Curable resin composition, laminate, method for producing laminate, and method for treating laminate

Abstract

To provide a curable resin composition having high transfer accuracy of an adherend transferred from another substrate when an adhesive layer is formed, to provide a laminate formed by using the curable resin composition, and to provide a method for producing the laminate and a method for treating the laminate.SOLUTION: The curable resin composition is a curable resin composition for forming an adhesive layer for holding an adherend peeled from a transfer source substrate by irradiating the transfer source substrate with light on a holding substrate for holding the peeled adherend and contains (A) an unsaturated group-containing polymerizable resin and (B) a solvent. The storage modulus of the ingredient (A) obtained under predetermined conditions is 200kPa or less. A cured film of the ingredient (A) obtained under predetermined conditions has an absorbance of 0.50 or more for light having a wave length of 266nm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a laminate, a method for producing a laminate, and a method for treating a laminate. [Background technology]

[0002] In recent years, as digital devices have become more sophisticated, the flexible displays and semiconductor chips they are equipped with have become thinner. However, as the flexible displays and semiconductor chips have become thinner, their strength has decreased, making it difficult to transport them using conventional automatic transport methods.

[0003] Therefore, methods for easily transporting thin flexible displays, semiconductor chips, etc. have been investigated. For example, a laminate is formed on a support, with a large number of elements such as semiconductor wafers fixed via an adhesive layer, and this laminate is transported. Thereafter, light is irradiated from the support side toward the adhesive layer, thereby altering or decomposing the adhesive layer and reducing the adhesive strength, and the elements are then peeled off from the support and transferred to another substrate.

[0004] Patent Document 1 describes that when carrying out this method, the transfer efficiency of the elements can be improved by providing an impact absorbing layer on another substrate to hold (catch) the elements peeled off from the support without misalignment, etc. Patent Document 1 further describes that the elements held on the substrate having the impact absorbing layer can also be transferred to yet another substrate such as a circuit board using a similar transfer method. Patent Document 1 describes that the impact absorbing layer is an adhesive layer and can be a layer made of an acrylic resin, etc. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-67892 Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to the findings of the present inventors, when a conventionally known acrylic resin or the like is used in an impact absorbing layer (adhesive layer) as described in Patent Document 1, there is a problem that when an adherend is to be transferred to another substrate, the resin has difficulty absorbing light such as a laser (low absorbance), and the adherend is difficult to peel from the impact absorbing layer (adhesive layer).

[0007] On the other hand, in order to increase the absorbance of a resin, it is necessary to introduce a certain proportion of light-absorbing moieties such as aromatic rings, etc. However, when an adhesive layer using such a resin catches an adherend that has been peeled off from another substrate, transfer defects such as bouncing occur, which creates a problem in that the ability to catch the adherend (transfer accuracy) is likely to deteriorate.

[0008] The present invention has been made in view of the above points, and has an object to provide a curable resin composition that, when an adhesive layer is formed, has high transfer accuracy of an adherend transferred from another substrate, a laminate formed using the curable resin composition, and a manufacturing method and processing method of the laminate. [Means for solving the problem]

[0009] One aspect of the present invention for solving the above problems relates to a curable resin composition as described in the following [1] to [4].

[0010] [1] A curable resin composition for forming an adhesive layer on a holding substrate that holds an adherend that has been peeled off from an original substrate by irradiating the original substrate with light, the curable resin composition comprising: (A) an unsaturated group-containing polymerizable resin; (B) a solvent; Including, a dry film obtained by applying the solution of the component (A) to a substrate and heating it at 100°C for 5 minutes has a storage modulus of 200 kPa or less; The solution of component (A) is applied to a substrate so that the film thickness after curing is 1.0 μm, and the solution is heat-treated at 100° C. for 5 minutes and then at 230° C. for 30 minutes, forming a cured film having an absorbance of 0.50 or more for light with a wavelength of 266 nm. Curable resin composition.

[0011] [2] (C) a polymerizable compound having at least two unsaturated bonds, The component (C) has an acrylic equivalent of 50 g / eq to 1000 g / eq. The curable resin composition according to [1].

[0012] [3] The weight average molecular weight of the component (A) is 1,000 to 40,000, The acid value of the component (A) is 20 mg KOH / g to 200 mg KOH / g. The curable resin composition according to [1] or [2].

[0013] [4] (D) containing an epoxy compound having at least two epoxy groups; The curable resin composition according to any one of [1] to [3].

[0014] One aspect of the present invention for solving the above problem relates to a laminate described in [5] below.

[0015] [5] a holding substrate; An adherend; an adhesive layer formed from the curable resin composition according to any one of [1] to [4] and disposed between the holding substrate and the adherend; having Laminate.

[0016] One aspect of the present invention for solving the above problems relates to a method for producing a laminate described in [6] or [7] below.

[0017] [6] A step of applying the curable resin composition according to any one of [1] to [4] to a surface of a support substrate to form an adhesive layer; a step of placing an original substrate having an adherend attached thereto at a position facing the adhesive layer of the holding substrate; a step of irradiating the original substrate with light to peel off the adherend, and holding the peeled adherend on the adhesive layer; A method for producing a laminate comprising the steps of:

[0018] [7] curing the adhesive layer of the holding substrate; The method for producing a laminate according to [6],

[0019] One aspect of the present invention for solving the above problem relates to a method for treating a laminate described in [8] below.

[0020] [8] A step of preparing a laminate according to [5]; a step of irradiating the adhesive layer of the laminate with light through the holding substrate to peel off the adherend from the holding substrate; having Methods for processing laminates. [Effects of the Invention]

[0021] According to the present invention, there are provided a curable resin composition that, when an adhesive layer is formed, has high transfer accuracy of an adherend transferred from another substrate, a laminate formed using the curable resin composition, and a manufacturing method and processing method for the laminate. [Brief explanation of the drawings]

[0022] [Figure 1] Fig. 1A is a schematic diagram showing a process of transferring an adherend from an original substrate to a holding substrate by irradiating light to alter and decompose the resin holding the adherend, and Fig. 1B is a schematic diagram showing a process of capturing the adherend peeled from the original substrate with an adhesive layer applied to the surface of the holding substrate to obtain a laminate including an adhesive layer to which multiple adherends are bonded. [Figure 2]Fig. 2A is a schematic diagram showing a process of peeling an adherend from an adhesive layer by irradiation with light (or laser) and transferring the adherend from the holding substrate to another substrate, and Fig. 2B is a schematic diagram showing a process of catching the adherend peeled from the holding substrate with an adhesive layer applied to the surface of another substrate to obtain an adhesive layer bonding multiple adherends. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In this specification, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted. Furthermore, unless otherwise specified, only one type of the exemplified compounds, functional groups, or structures may be used, or multiple types may be used in combination.

[0024] In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic, and "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and means one or both of them.

[0025] 1. Curable resin composition The curable resin composition according to the present embodiment relates to a curable resin composition for forming an adhesive layer on a holding substrate that holds an adherend that has been peeled off from an original substrate by irradiating the original substrate with light.

[0026] Further, the curable resin composition according to this embodiment is (A) an unsaturated group-containing polymerizable resin (hereinafter also referred to simply as "component (A)"); (B) a solvent (hereinafter also referred to simply as "component (B)"); The component (A) satisfies the following two requirements: (Requirement 1) A solution of the component (A) is applied to a substrate and heat-treated at 100° C. for 5 minutes to obtain a dry film having a storage modulus of 200 kPa or less. (Requirement 2) The solution of component (A) is applied to a substrate so that the film thickness after curing is 1.0 μm, and the solution is heat-treated at 100°C for 5 minutes, followed by heat-treatment at 230°C for 30 minutes to cure the film, which has an absorbance of 0.50 or more for light with a wavelength of 266 nm.

[0027] Each component will be described in detail below.

[0028] 1-1.(A) Polymerizable resin containing unsaturated groups As described above, the component (A) according to this embodiment is not particularly limited as long as it is an unsaturated group-containing polymerizable resin that satisfies the above (Requirement 1) and (Requirement 2).

[0029] (Requirement 1) specifies that the storage modulus of the dried film must be sufficiently low. An adhesive layer using such component (A) is prevented from elastically deforming when catching an adherend that has peeled off from the original substrate, and the stress applied to the adhesive layer is easily lost as thermal energy, making it easier to prevent a decrease in the transfer accuracy of the adherend due to the adherend bouncing back, etc.

[0030] From the viewpoint of easily achieving the above-mentioned effects, the upper limit of the storage modulus of the dry film is preferably 120 kPa or less, more preferably 50.0 kPa or less, and even more preferably 5.00 kPa or less. Furthermore, from the viewpoint of suppressing the fluidity of the adhesive layer and making it difficult for the adherend to shift position after being caught, the lower limit of the storage modulus of the dry film is preferably 0.01 kPa or more, and more preferably 0.10 kPa or more.

[0031] The storage modulus of the dried film is measured using the following procedure. The solution of component (A) was applied to a glass substrate (#1737) using a spin coater to a thickness of 30.0 μm after drying, and then heated at 100°C for 5 minutes using a hot plate to produce a dried film. The dried film on the glass substrate was then collected to prepare a sample for viscoelasticity evaluation. The storage modulus was measured at a frequency of 0.909 Hz using a modular compact rheometer (MCR302) (Anton Paar Japan Co., Ltd.). The solution of component (A) is, for example, a 50.0 wt. % PGMEA solution, but this can be adjusted appropriately depending on the solubility and viscosity of component (A).

