or oligomer.

[0312] Examples of the (B2) component include: (meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid esters of 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, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; Epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; and Examples of compounds having an ethylenic double bond include dendritic polymers having a (meth)acrylic group.

[0313] Component (B2) preferably has two or more (meth)acryloyl groups, and more preferably has three or more (meth)acryloyl groups. When component (B2) has two or more (meth)acryloyl groups, the crosslink density is improved and the solvent resistance of the adhesive layer is improved.

[0314] From the viewpoint of further improving the adhesion of the adhesive layer to the adherend, it is preferable that component (B2) is an alkylene oxide- or lactone-modified compound. These modified compounds are thought to increase the fluidity of the curable composition at the interface with the adherend, filling minute gaps between the adherend and the curable composition to increase the contact area (adhesion area), thereby further improving the adhesion of the adhesive layer to the adherend. In particular, when component (B) is a high-molecular-weight compound, the modified component (B2) compensates for the decrease in fluidity of the curable composition caused by component (B), thereby significantly improving the adhesion.

[0315] The alkylene oxide modified product is preferably a compound having an alkylene oxide group having 2 to 6 carbon atoms, more preferably a compound having an alkylene oxide group having 2 to 4 carbon atoms, and even more preferably a compound having an alkylene oxide group having 2 to 3 carbon atoms.

[0316] The lactone-modified product has a structure in which lactone having 2 to 6 carbon atoms is ring-opened (-C(=O)-(CH2) k -O-, where k is one less than the number of carbon atoms in the lactone), more preferably a compound having a ring-opened structure of a lactone having 4 to 6 carbon atoms, and even more preferably a compound having a ring-opened structure of a lactone having 6 carbon atoms.

[0317] The above alkylene oxide group and lactone ring-opened structure may exist alone in the molecule, or 2 to 6 of the above alkylene oxide groups or lactones may be consecutive, but it is preferable that the alkylene oxide group or lactone is present alone or two of the above alkylene oxide groups or lactones are consecutive.

[0318] The modified product can be, for example, a compound represented by the following general formula (B2-1).

[0319] [ka]

[0320] In formula (B2-1), V is independently an alkylene oxide group or a group having a structure in which a lactone ring is opened. f to j are independently integers of 0 to 6, provided that at least one of f to j is an integer of 1 to 6. f to j are preferably 1 or 2. R 41 ~R 45 are preferably independently a (meth)acryloyl group or a hydroxy group, provided that R 41 ~R 45 At least two of R are (meth)acryloyl groups. 41 ~R 45 are preferably all (meth)acryloyl groups. T is a group selected from the group consisting of substituted or unsubstituted monovalent to tetravalent hydrocarbon groups, -O-, and S-, and is preferably a substituted or unsubstituted divalent hydrocarbon group, -O-, or S-, with -O- being more preferred. q is independently 0 or 1, and is preferably 0. r is an integer of 1 to 4, the same as the valence of T, and is preferably 2.

[0321] Examples of the modified product represented by general formula (B2-1) include ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol hexacaprolactone hexaacrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide-modified triacrylate, and trimethylolpropane ethylene oxide-modified triacrylate (all manufactured by Toagosei Co., Ltd.).

[0322] Examples of the modified products other than the compound represented by general formula (B2-1) include bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified di- and triacrylate, diglycerin ethylene oxide-modified acrylate (all manufactured by Toagosei Co., Ltd.), and alkylene oxide-modified hexa(meth)acrylate of phosphazene.

[0323] The content of the (B2) component is preferably 5% to 60% by mass based on the total mass of the solids. When pattern formation is required (for example, in the case of the compositions described in (b) to (d) above), the content is more preferably 5% to 50% by mass, and even more preferably 5% to 40% by mass. When pattern formation is not required (for example, in the case of the composition described in (a) above), the content is more preferably 20% to 60% by mass, and even more preferably 40% to 60% by mass. When the content of the (B2) component is 5% by mass or more, sufficient crosslinking is formed, resulting in good pattern formation by development and improved solvent resistance of the adhesive layer. When pattern formation is required, the pattern formability is likely to be improved. When the content of the (B2) component is 60% by mass or less, the crosslink density of the adhesive layer after curing is sufficient, resulting in easy ablation when irradiated with light, and less residue.

[0324] 2-2.(C) Solvent The component (C) dissolves or disperses each component contained in the curable composition, and improves the applicability of the curable composition to a support.

[0325] Examples of component (C) include 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; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propanediol, propylene glycol mono ... Examples of suitable solvents include glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Dissolving and mixing these solvents can result in the curable composition becoming a uniform solution. Among these, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, and mixed solvents thereof are preferred from the viewpoint of increasing the solubility of component (A), making it easier to increase the solids concentration of the composition, and facilitating the formation of a thick adhesive layer.

[0326] The content of the component (C) varies depending on the target viscosity of the curable composition, but is preferably 50% by mass to 90% by mass relative to the total mass of the curable composition.

[0327] 2-3.(D) Epoxy compounds The composition may contain component (D), which improves the crosslink density after curing and improves chemical resistance and heat resistance.

[0328] Examples of component (D) include the compounds listed as raw materials for component (B1).

[0329] Among these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and biphenyl type epoxy compounds are preferred, and biphenyl type epoxy compounds are more preferred. Biphenyl type epoxy compounds have an excellent balance between the light absorption ability required for separation by light irradiation and the patterning ability of the photosensitive resin composition when photocured, and can increase the degree of freedom in designing the curable composition.

[0330] The epoxy equivalent of component (D) is preferably 100 g / eq to 300 g / eq, and more preferably 100 g / eq to 250 g / eq. Furthermore, the number average molecular weight (Mn) of component (E) is preferably 100 to 5000. When the epoxy equivalent is 100 g / eq to 300 g / eq and the number average molecular weight (Mn) is 100 to 5000, the solvent resistance of the adhesive layer can be improved. Furthermore, when the epoxy equivalent is 300 g / eq or less, sufficient alkali resistance can be maintained even when alkaline chemicals are used in a subsequent process.

[0331] The content of component (D) is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and even more preferably 7% by mass to 20% by mass, based on the total mass of the solid content. When the content of the epoxy compound is 5% by mass or more, a sufficient crosslinked structure can be formed, further improving chemical resistance. Furthermore, when the content of the epoxy compound is 60% by mass or less, the crosslink density of the adhesive layer after curing does not become too high, so that it is easily ablated when irradiated with light, and residue is less likely to be generated.

[0332] When component (D) is used, a curing agent may be used in combination. Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, and Lewis acid complex compounds.

[0333] 2-4.(E) Photopolymerization initiator Component (E) is not particularly limited as long as it is a compound that has a polymerizable unsaturated bond and can initiate polymerization of an addition-polymerizable compound. Examples of component (E) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and oxime ester compounds. In this specification, the term "photopolymerization initiator" is used to include sensitizers. When pattern formation is performed, it is preferable to include component (E).

