Composition for forming an adhesive layer, method for manufacturing a laminate, and method for processing a laminate

Abstract

To provide an adhesive layer-forming composition that exhibits excellent decomposition properties by light irradiation when forming an adhesive layer, and reduces the amount of residue after decomposition, as well as a method for manufacturing a laminate using the adhesive layer-forming composition as the adhesive layer, and a method for processing the laminate. [Solution] In a laminate comprising a light-transmitting support and an adherend, an adhesive layer is provided, wherein the support and adherend can be separated from the laminate by irradiating the laminate with light from the support side, the adhesive layer forming composition comprises (A) an unsaturated group-containing polymerizable resin and (E) a solvent. The absorbance of light at a wavelength of 266 nm of the cured film obtained under predetermined conditions is 0.50 or higher. The weight loss rate of component (A) obtained under predetermined conditions is 50% by mass or higher.

Description

[Technical Field]

[0001] The present invention relates to a composition for forming an adhesive layer, a method for manufacturing a laminate, and a method for processing a laminate. [Background technology]

[0002] In recent years, with the increasing sophistication of digital devices, flexible displays and semiconductor chips have become thinner. As a result of this thinning, the strength of these flexible displays and semiconductor chips has decreased, making it difficult to transport them using conventional automated transport systems.

[0003] Therefore, methods are being considered for easily transporting thin, flexible displays, semiconductor chips, and the like. In this method, for example, a laminate is formed on a support with numerous elements such as semiconductor wafers fixed via an adhesive layer, and this laminate is transported. Then, by irradiating the adhesive layer from the support side with light, the adhesive layer is altered or decomposed to reduce the adhesive strength, the elements are peeled off the support, and the elements are transferred to another substrate.

[0004] Patent Document 1 describes a laminate in which a photothermal conversion layer that decomposes upon light irradiation is provided between a substrate and a support that supports the substrate. According to Patent Document 1, the separation layer is altered and loses its adhesive properties when irradiated with light, so the support substrate and the supported substrate can be easily separated. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2004-64040 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, according to the inventors' findings, in laminates in which a photothermal conversion layer, as described in Patent Document 1, is used as an adhesive layer to bond a support and an adherend, there are problems such as unsatisfactory decomposition of the adhesive layer by light, or the presence of adhesive residue on the adherend when the adhesive layer is decomposed by light irradiation.

[0007] The present invention has been made in view of the above, and aims to provide an adhesive layer forming composition that exhibits excellent decomposition by light irradiation and reduces the amount of residue when decomposed, as well as a method for manufacturing a laminate using the adhesive layer forming composition as an adhesive layer, and a method for processing the laminate. [Means for solving the problem]

[0008] One aspect of the present invention for solving the above problems relates to the adhesive layer forming composition described in [1] to [5] below.

[0009] [1] A laminate comprising a light-transmitting support and an adhesive layer between them, A composition for forming an adhesive layer that allows the support and the adherend to be separated from the laminate by irradiating light from the support side, The aforementioned adhesive layer forming composition is (A) A polymerizable resin containing unsaturated groups, (E) Solvent and Includes, The solution of component (A) is applied to a substrate so that the cured film thickness is 1.0 μm, and the cured film is formed by heating at 100°C for 5 minutes followed by heating at 230°C for 30 minutes, wherein the absorbance of light at a wavelength of 266 nm is 0.50 or higher. The cured product obtained by applying the solution of component (A) to a substrate, heating it at 100°C for 5 minutes, and then heating it at 230°C for 30 minutes, has a weight loss rate of 50% by mass or more when heated from 30°C to 400°C under a nitrogen atmosphere. Composition for forming adhesive layer.

[0010] [2] The component (A) is an unsaturated group-containing polymer resin obtained by reacting a diol compound (a-1) represented by the following general formula (1) with a tetracarboxylic acid or its dianhydride (a-2). The composition for forming an adhesive layer according to [1].

[0011]

Chemical formula

[0012] In the general formula (1), R1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, or a substituent of the following general formula (2). R2 is independently a substituent represented by the following general formula (3) or general formula (4). X is a tetravalent carboxylic acid residue.

[0013]

Chemical formula

[0014] <00001​​​​​​​​​​​​​​​​​​​​​​​​​​

[0018] In general formula (5), R3 is a hydrogen atom or a methyl group. R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, and q is a number from 0 to 10. * indicates a bonding site with the structure represented by general formula (3) or general formula (4).

[0019] [3] (B) comprising an epoxy compound having at least two epoxy groups, The content of component (B) is 10% to 70% by mass relative to the total mass of component (A). The adhesive layer forming composition described in [1] or [2].

[0020] [4] (B) comprising an epoxy compound having at least two epoxy groups, The absorbance of a 0.001 wt% acetonitrile solution of component (B) is measured using an ultraviolet-visible-infrared spectrophotometer in a quartz cell with a path length of 1 cm, and the absorbance of light at a wavelength of 266 nm is 0.10 or higher. A composition for forming an adhesive layer as described in any of [1] to [3].

[0021] [5] (C) containing a photopolymerization initiator, A composition for forming an adhesive layer as described in any of [1] to [4].

[0022] One aspect of the present invention for solving the above problems relates to a method for manufacturing a laminate described in [6] below.

[0023] [6] A step of forming an adhesive layer on the surface of either the support or the adherend or both using the adhesive layer forming composition described in any of [1] to [5], A step of bonding the support and the adherend via the formed adhesive layer, A method for manufacturing a laminate containing a laminate.

[0024] One aspect of the present invention for solving the above problems relates to the method for processing laminates described in [7] below.

[0025] The process of preparing a laminate manufactured by the method described in [7] [6], A step of separating the support and the adherend by irradiating them with light, A method for processing a laminate, comprising: The support transmits light with wavelengths from 10 nm to 400 nm. A method for processing a laminate, wherein the laminate can be separated from the support and the adherend by irradiating the adhesive layer with light. [Effects of the Invention]

[0026] The present invention provides an adhesive layer-forming composition that exhibits excellent decomposition properties by light irradiation and reduces residue when decomposed, a method for manufacturing a laminate using the adhesive layer-forming composition as an adhesive layer, and a method for processing the laminate. [Brief explanation of the drawing]

[0027] [Figure 1] Figure 1A is a schematic diagram showing the process of irradiating a laminate, in which a support and an adherend are bonded via an adhesive layer, with light (or a laser) to detach the adherend from the adhesive layer and transfer the adherend from the support to another substrate. Figure 1B is a schematic diagram showing the process of catching the adherend detached from the support with a catch material layer applied to the surface of another substrate. [Figure 2] Figure 2A is a schematic diagram showing the process of transferring the adherend from the source substrate to the support by altering and decomposing the resin to which the adherend is attached through irradiation with light. Figure 2B is a schematic diagram showing the process of obtaining a laminate containing an adhesive layer to which multiple adherends are bonded by an adhesive layer applied to the surface of the support. [Modes for carrying out the invention]

[0028] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below. In this specification, when the first decimal place of the content of each component is 0, the decimal part may be omitted. Furthermore, unless otherwise specified, only one of the exemplified compounds, functional groups, or structures may be used, or multiple types may be used in combination.

[0029] 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, meaning one or both of these.

[0030] 1. Composition for forming adhesive layer The adhesive layer forming composition according to this embodiment is In a laminate comprising a light-transmitting support and an adherend, This is an adhesive layer forming composition that allows the support and the adherend to be separated from the laminate by irradiating them with light from the support side.

[0031] Furthermore, the adhesive layer forming composition according to this embodiment is (A) A polymerizable resin containing unsaturated groups (hereinafter also simply referred to as "component (A)"), (E) Solvent (hereinafter also simply referred to as "component (E)") and It includes, and component (A) satisfies the following two requirements: (Requirement 1) A solution of component (A) is applied to a substrate so that the film thickness after curing is 1.0 μm, and the cured film is formed by heating at 100°C for 5 minutes followed by heating at 230°C for 30 minutes, and the absorbance of light at a wavelength of 266 nm of the cured film is 0.50 or higher. (Requirement 2) When a solution of component (A) is applied to a substrate, and the cured product obtained by heating at 100°C for 5 minutes followed by heating at 230°C for 30 minutes is heated in a nitrogen atmosphere from 30°C to 400°C, the weight loss rate is 50% by mass or more.

[0032] 1-1.(A) Polymerizable resin containing unsaturated groups As described above, component (A) in this embodiment is not particularly limited as long as it is an unsaturated group-containing polymerizable resin that satisfies the above requirements (1) and (2).

[0033] Requirement 1 specifies the absorbance for light of a predetermined wavelength, and by setting such an absorbance, light at and near that wavelength is easily absorbed. As a result, such a (A) component absorbs light easily, and the thermal energy generated by light absorption is also large, making the (A) component more susceptible to alteration or decomposition. Therefore, light irradiation can easily reduce the adhesive strength of the adhesive layer, making it easier for the adherend to be transferred to another substrate.

[0034] From the viewpoint of facilitating the achievement of the above effects, the lower limit of the absorbance is preferably 0.90 or higher, and more preferably 1.00 or higher. Furthermore, when used as an adhesive layer and irradiated with light from any one side, from the viewpoint of facilitating more uniform light absorption in the thickness direction and uniform thermal decomposition of the entire film, the upper limit of the absorbance is preferably 8.00 or lower.

[0035] In this specification, the absorbance is a value measured as follows: A solution of component (A) is applied to a quartz glass substrate using a spin coater to a cured film thickness of 1.0 μm, and a dried film is prepared by heating it on a hot plate at 100°C for 5 minutes. Next, a substrate with a cured film is obtained by heating it on a hot air dryer at 230°C for 30 minutes. The absorbance is the absorbance of the substrate with a cured film at a wavelength of 266 nm, measured using a UV-Vis-Infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation). The solution of component (A) is, for example, a 20.0 wt% PGMEA solution, but it can be adjusted as appropriate depending on the solubility and viscosity of component (A).

[0036] Requirement 2 specifies the weight loss rate of the resin under predetermined temperature conditions, and by using a resin with such a weight loss rate, the resin becomes more susceptible to thermal decomposition. Therefore, such a component (A) is easily thermally decomposed by the heat generated when irradiated with light, and when used as an adhesive layer, the residue produced when decomposed by light irradiation is reduced.

[0037] From the viewpoint of making the above effects easier to achieve, the lower limit of the weight reduction rate is preferably 60% by mass or more, more preferably 68% by mass or more, and even more preferably 80% or more. The upper limit can be 100% by mass or less.