[0032] In the same manner as above, except for changing the frequency, the storage modulus can be measured under frequency conditions other than 0.909 Hz. The frequency is not particularly limited, but the storage modulus can be measured, for example, under conditions of 3.42 Hz or 0.1 Hz. Hereinafter, in this specification, when the term "storage modulus" is used simply without indicating the frequency conditions, it refers to the storage modulus measured under the condition of 0.909 Hz.

[0033] Generally, storage modulus measured under relatively high frequency conditions is more likely to reflect microscopic mobility in resins that can respond to fast stress (e.g., bond angle fluctuation of the main chain within a molecule, local motion, rotation of side chains, etc.) because stress is applied to resins, etc. relatively quickly. On the other hand, storage modulus measured under relatively low frequency conditions is more likely to reflect slow macroscopic mobility in resins, etc. (e.g., entanglement between molecules, etc.) because stress is applied to resins, etc. relatively slowly.

[0034] As mentioned above, modes of transfer failure of the adherend include (Mode 1) misalignment due to the adherend bouncing back when catching, and (Mode 2) misalignment due to the adhesive layer flowing after catching. Of these, (Mode 1) transfer failure is thought to be affected by the properties of the adhesive layer when stress is applied to the adhesive layer in a relatively short period of time (storage modulus at high frequency). On the other hand, (Mode 2) misalignment is thought to be affected by the properties of the adhesive layer when stress is applied to the adhesive layer in a relatively long period of time (storage modulus at low frequency).

[0035] In addition, it may be necessary to adjust the catchability of the adhesive layer depending on the characteristics (size, weight, shape) of the adherend to be held, the transfer process, etc. In this case, it is possible to design a formulation for the curable resin composition so that the adhesive layer is formed through at least a step of drying the solvent and a step of photocuring. By designing the formulation in this way, it becomes possible to control the transfer accuracy of the adhesive layer by adjusting the light irradiation energy, etc., depending on the required physical properties of the adhesive layer. Even when forming an adhesive layer by photocuring, an adhesive layer with high transfer accuracy is required.

[0036] When forming an adhesive layer by photocuring, the transfer accuracy of the adherend when a dry film obtained by photocuring under certain photocuring conditions is used as the adhesive layer is thought to be more affected by the properties (storage modulus) of the dry film obtained by photocuring under the same photocuring conditions. When measuring the storage modulus of the dry film obtained by photocuring, the dry film used for measuring the storage modulus is formed in the same manner as above, except that it is photocured after the heat treatment at 100°C for 5 minutes. The photocuring conditions are, for example, an i-line irradiance of 30 mW / cm. 2 500mJ / cm 2 or 1000mJ / cm 2 As described above, in this specification, when simply referring to "storage modulus" or "storage modulus of a dry film," it refers to the storage modulus measured under the condition of 0.909 Hz for a dry film that has not been photocured.

[0037] (Requirement 2) specifies the absorbance for light of a predetermined wavelength, and by setting this absorbance, light at or near this wavelength is easily absorbed. Therefore, such component (A) is easily altered or decomposed by light irradiation, which reduces the adhesive strength of the adhesive layer using this component, making it easier for the adherend to be transferred to another substrate.

[0038] From the viewpoint of easily achieving the above-mentioned effects, the lower limit of the absorbance is preferably 0.90 or more, more preferably 1.00 or more. In addition, from the viewpoint that the introduction of a large amount of aromatic skeletons with high absorbance increases the storage modulus of the dry film and causes rebound when caught, the upper limit of the absorbance is preferably 8.00 or less.

[0039] In this specification, the absorbance is a value measured as follows: The solution of component (A) is applied to a quartz glass substrate using a spin coater so that the dried film thickness is 1.0 μm, and then heated on a hot plate at 100°C for 5 minutes to produce a dried film. The film is then heated at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured film. The absorbance is the absorbance of the cured film-coated substrate 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 this can be adjusted appropriately depending on the solubility and viscosity of component (A).

[0040] The component (A) is not particularly limited as long as it is a resin that satisfies (Requirement 1) and (Requirement 2).

[0041] For example, by introducing an alkyl group having a linear or branched structure or a chain structure including an alkylene oxide structure into the main chain and / or side chain of component (A), it is possible to easily adjust the storage modulus of component (A) to fall within the above range.

[0042] Furthermore, by introducing an aromatic moiety into the main chain and / or side chain of component (A), it is possible to easily adjust the absorbance of light with a wavelength of 266 nm to fall within the above range. The aromatic moiety is preferably a biphenyl skeleton or a condensed polycyclic aromatic skeleton.

[0043] Specifically, component (A) is The unsaturated group-containing polymerizable resin preferably contains a structural unit derived from a diol compound having an aromatic hydrocarbon group and a structural unit derived from a diol compound (a-2) represented by the following general formula (2) (hereinafter, also simply referred to as "diol compound (a-2)"): It is more preferable that the unsaturated group-containing polymerizable resin contains a structural unit derived from a diol compound (a-1) represented by the following general formula (1) (hereinafter, also simply referred to as "diol compound (a-1)") and a structural unit derived from a diol compound (a-2): More preferably, the unsaturated group-containing polymerizable resin is obtained by reacting a resin obtained by reacting a diol compound (a-1), a diol compound (a-2), and a tetrabasic acid or a dianhydride thereof with an oxirane compound (a-3).

[0044] [ka]

[0045] [ka]

[0046] In general formulas (1) and (2), Ar independently represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R1 independently represents an alkylene group having 2 to 10 carbon atoms. l and m independently represent numbers from 0 to 3. R2 independently represents a hydrogen atom or a substituent represented by the following general formula (3), (4), or (5). However, when the oxirane compound (a-3) does not have a polymerizable unsaturated group, at least one R2 is a substituent represented by the following general formula (3), (4), or (5). X is independently -C(=O)-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (6): n is independently a number from 1 to 10.

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] In general formulas (3), (4), and (5), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R5 is independently a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates the bonding site to general formula (1).

[0051] [ka]

[0052] In general formula (6), * indicates the bonding site to general formula (1).

[0053] 1-1-1. (A) Method for synthesizing unsaturated group-containing polymerizable resin Below, an example of a method for synthesizing an unsaturated group-containing polymerizable resin obtained by reacting a resin obtained by reacting a diol compound (a-1), a diol compound (a-2), and a tetrabasic acid or a dianhydride thereof as component (A) with an oxirane compound (a-3) is shown, but the synthesis method is not limited to the following.

[0054] The unsaturated group-containing polymerizable resin can be synthesized by the following steps. (Step 1) Step of synthesizing diol compound (a-1) (Step 2) A step of reacting the diol compound (a-1), the diol compound (a-2), and a tetrabasic acid or a dianhydride thereof to obtain an intermediate product (a-4). (Step 3) A step of reacting the intermediate product (a-4) with an oxirane compound (a-3)

[0055] Of the above (Step 1) to (Step 3), only one of the steps may be performed, or none of the steps may be performed. For example, (Step 1) may be omitted to prepare a commercially available diol compound (a-1), or only (Step 3) may be performed to prepare a commercially available intermediate product (a-4).

[0056] 1-1-2. (Step 1) Step of synthesizing diol compound (a-1) The diol compound (a-1) represented by the general formula (1) can be synthesized by the following method.

[0057] First, an epoxy compound (a-0) (hereinafter simply referred to as "epoxy compound (a-0)") having a skeleton containing two or more aromatic hydrocarbon groups and which may have several alkylene oxide-modified groups in one molecule, represented by the following general formula (8), is prepared.

[0058] [ka]

[0059] In general formula (8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Ar is preferably a phenylene group, which is an aryl group having 6 carbon atoms, or a naphthylene group, which is an aryl group having 10 carbon atoms.

[0060] R1 is independently an alkylene group having 2 to 4 carbon atoms.

[0061] l is independently a number from 0 to 3.

[0062] X is independently -C(=O)-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (6): X is preferably a single bond or a group represented by general formula (6), and more preferably a group represented by general formula (6) from the viewpoint of increasing the adhesive strength to the adherend.

[0063] [ka]

[0064] In general formula (6), * indicates the bonding site to general formula (8).

[0065] Then, the epoxy compound (a-0) is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (9), and a (meth)acrylic acid derivative represented by the following general formula (10) to obtain the diol compound (a-1) represented by the general formula (1), which is an epoxy (meth)acrylate.

[0066] [ka]

[0067] [ka]

[0068] In general formulas (9) and (10), R3 is a hydrogen atom or a methyl group, R4 is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R5 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.

[0069] The reaction of the epoxy compound (a-0) with (meth)acrylic acid or a derivative thereof can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 discloses that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. Note that the epoxy compound (a-0) represented by general formula (8) used as a raw material may be partially oligomerized, resulting in the production of a diol compound (a-1) in which m is 1 to 3. In this specification, m of the diol compound (a-1) is the average value of these values.

[0070] 1-1-3. (Step 2) A step of reacting the diol compound (a-1), the diol compound (a-2), and a tetrabasic acid or a dianhydride thereof to obtain an intermediate product (a-4). Examples of the diol compound (a-2) represented by general formula (2) include alkanediols such as 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol, (poly)ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol, (poly)propylene glycols such as tripropylene glycol and tetrapropylene glycol, and (poly)butylene glycol. Of these, (poly)ethylene glycol and (poly)propylene glycol are preferred, and (poly)ethylene glycol is more preferred, from the viewpoint of improving the ability of the dried film (adhesive layer) of the curable resin composition to catch an adherend.

[0071] The larger the number n in the diol compound (a-2), the more the ability of the dried film (adhesive layer) of the curable resin composition to catch an adherend can be improved, while the smaller the number n, the more the transferability of the adherend and the adhesive strength and solvent resistance of the cured product can be improved. A compound with a number n appropriate for the desired properties can be used, and for example, n is preferably 1 to 6, and more preferably 1 to 4.