[0334] Examples of the acetophenone compound include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one. Examples of commercially available acetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad379EG, the Omnirad series is a product of IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0335] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, )-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(pipronyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0336] Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, and the like.

[0337] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

[0338] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

[0339] Examples of the imidazole compound include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0340] Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-acetate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one Oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione 2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] ]-, 1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, 5-(4-isopropylphenylthio)-1,2-indandione, 2-(O-acetyloxime), and the like. The above photopolymerization initiators may be used alone or in combination of two or more.

[0341] Commercially available oxime ester initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino) (hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), TR-PBG-345 (manufactured by Changzhou New Power Electronic Materials Co., Ltd.), TR-PBG-B (manufactured by Changzhou New Power Electronic Materials Co., Ltd.), Nikkacure YJ-04(T) (Nippon Chemical Industry Co., Ltd.), Nikkacure IW-15 (Nippon Chemical Industry Co., Ltd.), ADEKA ARCLES NCI-831E (manufactured by ADEKA Corporation), Omnirad 1312 (manufactured by IGM Resins BV), and DFI-020 (manufactured by Daito Chemix Co., Ltd.).

[0342] Of these, component (E) is preferably an oxime ester-based (including ketoxime) photopolymerization initiator. Because oxime ester-based photopolymerization initiators have high sensitivity, they can sufficiently increase the photosensitivity of the curable resin composition and sufficiently increase the developability (resolution) of the adhesive layer.

[0343] Examples of the oxime ester photopolymerization initiator include O-oxime ester photopolymerization initiators represented by general formula (E-1) or general formula (E-2).

[0344] [ka]

[0345] In formula (E-1), R 51 , R 52 each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms; R 53 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be a straight-chain, branched, or cyclic alkyl group.

[0346] [ka]

[0347] In formula (E-2), R 54 and R 55are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 56 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. 54 ~R 56 Some of the hydrogen atoms in the group may be substituted with halogen atoms.

[0348] Furthermore, the molar absorption coefficient of component (E) at 365 nm is preferably 10,000 L / (mol cm) or greater. Such photopolymerization initiators have high sensitivity, which can further enhance the photosensitivity of the curable composition and sufficiently improve the developability (resolution) of the curable resin composition. Examples of such photopolymerization initiators include Omnirad 1312 (manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company) and Adeka Arcles NCI-831E (manufactured by ADEKA Corporation, "Adeka Arcles" is a registered trademark of the company).

[0349] The molar absorption coefficient of the photopolymerization initiator is a value obtained by measuring the absorbance of a 0.001 wt % acetonitrile solution in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0350] The component (E) may be an active radical generator or an acid generator.

[0351] Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

[0352] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0353] The content of component (E) is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, based on the total mass of the solid content. When the content of the photopolymerization initiator is 0.01% by mass or more, photopolymerization can be promoted, increasing the photopolymerization rate. Furthermore, when the content of the photopolymerization initiator is 20% by mass or less, excessive increases in sensitivity can be suppressed, making it less likely that scorching, peeling residue, etc. will occur when ablation is performed by irradiating light.

[0354] The curable composition may also contain a photosensitizer in addition to the component (E).

[0355] Examples of the photosensitizer include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, n-butoxy 4-dimethylaminobenzoate, and n-butyl 4-dimethylaminobenzoate. Benzophenones such as methyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0356] The content of the photosensitizer is preferably 0.5 to 400 parts by mass, and more preferably 1 to 300 parts by mass, when the total mass of component (E) is 100 parts by mass. When the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved, and the photopolymerization rate can be increased. Furthermore, when the content of the photosensitizer is 400 parts by mass or less, excessive increases in sensitivity can be suppressed, making it less likely that scorching, peeling residue, etc. will occur when ablation is performed by irradiating light.

[0357] 2-5.Other ingredients The curable composition may contain, as needed, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, and the like.

[0358] Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, and imidazoles, which contribute to accelerating the curing of epoxy resins. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the defoamer and leveling agent include silicone-based, fluorine-based, acrylic, and hydrocarbon-based compounds. Examples of the surfactant include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0359] 3. Manufacturing method of laminate [Step of forming an adhesive layer on a holding substrate] The adhesive layer composition described above is applied (coated) to the surface of a holding substrate that catches and holds the adherend that has been peeled off from the original substrate, and then pre-baked, thereby forming an adhesive layer that holds the peeled adherend on the surface of the holding substrate.

[0360] Examples of methods for applying the adhesive layer composition include known methods such as solution immersion, spin coating, ink jetting, spraying, and methods using a roller coater, land coater, slit coater, or spinner.

[0361] After applying the adhesive layer composition using the above application method, the solvent is dried (prebaked) to form an adhesive layer. Prebaking is performed by heating using an oven, a hot plate, etc. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 60 to 110°C for 1 to 10 minutes.

[0362] The thickness of the adhesive layer can be selected arbitrarily. The thickness of the adhesive layer is preferably 1 μm to 50 μm, and more preferably 1 μm to 30 μm. When the thickness of the adhesive layer is 1 μm or more, the adhesive layer can have sufficient holding power to catch the adherend. Furthermore, when the thickness is 50 μm or less, the adhesive layer can be sufficiently cured by photo- or thermal curing.

[0363] After the pre-baking, an exposure step and a development step may be performed to pattern the adhesive layer. By patterning the adhesive layer, the adhesive layer can be formed only in the areas where the adhesive layer is required.

[0364] Examples of light used in the exposure step include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Of these, ultraviolet light (wavelength 250 to 400 nm) is preferred. Furthermore, in the development step, a developer suitable for alkaline development is used. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected according to the properties of the resin layer, and surfactants may be added as needed. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine or ultrasonic cleaner. After alkaline development, the film is usually washed with water. Examples of development methods that can be used include shower development, spray development, dip (immersion) development, and puddle (puddle) development.

[0365] [Holding of adherend by holding substrate] The holding substrate having the adhesive layer can hold the adherend that has been peeled off from the original substrate.

[0366] At this time, the original substrate is placed in a position where the surface to which the adherends are attached faces the adhesive layer of the holding substrate, preferably so that the surface of the original substrate to which the adherends are attached faces vertically upward. Note that the original substrate has multiple adherends attached to its surface by a resin that is altered and decomposed by light irradiation.

[0367] From the viewpoint of transferring the adherend at a higher speed, the adherend attached to the original substrate and the adhesive layer formed on the holding substrate are disposed so as to leave a gap between them. The gap is preferably 10 μm to 200 μm, and more preferably 30 μm to 100 μm.