[0038] The weight loss rate of the cured film refers to the value measured by the following procedure. The solution of component (A) is applied to the glass substrate "#1737" using a spin coater so that the film thickness after curing is 1.0 μm, and a dried film is prepared by heating it at 100°C for 5 minutes using a hot plate. Next, a substrate with a cured film is obtained by heating it at 230°C for 30 minutes using a hot air dryer. The cured material applied to the glass substrate is collected to prepare a sample for weight loss rate evaluation. The weight loss rate was measured using a TG-DTA apparatus "TG / DTA7220" (manufactured by Seiko Instruments Inc.) under a nitrogen atmosphere, by raising the temperature from 30°C to 450°C at a heating rate of 10°C / min, and measuring the weight loss of the sample when the temperature was raised from 30°C to 400°C. The weight loss rate of the cured film is measured by dividing the amount of weight loss by the weight of the sample at 30°C. The cured film thickness, as described above, is 1.0 μm, but can be adjusted as appropriate depending on the viscosity of component (A). The solution of component (A) is, for example, a 20.0 wt% PGMEA solution, but can be adjusted as appropriate depending on the solubility and viscosity of component (A).

[0039] Component (A) is a resin that satisfies requirements (1) and (2) and contains unsaturated groups, and is not particularly limited. Below, component (A) will be described using component (A-1) as the first embodiment and component (A-2) as the second embodiment, but is not limited to these. Among these, component (A) is preferably composed of component (A-1) or component (A-2), more preferably of component (A-1), and even more preferably composed of component (A-1), from the viewpoint of making it less likely for residue to remain when decomposed by light irradiation.

[0040] 1-1-1. (A-1) Component Component (A-1) is an unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-1) represented by the following general formula (1) with a tetrabasic acid or its dianhydride (a-2), and examples include unsaturated group-containing polymerizable resins containing structural units represented by general formula (6) or general formula (7).

[0041] [ka]

[0042] In general formula (1), R1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, or a substituent of general formula (2) below. R2 is independently a substituent represented by general formula (3) or general formula (4) below. X is a tetravalent carboxylic acid residue.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] In general formula (2), R3 is a hydrogen atom or a methyl group. R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, and p is a number from 0 to 10. In general formulas (3) and (4), R5 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, a substituent of general formula (5) below, or a hydrogen atom. * indicates a bonding site with the structure represented by general formula (1). However, in general formula (4), it is indicated that R5 is bonded to any carbon atom on the ring.

[0047] [ka]

[0048] In general formula (5), R3 is a hydrogen atom or a methyl group. R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, and q is a number from 0 to 10. * indicates a bonding site with the structure represented by general formula (3) or general formula (4).

[0049] However, component (A-1) is a polymerizable resin containing an unsaturated group, wherein at least one of the R1s in general formula (1) is a substituent represented by general formula (2), and / or at least one of the R2s is a substituent represented by general formula (5).

[0050] [ka]

[0051] In general formula (6), R1, R5, and X are the same as R1, R5, and X in general formulas (1) and (3). Y is a tetravalent carboxylic acid residue. n is a number from 1 to 100. Preferably, n is a number from 1 to 50, more preferably from 1 to 25, and even more preferably from 1 to 10.

[0052] [ka]

[0053] In general formula (7), R1, R5, and X are the same as R1, R5, and X in general formulas (1) and (4). Also, Y is a tetravalent carboxylic acid residue. m is a number from 1 to 100. Preferably, m is a number from 1 to 50, more preferably from 1 to 25, and even more preferably from 1 to 10.

[0054] General formula (6) shows an example of a structural unit that can be synthesized when both R2 atoms in diol compound (a-1) are substituents represented by general formula (3), and general formula (7) shows an example of a structural unit that can be synthesized when both R2 atoms in diol compound (a-1) are substituents represented by general formula (4). In diol compound (a-1), one R2 atom may be a substituent represented by general formula (3), and the other may be a substituent represented by general formula (4).

[0055] Furthermore, while general formulas (6) and (7) show structural units in which two carboxyl groups from the tetrabasic acid or its dianhydride (a-2) react with the diol compound (a-1), component (A-1) may include structural units in which one carboxyl group from the tetrabasic acid or its dianhydride (a-2) reacts, or structural units in which three carboxyl groups react, or structural units in which four carboxyl groups react.

[0056] In general formulas (1), (6), and (7), X is preferably a structure containing an aromatic ring, more preferably a structure in which at least one carboxyl group or ester group is directly bonded to the aromatic ring, and even more preferably a structure in which all carboxyl groups or ester groups are directly bonded to the aromatic ring. Direct bonding of ester groups to the aromatic ring tends to increase thermal decomposition properties.

[0057] Furthermore, in general formulas (1), (6), and (7), X preferably has a structure having one aromatic ring, from the viewpoint of reducing residue during light irradiation. In addition, from the viewpoint of improving processability with light and improving heat resistance, X preferably has a structure having two or more aromatic rings, and more preferably has a fluorene skeleton.

[0058] Furthermore, Y in general formulas (6) and (7) may include an aliphatic hydrocarbon structure or an aromatic hydrocarbon structure. From the viewpoint of reducing residue during light irradiation, it is preferable to have a structure with one or two aromatic rings or an aliphatic hydrocarbon structure. Furthermore, from the viewpoint of improving processability with light, it is preferable to have a structure with two or more aromatic rings, and it is more preferable to have a biphenyl skeleton or fluorene skeleton that has excellent absorbance.

[0059] In general formulas (1), (6), and (7), it is preferable that at least one of the two R1 substituents in each general formula is a substituent represented by general formula (2), and more preferably both are substituents represented by general formula (2). It is preferable that R1 is a substituent that does not have a hydroxyl group.

[0060] In general formula (2), R4 is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, and more preferably 2 to 4 carbon atoms. p is preferably a number from 1 to 4, and more preferably 1 to 2.

[0061] In general formulas (3), (4), (6), and (7), R5 may have a structure containing an unsaturated group or a structure without an unsaturated group. However, from the viewpoint of appropriately adjusting the crosslinking density and making it easier to improve photoprocessability, a structure without an unsaturated group is preferable. On the other hand, from the viewpoint of improving the chemical resistance of the adhesive layer, a structure containing an unsaturated group is preferable. Furthermore, the number of carbon atoms in R5 is preferably between 2 and 10.

[0062] 1-1-1-1. Synthesis method of component (A-1) The following is an example of a method for synthesizing an unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-1) with a tetrabasic acid or its dianhydride (a-2) as component (A-1), but the synthesis method is not limited to the following.

[0063] The above unsaturated group-containing polymerizable resin can be synthesized by the following process. (Step 1) A step to synthesize a dicarboxylic acid compound (a-0) represented by the following general formula (8). (Step 2) A step to synthesize a diol compound (a-1) by reacting a dicarboxylic acid compound (a-0) with an epoxy compound. (Step 3) A step to synthesize component (A-1) by reacting a diol compound (a-1) with a tetrabasic acid or its dianhydride (a-2).

[0064] [ka]

[0065] In general formula (8), R1 and X are the same as in general formula (1).

[0066] The above steps (1) to (3) may be performed individually or omitted entirely. For example, steps (1) and (2) may be omitted, and only step (3) may be performed after preparing a commercially available diol compound (a-1), or step (1) may be omitted, and only steps (2) and (3) may be performed after preparing a commercially available dicarboxylic acid compound (a-0).

[0067] 1-1-1-2. (Step 1) Step to synthesize dicarboxylic acid compound (a-0) The dicarboxylic acid compound (a-0) represented by general formula (8) can be synthesized by the following method.

[0068] First, a tetrabasic acid represented by the general formula (9) or a dianhydride of a tetrabasic acid represented by the general formula (10), or a mixture thereof, is prepared. Then, a dicarboxylic acid compound (a-0) is synthesized by reacting 1 mole of the tetrahydrochloric acid or dianhydride of a tetrabasic acid with approximately 2 moles of a monohydric alcohol represented by R1-OH. Note that R1 in R1-OH is the same as R1 in general formula (1).

[0069] [ka]

[0070] [ka]

[0071] In general formulas (9) and (10), X is a tetravalent carboxylic acid residue.

[0072] Examples of tetrabasic acids represented by general formula (9) include chain-type hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, and aromatic hydrocarbon tetracarboxylic acids.

[0073] Examples of the above-mentioned chain-like hydrocarbon tetracarboxylic acids include 1,2,3,4-butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and these chain-like hydrocarbon tetracarboxylic acids into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0074] Examples of the above-mentioned alicyclic hydrocarbon tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid, as well as these alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0075] Examples of aromatic hydrocarbon tetracarboxylic acids mentioned above include pyromellitic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, diphenyl sulfonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0076] Among these, from the viewpoint of heat resistance, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic acid are preferred as the tetrabasic acid represented by general formula (9).

[0077] Furthermore, among these, pyromellitic acid is more preferable from the viewpoint of reducing residue during light irradiation. Also, from the viewpoint of improving processability with light and improving heat resistance, 3,3',4,4'-biphenyltetracarboxylic acid and spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic acid are more preferable, and spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic acid is even more preferable.

[0078] Examples of dianhydrides of tetrabasic acids represented by general formula (10) include the dianhydrides of the exemplary compounds of tetrabasic acids represented by general formula (9) above. Of these, it is preferable to use the dianhydrides.

[0079] Examples of alcohols represented by R1-OH where R1 is represented by general formula (2) include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl acrylate. Furthermore, examples of alcohols represented by R1-OH where the R1-OH group is a monovalent hydrocarbon group having 1 to 20 carbon atoms that may contain an oxygen atom include ethanol, 1-butanol, and 2-ethylhexanol.

[0080] Among these, from the viewpoint of controlling the fluidity of component (A) and making it easier to improve the adhesive strength of the adhesive layer forming composition, it is preferable that 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 2-ethylhexanol be used as the alcohol represented by R1-OH, more preferably 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, and even more preferably 4-hydroxybutyl acrylate.

[0081] The conditions for the solvent, catalyst, etc., in the above reaction are not particularly limited, as long as known esterification reaction conditions are used.

[0082] Preferably, the solvent used is one that does not contain hydroxyl groups and has a boiling point higher than the reaction temperature. Suitable solvents include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling-point ether-based 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.

[0083] Furthermore, known catalysts such as tetraethylammonium bromide, triethylbenzylammonium chloride and other ammonium salts, triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine and other phosphines can be used. In addition, known polymerization inhibitors such as 2,6-di-tert-butyl-p-cresol can be used.

[0084] The reaction temperature is preferably in the range of 20 to 140°C, and more preferably in the range of 40 to 130°C.

[0085] The dicarboxylic acid compound (a-0) can be any compound that has approximately two carboxyl groups on average, and may include compounds in which all carboxyl groups are esterified, or compounds containing one, three, or four carboxyl groups. Specifically, the dicarboxylic acid compound (a-0) is a compound that has an average of 1.5 to 2.4 carboxyl groups.