[0072] In the unsaturated group-containing polymerizable resin, the molar ratio of diol compound (a-1) to diol compound (a-2) [(a-2) / (a-1)] is preferably 1.0 to 8.0. By setting the molar ratio to 1.0 or more, the diol compound (a-2) increases the flexibility of the dried film (adhesive layer) of the curable resin composition, lowering the storage modulus of the dried film of component (A), and facilitating improved adhesion to the adherend. By setting the molar ratio to 8.0 or less, it is possible to suppress a decrease in the absorbance of component (A), a decrease in transferability to the adherend, and a decrease in the adhesive strength and solvent resistance of the cured product, which are caused by an excess of structural units derived from diol compound (a-2). [(a-2) / (a-1)] is more preferably 1.0 to 5.0, and even more preferably 1.5 to 4.5.

[0073] Examples of the tetrabasic acid (c) include a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, and acid dianhydrides thereof. It is preferable to use the dianhydrides of these tetrabasic acids (c).

[0074] Examples of the chain hydrocarbon tetracarboxylic acid include 1,2,3,4-butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and these chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0075] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, as well as these alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0076] Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0077] Among these, the tetracarboxylic acids are preferably 1,2,3,4-butanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid, and more preferably 1,2,3,4-butanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and diphenylethertetracarboxylic acid. These tetracarboxylic acids can be selected depending on the performance required of the unsaturated group-containing polymerizable resin. For example, from the viewpoint of improving laser processability, aromatic hydrocarbon tetracarboxylic acids are preferred, and 3,3',4,4'-biphenyltetracarboxylic acid is more preferred. From the viewpoint of improving catchability, chain hydrocarbon tetracarboxylic acids are preferred, and 1,2,3,4-butanetetracarboxylic acid is more preferred.

[0078] Alternatively, instead of the tetracarboxylic acid or its dianhydride, a bis(trimellitic anhydride) aryl ester can be used. The bis(trimellitic anhydride) aryl ester is a compound produced by the method described in WO 2010 / 074065, and structurally is an acid dianhydride formed by ester bonding between two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, or terphenyldiol) and the carboxyl groups of two molecules of trimellitic anhydride.

[0079] In this case, a dibasic acid or tribasic acid (b) may or may not be used in combination. Examples of the dibasic acid or tribasic acid (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides thereof. It is preferable to use acid monoanhydrides as these dibasic acids or tribasic acids (b).

[0080] Examples of the above-mentioned chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0081] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0082] Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0083] Of these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid, and more preferably succinic acid, itaconic acid, or tetrahydrophthalic acid.

[0084] When a dibasic acid or a tribasic acid is used in combination, it is preferable to react the diol compound (a-1), the diol compound (a-2), the dibasic acid or tribasic acid or its monoanhydride (b), and the tetrabasic acid or its dianhydride (c) so that the molar ratio of ((a-1)+(a-2)):(b):(c) is 1.0:0.01-1.0:0.2-1.0, so that the terminals of the compounds become carboxy groups.

[0085] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them so that the molar ratio [[(b) / 2 + (c)] / [(a-1) + (a-2)]] of the amount of acid component [(b) / 2 + (c)] to the total amount of diol compounds (a-1) and (a-2) is greater than 0.5 and less than 1.0. When this molar ratio is 1.0 or less, the terminals of the unsaturated group-containing 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 stability of the curable resin composition over time. Furthermore, when this molar ratio is greater than 0.5, an increase in the amount of unreacted components remaining in diol compound (a-1) is suppressed, improving the stability of the curable resin composition over time. The molar ratio of each component can be arbitrarily changed within the above-mentioned ranges to adjust the acid value and molecular weight of component (A).

[0086] The reaction method of the diol compound (a-1), the diol compound (a-2) with the tetrabasic acid (and dibasic acid or tribasic acid) or its anhydride is not particularly limited, and known methods can be used. For example, JP-A-9-325494 describes a method of reacting an epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C. Under these conditions, the diol compound (a-2) can also be reacted simultaneously.

[0087] In this manner, the diol compound (a-1), the diol compound (a-2) and the tetrabasic acid are reacted to obtain the intermediate product (a-4).

[0088] 1-1-4. (Step 3) A step of reacting the intermediate product (a-4) with an oxirane compound (a-3) By reacting the intermediate product (a-4) with the oxirane compound (a-3), the ability of the dried film (adhesive layer) of the curable resin composition to catch an adherend can be more sufficiently improved.

[0089] The oxirane compound (a-3) may be a compound having a polymerizable unsaturated group, or may be a compound not having a polymerizable unsaturated group. If the oxirane compound (a-3) is a compound having a polymerizable unsaturated group, the crosslink density of the cured product can be improved, and the adhesiveness and solvent resistance of the cured product can be enhanced.

[0090] Examples of the oxirane compound (a-3) to be reacted with the intermediate product (a-4) include 1,2-butylene oxide, 1,2-epoxyheptane, 1,2-epoxytetradecane, 1,2-epoxyoctadecane, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

[0091] When forming an adhesive layer by photocuring, it is preferable that even if the light source used to photocur the adhesive layer deteriorates, causing fluctuations in the light irradiation energy, the physical properties of the adhesive layer fluctuate little, and elements can be transferred stably and with high precision (a wide irradiation dose margin for transfer accuracy). From the viewpoint of widening the irradiation dose margin for transfer accuracy, oxirane compounds that do not contain polymerizable unsaturated groups are preferred, and 1,2-epoxytetradecane and lauryl glycidyl ether are more preferred. The reason why such compounds have a wide irradiation dose margin is not necessarily clear, but is thought to be as follows: Because they do not contain polymerizable unsaturated groups, the reaction rate of the photocrosslinking reaction does not change excessively even if the light irradiation energy changes significantly, and flexibility can be maintained.

[0092] When intermediate product (a-4) does not have a substituent group represented by any one of general formulas (3), (4), and (5) as R2, it is preferable to use a compound having a polymerizable unsaturated group, such as glycidyl methacrylate or 4-hydroxybutyl acrylate glycidyl ether, as oxirane compound (a-3). When intermediate product (a-4) has a substituent group represented by any one of general formulas (3), (4), and (5), it is possible to use a compound having a polymerizable unsaturated group, or a compound not having a polymerizable unsaturated group, as oxirane compound (a-3).

[0093] When the oxirane compound (a-3) is a compound having a polymerizable unsaturated group, the crosslink density of the cured product can be improved, and the adhesiveness and solvent resistance of the cured product can be enhanced. For example, the oxirane compound (a-3) having a polymerizable unsaturated group may include a compound represented by the following general formula (7):

[0094] [ka]

[0095] In general formula (7), R6 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a straight or branched chain; R7 represents a hydrogen atom or a methyl group; and q represents a number of 0 to 3.

[0096] In the compound represented by general formula (7), q is preferably a number of 1 to 3. When the compound represented by general formula (7) has an alkylene oxide group, the ability of the cured product to catch an adherend can be further improved.

[0097] In the unsaturated group-containing polymerizable resin, the ratio of the number of moles of the oxirane compound (a-3) to the total number of moles of the diol compound (a-1) and the diol compound (a-2) [(a-3) / [(a-1)+(a-2)]] is preferably 0.3 to 1.6, more preferably 1.0 to 1.6. By setting this molar ratio to 0.3 or more, the effect of improving the catching ability by the oxirane compound (a-3) can be more fully exhibited. By setting this molar ratio to 1.0 or more, the effect of improving the catching ability can be more fully exhibited. By setting this molar ratio to 1.6 or less, a decrease in the solvent resistance of the cured product due to an excess of structural units derived from the oxirane compound (a-3) can be suppressed.

[0098] The reaction method of the intermediate product (a-4) and the oxirane compound (a-3) is not particularly limited, and known methods for the addition reaction of carboxylic acids and epoxy compounds can be used. Also, as described in the aforementioned Japanese Patent Laid-Open Publication No. 9-325494, a method for producing an epoxy (meth)acrylate compound by reacting an epoxy compound with (meth)acrylic acid, such as reacting a bisphenol fluorene epoxy resin with acrylic acid at 100°C using tetraethylammonium bromide or the like as a catalyst, can be used as a reference. The reaction temperature during the synthesis of component (A) is preferably in the range of 40°C to 120°C, more preferably 60°C to 110°C.

[0099] The reaction of the intermediate product (a-4) with the oxirane compound (a-3) is preferably carried out using a catalyst. JP-A-9-325494 discloses catalysts for use in the reaction of an epoxy group with a carboxy group, such as ammonium salts (e.g., tetraethylammonium bromide and triethylbenzylammonium chloride), and phosphines (e.g., triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine).

[0100] The reaction of the diol compound (a-1), the diol compound (a-2) with a tetrabasic acid (and a dibasic acid or a tribasic acid) or an anhydride thereof, and the subsequent reaction of the intermediate product (a-4) with the oxirane compound (a-3) are usually carried out in a solvent.

[0101] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions, such as the solvent and catalyst used, are not particularly limited, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0102] The unsaturated group-containing polymerizable resin thus obtained, when cured, has both high laser releasability due to the diol compound (a-1) and high catching properties due to the diol compound (a-2) and the oxirane compound (a-3).