[0368] 1A, for example, when light is irradiated onto resin 202 through original substrate 201 in this state, and resin 202 to which the adherends are attached is altered and decomposed, adherends 101 and 102 are peeled off from original substrate 201 and transferred to holding substrate 104. The transferred adherends 101 and 102 are caught by adhesive layer 103 and adhered to the holding substrate without misalignment.

[0369] In this way, for example, a laminate 100 is produced, as shown in FIG. 1B, having a holding substrate 104, adherends 101 and 102, and an adhesive layer 103 formed from the above-mentioned adhesive layer composition and disposed between the holding substrate 104 and the adherends 101 and 102.

[0370] [Uses and processing methods of laminates] This laminate can be used to transport multiple adherends held on a holding substrate. After transportation, the adherends 101 and 102 may be peeled from the adhesive layer 103 by irradiation with light (or laser) as shown in FIG. 2A, and then transferred from the holding substrate 104 to another substrate 302. In this case, the other substrate 302 to which the adherends 101 and 102 are transferred from the holding substrate 104 may have an adhesive layer 301 formed by applying the adhesive layer composition and pre-baking on the surface that catches the adherends 101 and 102 peeled from the holding substrate 104, as shown in FIG. 2B. This can also improve the ability of the other substrate 302 to catch the adherends 101 and 102 when transferring them from the holding substrate 104 to the other substrate 302.

[0371] The light to be irradiated is not particularly limited as long as it can separate the support and the adherend. In this embodiment, the light is preferably ultraviolet light. The wavelength of the light is more preferably 10 nm to 450 nm, even more preferably 100 nm to 450 nm, and particularly preferably 200 nm to 400 nm. When the wavelength of the light is 10 nm or longer, the polymer, which is a component of the adhesive layer, absorbs the light and changes or decomposes, reducing the strength and adhesive force, thereby making it easy to separate the support and the adherend. Furthermore, when the wavelength of the light is 450 nm or shorter, the adhesive layer in the processed portion absorbs the light, thereby preventing the generation of adhesive layer residue. For example, to reduce running costs, the wavelength of the ultraviolet light is preferably 350 nm or longer, since inexpensive glass substrates and acrylic substrates, especially glass substrates, can be used. On the other hand, to increase processing yield, the wavelength of the ultraviolet light is preferably 200 nm or longer but less than 350 nm, since it allows processing with high energy.

[0372] The transmittance of the adhesive layer at 266 nm and 355 nm is preferably 0% to 50%, and more preferably 0% to 30%. By setting the transmittance at 50% or less, the adhesive layer absorbs light, causing deterioration or decomposition, reducing its strength and adhesive power, thereby facilitating separation of the support and the adherend. The transmittance of the adhesive layer is measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) on a substrate with an adhesive layer obtained by applying the adhesive layer to a synthetic quartz glass substrate using a spin coater so that the film thickness after heat curing treatment is 1.0 μm, pre-baking using a hot plate at 100°C for 3 minutes, and then fully curing (post-baking) using a hot air dryer at 250°C for 30 minutes. The transmittance is measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) on a substrate with an adhesive layer, using the transmittance of the quartz glass alone as a baseline.

[0373] The transmittance of the adhesive layer at 400 nm is preferably 50% to 100%, and more preferably 70% to 100%. By making it 50% or more, coloring can be suppressed and visibility can be improved. The transmittance of the adhesive layer is a value measured in the same manner as above.

[0374] Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an extra-high-pressure mercury lamp, a metal halide lamp, and a deep ultraviolet laser lamp.

[0375] Examples of the laser include solid-state lasers, liquid lasers, and gas lasers. Examples of the solid-state laser include semiconductor-pumped lasers. Examples of liquid lasers include dye lasers. Examples of gas lasers include excimer lasers. Of the above lasers, semiconductor-pumped lasers are preferred.

[0376] Examples of the semiconductor pumped laser include Nd:YAG laser, Nd:YLF laser, Nd:glass laser, Nd:YVO4 laser, Yb:YAG laser, Yb-doped fiber laser, Er:YAG laser, Tm:YAG laser, etc. Examples of excimer laser include KrF laser, XeCl laser, ArF laser, F2 laser, etc. Of the above lasers, Nd:YAG laser is preferred.

[0377] The output and cumulative light quantity of the light irradiated onto the adhesive layer vary depending on the type of light source, etc., but when the irradiated light is a laser, the output can be 0.1 mW or more and 200 W or less. The cumulative light quantity can be 1 mJ / cm. 2 More than 50J / cm 2 It is preferable that the integrated light amount is 0.1 mJ / cm or less. 2 If the intensity is above 50J / cm, scorching and peeling residue are less likely to occur during ablation. 2 If the ablation speed is equal to or less than this, the ablation speed can be controlled appropriately to perform appropriate processing.

[0378] It is preferable that the adhesive layer is irradiated with light (laser) from the substrate side over the entire surface of the adhesive layer, or selectively irradiated to the area where the adherend to be transferred is adhered.

[0379] The method may include a step of processing the laminate before peeling the adherend from the holding substrate.

[0380] Examples of the above processing include thinning of adherends such as dicing and back grinding, photofabrication, stacking of semiconductor chips, mounting of various adherends, and resin sealing.

[0381] The type of the adherend is not particularly limited, and examples thereof include semiconductor wafers, semiconductor chips, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers.

[0382] After the adherend is held on the holding substrate to form the laminate, the adhesive layer may be post-cured (post-baked) to firmly bond the adherend to the holding substrate. Post-baking can reduce residues that may be left behind when the adherend is peeled off by light irradiation.

[0383] The post-baking can be carried out, for example, by heating the adherend while applying pressure to the adhesive layer. The temperature at this time is preferably room temperature or higher and 200°C or lower, more preferably 30°C to 150°C. The pressure at this time is preferably 0.01 MPa to 20 MPa, more preferably 0.03 MPa to 15 MPa. By adhering the holding substrate and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the holding substrate via the adhesive layer.

[0384] The adhesive may also be cured by photocuring. Photocuring prevents the adherend from becoming embedded in the adhesive layer, thereby improving the peelability of the adhesive layer when exposed to light. Photocuring of the adhesive layer can be carried out by irradiating light using a high-pressure mercury lamp, for example. The wavelength of the light irradiated in this case is preferably 200 nm to 500 nm. The exposure dose of the light irradiated in this case is 25 mJ / cm. 2 ~3000mJ / cm 2 and preferably 50 mJ / cm 2 ~2000mJ / cm 2When photocuring is performed, the adhesive layer composition preferably contains a photo-traverse initiator.

[0385] Either one of the post-baking and the light irradiation may be performed, or both may be performed, or neither may be performed.

[0386] The holding substrate to which the adherend has been firmly adhered in this way can be used as is in a product as a mounting substrate.