[0086] 1-1-1-3. (Step 2) Step to synthesize a diol compound (a-1) by reacting a dicarboxylic acid compound (a-0) with an epoxy compound. Next, diol compound (a-1) is synthesized by reacting 1 mole of dicarboxylic acid compound (a-0) with approximately 2 moles of epoxy compound represented by the following general formula (11) or general formula (12).

[0087] [ka]

[0088] [ka]

[0089] The R5 in general formulas (11) and (12) is the same as the R5 in general formulas (3) and (4).

[0090] Examples of compounds represented by the above general formula (11) include 1,2-epoxybutane, 1,2-epoxytetradecane, 2-ethylhexylglycidyl ether, glycidyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0091] Examples of compounds represented by the above general formula (12) include (3,4-epoxycyclohexyl)methyl acrylate and (3,4-epoxycyclohexyl)methyl methacrylate.

[0092] Among these, as the epoxy compound represented by the following general formula (11) or general formula (12), from the viewpoint of improving the adhesive strength of the adhesive layer forming composition, it is preferable to use 2-ethylhexylglycidyl ether, glycidyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate glycidyl ether, more preferably 2-ethylhexylglycidyl ether or 4-hydroxybutyl (meth)acrylate glycidyl ether, and even more preferably 2-ethylhexylglycidyl ether.

[0093] The addition reaction between the carboxyl group and the epoxy compound can be carried out using known methods. For example, a method for producing epoxy (meth)acrylate compounds by the reaction of an epoxy compound with (meth)acrylic acid can be referenced, such as the method described in Japanese Patent Application Publication No. 9-325494, in which a bisphenol fluorene type epoxy resin and acrylic acid are reacted at 100°C using tetraethylammonium bromide or the like as a catalyst. The reaction temperature is preferably in the range of 40 to 120°C, and more preferably 60 to 110°C.

[0094] A catalyst may be used in this addition reaction, and ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and phosphines such as tris(2,6-dimethoxyphenyl)phosphine may be used.

[0095] This reaction is usually carried out in a solvent. Examples of solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. There are no particular restrictions on the reaction conditions such as the solvent and catalyst used, but it is preferable to use a solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0096] 1-1-1-4. (Step 3) A step to synthesize component (A-1) by reacting a diol compound (a-1) with a tetrabasic acid or its dianhydride (a-2). Next, component (A-1) is synthesized by reacting the diol compound (a-1) represented by the general formula (1) with a tetrabasic acid represented by the general formula (13) or its dianhydride (a-2) represented by the general formula (14). In this case, it is preferable to react 0.2 moles to 1.0 mole of the tetrabasic acid or its dianhydride (a-2) with 1 mole of the diol compound (a-1). By doing so, the molecular weight of component (A-1) can be appropriately adjusted as shown in the general formulas (6) and (7), and the adhesive strength of the adhesive layer forming composition is easily increased.

[0097] [ka]

[0098] [ka]

[0099] In general formulas (13) and (14), Y is a tetravalent carboxylic acid residue.

[0100] Examples of the tetrabasic acid represented by general formula (13) or its dianhydride (a-2) represented by general formula (14) include the tetrabasic acid or its dianhydride exemplified in (Step 1) above.

[0101] The preferred embodiments of Y in general formulas (13) and (14) are the same as the preferred embodiments of Y in general formulas (6) and (7).

[0102] In this case, a dibasic acid or tribasic acid (b) may or may not be used in combination. Examples of the above dibasic acid or tribasic acid (b) include chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, and their acid monoanhydrides. It is preferable to use an acid monoanhydride for these dibasic or tribasic acids (b).

[0103] Examples of the above-mentioned chain-like hydrocarbon dicarboxylic acids or tricarboxylic acids 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 to which any substituent has been introduced.

[0104] Examples of the above-mentioned alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chloridenic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0105] Examples of the above aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, as well as these dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0106] Of the dicarboxylic acids or tricarboxylic acids mentioned above, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, with succinic acid, itaconic acid, and tetrahydrophthalic acid being more preferred.

[0107] When using a dibasic or tribasic acid in combination, it is preferable to react the diol compound (a-1), the dibasic or tribasic acid or its monoanhydride (b), and the tetrabasic acid or its dianhydride (a-2) in such a molar ratio that (a-1):(b):(a-2) = 1.0:0.01 to 1.0:0.2 to 1.0, so that the terminal end of the compound becomes a carboxyl group.

[0108] For example, when using an acid monoanhydride (b), it is preferable to react the components such that the molar ratio of the amount of acid component [(b) / 2 + (a-2)] to the total amount of diol compounds (a-1) [[(b) / 2 + (a-2)] / (a-1)] is greater than 0.5 and less than or equal to 1.0. When the above molar ratio is 1.0 or less, the ends of the unsaturated group-containing polymerizable resin represented by general formula (1) do not become acid anhydrides, thereby suppressing an increase in the content of unreacted acid dianhydrides and improving the long-term stability of the adhesive layer-forming composition. Also, when the above molar ratio is greater than 0.5, it is possible to suppress an increase in the amount of unreacted components remaining in the diol compound (a-1) and improve the long-term stability of the adhesive layer-forming composition. Note that the molar ratio of each component can be arbitrarily changed within the above range in order to adjust the acid value and molecular weight of component (A).

[0109] The reaction method between the diol compound (a-1) and the tetrabasic acid or its dianhydride (a-2) is not particularly limited, and known methods can be employed. For example, Japanese Patent Publication No. 9-325494 describes a method of reacting epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0110] By reacting the diol compound (a-1) with the tetrabasic acid in this manner, component (A-1) is obtained.

[0111] 1-1-2. (A-2) Component Component (A-2) is an unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-3) represented by the following general formula (15) with a tetrabasic acid or its dianhydride (a-2).

[0112] [ka]

[0113] R1 in general formula (15) is the same as R1 in general formula (1). Also, Z is a divalent epoxy residue, and at least one of them has an aromatic ring structure. If there are two or more aromatic ring structures, the aromatic ring structures are either all directly linked or all fused. However, at least one of R1 is a substituent represented by general formula (16). The reason why such a structure reduces the residue when photodegraded is not entirely clear, but it is thought to be as follows: It is thought that the presence of an aromatic ring in Z makes it easier to absorb light energy, thereby increasing photodegradability. On the other hand, when there are two or more aromatic ring structures, if the aromatic ring structures are either all directly linked or all fused, the structure becomes relatively linear. In contrast, if the structure is such that multiple aromatic rings are not directly linked, as in the structure derived from bisphenol A, for example, it is thought that the rotational motion of the carbon atoms sandwiched between the aromatic rings makes the structure more prone to bending. In this case, if the resin has a structure that is easily bent, the energy added by light irradiation is more easily dissipated by the bending motion of the molecular chains. Therefore, when a resin has two or more aromatic ring structures, it is thought that the decomposition rate of the resin tends to increase if all of the aromatic ring structures are directly connected or all of them are fused rings.

[0114] [ka]

[0115] R3, R4, and p in general formula (16) are the same as R3, R4, and p in general formula (2). * indicates a bonding site with the structure represented by general formula (15).

[0116] In general formula (15), Z preferably has two or more aromatic ring structures, all of which are directly connected or all are fused rings, more preferably contains a biphenyl structure or a fluorene structure, even more preferably contains a biphenyl structure, and most preferably contains a structure derived from 4,4'-bis(glycidyloxy)biphenyl, which may contain substituents on the aromatic ring. Having such a Z tends to increase heat resistance and improve laser processability by making it easier to absorb light.

[0117] In general formula (15), it is preferable that both R1 substituents are those represented by general formula (16) among the two R1 substituents included in each general formula. Furthermore, in general formula (16), R4 is preferably a divalent hydrocarbon group between 2 and 10, and p is preferably a number between 0 and 4.

[0118] 1-1-2-1. Synthesis method of component (A-2) The following is an example of a method for synthesizing an unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-3) with a tetrabasic acid or its dianhydride (a-2) as component (A-2), but the synthesis method is not limited to the following.

[0119] The above unsaturated group-containing polymerizable resin can be synthesized by the following process. (Step 1) A step to synthesize the diol compound (a-3) represented by the above general formula (15). (Step 2) A step to synthesize component (A-2) by reacting a diol compound (a-3) with a tetrabasic acid or its dianhydride (a-2).

[0120] The above steps (1) and (2) may be performed individually or omitted. For example, step (1) may be omitted, and a commercially available diol compound (a-2) may be prepared, and only step (2) may be performed.

[0121] 1-1-2-2. (Step 1) Step to synthesize the diol compound (a-3) represented by the above general formula (15). Diol compound (a-3) represented by general formula (15) is synthesized by reacting 1 mole of a diexope compound represented by the following general formula (17) with approximately 2 moles of alcohol or carboxylic acid.

[0122] [ka]

[0123] The Z in general formula (17) is the same as the Z in general formula (15).

[0124] Examples of diexo compounds represented by general formula (17) include 4,4'-bis(glycidyloxy)biphenyl, which may contain substituents on the aromatic ring. Examples of commercially available diexo compounds represented by general formula (17) include jER YX4000 (manufactured by Mitsubishi Chemical Corporation).

[0125] The addition reaction between a carboxyl group or an alcohol and an epoxy compound can be carried out using known methods. For example, the reaction conditions (catalyst, reaction temperature, solvent) exemplified in "1-1-1-3. (Step 2) Step to synthesize a diol compound (a-1) by reacting a dicarboxylic acid compound (a-0) with an epoxy compound" can be used.

[0126] 1-1-2-3. (Step 2) A step to synthesize component (A-2) by reacting a diol compound (a-3) with a tetrabasic acid or its dianhydride (a-2). Next, component (A-2) is synthesized by reacting the diol compound (a-3) represented by the general formula (15) with a tetrabasic acid represented by the general formula (13) or its dianhydride (a-2) represented by the general formula (14). In this case, it is preferable to react 0.2 moles to 1.0 mole of the tetrabasic acid or its dianhydride (a-2) with 1 mole of the diol compound (a-3). By doing so, the molecular weight of component (A-2) can be appropriately adjusted, and the adhesive strength of the adhesive layer forming composition is more easily increased.

[0127] The exemplary compounds and preferred embodiments of the tetrabasic acid or its dianhydride (a-2) used in the synthesis of component (A-2) are the same as those of the tetrabasic acid or its dianhydride shown in "1-1-1-2. (Step 1) Step to synthesize the dicarboxylic acid compound (a-0)" of the synthesis method for component (A-1).