[0103] 1-1-5. Other characteristics of component (A) The weight-average molecular weight (Mw) of the unsaturated group-containing polymerizable resin, measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) in terms of polystyrene, 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 can improve the adhesion between the adhesive layer and the adherend. Furthermore, a weight-average molecular weight (Mw) of 40,000 or less can easily adjust the solution viscosity of the curable resin composition to a range suitable for application, facilitating application to the surface of a support substrate. Furthermore, a weight-average molecular weight (Mw) of 40,000 or less can improve the fluidity of the adhesive layer after prebaking, further enhancing the adhesive layer's ability to catch the adherend. The weight-average molecular weight of the above-mentioned component (A) is a value measured as follows. The components to be measured are measured using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight average molecular weight (Mw) is calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0104] The acid value of the unsaturated group-containing polymerizable resin is preferably 20 mgKOH / g to 200 mgKOH / g, and more preferably 25 mgKOH / g to 200 mgKOH / g. An acid value of 20 mgKOH / g or higher reduces the likelihood of residue remaining during alkaline development. An acid value of 200 mgKOH / g or lower prevents the alkaline developer from penetrating too quickly, reducing peeling. An acid value of 20 mgKOH / g or higher improves the strength of the adhesive layer through a crosslinking reaction with component (D) and reduces residue upon light irradiation. The acid value can be determined by titration with a 1 / 10 N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0105] The content of component (A) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, based on the total mass of solids. When peelability upon light irradiation is important, it is even more preferably 25% to 80% by mass, and most preferably 30% to 75% by mass. When the content of component (A) is 10% by mass or more, the adhesive layer has high adhesion to the support substrate, 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 substrate and the adherend. When the content is 90% by mass or less, the fluidity of the adhesive layer is not too high, making it less likely for the adherend to be misaligned when transferred.

[0106] 1-2.(B) Solvent The component (B) dissolves or disperses each component contained in the curable resin composition, and improves the applicability of the curable resin composition to a supporting substrate.

[0107] Examples of component (B) 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, propylene glycol monobutyl ... Examples of suitable solvents include 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 solvents, the curable resin composition can be made into a uniform solution. Of these, component (B) preferably contains propylene glycol monomethyl ether acetate.

[0108] The content of component (B) varies depending on the target viscosity of the curable resin composition, but is preferably 10% by mass to 90% by mass, and more preferably 25% by mass to 90% by mass, based on the total mass of the curable resin composition. By setting the content in this range, it becomes easier to impart appropriate coating suitability.

[0109] 1-3.(C) Polymerizable compound having at least two unsaturated bonds The curable resin composition according to this embodiment preferably contains (C) a polymerizable compound having at least two unsaturated bonds (hereinafter also referred to simply as "component (C)"). Component (C) improves the flatness of the dried film obtained by heat-treating the curable resin composition and reduces the hardness of the dried film (adhesive layer), making it less likely to be misaligned when transferred to an adherend.

[0110] Component (C) may have at least two polymerizable unsaturated groups capable of reacting (polymerizing) with the polymerizable unsaturated groups of component (A). The polymerizable unsaturated groups are preferably the same functional groups as the polymerizable unsaturated groups of component (A). Specifically, the polymerizable unsaturated groups are preferably (meth)acryloyl groups. Component (C) may be a monomer, oligomer, or polymer, but is preferably a monomer or oligomer.

[0111] Examples of component (C) 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, 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 dipentaerythritol 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; Epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; and Compounds having an ethylenic double bond include dendritic polymers having a (meth)acrylic group.

[0112] Component (C) preferably has two or more (meth)acryloyl groups, and more preferably three or more (meth)acryloyl groups. When component (C) has two or more (meth)acryloyl groups, the crosslink density increases during thermal curing, and the solvent resistance of the adhesive layer improves.

[0113] Component (C) preferably has an acrylic equivalent of 50 g / eq to 1000 g / eq, more preferably 100 g / eq to 1000 g / eq, and even more preferably 200 g / eq to 1000 g / eq. When component (C) has an acrylic equivalent of 50 g / eq or more, the crosslink density after light irradiation of the adhesive layer is not excessively increased, and the adhesive layer's ability to catch the adherend can be further improved. Furthermore, when component (C) has an acrylic equivalent of 100 g / eq or less, the dried film (adhesive layer) is sufficiently cured by light irradiation, making it less likely to misalign when transferred to the adherend.

[0114] The viscosity of component (C) at 23°C is preferably 2000 mPa·s or less, more preferably 1500 mPa·s or less, and even more preferably 1000 mPa·s or less. When the viscosity of component (C) is 2000 mPa·s or less, the fluidity of the resulting adhesive layer is improved, and the adhesive layer's ability to catch the adherend can be further enhanced. In this specification, the viscosity of component (C) at 23°C can be a value measured using a BF type viscometer (B type viscometer).

[0115] From the viewpoint of further reducing the viscosity, the component (C) is preferably an alkylene oxide-modified or lactone-modified compound.

[0116] On the other hand, when it is desired to easily increase the Martens hardness of the cured film (adhesive layer), it is preferable to use a compound that is not modified with an alkylene oxide or a lactone as component (C).

[0117] The alkylene oxide modified product is preferably a compound having an alkylene oxide group having 2 to 6 carbon atoms, more preferably a compound having an alkylene oxide group having 2 to 4 carbon atoms, and even more preferably a compound having an alkylene oxide group having 2 to 3 carbon atoms.

[0118] The lactone-modified product has a structure in which lactone having 2 to 6 carbon atoms is ring-opened (-C(=O)-(CH2) k -O-, where k is one less than the number of carbon atoms in the lactone), more preferably a compound having a ring-opened structure of a lactone having 4 to 6 carbon atoms, and even more preferably a compound having a ring-opened structure of a lactone having 6 carbon atoms.

[0119] The structure in which the alkylene oxide group or lactone is ring-opened may exist alone in the molecule, or 2 to 30 of the alkylene oxide groups or lactones may be consecutive, but it is preferable that the structure exists alone or that two of the alkylene oxide groups or lactones are consecutive.

[0120] Preferably, the molecule contains 5 to 100, more preferably 15 to 80, and even more preferably 25 to 50, alkylene oxide or lactone ring-opened structures. When five or more such ring-opened structures are contained in the molecule, the exposure dose margin for transfer accuracy of the adherend can be expanded when an adhesive layer is formed. Furthermore, when 15 or more such ring-opened structures are contained in the molecule, the adhesive layer is more likely to have improved catchability of the adherend, and the exposure dose margin can be further expanded.

[0121] The modified product can be, for example, a compound represented by the following general formula (13).

[0122] [ka]

[0123] In general formula (13), V independently represents an alkylene oxide group or a group having a structure in which a lactone is ring-opened. a to e independently represent integers of 0 to 6, provided that at least one of a to e is an integer of 1 to 6. a to e are preferably 1 or 2. R8 to R12 independently represent preferably a (meth)acryloyl group or a hydroxy group, provided that at least two of R8 to R12 are (meth)acryloyl groups. R8 to R12 are preferably all (meth)acryloyl groups. W represents a group selected from the group consisting of substituted or unsubstituted monovalent to tetravalent hydrocarbon groups, -O-, and -S-, preferably a substituted or unsubstituted divalent hydrocarbon group, -O-, or -S-, and more preferably -O-. X represents a group selected from the group consisting of a single bond, a substituted or unsubstituted divalent hydrocarbon group, -O-, and -S-. r independently represents 0 or 1, preferably 0. s is an integer of 1 to 4, the same as the valence of W, and is preferably 2.

[0124] Examples of the modified product represented by general formula (13) include ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol hexacaprolactone hexaacrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide-modified triacrylate, and trimethylolpropane ethylene oxide-modified triacrylate (all manufactured by Toagosei Co., Ltd.), A-TMPT-9EO (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0125] Examples of the modified products other than the compound represented by general formula (13) include bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified di- and triacrylate, diglycerin ethylene oxide-modified acrylate (all manufactured by Toagosei Co., Ltd.), ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and alkylene oxide-modified hexa(meth)acrylate of phosphazene.

[0126] The content of component (C) is preferably 5 to 1,000 parts by mass, more preferably 10 to 600 parts by mass, and even more preferably 20 to 300 parts by mass, relative to 100 parts by mass of the total mass of component (A). When the content of component (C) is 5 parts by mass or more, the fluidity of the curable resin composition is increased, and the flatness of the dried film (adhesive layer) after application is improved. Furthermore, when the content is 1,000 parts by mass or less, the content of component (A) is sufficient, resulting in sufficient light absorption of the dried film (adhesive layer), making it easy to peel when irradiated with light.

[0127] 1-4.(D) Epoxy compounds having at least two epoxy groups The curable resin composition according to this embodiment preferably contains (D) an epoxy compound having at least two epoxy groups (hereinafter, also referred to simply as "component (D)"). In the dried film, component (D) forms little or no crosslinking structure, thereby appropriately plasticizing the dried film and reducing the storage modulus of the dried film, facilitating improved transfer accuracy to the adherend. Furthermore, since the contents of components (A) and (B) in the curable resin composition can be adjusted so as not to be too high in the dried film, the content of unsaturated groups can be appropriately adjusted, preventing excessive sensitivity during photocuring and facilitating a wider exposure dose margin for transfer accuracy. Furthermore, in the cured film, the strength (crosslink density) of the adhesive layer is increased by reaction with component (A), reducing residues during peeling by light irradiation.

[0128] Examples of component (D) include bisphenol A type epoxy compounds (e.g., jER 828, "jER" is a registered trademark of the company; manufactured by 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, jER YX4000H, manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols not containing an aromatic ring (e.g., Epotote ZX-1542 ("Epotohto" is a registered trademark of the company; manufactured by Nippon Steel Chemical & Material Co., Ltd.) and Showfree CDMDG (manufactured by Resonac Co., Ltd.), glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., celloxide), 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups, such as HiREM-1 manufactured by Shikoku Chemical Industry Co., Ltd., multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton. These compounds may be used alone or in combination.