[0387] The shape and size of the adherend are not particularly limited. For example, when the surface of the adherend that adheres to the adhesive layer is rectangular, the length of the long side of the rectangle (the length of any one side when the adherend is square) is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm. A semiconductor element is a suitable example of an adherend whose surface adheres to the adhesive layer.

[0388] Methods for processing the laminate include thinning of the adherend such as dicing and back grinding, photofabrication, stacking of semiconductor chips, mounting of various elements, resin sealing, and the like.

[0389] This embodiment may also include a step of transferring the processed laminate from one device to another. Examples of a method for transferring the laminate include a method using a robot arm.

[0390] In this manner, the laminate of this embodiment is processed.

[0391] 4. Applications of laminates As described above, the adhesive layer-forming composition according to this embodiment is suitable as an adhesive layer-forming composition that enables separation of a support and an adherend from a laminate having an adhesive layer between the support and the adherend by irradiating light from the support side. In particular, the adhesive layer-forming composition according to this embodiment is suitable for use in a process (LLO process) in which the adherend is separated (peeled) from the support and transferred to, for example, another substrate. [Example]

[0392] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0393] First, synthesis examples of the unsaturated group-containing alkali-soluble resin, component (A), will be explained. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0394] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place. In the examples, all glass substrates used to prepare substrates with adhesive layers for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0395] [Solid content concentration] The resin content was calculated from the weight [W1(g)] of 1 g of the resin solution obtained in the synthesis example impregnated into a glass filter [weight: W0(g)] and weighed, and the weight [W2(g)] after heating at 160°C for 2 hours, using the following formula: Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0396] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0397] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0398] [Absorbance, molar extinction coefficient] Using a UV-Vis-Infrared Spectrophotometer "UH4150" (Hitachi High-Tech Science Corporation), the absorbance at wavelengths of 266 nm and 355 nm was measured for a 0.001 wt% acetonitrile solution of the material to be measured in a quartz cell with an optical path length of 1 cm. The molar absorption coefficient at wavelengths of 266 nm and 355 nm was calculated by dividing the measured absorbance by the molar concentration.

[0399] [Ratio of the total mass of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units] The total mass X1+X2(g) of the content mass X1(g) of only the dinaphthothiophene moiety calculated by the following formula (I) and the content mass X2(g) of only the dinaphthofuran moiety calculated by the following formula (II) was divided by the total mass TM(g) of all structural units constituting the (meth)acrylic copolymer to calculate the ratio of the total mass of the content mass of only the dinaphthothiophene moiety and the content mass of only the dinaphthofuran moiety to the total mass of all structural units. Formula (I) X1(g) = Y1(g) × M X1 (g / mol) / M Y1 (g / mol) Formula (II) X2(g)=Y2(g)×M X2 (g / mol) / M Y2 (g / mol) (In the formula, X1(g): Mass of the dinaphthothiophene moiety alone Y1(g): the mass of the structural unit containing the dinaphthothiophene moiety M X1 (g / mol): Molar mass of the dinaphthothiophene moiety alone M Y1 (g / mol): Molar mass of the structural unit containing the dinaphthothiophene moiety X2 (g): Mass of the dinaphthofuran moiety alone Y2(g): Mass of the structural unit containing the dinaphthofuran moiety M X2 (g / mol): Molar mass of the dinaphthofuran moiety alone M Y2 (g / mol): Molar mass of the structural unit containing the dinaphthofuran moiety indicates.)

[0400] The abbreviations used in the synthesis examples are as follows. MMA: methyl methacrylate MA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate MOI: 2-isocyanatoethyl methacrylate 6MDNTMA: 6-methyl methacrylate-dinaphtho[2,1-b:1',2'-d]thiophene (manufactured by Sugai Chemical Co., Ltd., molecular weight: 382.5, absorbance at 266 nm: 0.48, absorbance at 355 nm: 0.18) 6MDNTA: 6-methylacrylate-dinaphtho[2,1-b:1',2'-d]thiophene (manufactured by Sugai Chemical Co., Ltd., molecular weight: 367.5, absorbance at 266 nm: 0.47, absorbance at 355 nm: 0.17) 5EDNFMA: 5-ethyl methacrylate dinaphtho[2,1-b:1',2'-d]furan (manufactured by Sugai Chemical Co., Ltd., molecular weight 380.1, absorbance at 266 nm: 0.32, absorbance at 355 nm: 0.24) 5EDNFA: 5-ethylacrylatedinaphtho[2,1-b:1',2'-d]furan (manufactured by Sugai Chemical Co., Ltd., molecular weight 366.4, absorbance at 266 nm: 0.35, absorbance at 355 nm: 0.30) AIBN: 2,2'-azobisisobutyronitrile TPP: Triphenylphosphine BPFE: Bisphenol fluorene type epoxy resin (epoxy resin with general formula (B1-5) where Ar is a benzene ring and l is 0.) (epoxy equivalent: 256 g / eq) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride NMP: N-methyl-2-pyrrolidone PGMEA: Propylene glycol monomethyl ether acetate

[0401] [Synthesis example A-1] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 70 parts by weight of NMP as a solvent, 15 parts by weight (0.04 mol) of 6MDNTMA as a UV-absorbing moiety-containing unsaturated monomer, and 15 parts by weight (0.15 mol) of MMA as another unsaturated monomer. The mixture was heated to 80°C and then purged with nitrogen. 0.1 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 6 hours, yielding a solution of (A1)-1 with a 30% solids content. GPC analysis of the resulting resin solution revealed a Mw of 25,300. The combined mass ratio of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 37.2% by mass. The molar extinction coefficients of the resulting resin at each wavelength were 14,200 L / (mol cm) (266 nm) and 4,380 L / (mol cm) (355 nm).

[0402] [Synthesis example A-2] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 70 parts by weight of NMP as a solvent, 15 parts by weight (0.04 mol) of 6MDNTA as a UV-absorbing moiety-containing unsaturated monomer, and 15 parts by weight (0.15 mol) of MMA as another unsaturated monomer. The mixture was heated to 80°C and then purged with nitrogen. 0.1 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 6 hours, yielding a solution of (A1)-2 with a 30% solids content. GPC analysis of the resulting resin solution revealed a Mw of 20,300. The combined mass ratio of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 38.6% by mass. The molar extinction coefficients of the resulting resin at each wavelength were 4,270 L / (mol cm) (266 nm) and 14,000 L / (mol cm) (355 nm).

[0403] [Synthesis example A-3] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 23.6 parts by weight of NMP as a solvent, 21 parts by weight (0.06 mol) of 6MDNTA as a UV-absorbing moiety-containing unsaturated monomer, and 9 parts by weight (0.09 mol) of MMA as another unsaturated monomer. The mixture was heated to 80°C and then purged with nitrogen. 0.1 parts by weight of AIBM was added as a polymerization initiator and the reaction was allowed to proceed for 6 hours, yielding a solution of (A1)-3 with a 30% solids content. GPC analysis of the resulting resin solution revealed a Mw of 13,700. The combined mass ratio of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 54.0% by mass. The molar extinction coefficients of the resulting resin at each wavelength were 18,150 L / (mol cm) (266 nm) and 5,980 L / (mol cm) (355 nm).