[0128] Furthermore, a dibasic acid or tribasic acid (b) may be used in combination with the synthesis of component (A-2). Exemplary compounds of the dibasic acid or tribasic acid (b), and preferred embodiments, are the same as the dibasic acid or tribasic acid (b) shown in "1-1-1-4. (Step 3) Step of synthesizing component (A-1) by reacting a diol compound (a-1) with a tetrabasic acid or its dianhydride (a-2)" in the method for synthesizing component (A-1).

[0129] In the synthesis of component (A-2), when a dibasic or tribasic acid is used in combination, it is preferable to react the diol compound (a-3), the dibasic or tribasic acid or its monoanhydride (b), and the tetrabasic acid or its dianhydride (a-2) in such a way that the terminal end of the compound becomes a carboxyl group that the molar ratio is (a-1):(b):(a-2) = 1.0:0.01~1.0:0.2~1.0.

[0130] For example, when using acid monoanhydride (b), it is preferable to react the components such that the molar ratio of the amount of acid component [(b) / 2 + (a-2)] to the total amount of diol compounds (a-3) [[(b) / 2 + (a-2)] / (a-3)] is greater than 0.5 and less than or equal to 1.0. When the above molar ratio is 1.0 or less, the ends of the unsaturated group-containing polymerizable resin represented by general formula (1) do not become acid anhydrides, thereby suppressing an increase in the content of unreacted acid dianhydrides and improving the long-term stability of the adhesive layer-forming composition. Also, when the above molar ratio is greater than 0.5, it is possible to suppress an increase in the remaining amount of unreacted components among the diol compounds (a-1) and improve the long-term stability of the adhesive layer-forming composition. Note that the molar ratio of each component can be arbitrarily changed within the above range in order to adjust the acid value and molecular weight of component (A).

[0131] The method for reacting the diol compound (a-3) with the tetrabasic acid or its dianhydride (a-2) is not particularly limited, and known methods can be employed. For example, Japanese Patent Publication No. 9-325494 describes a method for reacting epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0132] By reacting the diol compound (a-3) with the tetrabasic acid in this manner, component (A-2) is obtained.

[0133] 1-1-3. Other properties of component (A) The weight-average molecular weight (Mw) of the unsaturated group-containing polymerizable resin, measured by gel permeation chromatography (GPC), 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 more improves the adhesion between the adhesive layer and the adherend. A weight-average molecular weight (Mw) of 40,000 or less makes it easier to adjust the solution viscosity of the adhesive layer-forming composition to a range suitable for application, facilitating application to the surface of the support. Furthermore, a weight-average molecular weight (Mw) of 40,000 or less improves the fluidity of the adhesive layer after pre-baking, making it easier to enhance its smoothness. The weight-average molecular weight (Mw) was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the value was determined as a conversion to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0134] The acid value of the unsaturated group-containing polymerizable resin is preferably 20 mg KOH / g to 200 mg KOH / g, and more preferably 25 mg KOH / g to 200 mg KOH / g. If the acid value is 20 mg KOH / g or higher, the strength of the adhesive layer can be improved through a crosslinking reaction with component (B). If the acid value is 200 mg KOH / g or lower, the penetration of the alkaline chemical solution into the adhesive layer can be suppressed during the washing process using the alkaline chemical solution. The acid value can be determined by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0135] The content of component (A) is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, even more preferably 25% to 100% by mass, and most preferably 30% to 100% by mass, based on the total mass of the solids of the adhesive layer forming composition. When the above content of component (A) is 10% by mass or more, the adhesion of the adhesive layer to the support is increased, and the adhesive layer is more likely to absorb the irradiated laser (e.g., ultraviolet light) and be altered or decomposed, making it easier to separate the support from the adherend.

[0136] 1-2. (B) Epoxy compounds having at least two epoxy groups The adhesive layer-forming composition according to this embodiment preferably contains (B) an epoxy compound having at least two epoxy groups (hereinafter also simply referred to as "component (B)"). When component (A) has a carboxyl group or a hydroxyl group in the adhesive layer, the reaction with the carboxyl group can increase the strength (crosslinking density) of the adhesive layer and make it easier to improve heat resistance.

[0137] (B) Examples of components include bisphenol A type epoxy compounds (e.g., jER 828, "jER" is a registered trademark of Mitsubishi Chemical Corporation), 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 YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, and glycidyl ethers of polyhydric alcohols that do not contain aromatic rings (e.g., Epoxy ZX-1542, "Epotote" is a registered trademark of the company (manufactured by Nippon Steel Chemical & Material Co., Ltd.), polycarboxylic acid glycidyl esters, copolymers of monomers having a (meth)acrylic group containing (meth)acrylic acid glycidyl as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., celoxide These include 2021P (manufactured by Daicel Corporation), tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone butanetetracarboxylic acid (e.g., Epolid GT401, manufactured by Daicel Corporation), epoxy compounds having an epoxycyclohexyl group, such as HiREM-1 manufactured by Shikoku Chemicals, Ltd., polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxyranyl)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. These compounds may be used individually or in combination of two or more.

[0138] Of these, from the viewpoint of further enhancing the light absorption capacity of the adhesive layer and making it easier to decompose by light irradiation, a structure containing an aromatic ring is preferred, and a structure containing a structure in which multiple aromatic rings are directly linked to each other (for example, a biphenyl or triphenyl structure) is more preferred.

[0139] Furthermore, the absorbance of component (B) at a wavelength of 266 nm is preferably 0.10 or higher, more preferably 0.10 to 8.00, even more preferably 0.20 to 8.00, and most preferably 0.25 to 8.00. By setting the absorbance of component (B) at 266 nm to 0.10 or higher, the light absorption of the adhesive layer at 266 nm can be increased, making it easier to improve laser processability. By setting the absorbance of component (B) at 266 nm to 8.00 or lower, when used as an adhesive layer and irradiated with light from any one side, the light can be absorbed more uniformly in the thickness direction, making it easier to uniformly thermally decompose the entire film. The above absorbance can be the value obtained by measuring the absorbance of a 0.001 wt% acetonitrile solution in a 1 cm path length quartz cell using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0140] The epoxy equivalent of component (B) is preferably 100 g / eq to 300 g / eq, and more preferably 100 g / eq to 250 g / eq. When the epoxy equivalent is 100 g / eq or more, the amount of residue when the adhesive layer is decomposed by light irradiation is reduced. When the epoxy equivalent is 300 g / eq or less, the crosslinking density can be increased, making it easier to improve heat resistance.

[0141] The content of component (B) is preferably 3% to 70% by mass, more preferably 10% to 70% by mass, and even more preferably 10% to 50% by mass, relative to the total mass of component (A). If the content of component (B) is 3% by mass or more relative to the total mass of component (A), a sufficient crosslinked structure can be formed when component (A) has a carboxyl group or a hydroxyl group, making it easier to improve heat resistance. Also, if the content is 70% by mass or less, it suppresses the crosslinking density of the adhesive layer after curing from becoming excessively high, making it easier to reduce the residue when decomposed by light irradiation.

[0142] The adhesive layer-forming composition may also contain a curing agent and a curing accelerator as needed. Examples of curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamides, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing of epoxy resins.

[0143] 1-3. (C) Photopolymerization initiator (C) The photopolymerization initiator (hereinafter also referred to as "component (C)") is a compound that generates active species such as radicals, cations, and anions upon light stimulation, thereby initiating the polymerization reaction. A photopolymerization initiator that generates radicals upon light irradiation is preferred.

[0144] The adhesive layer-forming composition preferably contains component (C) from the following viewpoints: Including component (C) makes it easier to control the physical properties of the adhesive layer by light irradiation. In addition, including component (C) facilitates patterning of the adhesive layer by photolithography.

[0145] Furthermore, the adhesive layer-forming composition does not need to contain component (C) if the physical properties of the adhesive layer are not controlled by light irradiation or patterning is not performed.

[0146] (C) Examples of components include biimidazole compounds such as 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (e.g., "Omnirad907" manufactured by IGM Resins BV [Omnirad is a registered trademark of the company]), 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole; Halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 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-methoxyphenyl) Halomethyl-s-triazine compounds such as cinnaphthyl)-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, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-Octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (e.g., BASF's "Irgacure OXE-01" [Irgacure is a registered trademark of the company]), 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)butane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantilmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-adamantilmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-oneoxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-oneoxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-oneoxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-Dione=2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-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-acetyl oxime), ethanone,1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime, and ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (e.g., BASF's "Irgacure") O-acyloxime compounds such as "OXE-02" (Irgacure is a registered trademark of the company); Sulfur compounds such as benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; Furthermore, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. This includes things like:

[0147] If component (C) is included, the content of component (C) is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, when the total mass of components (A) and (D) is 100 parts by mass. If the above content of component (C) is 0.1 parts by mass or more, it can promote photopolymerization and increase the rate of photopolymerization. Furthermore, if the above content of component (C) is 30 parts by mass or less, it can suppress an excessive increase in sensitivity and make it less likely for charring, peeling residue, etc. to occur when ablation is performed by irradiating with light.

[0148] 1-4. (D) Polymerizable compounds having at least two unsaturated bonds The adhesive layer-forming composition according to this embodiment preferably contains (D) a polymerizable compound having at least two unsaturated bonds (hereinafter also simply referred to as "component (D)"). Component (D) can help to reduce the viscosity of the adhesive layer-forming composition, thereby improving the flatness of the film and increasing the crosslinking density after curing.

[0149] Component (D) may have at least two polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups of component (A). Preferably, the polymerizable unsaturated groups are the same functional groups as the polymerizable unsaturated groups of component (A). Specifically, the polymerizable unsaturated groups are preferably (meth)acryloyl groups. Component (D) may be a monomer, an oligomer, or a polymer, but is preferably a monomer or oligomer.

[0150] Examples of component (D) include: 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, tetramethylene glycol di(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 (meth)acrylic acid esters of (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 (for example, a mixture of dipentaerythritol pentaacrylate and hexaacrylate, "DPHA" manufactured by Nippon Kayaku Co., Ltd.); 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; This includes 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; as well as dendritic polymers having a (meth)acrylic group as compounds having an ethylenic double bond.

[0151] Component (D) preferably has two or more (meth)acryloyl groups, and more preferably has three or more (meth)acryloyl groups. When component (D) has two or more (meth)acryloyl groups, the crosslinking density is improved during thermal curing, and the solvent resistance of the adhesive layer is improved.

[0152] Component (D) preferably has an acrylic equivalent of 50 g / eq to 1000 g / eq, and more preferably 50 g / eq to 500 g / eq. When the acrylic equivalent of component (D) is 50 g / eq or more, the amount of residue when the adhesive layer is decomposed by light irradiation is reduced. Furthermore, when the acrylic equivalent of component (D) is 1000 g / eq or less, the crosslinking density is increased, making it easier to control the physical properties of the adhesive layer by light curing.