[0129] Among these, from the viewpoint of easily improving transfer accuracy and easily widening the exposure dose margin for transfer accuracy, a structure that does not contain a structure in which multiple aromatic rings are directly linked to each other (for example, a biphenyl or triphenyl structure, etc.) is preferred, and a structure that does not contain an aromatic ring is more preferred. Furthermore, from the viewpoint of further increasing the light absorption ability of the adhesive to make it easier to peel the adherend by laser irradiation and also improving the patterning ability of the curable resin composition during photocuring, a structure that contains an aromatic ring is preferred, and a structure that contains a structure in which multiple aromatic rings are directly linked to each other (for example, a biphenyl or triphenyl structure, etc.) is more preferred.

[0130] The viscosity of component (D) at 23°C is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, even more preferably 250 mPa·s or less, and most preferably 100 mPa·s or less. When the viscosity of component (D) is 1000 mPa·s or less, the fluidity of the resulting adhesive layer is improved, and the adhesive layer's ability to catch the adherend can be further enhanced. The lower limit of the viscosity of component (D) at 23°C can be, for example, 0.1 mPa·s. In this specification, the viscosity of component (D) at 23°C can be a value measured using a BF type viscometer (B type viscometer).

[0131] From the viewpoint of further improving the transfer accuracy and the exposure dose margin for the transfer accuracy, it is preferable that component (D) has a structure that does not contain an aromatic ring and has a viscosity at 23°C of 250 mPa s or less, and it is even more preferable that component (D) has a structure that does not contain an aromatic ring and has a viscosity at 23°C of 100 mPa s or less.

[0132] The epoxy equivalent of component (D) is preferably 100 g / eq to 300 g / eq, and more preferably 100 g / eq to 250 g / eq. When the epoxy equivalent is 100 g / eq to 300 g / eq, a cured film with good solvent resistance can be obtained. Furthermore, when the epoxy equivalent is 300 g / eq or less, sufficient alkali resistance can be maintained even when alkaline chemicals are used in a subsequent process.

[0133] The content of component (D) is preferably 3% to 60% by mass, more preferably 5% to 60% by mass, and even more preferably 10% to 50% by mass, based on the total mass of the solids. When the content of component (D) is 3% by mass or more based on the total mass of the solids, a sufficient crosslinked structure can be formed, thereby reducing residue when peeled by light irradiation. Furthermore, when the content is 60% by mass or less, the crosslink density of the adhesive layer after curing is prevented from becoming excessively high, making peeling easier when irradiated with light.

[0134] The curable resin composition may contain a curing agent and a curing accelerator in combination as needed. Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of the epoxy resin. Examples of the curing accelerator 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 the epoxy resin.

[0135] 1-5.(E) Leveling agent The leveling agent (E) (hereinafter also referred to as "component (E)") segregates on the coating film surface and controls the viscosity and surface tension of the coating film surface, thereby making it easier to increase the surface smoothness of the cured resin film.

[0136] From the viewpoint of easily improving the smoothness of the cured resin film, it is preferred to contain the component (E).

[0137] Examples of component (E) include silicone-containing compounds, (meth)acrylic polymers, fluorine-based compounds, etc. Component (E) preferably contains a silicone-containing compound and / or a fluorine-based compound from the viewpoint of easily improving smoothness. Furthermore, when a coating layer is further provided on the adhesive layer, component (E) is preferably a (meth)acrylic polymer from the viewpoint of easily suppressing cissing and the like of the coating layer.

[0138] Examples of commercially available products of component (E) include Polyflow No. 77 (manufactured by Kyoeisha Chemical Co., Ltd.) and LE-302N (manufactured by Kyoeisha Chemical Co., Ltd.).

[0139] The content of component (E) in the curable resin composition according to this embodiment is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, even more preferably 0.01% by mass to 5.0% by mass, and most preferably 0.1% by mass to 1.0% by mass, based on the total mass of the solids in the curable resin composition. By setting the content of component (E) at 0.01% by mass or more, smoothness is likely to be improved, and by setting it at 10.0% by mass or less, when a coating layer is formed on the cured resin film, cissing of the coating layer can be easily suppressed.

[0140] 1-6.(F) Photopolymerization initiator The (F) photopolymerization initiator (hereinafter also referred to as "component (F)") is a compound that generates active species such as radicals, cations, and anions upon stimulation with light, and initiates a polymerization reaction. Photopolymerization initiators that generate radicals upon irradiation with light are preferred.

[0141] When forming an adhesive layer by photocuring, the curable resin composition preferably contains component (F), which allows the curing reaction to proceed upon light irradiation and makes it easier to control the transfer accuracy of the adherend.

[0142] Examples of component (F) include: α-aminoalkylphenone compounds such as 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane; biimidazole compounds such as 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-oxadiazole, 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)-4,6-bis(trichloromethyl)-1,3,5-triazine, halomethyl-s-triazine compounds such as 2-(4-sinaphthyl)-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) (Irgacure OXE01), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-Dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol- 3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,O-Acyloxime compounds such as 2-dione = 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-O-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyloxime, and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (Irgacure OXE02); sulfur compounds such as benzil dimethyl 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; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; These include:

[0143] Examples of commercially available α-aminoalkylphenone compounds include Omnirad907 (Omnirad series manufactured by IGM Resins BV).

[0144] Examples of commercially available phosphine oxide compounds include Omnirad TPO H and Omnirad 819 (the Omnirad series is manufactured by IGM Resins BV).

[0145] The content of component (F) is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, relative to 100 parts by mass of the total mass of components (A) and (C). When the content of component (F) is 0.1 part by mass or more, photopolymerization can be promoted, increasing the photopolymerization rate. When the content of component (F) is 30 parts by mass or less, excessive sensitivity can be suppressed, making it less likely that scorching or peeling residue will occur during ablation by light irradiation. The curable resin composition preferably contains a photopolymerization initiator when controlling the transfer accuracy of the dry film (adhesive layer) onto an adherend by photocuring. However, the curable resin composition does not need to contain a photopolymerization initiator when control of transfer accuracy by photocuring is not performed or when control of transfer accuracy by a method other than photocuring is performed.

[0146] 1-7.(G) Photosensitizers (G) Photosensitizer (hereinafter also referred to as "(G) component") is a substance that plays a role in promoting photoreaction by transferring the energy obtained by absorbing light to another substance.

[0147] When forming an adhesive layer by photocuring, the curable resin composition preferably contains component (G), which accelerates the curing reaction upon irradiation with light and makes it easier to control the transfer accuracy of the adherend.

[0148] Examples of the (G) component include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, and (n-butoxy) 4-dimethylaminobenzoate. Benzophenones such as methyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0149] The content of component (G) is preferably 0.5 to 400 parts by mass, and more preferably 1 to 300 parts by mass, when the total mass of component (F) is 100 parts by mass. When the content of component (G) is 0.5 parts by mass or more, the sensitivity of component (F) can be improved, and the photopolymerization rate can be increased. Furthermore, when the content of component (G) is 400 parts by mass or less, excessive increases in sensitivity can be suppressed, making it less likely that scorching or peeling residue will occur when ablated by light irradiation.

[0150] 1-8.Other ingredients The curable resin composition may contain, as needed, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, an antifoaming agent, a surfactant, a coupling agent, and the like.

[0151] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of antifoaming agents include silicone-based, fluorine-based, and acrylic compounds. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0152] 1-9. Characteristics of curable resin compositions The curable resin composition was applied to a substrate, and after heat treatment at 100°C for 5 minutes, light with a wavelength of 365 nm was applied at 500 mJ / cm 2 The storage modulus of the dried film obtained by irradiation at a frequency of 10 Hz after exposure is preferably 200 MPa or less, more preferably 50.0 MPa or less, and even more preferably 5.00 MPa or less. After heat treatment at 100°C for 5 minutes, the film is exposed to light of 365 nm wavelength at 500 mJ / cm 2The lower limit of the storage modulus after exposure at a frequency of 10 Hz of the dried film obtained by irradiation may be, for example, 0.01 MPa.

[0153] Similarly, the curable resin composition was applied to a substrate, and after heat treatment at 100°C for 5 minutes, light with a wavelength of 365 nm was irradiated at 1000 mJ / cm 2 The storage modulus of the dried film obtained by irradiation at a frequency of 10 Hz after exposure is preferably 200 MPa or less, more preferably 50.0 MPa or less, and even more preferably 5.00 MPa or less. After heat treatment at 100°C for 5 minutes, the film is irradiated with light of 365 nm wavelength at 1000 mJ / cm 2 The lower limit of the storage modulus after exposure at a frequency of 10 Hz of the dried film obtained by irradiation may be, for example, 0.01 MPa.

[0154] The details of the method for measuring the post-exposure storage modulus of a dried film obtained from the above-mentioned curable resin composition are as follows. The curable resin composition is applied to a glass substrate "#1737" using a spin coater so that the film thickness after drying is 30.0 μm, and the dried film is pre-baked using a hot plate at 100°C for 5 minutes to produce a dried film. The dried film is collected from the glass substrate, and the collected sample for evaluating the post-exposure storage modulus is measured using a modular compact rheometer "MCR302" (Anton Paar Japan Co., Ltd.) while irradiating the sample with light of 365 nm wavelength at 23°C under an air atmosphere at a frequency of 10 Hz, and the storage modulus of the sample is measured at 500 mJ / cm. 2 or 1000mJ / cm 2 The storage modulus after exposure when the integrated exposure amount reaches 100% is taken as the measured value.