[0404] [Synthesis Example A-4] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 233 parts by weight of NMP as a solvent, 50 parts by weight (0.13 mol) of 6MDNTMA as a UV-absorbing moiety-containing unsaturated monomer, 13.8 parts by weight (0.14 mol) of MMA, 7.7 parts by weight (0.09 mol) of MA, and 13.0 parts by weight (0.10 mol) of HEMA as other unsaturated monomers, and heated to 80°C. The atmosphere was then purged with nitrogen. 4 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 1 hour. 0.5 parts by weight of AIBN was then added, and the mixture was heated to 90°C and aged for 3 hours to synthesize a UV-absorbing copolymer. 15.5 parts by weight (0.10 mol) of MOI, 0.01 parts by weight of a tin compound as a catalyst, and 0.04 parts by weight of methoquinone as a polymerization inhibitor were added, and the MOI addition reaction to the UV-absorbing copolymer was carried out at 60°C for approximately 6 hours. The end of the reaction was confirmed by the disappearance of the isocyanate peak in FT-IR. After the reaction was complete, NMP was added to the mixture to adjust the solids content to 30% by weight, yielding a solution of (A2)-1. The acid value (solids equivalent) of the resulting resin solution was 50 mg KOH / g, and the Mw determined by GPC analysis was 18,000. The ratio of the total mass of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer calculated from the feed ratio was 37.2% by mass. The acrylic equivalent calculated from the feed ratio was 1001.0. The molar absorption coefficients of the resulting resin at each wavelength were 4,380 L / (mol cm) (266 nm) and 14,200 L / (mol cm) (355 nm).

[0405] [Synthesis Example A-5] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 233 parts by weight of NMP as a solvent, 50 parts by weight (0.13 mol) of 6MDNTMA as a UV-absorbing moiety-containing unsaturated monomer, 13.8 parts by weight (0.14 mol) of MMA, 7.7 parts by weight (0.09 mol) of MA, and 13.0 parts by weight (0.10 mol) of HEMA as other unsaturated monomers, and heated to 80°C. The atmosphere was then purged with nitrogen. 2 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 1 hour. 0.5 parts by weight of AIBN was then added, and the mixture was heated to 90°C and aged for 3 hours to synthesize a UV-absorbing copolymer. 15.5 parts by weight (0.10 mol) of MOI, 0.01 parts by weight of a tin compound as a catalyst, and 0.04 parts by weight of methoquinone as a polymerization inhibitor were added, and the MOI addition reaction to the UV-absorbing copolymer was carried out at 60°C for approximately 6 hours. The end of the reaction was confirmed by the disappearance of the isocyanate peak in FT-IR. After the reaction was complete, NMP was added to the mixture to adjust the solids content to 30% by weight, yielding a solution of (A2)-2. The acid value (solids equivalent) of the resulting resin solution was 50 mg KOH / g, and the Mw by GPC analysis was 25,000. The ratio of the total mass of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer calculated from the feed ratio was 37.2% by mass. The acrylic equivalent calculated from the feed ratio was 1001.0. The molar absorption coefficients of the resulting resin at each wavelength were 4,380 L / (mol cm) (266 nm) and 14,200 L / (mol cm) (355 nm).

[0406] [Synthesis Example A-6] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 70 parts by weight of PGMEA as a solvent, 15 parts by weight (0.04 mol) of 5EDNFMA as a UV-absorbing moiety-containing unsaturated monomer, and 15 parts by weight (0.15 mol) of MMA as another unsaturated monomer. The mixture was heated to 80°C and then purged with nitrogen. 0.1 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 6 hours, yielding a solution of (A1)-4 with a 30% solids content. GPC analysis of the resulting resin solution revealed a Mw of 24,500. The combined mass ratio of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 35.3% by mass. The molar extinction coefficients of the resulting resin at each wavelength were 7,050 L / (mol cm) (266 nm) and 7,880 L / (mol cm) (355 nm).

[0407] [Synthesis Example A-7] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 70 parts by weight of NMP as a solvent, 15 parts by weight (0.04 mol) of 5EDNFA as a UV-absorbing moiety-containing unsaturated monomer, and 15 parts by weight (0.15 mol) of MMA as another unsaturated monomer. The mixture was heated to 80°C and then purged with nitrogen. 0.1 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 6 hours, yielding a solution of (A1)-5 with a 30% solids content. GPC analysis of the resulting resin solution revealed a Mw of 17,500. The combined mass ratio of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 36.6% by mass. The molar extinction coefficients of the resulting resin at each wavelength were 8790 L / (mol cm) (266 nm) and 8510 L / (mol cm) (355 nm).

[0408] [Synthesis Example A-8] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 70 parts by weight of NMP as a solvent, 7.5 parts by weight (0.02 mol) of 6MDNTMA and 7.5 parts by weight (0.02 mol) of 5EDNFMA as UV-absorbing moiety-containing unsaturated monomers, and 15 parts by weight (0.15 mol) of MMA as another unsaturated monomer, and heated to 80°C. The atmosphere was then purged with nitrogen. 0.1 parts by weight of AIBN was added as a polymerization initiator and the reaction was carried out for 6 hours to obtain a solution of (A1)-6 with a solids content of 30%. GPC analysis of the resulting resin solution revealed a Mw of 23,200. The ratio of the combined mass of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer was 35.2% by mass. The molar absorption coefficients of the resin were 11,040 L / (mol·cm) (266 nm) and 5,717 L / (mol·cm) (355 nm).

[0409] [Synthesis Example A-9] Alkali-soluble resin A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 233 parts by weight of PGMEA as a solvent, 50 parts by weight (0.13 mol) of 5EDNFMA as a UV-absorbing moiety-containing unsaturated monomer, 13.8 parts by weight (0.14 mol) of MMA, 7.7 parts by weight (0.09 mol) of MA, and 13.0 parts by weight (0.10 mol) of HEMA as other unsaturated monomers, and heated to 80°C. The atmosphere was then purged with nitrogen. 4 parts by weight of AIBN was added as a polymerization initiator and the reaction was allowed to proceed for 1 hour. 0.5 parts by weight of AIBN was then added, and the mixture was heated to 90°C and aged for 3 hours to synthesize a UV-absorbing copolymer. 15.5 parts by weight (0.10 mol) of MOI, 0.01 parts by weight of a tin compound as a catalyst, and 0.04 parts by weight of methoquinone as a polymerization inhibitor were added, and the MOI addition reaction to the UV-absorbing copolymer was carried out at 60°C for approximately 6 hours. The end of the reaction was confirmed by the disappearance of the isocyanate peak in FT-IR. After the reaction was complete, NMP was added to adjust the solids content to 30% by weight, yielding a solution of (A2)-3. The acid value (solids equivalent) of the resulting resin solution was 51 mg KOH / g, and the Mw by GPC analysis was 17,000. The ratio of the total mass of the dinaphthothiophene moiety and the dinaphthofuran moiety to the total mass of all structural units constituting the polymer calculated from the feed ratio was 35.3% by mass. The acrylic equivalent calculated from the feed ratio was 1001.0. The molar extinction coefficients of the resulting resin at each wavelength were 7,040 L / (mol cm) (266 nm) and 7,870 L / (mol cm) (355 nm).