[0153] From the viewpoint of lowering the viscosity of the adhesive layer-forming composition and making it easier to improve the flatness of the film, component (D) may be an alkylene oxide-modified or lactone-modified compound.

[0154] On the other hand, if it is desirable to increase the crosslinking density of the cured film (adhesive layer), a compound that has not been modified with alkylene oxide or lactone may be used as component (D).

[0155] Examples of alkylene oxide-modified or lactone-modified compounds 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 Examples include ethylene oxide-modified triacrylate (all manufactured by Toagosei Co., Ltd.), A-TMPT-9EO (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanurate ethylene oxide-modified di and triacrylate, diglycerin ethylene oxide-modified acrylate (all manufactured by Toagosei Co., Ltd.), ATM-35E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and phosphazene alkylene oxide-modified hexa(meth)acrylate.

[0156] The content of component (D) is preferably 3 to 1000 parts by mass, more preferably 10 to 600 parts by mass, and even more preferably 20 to 300 parts by mass, when the total mass of component (A) is 100 parts by mass. When the above content of component (D) is 3 parts by mass or more, the fluidity of the adhesive layer forming composition is increased, and the flatness of the dried film (adhesive layer) when applied is improved. Also, when it is 1000 parts by mass or less, component (A) is sufficiently contained, so the light absorption of the dried film (adhesive layer) is sufficient, making it easy to peel off when irradiated with light.

[0157] 1-5. (E) Solvent Component (E) dissolves or disperses each component contained in the adhesive layer-forming composition, thereby improving the applicability of the adhesive layer-forming composition to the support.

[0158] Examples of component (E) 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 dimethyl ether, diethylene glycol ethyl methyl ether, and propylene glycol monobutyl ether. This includes glycol ethers such as methyl ether, 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. By dissolving and mixing these, a composition for forming an adhesive layer can be made into a uniform solution. Of these, component (E) preferably contains propylene glycol monomethyl ether acetate.

[0159] The content of component (E) varies depending on the target viscosity of the adhesive layer-forming composition, but is preferably 10% to 90% by mass, and more preferably 40% to 90% by mass, relative to the total mass of the adhesive layer-forming composition. This content makes it easier to impart appropriate coating properties.

[0160] 1-6. Other ingredients The adhesive layer-forming composition may optionally contain leveling agents, photosensitizers, thermal polymerization inhibitors, antioxidants, plasticizers, fillers, defoamers, surfactants, and coupling agents.

[0161] (Leveling agent) Leveling agents segregate on the surface of the coating film, controlling its viscosity and surface tension, thereby making it easier to improve the surface smoothness of the resin-cured film.

[0162] From the viewpoint of improving the smoothness of the cured resin film, it is preferable to include a leveling agent.

[0163] Examples of leveling agents include (meth)acrylic polymers and fluorinated compounds. Component (E) preferably contains a silicone-containing compound and / or a fluorinated compound, from the viewpoint of improving smoothness. Furthermore, if a coating layer is provided on top of the adhesive layer, a (meth)acrylic polymer is preferred, from the viewpoint of suppressing the repellency of the coating layer.

[0164] The leveling agent content in the adhesive layer-forming composition according to this embodiment is preferably 0.01% to 10.0% by mass, more preferably 0.01% to 8.0% by mass, even more preferably 0.01% to 5.0% by mass, and most preferably 0.01% to 1.0% by mass, based on the total mass of the solid content of the adhesive layer-forming composition. Here, by setting the leveling agent content to 0.01% by mass or more, smoothness tends to be increased, and by setting it to 10.0% by mass or less, when a coating layer is provided on a resin-cured film, it is possible to suppress the repellency of the coating layer.

[0165] (Photosensitizer) A photosensitizer is a substance that accelerates a photoreaction by absorbing light and transferring the resulting energy to other substances.

[0166] When forming an adhesive layer by photocuring, the adhesive layer-forming composition preferably contains a photosensitizer. Including a photosensitizer promotes the curing reaction by light irradiation, making it easier to control the transfer accuracy of the adherend.

[0167] Examples of photosensitizers include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler 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, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate (n-butoxy)ethyl This includes benzophenone derivatives such as 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylic benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone derivatives such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenone derivatives such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0168] The amount of 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 (C) is 100 parts by mass. If the amount of photosensitizer is 0.5 parts by mass or more, the sensitivity of component (C) can be improved and the rate of photopolymerization can be increased. If the amount of photosensitizer is 400 parts by mass or less, an excessive increase in sensitivity can be suppressed, making it less likely for charring, peeling residue, etc., to occur when ablation is performed by irradiating with light.

[0169] (others) Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-p-cresol. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers include silicone-based, fluorine-based, and acrylic compounds. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0170] 1-7. Method for preparing a composition for forming an adhesive layer The adhesive layer-forming composition can be prepared by mixing the above components.

[0171] 2. Laminate and method for manufacturing the same The above-described adhesive layer-forming composition is applied to the surface of either the support or the adherend, or both, to form an adhesive layer. The support and the adherend are then bonded together via the formed adhesive layer to produce a laminate having at least the support, the adherend, and the adhesive layer.

[0172] [Steps to form an adhesive layer] The adhesive layer formation step involves applying the adhesive layer forming composition to the surface of a support and / or adherend to form an adhesive layer containing the adhesive layer forming composition.

[0173] The type of support is not limited as long as an adhesive layer can be formed on its surface. In this embodiment, it is preferable that the support is light (laser) transparent. It is more preferable that the support transmits light (laser) with a wavelength of 10 nm to 400 nm, and even more preferable that it transmits light (laser) with a wavelength of 100 nm to 400 nm. Examples of light (laser) transparent supports include glass substrates, acrylic substrates, sapphire substrates, and quartz substrates. However, for glass substrates and acrylic substrates, it is necessary to use substrates with a composition that has sufficient transmittance for the wavelength of light (laser) used. Among the supports, quartz substrates and sapphire substrates are preferred.

[0174] Examples of substrates include semiconductor wafers, semiconductor chips, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers. The substrate may be a single layer or have a multilayer structure of two or more layers, and some or all of the layers may be patterned.

[0175] Examples of methods for applying adhesive layer-forming compositions include known methods such as solution immersion, spin coating, inkjet, spray, roller coater, land coater, slit coater, and spinner machines.

[0176] After applying the adhesive layer-forming composition to the surface of the support and / or adherend using the above application method, a dry film (adhesive layer) is formed by drying the solvent (pre-baking). Pre-baking is performed by heating using an oven, hot plate, etc. The heating temperature and time during pre-baking are appropriately selected depending on the solvent used, for example, at a temperature of 60 to 110°C for 1 to 10 minutes.

[0177] After the pre-baking process, a dry film (adhesive layer) may be formed by light irradiation. Examples of light used for irradiation include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. The wavelength of the light used for irradiation may be between 200 nm and 500 nm. The amount of light irradiation used to form the dry film is 25 mJ / cm². 2 ~3000 mJ / cm 2 It is preferable that this is the case. Furthermore, considering the variation in irradiation dose during light irradiation, the irradiation dose margin is 100 mJ / cm². 2 It is preferable that the above conditions are met.

[0178] The thickness of the dried film (adhesive layer) can be arbitrarily selected. The adhesive layer thickness is preferably 0.3 μm to 50 μm, more preferably 0.5 μm to 30 μm, and even more preferably 0.5 μm to 5 μm. If the adhesive layer thickness is 0.3 μm or more, the adhesive layer can conform to the surface of the adherend and have sufficient holding power. If the thickness is 50 μm or less, the adhesive layer can be sufficiently cured by light or heat curing.

[0179] [Patterning process for the adhesive layer] The process may include an exposure step and a development step to pattern the adhesive layer after pre-baking. By patterning the adhesive layer, the adhesive layer can be formed only in the areas where it is needed.

[0180] Examples of light used in the exposure process include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Of these, ultraviolet light (wavelength 250-400 nm) is preferred. In the development process, a developer suitable for alkaline development is used. Examples of the above-mentioned developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. These developers can be appropriately selected according to the characteristics of the resin layer, and surfactants may be added as needed. The development temperature is preferably 20-35°C, and fine images can be precisely formed using commercially available developers or ultrasonic cleaners. After alkaline development, the image is usually washed with water. As for development methods, shower development, spray development, dip development, and paddle development can be applied.

[0181] [Steps for bonding the support and the adherend] The step of bonding the support and the adherend is the step of bonding the support and the adherend via the adhesive layer described above.

[0182] One method for bonding the support and the adherend is to bring the adherend (which may have adhesive applied to its surface that comes into contact with the adhesive layer applied to the support surface) into contact with the surface of an adhesive layer formed on the surface of the support, and then apply light (or laser), pressure, heat, etc., to bond them together. In this case, the adherend may be formed on a transfer source substrate, and the adherend formed on the transfer source substrate may be brought into contact with the surface of the adhesive layer, and then light (or laser), pressure, heat, etc., may be applied to transfer the adherend to the adhesive layer.

[0183] Furthermore, when applying pressure, the bonding conditions between the support and the adherend are preferably between room temperature and 200°C, and more preferably between 30°C and 150°C. The bonding pressure is preferably between 0.01 MPa and 20 MPa, and more preferably between 0.03 MPa and 15 MPa.

[0184] Furthermore, regardless of whether or not pressure bonding is performed, heat treatment may be carried out, with the heating temperature preferably being 120°C to 250°C, and more preferably 150°C to 230°C. The heat treatment time is preferably 10 minutes to 120 minutes, and more preferably 30 minutes to 90 minutes. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support via the adhesive layer.

[0185] Furthermore, in the bonding process described above, the support and the adherend may be bonded by photocuring. An example of a method for photocuring the adhesive layer is to irradiate it with light using a high-pressure mercury lamp. In addition, the bonding conditions between the support and the adherend are preferably such that the wavelength of the irradiated light is 200 nm to 500 nm. The exposure amount of the irradiated light is 25 mJ / cm². 2 ~3000 mJ / cm 2 Preferably, it is 50 mJ / cm². 2 ~2000 mJ / cm 2 It is more preferable that this is the case. When photocuring is performed, it is preferable that the adhesive layer forming composition contains a photopolymerization initiator.

[0186] The above-mentioned pressurization, heat treatment, and light irradiation may be performed individually, individually or incompletely, or all of them may be performed.

[0187] In this way, the laminate of this embodiment is formed. This laminate can be used to transport a plurality of adherends held on a support.

[0188] Furthermore, the laminate described above can be separated from the support and the adherend by irradiating the adhesive layer from the support side with light (or laser) with a wavelength of 10 nm to 400 nm, as described later.