[0155] As described above, the storage modulus at a relatively high frequency, such as 10 Hz, is thought to affect misalignment due to rebound of the adherend during (mode 1) catching. If the storage modulus at 10 Hz of the dried film obtained by heating and exposing the curable resin composition is 200 MPa or less, transfer defects in (mode 1) are likely to be suppressed. Furthermore, if the storage modulus at 10 Hz of the dried film obtained by heating and exposing the curable resin composition is 0.01 MPa or more, the fluidity of the adhesive layer is suppressed, making it less likely for the adherend to misalign after catching.

[0156] In addition, the curable resin composition was applied to a substrate, and after heat treatment at 100°C for 5 minutes, light with a wavelength of 365 nm was irradiated at 500 mJ / cm 2 The dried film obtained by irradiation and the curable resin composition were applied to a substrate, and after heat treatment at 100°C for 5 minutes, light with a wavelength of 365 nm was applied at 1000 mJ / cm 2 The post-exposure storage modulus of the dried film obtained by irradiation at a frequency of 10 Hz is preferably 200 MPa or less, more preferably 50.0 MPa or less, and even more preferably 5.00 MPa or less. 2 Storage modulus after exposure and 1000mJ / cm 2 The lower limit of the storage modulus after exposure may be, for example, 0.01 MPa for both.

[0157] The irradiation dose was 500 mJ / cm 2 Dry film prepared under the conditions of 1000mJ / cm 2 The fact that the storage moduli after exposure at a frequency of 10 Hz for the dried films prepared under these conditions were both 200 MPa or less indicates that transfer defects are easily suppressed within a certain range of exposure dose, and it can be said that the exposure dose margin for the transfer accuracy of the obtained dried films is good.

[0158] For example, by introducing an alkyl group having a linear or branched structure or a chain structure including an alkylene oxide structure into the main chain and / or side chain of component (A), it is possible to easily adjust the storage modulus of component (A) to fall within the above range.

[0159] [Preparation method] The curable resin composition can be prepared by mixing the above components.

[0160] [How to use] The curable resin composition can be used by being applied to a required portion of the surface of a support substrate, or can be used after undergoing a process of forming a required pattern by photolithography.

[0161] 2. Laminate and manufacturing method thereof [Holding substrate with adhesive layer] The laminate according to this embodiment preferably has a holding substrate, an adherend, and an adhesive layer formed from the above-described curable resin composition and disposed between the holding substrate and the adherend.

[0162] The method for producing the laminate according to this embodiment is not particularly limited, but may be a step of applying the curable resin composition to a surface of a support substrate to form an adhesive layer; a step of placing an original substrate having an adherend attached thereto at a position facing the adhesive layer of the holding substrate; a step of irradiating the original substrate with light to peel off the adherend, and holding the peeled adherend on the adhesive layer; It is preferred that the compound has the following structure:

[0163] The method for producing a laminate according to this embodiment further includes: curing the adhesive layer of the carrier substrate; It is more preferable that the step of curing the adhesive layer is carried out after the step of forming the adhesive layer and before the step of holding the peeled adherend to the adhesive layer. Furthermore, the curing referred to here may be caused by an external stimulus, and examples of the external stimulus include heat and / or light.

[0164] (Step of forming adhesive layer) The curable resin composition described above can be applied (coated) to the surface of a substrate and prebaked to form a dry film. After the prebaking, heating and / or light irradiation may be performed to form a dry film. For example, a curable resin composition serving as an adhesive layer composition can be applied (coated) to the surface of a holding substrate that catches and holds an adherend peeled from a transfer source substrate, prebaked, and optionally thermally cured by heating and / or photocured by light irradiation, thereby forming an adhesive layer on the surface of the holding substrate that holds the peeled adherend. By thermally curing by heating and / or photocuring by light irradiation in this manner, the storage modulus of the adhesive layer can be easily adjusted to a value appropriate for the characteristics (size, weight, shape) of the adherend to be held, the transfer process, etc.

[0165] Examples of methods for applying the curable resin composition include known methods such as solution immersion, spin coating, inkjet printing, spraying, and methods using a roller coater, land coater, slit coater, or spinner.

[0166] After applying the curable resin composition by the above application method, the solvent is dried (prebaked) to form a dry film (adhesive layer). Prebaking is performed by heating using an oven, a hot plate, etc. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 60°C to 110°C for 1 minute to 10 minutes.

[0167] The conditions for light irradiation after the pre-baking may be, for example, as follows. Examples of light used for light irradiation include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. The wavelength of light used for light irradiation may be 200 nm to 500 nm. The light irradiation dose for forming a dry film may be 25 mJ / cm. 2 ~3000mJ / cm 2 In addition, in consideration of variations in the amount of irradiation in light irradiation, the irradiation amount margin is preferably 100 mJ / cm 2 It is preferable that this is equal to or greater than this.

[0168] The conditions for heating after the pre-baking may be, for example, as follows: Baking is carried out by heating using an oven, a hot plate, etc. The heating temperature and heating time for baking are appropriately selected depending on the solvent used, and baking is carried out, for example, at a temperature of 100°C to 150°C for 1 minute to 10 minutes.

[0169] The thickness of the dry film (adhesive layer) can be selected arbitrarily. The thickness of the adhesive layer is preferably 1 μm to 50 μm, more preferably 1 μm to 30 μm, and even more preferably 1 μm to 20 μm. When the adhesive layer is 1 μm or thicker, it can have sufficient holding power to catch an adherend. Furthermore, when it is 50 μm or thinner, the adhesive layer can be sufficiently cured by light or heat curing. When the adhesive layer is 20 μm or thinner, the light irradiation energy is less likely to attenuate in the thickness direction of the adhesive layer, which facilitates increasing the accuracy when peeling off an adherend by light (or laser). Generally, the holding power of an adhesive tends to increase as the adhesive layer becomes thicker, but the adhesive layer according to this embodiment has significantly excellent catching properties, and therefore, even when the adhesive layer is 20 μm or thinner, an adhesive layer with significantly excellent catching properties can be formed.

[0170] After the pre-baking, an exposure step and a development step may be performed to pattern the adhesive layer. By patterning the adhesive layer, the adhesive layer can be formed only in the areas where the adhesive layer is required.

[0171] Examples of light used in the exposure step include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Of these, ultraviolet light (wavelength 250 nm to 400 nm) is preferred. Furthermore, in the development step, a developer suitable for alkaline development is used. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected according to the properties of the resin layer, and surfactants may be added as needed. The development temperature is preferably 20°C to 35°C, and fine images can be precisely formed using a commercially available developer or ultrasonic cleaner. After alkaline development, the film is usually washed with water. Examples of development methods that can be used include shower development, spray development, dip (immersion) development, and puddle (puddle) development.

[0172] (Step of placing the original substrate to which the adherend is attached, and step of holding the adherend on the adhesive layer) The holding substrate having the adhesive layer can hold the adherend that has been peeled off from the original substrate.

[0173] In this case, the original substrate is placed in a position where the surface to which the adherends are attached faces the adhesive layer of the holding substrate, preferably so that the surface to which the adherends are attached faces vertically upward. The original substrate has a plurality of adherends attached to its surface by a resin that decomposes or changes in quality when irradiated with light.

[0174] From the viewpoint of transferring the adherend at a higher speed, the adherend attached to the original substrate and the adhesive layer formed on the holding substrate are disposed so as to leave a gap between them. The gap is preferably 10 μm to 200 μm, and more preferably 30 μm to 100 μm.

[0175] 1A, for example, when light is irradiated onto resin 202 through original substrate 201 in this state, and resin 202 to which the adherends are attached is altered and decomposed, adherends 101 and 102 are peeled off from original substrate 201 and transferred to holding substrate 104. The transferred adherends 101 and 102 are caught by adhesive layer 103 and adhered to the holding substrate without misalignment.

[0176] In this way, for example, a laminate 100 is produced, as shown in FIG. 1B, having a holding substrate 104, adherends 101 and 102, and an adhesive layer 103 formed from the above-mentioned curable resin composition, disposed between the holding substrate 104 and the adherends 101 and 102.

[0177] Before peeling the adherends 101 and 102 from the holding substrate 104, a step of processing the laminate 100 may be included.

[0178] Examples of the above processing include thinning of adherends such as dicing and back grinding, photofabrication, stacking of semiconductor chips, mounting of various adherends, and resin sealing.

[0179] There is no particular limitation on the type of adherends 101 and 102. Examples of adherends 101 and 102 include semiconductor wafers, semiconductor chips, light-emitting elements, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers.

[0180] Furthermore, after the adherends 101 and 102 are held on the holding substrate 104 to form the laminate 100, the adhesive layer 103 may be post-baked to firmly bond the adherends 101 and 102 to the holding substrate 104. Post-baking can reduce residues that may be left behind when the adherends are subsequently peeled off by light irradiation.

[0181] The post-bake may be performed, for example, while applying pressure to the adhesive layer 103 to the adherends 101 and 102, or without applying pressure. The temperature 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. When applying pressure, the pressure is preferably 0.01 MPa to 20 MPa, and more preferably 0.03 MPa to 15 MPa. By bonding the holding substrate 104 and the adherends 101 and 102 under the above conditions, the adherends 101 and 102 are more firmly fixed to the surface of the holding substrate 104 via the adhesive layer 103.

[0182] The adhesive layer 103 may also be cured by photocuring. Photocuring prevents the adherend from becoming embedded in the adhesive layer 103, thereby improving the peelability of the adhesive layer 103 when exposed to light. Photocuring of the adhesive layer 103 can be carried out by a method of irradiating light using a high-pressure mercury lamp. 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 / cm. 2 ~3000mJ / cm 2 and preferably 50 mJ / cm 2 ~2000mJ / cm 2 When photocuring is performed, the curable resin composition preferably contains a photopolymerization initiator.