[0410] [Synthesis example B-1] A reaction product was obtained by adding 50 parts by weight (0.10 mol) of BPFE, 14 parts by weight (0.20 mol) of AA, 0.26 parts by weight of TPP, and 40 parts by weight of PGMEA to a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and stirring for 12 hours at 100 to 105°C. Thereafter, 25 parts by weight of PGMEA was added and the solid content was adjusted to 50% by mass.

[0411] Next, 14 parts by weight (0.05 mol) of BPDA and 7 parts by weight (0.05 mol) of THPA were added to the resulting reaction product and stirred at 115 to 120°C for 6 hours to obtain an unsaturated group-containing curable resin (B1)-1. The solids concentration of the resulting resin solution was 57% by mass, the acid value (solids equivalent) was 96 mgKOH / g, and the Mw by GPC analysis was 3600.

[0412] [Synthesis example B-2] A reactor equipped with a temperature controller, a stirrer, and a reflux condenser was charged with 50 parts by weight (0.10 mol) of BPFE, 14 parts by weight (0.20 mol) of AA, 0.26 parts by weight of TPP, and 40 parts by weight of PGMEA, and the mixture was stirred at 100 to 105°C for 12 hours to obtain a reaction product. Then, 25 parts by weight of PGMEA was added to adjust the solid content to 50% by mass.

[0413] Next, 10 parts by weight (0.03 mol) of BPDA and 12 parts by weight (0.08 mol) of THPA were added to the resulting reaction product and stirred at 115 to 120°C for 6 hours to obtain an unsaturated group-containing curable resin (B1)-2. The solids concentration of the resulting resin solution was 57% by mass, the acid value (solids equivalent) was 98 mgKOH / g, and the Mw by GPC analysis was 2300.

[0414] Compositions for forming an adhesive layer were prepared in the blending amounts (unit: parts by mass) shown in Tables 1 and 2. The blending components used in Tables 1 and 2 are as follows.

[0415] (Alkali-soluble resin containing an unsaturated group having a dinaphthothiophene moiety or a dinaphthofuran moiety) (A1)-1: Resin solution obtained in Synthesis Example A-1 (solid content concentration: 30% by mass) (A1)-2: Resin solution obtained in Synthesis Example A-2 (solid content concentration: 30% by mass) (A1)-3: Resin solution obtained in Synthesis Example A-3 (solid content concentration: 30% by mass) (A1)-4: Resin solution obtained in Synthesis Example A-6 (solid content concentration: 30% by mass) (A1)-5: Resin solution obtained in Synthesis Example A-7 (solid content concentration: 30% by mass) (A1)-6: Resin solution obtained in Synthesis Example A-8 (solid content concentration: 30% by mass) (A2)-1: Resin solution obtained in Synthesis Example A-4 (solid content concentration: 30% by mass) (A2)-2: Resin solution obtained in Synthesis Example A-5 (solid content concentration: 30% by mass) (A2)-3: Resin solution obtained in Synthesis Example A-9 (solid content concentration: 30% by mass)

[0416] (Unsaturated Group-Containing Polymerizable Compound Having Neither a Dinaphthothiophene Moiety nor a Dinaphthofuran Moiety) (B1)-1: Resin solution obtained in Synthesis Example B-1 (solid content concentration: 57% by mass) (B1)-2: Resin solution obtained in Synthesis Example B-2 (solid content concentration: 57% by mass) (B2)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (B2)-2: Trimethylolpropane triacrylate with 6 moles of ethylene oxide (Aronix M-360, manufactured by Toagosei Co., Ltd.)

[0417] (solvent) (C1): N-methyl-2-pyrrolidone (NMP) (C2): Propylene glycol monomethyl ether acetate (PGMEA)

[0418] (epoxy resin) (D): Tetramethylbiphenol-type solid epoxy resin (jER YX4000HK, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 180 g / eq)

[0419] (Photopolymerization initiator) (E): Oxime ester photopolymerization initiator (ADEKA ARCLES NCI-831E, (Manufactured by ADEKA Corporation)

[0420] [Table 1]

[0421] [Table 2]

[0422] [evaluation] The adhesive layer obtained by curing the adhesive layer-forming composition was used to carry out the following evaluations.

[0423] [Preparation of substrates with adhesive layers for evaluating transmittance and laser processability] Each adhesive layer-forming composition was previously exposed to a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm 2 The coating was applied using a spin coater to a 125 mm x 125 mm synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 100°C, so that the film thickness after heat curing would be 1.0 μm, and the coating was pre-baked on a hot plate at 100°C for 3 minutes to produce a dried film. The coating was then fully cured (post-baked) at 250°C for 30 minutes using a hot air dryer to obtain a substrate with an adhesive layer (coating). The transmittance of the synthetic quartz glass substrate for light with wavelengths of 240 nm to 450 nm was 90% or higher over the entire wavelength range.

[0424] The transmittance is a value measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) with the transmittance of the quartz glass alone as a baseline.

[0425] [Transmittance evaluation] Using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), the transmittance of the substrate with the adhesive layer after full curing was measured at wavelengths of 266 nm, 355 nm and 400 nm.

[0426] [Laser processability (peelability) evaluation] (Evaluation method) After the adhesive layer was fully cured, a laser (laser wavelength: 355 nm) was irradiated from the quartz glass substrate side using a flash lamp pumped Nd:YAG Q-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.). The laser was irradiated at 100-600 mJ / cm. 2 The adhesive layer was processed (coating removed) using a laser energy of 1000 kJ / cm2, and the processed adhesive layer was observed under an optical microscope.