[0189] 3. Processing method for laminated materials The processing method for a laminate according to this embodiment includes (a) a step of preparing the laminate described above, and (b) a step of irradiating the laminate with light (or a laser) to separate the support and the adherend. Each step will be described below. Step (a) and step (b) may be performed in a continuous manner, or step (b) may be performed after a period of time following step (a).

[0190] Since the laminate described above has an adhesive layer according to this embodiment, the support and the adherend can be separated by irradiating the adhesive layer with light (or a laser).

[0191] Step (b) described above will be explained with reference to Figure 1. For example, as shown in Figure 1A, the adherends 101 and 102 can be peeled off the adhesive layer 103 by irradiation with light (or laser), and the adherends 101 and 102 can be transferred from the support 104 to another substrate 202. At this time, for example, as shown in Figure 1B, the other substrate 202 to which the adherends 101 and 102 are transferred from the support 104 may have the catch material 201 on the surface that catches the adherends 101 and 102 peeled off from the support 104. The catch material 201 can be a known catch material, but the adhesive layer according to this embodiment may also be used.

[0192] The light (or laser) used for irradiation is not particularly limited, as long as it can separate the support and the adherend. In the present invention, the light (or laser) is preferably ultraviolet light, and the wavelength of the ultraviolet light is more preferably 10 nm to 400 nm, and even more preferably 100 nm to 400 nm. If the wavelength of the ultraviolet light is 10 nm or more, the components of the adhesive layer absorb the light, causing decomposition or alteration, which reduces the strength and adhesive force, making it easy to separate the support and the adherend. If the wavelength is 400 nm or less, the adhesive layer in the processed area absorbs the light, which suppresses the generation of cured film residue.

[0193] From the perspective of enhancing the transfer efficiency to another substrate by irradiating with this light (or laser), the support preferably has light transmissibility. In particular, it is more preferable for the support to transmit light (laser) with a wavelength of 10 nm to 400 nm, and even more preferable to transmit light (laser) with a wavelength of 100 nm to 400 nm. Examples of the substrate having the above laser transmissibility include a glass substrate, an acrylic substrate, a sapphire substrate, a quartz substrate, etc. However, for glass substrates and acrylic substrates, it is desirable to use substrates with a composition that has sufficient transmittance for the wavelength of the light used (especially a wavelength of 266 nm). Among these, sapphire substrates and quartz substrates are preferred.

[0194] Examples of the above ultraviolet light sources include a low mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp laser.

[0195] Examples of the above lasers include solid state lasers, liquid lasers, and gas lasers. Also, examples of the above solid state lasers include semiconductor excited lasers, etc. Examples of liquid lasers include dye lasers, etc. Examples of gas lasers include excimer lasers, etc. Among the above lasers, a semiconductor excited laser is preferred.

[0196] Examples of the above semiconductor excited lasers include Nd:YAG lasers, Nd:YLF lasers, Nd:glass lasers, Nd:YVO4 lasers, Yb:YAG lasers, Yb-doped fiber lasers, Er:YAG lasers, Tm:YAG lasers, etc. Examples of excimer lasers include KrF lasers, XeCl lasers, ArF lasers, F2 lasers, etc. Among the above lasers, a Nd:YAG laser is preferred.

[0197] Also, the output and integrated light amount of the light irradiated to the adhesive layer vary depending on the type of light source, etc. When the irradiated light is a laser, an output of 0.1 mW to 200 W can be used. Also, the above integrated light amount is 1 mJ / cm 2 ~50 J / cm 2Preferably, it is 1 mJ / cm 2 ~10J / cm 2 It is more preferable that it be 1 mJ / cm 2 ~1J / cm 2 It is even more preferable that the integrated light intensity is 1 mJ / cm². 2 At this level, charring and peeling residue are less likely to occur during ablation. 50 J / cm 2 The following conditions allow for proper control of the ablation speed and enables proper processing.

[0198] It is preferable to irradiate the entire surface of the adhesive layer with light (laser) from the substrate side, or to selectively irradiate the area to which the object to be transferred is adhered.

[0199] Furthermore, the process may include a step of processing the laminate before peeling the adherend off the support.

[0200] Examples of the above processing include thinning of the substrate by dicing, back grinding, photofabrication, semiconductor chip stacking, mounting of various substrates, and resin encapsulation.

[0201] The type of substrate is not particularly limited. Examples of substrates include semiconductor wafers, semiconductor chips, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers.

[0202] 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 longest side of the rectangle (or the length of any one side if it is a square) is preferably 1 μm to 100,000 μm, and more preferably 5 μm to 800 μm. A suitable example of a surface of the adherend that adheres to the adhesive layer is a semiconductor device.

[0203] 4. Other uses of adhesive layers As described above, the adhesive layer according to this embodiment can be used as a catch material to hold (catch) an object that has been peeled off from the source substrate.

[0204] The process of catching the adherends peeled off the source substrate using the adhesive layer according to this embodiment will be explained with reference to Figure 2. As shown in Figure 2A, light is irradiated onto the resin 302 via the source substrate 301, causing the resin 302 to which the adherends are attached to change and decompose. As a result, the adherends 101 and 102 are peeled off from the source substrate 301 and transferred to the support 104. The transferred adherends 101 and 102 are caught by the adhesive layer 103 and adhere to the support without any misalignment.

[0205] In this way, for example, a laminate 100 may be manufactured having a support 104, adherends 101 and 102, and an adhesive layer 103 formed by the adhesive layer-forming composition, which is disposed between the support 104 and the adherends 101 and 102, as shown in Figure 2B.

[0206] Alternatively, after forming the laminate by holding the adherend on the support, the adhesive layer may be post-baked to firmly bond the adherend to the support. Post-baking can reduce the residue that remains when peeled off by light irradiation.

[0207] The above post-bake may be performed, for example, by heating the adherend while applying pressure to the adhesive layer, or by heating without applying pressure. The temperature at this time is preferably 120°C to 250°C, and more preferably 150°C to 230°C. The heat treatment time is preferably 10 minutes to 120 minutes, and more preferably 30 minutes to 90 minutes. If pressure is applied, the pressure is preferably 0.01 MPa to 20 MPa, and more preferably 0.03 MPa to 15 MPa. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support via the adhesive layer.

[0208] Alternatively, the adhesive may be cured by light curing. Light curing prevents the adherend from becoming embedded in the adhesive layer, thereby improving the peelability by light irradiation. The adhesive layer can be cured by light irradiation using a high-pressure mercury lamp, for example. The wavelength of the light irradiated at this time is preferably 200 nm to 500 nm. The exposure dose of the light irradiated at this time is 25 mJ / cm². 2 ~3000 mJ / cm 2 Preferably, it is 50 mJ / cm². 2 ~2000 mJ / cm 2 It is more preferable that this is the case. When photocuring is performed, it is preferable that the adhesive layer forming composition contains a photopolymerization initiator.

[0209] The above post-bake and light irradiation may be performed either individually, both, or neither.

[0210] The support, to which the adherend has been firmly bonded in this manner, can then be used directly as a mounting board in the product.

[0211] Preferably, the source substrate is positioned so that the surface to which the adherend is attached faces the adhesive layer of the support, and the surface to which the adherend is attached to the source substrate is positioned vertically upward. The source substrate may have multiple adherends attached to its surface using a resin that decomposes or changes in quality upon light irradiation.

[0212] From the viewpoint of transferring the adherend at a higher speed, the adherend attached to the transfer source substrate and the adhesive layer formed on the support are arranged to create a gap between them. The gap is preferably 10 μm to 200 μm, and more preferably 30 μm to 100 μm.

[0213] Furthermore, the applications of the adhesive layer-forming composition are not limited to the adhesive layer described above. For example, the adhesive layer-forming composition can also be used as a tack or adhesive, or as a protective film and insulating film on semiconductor packages and printed circuit boards. [Examples]

[0214] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto.

[0215] First, we will explain the synthesis examples of the unsaturated group-containing polymerizable resin, which is component (A). Unless otherwise noted, the evaluation of the resin in these synthesis examples was performed as follows.

[0216] Furthermore, when the same model of measuring instrument is used, the manufacturer's name is omitted from the second instance onward. Also, in the examples, the glass substrates used to prepare the hardened film substrates for measurement are all treated in the same way. In addition, when the first decimal place of the content of each component is 0, the decimal part may be omitted.

[0217] [Solid content concentration] The weight of 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)], and the weight after heating at 160°C for 2 hours [W2 (g)] was calculated using the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0218] [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 result.

[0219] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0220] The abbreviations used in the synthesis examples are as follows: jER YX4000: Tetramethylbiphenyl type epoxy resin (epoxy equivalent 192g / eq, manufactured by Mitsubishi Chemical Corporation; "jER" is a registered trademark of the company) AA: Acrylic acid TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate PMDA: Pyromellitic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride BHT: 2,6-di-tert-butyl-p-cresol SFDA: Spiro[fluorene-9,9'-xanthene]-2',3',6',7'-tetracarboxylic dianhydride (manufactured by Air Water Performance Chemicals) jER 828: Bisphenol A type epoxy resin (epoxy equivalent 185g / eq, manufactured by Mitsubishi Chemical Corporation; "jER" is a registered trademark of the company) DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone SA: Succinic anhydride TEA: Triethylamine

[0221] [Synthesis Example 1] Into a 250 mL four-necked flask equipped with a reflux condenser, jER YX4000 (50.00 g, 0.13 mol), AA (18.95 g, 0.26 mol), TPP (0.37 g), and PGMEA (first 12.00 g) were charged, and stirred at 100 - 105 °C for 12 hours to obtain a reaction product. Then, PGMEA (57.00 g) was added to the above reaction product and adjusted so that the solid content became 50 mass%.

[0222] Next, PMDA (14.32 g, 0.06 mol) and THPA (9.99 g, 0.06 mol) were added to the obtained reaction product, and stirred at 115 - 120 °C for 6 hours to obtain an unsaturated group-containing polymerizable resin (A)-1. The solid content concentration of the obtained resin solution was 57.6 mass%, the acid value (in terms of solid content) was 118 mg KOH / g, and Mw by GPC analysis was 3200.

[0223] [Synthesis Example 2] Into a 250 mL four-necked flask equipped with a reflux condenser, jER YX4000 (50.00 g, 0.13 mol), AA (18.95 g, 0.26 mol), TPP (0.37 g), and PGMEA (first 12.00 g) were charged, and stirred at 100 - 105 °C for 12 hours to obtain a reaction product. Then, PGMEA (57.00 g) was added to the above reaction product and adjusted so that the solid content became 50 mass%.

[0224] Next, BPDA (19.32 g, 0.06 mol) and THPA (9.99 g, 0.06 mol) were added to the obtained reaction product, and stirred at 115 - 120 °C for 6 hours to obtain an unsaturated group-containing polymerizable resin (A)-2. The solid content concentration of the obtained resin solution was 58.8 mass%, the acid value (in terms of solid content) was 112 mg KOH / g, and Mw by GPC analysis was 3600.