[0183] Either one of the post-baking and the light irradiation may be performed, or both may be performed, or neither may be performed.

[0184] The holding substrate 104 to which the adherends 101 and 102 are firmly bonded in this manner may be used as it is in a product as a mounting substrate.

[0185] There are no particular limitations on the shape and size of the adherends 101 and 102. For example, when the surfaces of the adherends 101 and 102 that adhere to the adhesive layer 103 are rectangular, the length of the long side of the rectangle (the length of any one side when the adherend is square) is preferably 1 μm to 500 μm, and more preferably 5 μm to 500 μm. A semiconductor element is a suitable example of the surface of the adherends 101 and 102 that adheres to the adhesive layer 103.

[0186] [Uses and processing methods of laminates] The method for treating a laminate according to this embodiment includes the steps of: a step of irradiating the adhesive layer of the laminate with light through a holding substrate to peel off the adherend from the holding substrate; and the adherend can be further transferred to another substrate.

[0187] For example, the laminate according to this embodiment can be used to transport multiple adherends held on a holding substrate. After transport, the adherends 101 and 102 may be peeled from the adhesive layer 103 by irradiation with light (or laser) as shown in FIG. 2A , and then transferred from the holding substrate 104 to another substrate 302. In this case, for example, as shown in FIG. 2B , the other substrate 302 to which the adherends 101 and 102 are transferred from the holding substrate 104 may have an adhesive layer 301 formed on the surface that catches the adherends 101 and 102 peeled from the holding substrate 104 by applying the curable resin composition, pre-baking, and optionally heating or irradiating with light. This can also improve the ability of the other substrate 302 to catch the adherends 101 and 102 when transferring them from the holding substrate 104 to the other substrate 302.

[0188] The light or laser to be irradiated is not particularly limited as long as it can separate the holding substrate 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. When the wavelength of the ultraviolet light is 10 nm or longer, the components of the adhesive layer absorb the light, causing decomposition or deterioration, thereby reducing the strength and adhesive force, and therefore the holding substrate and the adherend can be easily separated. Furthermore, when the wavelength is 400 nm or shorter, the adhesive layer in the processed portion absorbs light, thereby preventing the generation of cured film residue.

[0189] From the viewpoint of increasing the efficiency of transfer to another substrate by irradiation with this light or laser, the holding substrate preferably has optical transparency. In particular, the holding substrate more preferably transmits light (laser) with a wavelength of 10 nm to 400 nm, and even more preferably transmits light (laser) with a wavelength of 100 nm to 400 nm. Examples of the laser-transmitting substrate include glass substrates, acrylic substrates, sapphire substrates, and quartz substrates. However, for glass substrates and acrylic substrates, it is desirable to use substrates with a composition that has sufficient transmittance for the wavelength of light used (particularly a wavelength of 266 nm). Of these, sapphire substrates and quartz substrates are preferred.

[0190] Examples of the ultraviolet light source include a low mercury lamp, a high pressure mercury lamp, an extra-high pressure mercury lamp, a metal halide lamp, and a deep ultraviolet laser lamp.

[0191] Examples of the laser include solid-state lasers, liquid lasers, and gas lasers. Examples of the solid-state laser include semiconductor-pumped lasers. Examples of liquid lasers include dye lasers. Examples of gas lasers include excimer lasers. Of the above lasers, semiconductor-pumped lasers are preferred.

[0192] Examples of the semiconductor pumped laser include Nd:YAG laser, Nd:YLF laser, Nd:glass laser, Nd:YVO4 laser, Yb:YAG laser, Yb-doped fiber laser, Er:YAG laser, Tm:YAG laser, etc. Examples of excimer laser include KrF laser, XeCl laser, ArF laser, F2 laser, etc. Of the above lasers, Nd:YAG laser is preferred.

[0193] The output and cumulative light quantity of the light irradiated onto the adhesive layer vary depending on the type of light source, etc., but when the irradiated light is a laser, the output can be 0.1 mW to 200 W. The cumulative light quantity can be 1 mJ / cm. 2 ~50J / cm 2 It is preferable that the integrated light amount is 1 mJ / cm 2 If the intensity is above 50J / cm, scorching and peeling residue are less likely to occur during ablation. 2 If the ablation speed is equal to or less than this, the ablation speed can be controlled appropriately to perform appropriate processing.

[0194] It is preferable that the adhesive layer is irradiated with light (laser) from the substrate side over the entire surface of the adhesive layer, or selectively irradiated to the area where the adherend to be transferred is adhered.

[0195] The applications of the unsaturated group-containing polymerizable resin and the curable resin composition are not limited to the adhesive layer described above. For example, the unsaturated group-containing polymerizable resin and the curable resin composition can also be used as pressure-sensitive adhesives and adhesives, or as protective films and insulating films on semiconductor packages and printed circuit boards. [Example]

[0196] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0197] First, synthesis examples of the unsaturated group-containing polymerizable resin, component (A), will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0198] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place onwards. In the examples, all glass substrates used to prepare the cured film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0199] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0200] First, synthesis examples of the unsaturated group-containing polymerizable resin, component (A), will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0201] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place onwards. In the examples, all glass substrates used to prepare the cured film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0202] [Solid content concentration] The mass [W1(g)] of 1 g of the resin solution obtained in the synthesis example impregnated into a glass filter [mass: W0(g)] was calculated using the following formula from the mass [W2(g)] of component (A) after heating at 130°C for 2 hours. Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0203] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0204] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0205] The abbreviations used in the synthesis examples are as follows. BPFE: Bisphenol fluorene type epoxy resin (general formula (X1) is Ar x is a benzene ring, u is 0, epoxy resin, epoxy equivalent 250g / eq) AA: acrylic acid TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride SA: Succinic anhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride DCPMA: dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: styrene AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine jER YX4000: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation)

[0206] [ka]

[0207] [Synthesis Example 1] In a 500 mL four-neck flask equipped with a reflux condenser, BPFE (38.64 g, 0.08 mol), AA (11.14 g, 0.16 mol), TPP (0.20 g), and PGMEA (8.80 g) were charged and stirred at 100 to 105 ° C for 12 hours to obtain a reaction product. Then, PGMEA (41.22 g) was charged and adjusted to a solid content of 50 mass %, to obtain a resin solution (a-1)-1 containing a diol compound represented by general formula (1).

[0208] Next, triethylene glycol (34.97 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (90.49 g) were added to the obtained resin solution (a-1)-1 containing the diol compound, and the mixture was stirred at 115 to 120°C for 6 hours.

[0209] Next, 4-hydroxybutyl acrylate glycidyl ether (78.34 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-1. The solids concentration of the resulting resin solution was 60.1 mass%, the acid value (solids equivalent) was 43 mgKOH / g, and the Mw by GPC analysis was 6500.

[0210] [Synthesis Example 2] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (90.49 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0211] Next, 2-ethylhexyl glycidyl ether (72.89 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-2. The solids concentration of the resulting resin solution was 60.4 mass%, the acid value (solids equivalent) was 44 mgKOH / g, and the Mw by GPC analysis was 7500.

[0212] [Synthesis Example 3] A 500 mL four-neck flask equipped with a reflux condenser was charged with resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (90.49 g), and the mixture was stirred at 115 to 120 ° C for 6 hours to obtain unsaturated group-containing polymerizable resin (A)-3. The solids concentration of the resulting resin solution was 50.0 mass%, the acid value (solids equivalent) was 220 mg KOH / g, and the Mw by GPC analysis was 4000.

[0213] [Synthesis Example 4] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (23.67 g, 0.16 mol), 1,2,3,4-butanetetracarboxylic dianhydride (37.29 g, 0.19 mol), SA (4.71 g, 0.05 mol), and PGMEA (65.79 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0214] Next, 4-hydroxybutyl acrylate glycidyl ether (59.35 g, 0.30 mol) and TPP (0.78 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-4. The solids concentration of the resulting resin solution was 60.3 mass%, the acid value (solids equivalent) was 41 mgKOH / g, and the Mw by GPC analysis was 4700.

[0215] [Synthesis Example 5] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (80.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (45.53 g, 0.30 mol), 1,2,3,4-butanetetracarboxylic dianhydride (57.90 g, 0.29 mol), SA (7.31 g, 0.07 mol), and PGMEA (110.85 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0216] Next, 4-hydroxybutyl acrylate glycidyl ether (92.16 g, 0.46 mol) and TPP (1.21 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-5. The solids concentration of the resulting resin solution was 61.8 mass%, the acid value (solids equivalent) was 45 mgKOH / g, and the Mw by GPC analysis was 6000.

[0217] [Synthesis Example 6] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, tripropylene glycol (44.77 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (99.97 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0218] Next, 4-hydroxybutyl acrylate glycidyl ether (78.34 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-6. The solids concentration of the resulting resin solution was 60.5 mass%, the acid value (solids equivalent) was 41 mgKOH / g, and the Mw by GPC analysis was 6000.

[0219] [Synthesis Example 7] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, 1,8-octanediol (34.05 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (89.18 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0220] Next, 4-hydroxybutyl acrylate glycidyl ether (78.34 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-7. The solids concentration of the resulting resin solution was 61.1 mass%, the acid value (solids equivalent) was 43 mgKOH / g, and the Mw by GPC analysis was 6,800.

[0221] [Synthesis Example 8] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), BPDA (73.09 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (114.28 g) were charged and stirred at 115 to 120°C for 6 hours.

[0222] Next, 4-hydroxybutyl acrylate glycidyl ether (78.34 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-8. The solids concentration of the resulting resin solution was 59.7% by mass, the acid value (solids equivalent) was 39 mgKOH / g, and the Mw by GPC analysis was 5500.