[0427] (Evaluation criteria) ◎: 400mJ / cm 2 There is no paint residue in the laser irradiated area. ○: 400mJ / cm 2 Super 500mJ / cm 2 There is no paint residue in the laser irradiated area. △: 500mJ / cm 2 Super 600mJ / cm 2 There is no paint residue in the laser irradiated area. ×:600mJ / cm 2 There is paint residue in the laser irradiated area

[0428] [Preparation of substrate with adhesive layer for developing evaluation] Of the above adhesive layer-forming compositions, the compositions of Examples 6 to 12, Examples 17 and 18, and Comparative Example 1 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 5.0 μm, and the substrate was prebaked at 100°C for 3 minutes using a hot plate to produce a dried film. Next, a negative photomask of 10 to 50 μm (in 1 μm increments) was placed on the dried film, and an i-line illuminance of 30 mW / cm was applied. 2 500mJ / cm 2 The photocuring reaction was carried out by irradiating the resin with ultraviolet light.

[0429] Next, the exposed adhesive layer was subjected to dip development in a 0.8% aqueous tetramethylammonium hydroxide solution at 25°C. The development process was continued for 20 seconds from the development time (break time = BT) at which the pattern began to appear, and then the layer was washed with water to remove the unexposed parts of the adhesive layer, forming an adhesive layer pattern on the glass substrate. The layer was then post-cured (post-baked) for 30 minutes using a hot air dryer to obtain a substrate with an adhesive layer for development evaluation.

[0430] The substrate with the adhesive layer for evaluating the developability was used to carry out the following evaluations.

[0431] [Developability evaluation] (pattern forming) (Evaluation method) After main curing (post-baking), the 10-50 μm mask patterns were observed under an optical microscope. Among the formed mask patterns, the width of the narrowest mask pattern was evaluated and judged according to the following evaluation criteria.

[0432] (Evaluation criteria) ◎: A pattern of 10 μm or more and less than 20 μm is formed ○: A pattern of 20 μm or more and less than 30 μm is formed △: A pattern of 30 μm or more and 50 μm or less is formed ×: No pattern is formed

[0433] [Creating a substrate with an adhesive layer for evaluating adhesive strength] The adhesive layer-forming compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 5.0 μm, and the substrate was prebaked on a hot plate at 100°C for 3 minutes to produce a dried film. Next, a glass substrate "#1737" cut to 2 mm x 2 mm was placed on the dried film and temporarily bonded by heating on a hot plate at 110°C for 1 minute. After that, the substrate was post-baked at 230°C for 30 minutes using a hot air dryer to obtain a substrate with an adhesive layer.

[0434] [Evaluation of adhesive strength (shear strength)] (Evaluation method) The 2mm x 2mm glass substrate "#1737" adhered to the adhesive layer was subjected to an adhesive strength test using a die shear tester (manufactured by Arctec Co., Ltd.) A grade of △ or higher was considered to be a pass.

[0435] (Evaluation criteria) ◎: Adhesive strength is 10 MPa or more ○: Adhesion strength is 8 MPa or more and less than 10 MPa △: Adhesion strength is 5 MPa or more and less than 8 MPa ×: Adhesion strength is less than 5 MPa

[0436] [Creating heat-resistant and solvent-resistant adhesive layers] Each adhesive layer-forming composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 5.0 μm, and then pre-baked at 100°C for 3 minutes using a hot plate to produce a dried film. This was then post-baked at 230°C for 30 minutes using a hot air dryer to obtain a substrate with an adhesive layer. For heat resistance evaluation, the resulting adhesive layer was scraped off and used for TG-DTA measurements.

[0437] [Heat resistance evaluation] (Evaluation method) The obtained powder of the adhesive layer was heated in air from 30°C to 400°C at a heating rate of 5°C / min using a TG-DTA device "TG / DTA6200" (manufactured by Seiko Instruments Inc.), and the temperature at which the sample lost 5% of its weight was measured. A rating of △ or higher was considered to be acceptable.

[0438] (Evaluation criteria) ◎: 5% weight loss temperature is 280℃ or higher 〇: 5% weight loss temperature is 260℃ or higher and lower than 280℃ △: 5% weight loss temperature is 240℃ or higher and lower than 260℃ ×: 5% weight loss temperature is less than 240°C

[0439] [Solvent resistance evaluation] (Evaluation method) The adhesive layer (coating film) of the obtained adhesive layer-attached substrate was immersed in N-methyl-2-pyrrolidone for 10 minutes, then washed and dried. The thickness of the adhesive layer (coating film) after the test was then measured using a stylus-type step shape measuring device "P-17" (manufactured by KLA Tencor Corporation). A grade of △ or higher was considered to be a pass.

[0440] The residual film rate in the solvent resistance evaluation was calculated from the following formula, where the film thickness before the test was L1 and the film thickness after the test was L2. Remaining film rate (%)=L2 / L1×100

[0441] (Evaluation criteria) ◎: Remaining film rate is 90% or more ○: Remaining film rate is 85% or more and less than 90% △: Remaining film rate is 80% or more but less than 85% ×: Residual film rate is less than 80%

[0442] The evaluation results are shown in Tables 3 and 4.

[0443] [Table 3]

[0444] [Table 4]

[0445] As shown in Tables 3 and 4, it was found that the laminate using the above-mentioned adhesive layer-forming composition in the adhesive layer had low transmittance at wavelengths of 266 nm and 355 nm and had excellent processability (peelability) with lasers of both wavelengths. This is thought to be because the addition of component (A) allowed light of those wavelengths to be efficiently absorbed by the adhesive layer, causing the adhesive layer to change in quality and decompose. [Industrial Applicability]

[0446] The present invention can provide a laminate having an adhesive that can be used in the manufacture of various products, and in particular, can provide a laminate that is suitable for a process in which the laminate is temporarily attached to a support such as a semiconductor wafer and processed. [Explanation of symbols]

[0447] 100 laminate 101, 102 Adherent 103 Adhesive layer 104 Holding board 201 Original substrate 202 Resins that change and decompose when exposed to light 301 Adhesive layer 302 Substrate to which the adherend is transferred from the holding substrate

Claims

1. a structural unit derived from a polymerizable monomer having an ultraviolet absorbing moiety represented by the following general formula (1), A structural unit different from the structural unit; A (meth)acrylic copolymer comprising: 【Chemical 1】 (In general formula (1), Z is a sulfur atom or an oxygen atom. R １ and R ２ may be bonded to any substitutable carbon of the naphthalene ring. １ R independently represents a (meth)acryloyloxyalkyl group or a (meth)acryloyloxy group which may contain a hetero atom. ２ independently represent a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a vinyl group, a styryl group, an allyl group, a (meth)acryloyloxyalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. In general formula (1), a is an integer of 1 to 6, and b is an integer of 0 to 6.