[0225] [Synthesis Example 3] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (52.32 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (53.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0226] Next, PMDA (24.00 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-3. The solid content concentration of the obtained resin solution was 54.7% by mass, the acid value (based on solid content) was 89 mg KOH / g, and the Mw value determined by GPC analysis was 3600.

[0227] [Synthesis Example 4] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (52.32 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (53.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0228] Next, BPDA (32.37 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-4. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (based on solid content) was 84 mg KOH / g, and the Mw value determined by GPC analysis was 3700.

[0229] [Synthesis Example 5] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (52.32 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (53.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0230] Next, SFDA (51.98 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-5. The solid content concentration of the obtained resin solution was 59.2% by mass, the acid value (based on solid content) was 74 mg KOH / g, and the Mw value determined by GPC analysis was 4100.

[0231] [Synthesis Example 6] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (52.32 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (53.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0232] Next, 1,2,3,4-butanetetracarboxylic dianhydride (21.80 g, 0.11 mol) was added to the reaction product, and the mixture was stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-6. The solid content concentration of the obtained resin solution was 54.3% by mass, the acid value (based on solid content) was 90 mg KOH / g, and the Mw value determined by GPC analysis was 3100.

[0233] [Synthesis Example 7] In a 500 mL four-necked flask equipped with a reflux condenser, BPDA (35.00 g, 0.12 mol), 4-hydroxybutyl acrylate (27.16 g, 0.24 mol), TPP (0.62 g), BHT (0.11 g), and PGMEA (63.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (45.26 g, 0.23 mol) and TPP (0.59 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (46.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0234] Next, PMDA (20.76 g, 0.10 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-7. The solid content concentration of the obtained resin solution was 54.2% by mass, the acid value (based on solid content) was 82 mg KOH / g, and the Mw value determined by GPC analysis was 3900.

[0235] [Synthesis Example 8] In a 500 mL four-necked flask equipped with a reflux condenser, SFDA (50.00 g, 0.11 mol), 4-hydroxybutyl acrylate (24.17 g, 0.21 mol), TPP (0.56 g), BHT (0.09 g), and PGMEA (75.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (40.27 g, 0.20 mol) and TPP (0.53 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (40.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0236] Next, PMDA (18.47 g, 0.08 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-8. The solid content concentration of the obtained resin solution was 53.8% by mass, the acid value (based on solid content) was 71 mg KOH / g, and the Mw value determined by GPC analysis was 3900.

[0237] [Synthesis Example 9] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 2-ethylhexylglycidyl ether (48.68 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (49.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0238] Next, PMDA (24.00 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-9. The solid content concentration of the obtained resin solution was 54.9% by mass, the acid value (based on solid content) was 91 mg KOH / g, and the Mw value determined by GPC analysis was 3700.

[0239] [Synthesis Example 10] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g) and PGMEA (62.00 g) were charged, and the mixture was stirred at 100 - 105 °C for 8 hours. Then, 2-ethylhexyl glycidyl ether (48.68 g, 0.26 mol) and TPP (0.69 g) were added, and the mixture was stirred at 100 - 105 °C for 8 hours to obtain a reaction product. Thereafter, PGMEA (49.00 g) was added to the above reaction product, and the mixture was adjusted so that the solid content became 50 mass%.

[0240] Next, BPDA (32.37 g, 0.11 mol) was added to the obtained reaction product, and the mixture was stirred at 115 - 120 °C for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-10. The solid content concentration of the obtained resin solution was 56.4 mass%, the acid value (in terms of solid content) was 86 mgKOH / g, and Mw by GPC analysis was 4200.

[0241] [Synthesis Example 11] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g) and PGMEA (62.00 g) were charged, and the mixture was stirred at 100 - 105 °C for 8 hours. Then, (3,4-epoxycyclohexyl)methyl acrylate (47.62 g, 0.26 mol) and TPP (0.69 g) were added, and the mixture was stirred at 100 - 105 °C for 8 hours to obtain a reaction product. Thereafter, PGMEA (48.00 g) was added to the above reaction product, and the mixture was adjusted so that the solid content became 50 mass%.

[0242] Next, PMDA (24.00 g, 0.11 mol) was added to the obtained reaction product, and the mixture was stirred at 115 - 120 °C for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-11. The solid content concentration of the obtained resin solution was 55.0 mass%, the acid value (in terms of solid content) was 92 mgKOH / g, and Mw by GPC analysis was 5200.

[0243] [Synthesis Example 12] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, glycidyl methacrylate (37.15 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (38.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0244] Next, PMDA (24.00 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-12. The solid content concentration of the obtained resin solution was 55.3% by mass, the acid value (based on solid content) was 100 mg KOH / g, and the Mw value determined by GPC analysis was 4000.

[0245] [Synthesis Example 13] In a 500 mL four-necked flask equipped with a reflux condenser, PMDA (30.00 g, 0.14 mol), 4-hydroxybutyl acrylate (31.41 g, 0.28 mol), TPP (0.72 g), BHT (0.12 g), and PGMEA (62.00 g) were charged and stirred at 100-105°C for 8 hours. Next, glycidyl methacrylate (37.15 g, 0.26 mol) and TPP (0.69 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (38.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0246] Next, BPDA (32.37 g, 0.11 mol) was added to the reaction product and stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)-13. The solid content concentration of the obtained resin solution was 56.9% by mass, the acid value (based on solid content) was 93 mg KOH / g, and the Mw value determined by GPC analysis was 4200.

[0247] [Synthesis Example 14] In a 250 mL four-necked flask equipped with a reflux condenser, jER 828 (50.00 g, 0.14 mol), AA (19.67 g, 0.27 mol), TPP (0.39 g), and PGMEA (12.00 g) were charged and stirred at 100-105°C for 12 hours to obtain the reaction product. Subsequently, PGMEA (58.20 g) was added to the reaction product to adjust the solid content to 50% by mass.

[0248] Next, PMDA (14.87 g, 0.07 mol) and THPA (10.37 g, 0.07 mol) were added to the reaction product, and the mixture was stirred at 115-120°C for 6 hours to obtain unsaturated group-containing polymerizable resin (A)'-14. The solid content concentration of the obtained resin solution was 57.6% by mass, the acid value (based on solid content) was 120 mg KOH / g, and the Mw value determined by GPC analysis was 4400.

[0249] [Synthesis Example 15] In a 250 mL four-necked flask equipped with a reflux condenser, jER 828 (50.00 g, 0.14 mol), AA (19.67 g, 0.27 mol), TPP (0.39 g), and PGMEA (12.00 g) were charged and stirred at 100-105°C for 12 hours to obtain the reaction product. Subsequently, PGMEA (58.20 g) was added to the reaction product to adjust the solid content to 50% by mass.

[0250] Next, BPDA (20.05 g, 0.07 mol) and THPA (10.37 g, 0.06 mol) were added to the reaction product, and the mixture was stirred at 115-120°C for 6 hours to obtain unsaturated group-containing polymerizable resin (A)'-15. The solid content concentration of the obtained resin solution was 58.9% by mass, the acid value (based on solid content) was 114 mg KOH / g, and the Mw value determined by GPC analysis was 4300.

[0251] [Synthesis Example 16] In a 500 mL four-necked flask equipped with a reflux condenser, 1,2,3,4-butanetetracarboxylic dianhydride (30.00 g, 0.15 mol), 4-hydroxybutyl acrylate (34.57 g, 0.30 mol), TPP (0.79 g), BHT (0.13 g), and PGMEA (65.00 g) were charged and stirred at 100-105°C for 8 hours. Next, 4-hydroxybutyl acrylate glycidyl ether (57.60 g, 0.29 mol) and TPP (0.76 g) were added and stirred at 100-105°C for 8 hours to obtain the reaction product. Subsequently, PGMEA (58.00 g) was added to the above reaction product to adjust the solid content to 50% by mass.

[0252] Next, 1,2,3,4-butanetetracarboxylic dianhydride (24.00 g, 0.12 mol) was added to the reaction product, and the mixture was stirred at 115-120°C for 8 hours to obtain unsaturated group-containing polymerizable resin (A)'-16. The solid content concentration of the obtained resin solution was 54.5% by mass, the acid value (based on solid content) was 92 mg KOH / g, and the Mw value determined by GPC analysis was 3300.

[0253] [Synthesis Example 17] 300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the flask system was purged with nitrogen before being heated to 120°C. A monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), and St (31.2 g, 0.30 mol) in which AIBN (10 g) was dissolved was added dropwise to the flask from a dropping funnel over 2 hours, and the mixture was stirred at 120°C for another 2 hours to obtain a copolymer solution.

[0254] Next, after replacing the flask system with air, AA (24.0 g, 95% of the glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution and stirred at 120°C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the moles of AA added) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120°C for 4 hours to obtain unsaturated group-containing polymerizable resin (A)'-17. The solid content concentration of the resin solution was 46.0% by mass, the acid value (based on solid content) was 76 mgKOH / g, and the Mw calculated by GPC analysis was 5300.

[0255] Adhesive layer-forming compositions were prepared using the formulation amounts (in parts by mass) listed in Tables 1-3. The formulation components used in Tables 1-3 are as follows:

[0256] (Component A) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 57.6% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 58.8% by mass) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 54.7% by mass) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 56.1% by mass) (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 59.2% by mass) (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration 54.3% by mass) (A)-7: Resin solution obtained in Synthesis Example 7 (solid content concentration 54.2% by mass) (A)-8: Resin solution obtained in Synthesis Example 8 (solid content concentration 53.8% by mass) (A)-9: Resin solution obtained in Synthesis Example 9 (solid content concentration 54.9% by mass) (A)-10: Resin solution obtained in Synthesis Example 10 (solid content concentration 56.4% by mass) (A)-11: Resin solution obtained in Synthesis Example 11 (solid content concentration 55.0% by mass) (A)-12: Resin solution obtained in Synthesis Example 12 (solid content concentration 55.3% by mass) (A)-13: Resin solution obtained in Synthesis Example 13 (solid content concentration 56.9% by mass) (A)'-14: Resin solution obtained in Synthesis Example 14 (solid content concentration 57.6% by mass) (A)'-15: Resin solution obtained in Synthesis Example 15 (solid content concentration 58.9% by mass) (A)'-16: Resin solution obtained in Synthesis Example 16 (solid content concentration 54.5% by mass) (A)'-17: Resin solution obtained in Synthesis Example 17 (solid content concentration 46.0% by mass) Furthermore, (A)-1 and (A)-2 above are polymerizable resins containing unsaturated groups corresponding to component (A-2) above, and (A)-3 to (A)-13 above are polymerizable resins containing unsaturated groups corresponding to component (A-1) above.