2. a structural unit including an ultraviolet absorbing moiety represented by the following general formula (2), A structural unit represented by the following general formula (3), A (meth)acrylic copolymer comprising: 【Chemistry 2】 (In general formula (2), Z is a sulfur atom or an oxygen atom. R ４ and R ５ may be bonded to any substitutable carbon atom of the naphthalene ring. ３ R independently represents a hydrogen atom or a methyl group. ４ R independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. ５ are independently a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. c is an integer from 0 to 6. * indicates a bonding site to another structural unit. 【Chemistry 3】 (In general formula (3), R ６ R independently represents a hydrogen atom or a methyl group. ７ represents an alkyl group having 1 to 10 carbon atoms, which may contain a heteroatom, a cyclic structure, or an aromatic ring. * indicates a bonding site with other structural units.)

3. a structural unit including an ultraviolet absorbing moiety represented by the following general formula (2), a structural unit containing a polymerizable unsaturated group represented by the following general formula (4), A structural unit containing a carboxy group represented by the following general formula (5), A (meth)acrylic copolymer comprising: 【Chemistry 4】 (In general formula (2), Z is a sulfur atom or an oxygen atom. R ４ and R ５ may be bonded to any substitutable carbon atom of the naphthalene ring. ３ R independently represents a hydrogen atom or a methyl group. ４ R independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain a heteroatom. ５ are independently a substituent selected from the group consisting of an alkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a cycloalkyl group having 3 to 15 carbon atoms which may contain a heteroatom, an aryl group having 6 to 15 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 15 carbon atoms which may contain a heteroatom, a carboxy group, a hydroxy group, a hydroxyalkyl group having 1 to 15 carbon atoms which may contain a heteroatom, a hydroxyalkyl ether group having 1 to 15 carbon atoms which may contain a heteroatom, a glycidyl group, a glycidylalkyl group having 4 to 15 carbon atoms which may contain a heteroatom, a glycidyl alkyl ether group having 4 to 15 carbon atoms which may contain a heteroatom, an amino group, a nitro group, a thiol group, a sulfo group, and a silyl group. c is an integer from 0 to 6. * indicates a bonding site to another structural unit. 【Chemistry 5】 【Chemistry 6】 (In general formula (4) and general formula (5), R ８ , R １１ and R １２ R each independently represents a hydrogen atom or a methyl group. ９ ~R １０ and R １３ ~R １４ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond. d and e each independently represent 0, 1, or 2. X １ and X ２ each independently represents an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. * indicates a bonding site with other structural units.)

4. The weight average molecular weight is 1,000 to 100,000. The (meth)acrylic copolymer according to any one of claims 1 to 3.

5. an acid value of 20 mg KOH / g to 200 mg KOH / g; The (meth)acrylic copolymer according to claim 3 .

6. In the following general formula (6), the content mass X1 (g) of only the dinaphthothiophene moiety calculated from the content mass Y1 (g) of the structural unit including the dinaphthothiophene moiety in which Z is a sulfur atom using the following formula (I), In the following general formula (6), the content mass X2 (g) of only the dinaphthofuran moiety is calculated using the following formula (II) from the content mass Y2 (g) of the structural unit containing the dinaphthofuran moiety in which Z is an oxygen atom; and The total mass X1+X2 (g) is 10% by mass to 60% by mass with respect to the total mass TM (g) of all structural units constituting the (meth)acrylic copolymer. The (meth)acrylic copolymer according to any one of claims 1 to 3. Equation (I) X1(g) = Y1(g) × M Ｘ１ (g / mol) / M Ｙ１ (g / mol) Formula (II) X2(g) = Y2(g) × M Ｘ２ (g / mol) / M Ｙ２ (g / mol) (In the formula, X1 (g): Mass of the dinaphthothiophene moiety alone Y1(g): Mass of the structural unit containing the dinaphthothiophene moiety M Ｘ１ (g / mol): Molar mass of only the dinaphthothiophene moiety M Ｙ１ (g / mol): molar mass of the structural unit containing the dinaphthothiophene moiety X2 (g): Mass of the dinaphthofuran moiety alone Y2(g): Mass of the structural unit containing the dinaphthofuran moiety M Ｘ２ (g / mol): Molar mass of only the dinaphthofuran moiety M Ｙ２ (g / mol): Molar mass of the structural unit containing the dinaphthofuran moiety Indicates.) 【Chemistry 7】 (In general formula (6), Z is a sulfur atom or an oxygen atom.)

7. An adhesive layer-forming composition for forming an adhesive layer that bonds a support and an adherend and enables the support and the adherend to be separated by irradiation with light, (A) the (meth)acrylic copolymer according to any one of claims 1 to 3; (B) an unsaturated group-containing polymerizable compound having neither a dinaphthothiophene moiety nor a dinaphthofuran moiety; (C) a solvent; Including, The content by mass of the component (A) is 10% by mass or more relative to the total mass of the solid content of the adhesive layer-forming composition. Composition for forming adhesive layer.

8. The unsaturated group-containing polymerizable compound (B) contains an alkali-soluble resin (B1), The weight average molecular weight of the component (B1) is 1,000 to 40,000. The adhesive layer-forming composition according to claim 7 .

9. The alkali-soluble resin (B1) is a resin represented by the following general formula (B1-1): The adhesive layer-forming composition according to claim 8 . 【Chemistry 8】 In formula (B1-1), Ar independently represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R ３１ are independently an alkylene group having 2 to 4 carbon atoms. 1 is independently a number from 0 to 3. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (B1-2) or (B1-3). Y is a tetravalent carboxylic acid residue. Z ２ are independently a hydrogen atom or a substituent represented by the following general formula (B1-4), and Z ２ At least one of the groups is a substituent represented by the following general formula (B1-4), and n is a number with an average value of 1 to 20. 【Chemistry 9】 【Chemistry 10】 (In formulas (B1-2) and (B1-3), R ３２ is a hydrogen atom or a methyl group, and R ３３ is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ３４ is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number between 0 and 10. * indicates a bonding site. 【Chemistry 11】 (In formula (B1-4), W is a divalent or trivalent carboxylic acid residue, m is the number 1 or 2, and * indicates a bonding site.)

10. The (B) unsaturated group-containing polymerizable compound includes (B2) an unsaturated group-containing polymerizable compound having no alkali-soluble group, The adhesive layer-forming composition according to claim 7 .

11. A support; An adherend; an adhesive layer disposed between the support and the adherend, the adhesive layer comprising a cured product of the adhesive layer-forming composition according to claim 7; A laminate having:

12. a step of applying the adhesive layer-forming composition according to claim 7 to the surface of at least one of a support and an adherend to form an adhesive layer; exposing the adhesive layer to light through a photomask; developing the exposed adhesive layer; A method for producing an adhesive layer comprising the steps of:

13. The method includes a step of adhering the support and the adherend via an adhesive layer produced by the method for producing an adhesive layer according to claim 12. A method for manufacturing a laminate.

14. Providing a laminate according to claim 11; a step of irradiating the adhesive layer of the laminate with light to separate the support and the adherend; A method for treating a laminate, comprising:

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