[0257] ((B) component) (B)-1: Biphenyl-type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company, epoxy equivalent 192 g / eq, absorbance at 266 nm: 0.49) (B)-2: Bisphenol A type epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company, epoxy equivalent 185 g / eq, absorbance at 266 nm: 0.06)

[0258] ((C) component) (C)-1:2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (Omnirad907, manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company) (C)-2: 1,2-Octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (Manufactured by BASF, "IrgacureOXE-01" and "Irgacure" are registered trademarks of the company)

[0259] ((D) component) (D)-1: A mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0260] ((E) component) (E)-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0261] [Table 1]

[0262] [Table 2]

[0263] [Table 3]

[0264] [evaluation] The following evaluations were performed on component (A), synthesized according to the above synthesis example, and on the adhesive layer-forming compositions of the examples and comparative examples. The results are shown in Tables 4 to 6.

[0265] [(A) Absorbance evaluation of component] (Fabrication of substrates for absorbance evaluation) (A) Unsaturated group-containing polymerizable resin, synthesized according to the above synthesis example, was coated onto a quartz glass substrate using a spin coater as a 20% by weight PGMEA solution to a cured film thickness of 1.0 μm. A dried film was then prepared by pre-baking at 100°C for 5 minutes using a hot plate. Subsequently, a post-bake was performed at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured film.

[0266] (Evaluation method) Using a UV-Vis-Infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), the absorbance of the substrate with the cured film at a wavelength of 266 nm was measured after post-baking.

[0267] [Evaluation of the weight loss rate of component (A) at 400°C] (Fabrication of substrates for weight loss rate evaluation) (A) Unsaturated group-containing polymerizable resin, synthesized according to the above synthesis example, was applied to a glass substrate "#1737" using a spin coater as a 20% by weight PGMEA solution to a cured film thickness of 1.0 μm. A dry film was then prepared by pre-baking at 100°C for 5 minutes using a hot plate. Subsequently, a post-bake was performed at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured film.

[0268] (Evaluation method) A sample of the cured film (cured material) was taken from the substrate with the cured film mentioned above. Using a TG-DTA apparatus "TG / DTA7220" (manufactured by Seiko Instruments Inc.), the sample was heated from 30°C to 450°C at a heating rate of 10°C / min under a nitrogen atmosphere, and the weight loss of the sample (cured material) was measured when the temperature was raised from 30°C to 400°C. The weight loss rate of the cured film was measured by dividing the weight loss by the weight of the sample at 30°C.

[0269] [Evaluation of film reduction during laser irradiation] (Fabrication of substrates for evaluating film reduction during laser irradiation and minimum laser processing energy) The adhesive layer-forming compositions shown in Tables 1-3 were applied to the glass substrate "#1737" using a spin coater to achieve a cured film thickness of 1.0 μm. A pre-baked film was then prepared by pre-baking at 100°C for 5 minutes using a hot plate. Subsequently, post-curing (post-baking) was performed at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1-25 and Comparative Examples 1-4.

[0270] (Evaluation method) After the final curing (post-bake) of the cured film, a laser (laser wavelength: 266 nm) was irradiated using a flash lamp-excited Nd:YAGQ-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.). 400 mJ / cm 2 The hardened film was processed using laser energy, and the amount of film reduction in the laser-irradiated area was measured using a non-contact three-dimensional optical interference microscope "WYKO Contour-GT" (manufactured by Bruker Japan). A result of △ or higher was considered acceptable.

[0271] (Evaluation Criteria) ◎: The amount of film reduction is 0.45 μm or more. ○: The amount of film reduction is 0.40 μm or more and less than 0.45 μm. △: The amount of film reduction is 0.35 μm or more, but less than 0.40 μm. ×: The amount of film reduction is less than 0.35 μm.

[0272] [Evaluation of minimum laser processing energy] (Evaluation method) The above-mentioned cured film was irradiated with a laser (laser wavelength: 266 nm) using a flash lamp-excited Nd:YAG Q-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.). 100~400 mJ / cm 2 The hardened film was processed using laser energy, and the amount of film reduction in the laser-irradiated area was measured using a non-contact three-dimensional optical interference microscope "WYKO Contour-GT" (manufactured by Bruker Japan). Based on the laser irradiation dose required to reduce the film thickness to 0.2 μm, the following criteria were used for evaluation. A score of △ or higher was considered acceptable.

[0273] (Evaluation Criteria) ◎: 140 mJ / cm 2 If less than this, the film reduction amount will be 0.2 μm. ○: 140 mJ / cm 2 More than 200mJ / cm 2 If less than this, the film reduction amount will be 0.2 μm. △: 200 mJ / cm 2 More than 250mJ / cm 2 If less than this, the film reduction amount will be 0.2 μm. ×: 250 mJ / cm 2 This completes the reduction in film thickness to 0.2 μm.

[0274] [Heat resistance] The adhesive layer-forming compositions shown in Tables 1-3 were applied to the glass substrate "#1737" using a spin coater to achieve a cured film thickness of 1.0 μm. A pre-baked film was then prepared by pre-baking at 100°C for 5 minutes using a hot plate. Subsequently, post-curing (post-baking) was performed at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1-25 and Comparative Examples 1-4.

[0275] (Evaluation method) Samples of the cured film were taken from the above-mentioned substrate with the cured film, and the temperature was increased from 30°C to 450°C at a rate of 10°C / min under a nitrogen atmosphere using a TG-DTA apparatus "TG / DTA7220" (manufactured by Seiko Instruments Inc.). The weight loss of the sample was measured when the temperature was increased from 30°C to 400°C. The weight loss rate of the cured film was measured by dividing the weight loss by the sample weight at 30°C. The temperature at which the weight loss rate first exceeded 5% when the temperature was increased from 30°C was measured, and the sample was evaluated based on the following criteria. A score of △ or higher was considered a pass.

[0276] (Evaluation Criteria) ◎: The temperature at which the weight loss rate exceeds 5% is 320℃ or higher. ○: The temperature at which the weight loss rate is 5% or more is between 300°C and 320°C. △: The temperature at which the weight loss rate is 5% or more is between 280°C and 300°C. ×: The temperature at which the weight loss rate exceeds 5% is below 280°C.

[0277] [Table 4]

[0278] [Table 5]

[0279] [Table 6]

[0280] As is clear from Tables 4-6, using component (A), which has an absorbance of 0.5 or more per 1.0 μm of cured film at 266 nm and a weight loss rate of 50% by mass or more at 400°C when heated in a nitrogen atmosphere, results in a larger film reduction when the cured film is irradiated with a laser. This reduces residue when used as an adhesive layer and also lowers the minimum laser processing energy, demonstrating excellent decomposition by light irradiation.

[0281] Furthermore, as can be seen from the comparison of Examples 1 to 13 and Comparative Examples 1 to 4, by using component (A-1) as the (A) unsaturated polymerizable resin, it is possible to increase the amount of film reduction during laser irradiation.

[0282] As can be seen from a comparison of Examples 1-13 and Examples 14-25, the heat resistance of the curable resin composition can be improved by using (B) an epoxy compound having at least two epoxy groups. Furthermore, by setting the absorbance of component (B) at 266 nm to 0.1 or higher, the minimum laser processing energy can be reduced. [Industrial applicability]

[0283] The present invention can provide a laminate having an adhesive that can be used in the manufacture of various products. In particular, it can provide a laminate suitable for processes in which the laminate is temporarily fixed to a support such as a semiconductor wafer and then processed. [Explanation of Symbols]

[0284] 100-layer structure 101, 102 Adherent 103 Adhesive layer 104 Support 201 Catch material 202 Substrate onto which the adherend is transferred from the support. 301 Source substrate for transfer 302 Resins that change or decompose upon light irradiation

Claims

1. In a laminate comprising a light-transmitting support and an adherend, A composition for forming an adhesive layer that allows the support and the adherend to be separated from the laminate by irradiating light from the support side, The aforementioned adhesive layer forming composition is (A) Polymerizable resin containing unsaturated groups, (E) Solvent and Includes, The solution of component (A) is applied to a substrate so that the cured film thickness is 1.0 μm, and the cured film is formed by heating at 100°C for 5 minutes followed by heating at 230°C for 30 minutes, wherein the absorbance of light at a wavelength of 266 nm is 0.50 or higher. The cured product obtained by applying the solution of component (A) to a substrate, heating it at 100°C for 5 minutes, and then heating it at 230°C for 30 minutes, has a weight loss rate of 50% by mass or more when heated from 30°C to 400°C in a nitrogen atmosphere. Composition for forming adhesive layer.

2. The aforementioned component (A) is an unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-1) represented by the following general formula (1) with a tetrabasic acid or its dianhydride (a-2). The adhesive layer forming composition according to claim 1. 【Chemistry 1】 (In general formula (1), R1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, or a substituent of general formula (2) below. R2 is independently a substituent represented by general formula (3) or general formula (4) below. X is a tetravalent carboxylic acid residue.) 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (In general formula (2), R3 is a hydrogen atom or a methyl group. R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, and p is a number from 0 to 10. In general formulas (3) and (4), R5 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, a substituent of general formula (5) below, or a hydrogen atom. * indicates a bonding site with the structure represented by general formula (1). However, in general formula (4), it is indicated that R5 is bonded to any carbon atom on the ring.) 【Transformation 5】 (In general formula (5), R3 is a hydrogen atom or a methyl group. R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, and q is a number from 0 to 10. * indicates a bonding site with the structure represented by general formula (3) or general formula (4).)

3. (B) comprising an epoxy compound having at least two epoxy groups, The content of component (B) is 10% to 70% by mass relative to the total mass of component (A). The adhesive layer forming composition according to claim 1.

4. (B) comprising an epoxy compound having at least two epoxy groups, The absorbance of a 0.001% by weight acetonitrile solution of component (B) is measured using an ultraviolet-visible-infrared spectrophotometer in a quartz cell with a path length of 1 cm, and the absorbance of light at a wavelength of 266 nm is 0.10 or higher. The adhesive layer forming composition according to claim 1.

5. (C) Containing a photopolymerization initiator, The adhesive layer forming composition according to claim 1.

6. A step of forming an adhesive layer on the surface of either the support or the adherend or both using the adhesive layer forming composition described in any one of claims 1 to 5, A step of bonding the support and the adherend via the formed adhesive layer, A method for manufacturing a laminate containing a laminate.

7. A step of preparing a laminate manufactured by the method of claim 6, A step of separating the support and the adherend by irradiating them with light, A method for processing a laminate, comprising: The support transmits light with wavelengths from 10 nm to 400 nm. A method for processing a laminate, wherein the laminate can be separated from the support and the adherend by irradiating the adhesive layer with light.

Images