[0223] [Synthesis Example 9] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), BPDA (73.09 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (114.28 g) were charged and stirred at 115 to 120°C for 6 hours.

[0224] Next, 2-ethylhexyl glycidyl ether (72.89 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-9. The solids concentration of the resulting resin solution was 59.2 mass%, the acid value (solids equivalent) was 39 mgKOH / g, and the Mw by GPC analysis was 5800.

[0225] [Synthesis Example 10] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), 1,2,3,4-butanetetracarboxylic dianhydride (49.22 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (90.49 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0226] Next, 1,2-epoxytetradecane (83.09 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-10. The solids concentration of the resulting resin solution was 61.5 mass%, the acid value (solids equivalent) was 42 mgKOH / g, and the Mw by GPC analysis was 6000.

[0227] [Synthesis Example 11] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), BPDA (73.09 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (114.28 g) were charged and stirred at 115 to 120°C for 6 hours.

[0228] Next, 1,2-epoxytetradecane (83.09 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-11. The solids concentration of the resulting resin solution was 60.2 mass%, the acid value (solids equivalent) was 38 mg KOH / g, and the Mw by GPC analysis was 5800.

[0229] [Synthesis Example 12] In a 500 mL four-neck flask equipped with a reflux condenser, jER YX4000 (36.00 g, 0.09 mol), AA (13.65 g, 0.19 mol), TPP (0.30 g), and PGMEA (8.80 g) were charged and stirred at 100 to 105 ° C for 12 hours to obtain a reaction product. Then, PGMEA (41.30 g) was charged and adjusted to a solids content of 50 mass%, to obtain a resin solution (a-1)-2 containing a diol compound represented by general formula (1).

[0230] Next, the resin solution (a-1)-2 (100.00 g) containing the diol compound, triethylene glycol (42.65 g, 0.28 mol), 1,2,3,4-butanetetracarboxylic dianhydride (60.03 g, 0.30 mol), SA (7.58 g, 0.08 mol), and PGMEA (110.37 g) were charged and stirred at 115 to 120°C for 6 hours.

[0231] Finally, 2-ethylhexyl glycidyl ether (63.50 g, 0.34 mol) and TPP (0.89 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-12. The solids concentration of the resulting resin solution was 58.4 mass%, the acid value (solids equivalent) was 85 mgKOH / g, and the Mw by GPC analysis was 6200.

[0232] [Synthesis Example 13] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (34.97 g, 0.23 mol), BPDA (73.09 g, 0.25 mol), SA (6.21 g, 0.06 mol), and PGMEA (114.28 g) were charged and stirred at 115 to 120°C for 6 hours.

[0233] Next, lauryl glycidyl ether (94.54 g, 0.39 mol) and TPP (1.03 g) were added to the resulting reaction mixture, and the mixture was stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)-13. The solid content of the resulting resin solution was 62.8 mass%, the acid value (solid content equivalent) was 34 mgKOH / g, and the Mw by GPC analysis was 10 It was 300.

[0234] [Synthesis Example 14] In a 500 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, triethylene glycol (11.66 g, 0.08 mol), 1,2,3,4-butanetetracarboxylic dianhydride (24.61 g, 0.12 mol), SA (3.11 g, 0.03 mol), and PGMEA (39.41 g) were charged, and the mixture was stirred at 115 to 120°C for 6 hours.

[0235] Next, 4-hydroxybutyl acrylate glycidyl ether (39.17 g, 0.20 mol) and TPP (0.51 g) were added to the resulting reaction mixture and stirred at 100 to 105°C for 10 hours to obtain unsaturated group-containing polymerizable resin (A)'-14. The solid content of the resulting resin solution was 59.1 mass%, the acid value (solid content equivalent) was 36 mgKOH / g, and the Mw by GPC analysis was 5800.

[0236] [Synthesis Example 15] A 500 mL four-neck flask equipped with a reflux condenser was charged with resin solution (a-1)-1 (100.00 g) containing the diol compound described in Synthesis Example 1, 1,2,3,4-butanetetracarboxylic dianhydride (7.69 g, 0.04 mol), and THPA (5.91 g, 0.04 mol), and the mixture was stirred at 115 to 120°C for 6 hours to obtain unsaturated group-containing polymerizable resin (A)'-15. The solids concentration of the resulting resin solution was 56.0 mass%, the acid value (solids equivalent) was 103 mg KOH / g, and the Mw by GPC analysis was 5000.

[0237] [Synthesis Example 16] PGMEA (300 g) was placed in a 1 L four-neck flask equipped with a reflux condenser. After replacing the atmosphere in the system with nitrogen, the temperature was raised to 120°C. A monomer mixture (DCPMA ( 77.1g, 0.35mol), GMA (49.8g, 0.35mol), St(31. A mixture of AIBN (10 g) dissolved in 2 g of ethanol (0.30 mol) was added from a dropping funnel for 2 hours. The mixture was added dropwise over a period of 1 hour, and then stirred at 120°C for a further 2 hours to obtain a copolymer solution.

[0238] Next, after replacing the atmosphere in the flask with air, AA (24.0 g, 95% of the glycidyl group), TDMAMP (0.8 g), and HQ (0.15 g) were added to the resulting 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 resulting polymerizable unsaturated group-containing copolymer solution and reacted at 120 °C for 4 hours to obtain unsaturated group-containing polymerizable resin (A)'-16. The solids concentration of the resin solution was 46.0 mass%, the acid value (solids equivalent) was 76 mg KOH / g, and the Mw by GPC analysis was 5300.

[0239] Each curable resin composition was prepared in the blending amounts (unit: mass %) shown in Tables 1 and 2. The blending components used in Tables 1 and 2 are as follows.

[0240] (Polymerizable resin containing unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration: 60.1% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration: 60.4% by mass) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration: 50.0% by mass) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration: 60.3% by mass) (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration: 61.8% by mass) (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration: 60.5% by mass) (A)-7: Resin solution obtained in Synthesis Example 7 (solid content concentration: 61.1% by mass) (A)-8: Resin solution obtained in Synthesis Example 8 (solid content concentration: 59.7% by mass) (A)-9: Resin solution obtained in Synthesis Example 9 (solid content concentration: 59.2% by mass) (A)-10: Resin solution obtained in Synthesis Example 10 (solid content concentration 61.5% by mass) (A)-11: Resin solution obtained in Synthesis Example 11 (solid content concentration: 60.2% by mass) (A)-12: Resin solution obtained in Synthesis Example 12 (solid content concentration: 58.4% by mass) (A)-13: Resin solution obtained in Synthesis Example 13 (solid content concentration 62.8% by mass) (A)'-14: Resin solution obtained in Synthesis Example 14 (solid content concentration: 59.1% by mass) (A)'-15: Resin solution obtained in Synthesis Example 15 (solid content concentration: 56.0% by mass) (A)'-16: Resin solution obtained in Synthesis Example 16 (solid content concentration 46.0% by mass)

[0241] (solvent) (B): Propylene glycol monomethyl ether acetate (PGMEA)

[0242] (Polymerizable compound having at least two unsaturated bonds) (C)-1: Ethoxylated trimethylolpropane triacrylate (NK Ester A-TMPT-9EO, manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent: 231 g / eq) (C)-2: A mixture of dipentaerythritol pentaacrylate and hexaacrylate Compound (DPHA, manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent 96g / eq) (C)-3: Ethoxylated pentaerythritol tetraacrylate (NK Ester ATM-35E, manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent: 474 g / eq)

[0243] (Epoxy compound having at least two epoxy groups) (D)-1: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER YX40 00, epoxy equivalent 180g / eq~192g / eq) (D)-2: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER 828, "jER" is a registered trademark of the company, epoxy equivalent 120 g / eq to 150 g / eq) (D)-3: Glycidyl polyether of trimethylolpropane (Epototo ZX-1542, manufactured by Nippon Steel Chemical & Material Co., Ltd., "Epototo" is a registered trademark of the company, epoxy equivalent 110 g / eq to 130 g / eq)

[0244] (Leveling agent) (E)-1: LE-302N (Kyoeisha Chemical Co., Ltd.) (E)-2: Polyflow No. 77 (manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow" is a registered trademark of the company)

[0245] (Photopolymerization initiator) (F): 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane ("Omnirad907" manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company)

[0246] (sensitizer) (G): Michler's ketone

[0247] [Table 1]

[0248] [Table 2]

[0249] The following evaluations were carried out on the unsaturated group-containing polymerizable resin (component (A)) synthesized in the above Synthesis Examples and the curable resin compositions shown in Tables 1 and 2. The results are shown in Tables 1 and 2 or Tables 3 and 4.

[0250] [Evaluation of storage modulus of component (A)] (Preparation of sample for evaluation of storage modulus) The unsaturated group-containing polymerizable resin (A) synthesized in the above Synthesis Example was prepared as a 50 wt % PGMEA solution and applied to a glass substrate "#1737" using a spin coater so that the film thickness after drying would be 30.0 μm. The substrate was then pre-baked on a hot plate at 100°C for 5 minutes to produce a dry film. The dry film was then collected from the glass substrate and used as a sample for evaluating the storage modulus.

[0251] (Evaluation method) The collected samples for evaluation of storage modulus were measured for storage modulus using a modular compact rheometer "MCR302" (Anton Paar Japan Co., Ltd.) at a frequency of 0.909 Hz. The measured values ​​are shown in Tables 1 and 2, and the results of evaluation according to the following criteria are shown in Tables 3 and 4. A rating of △ or higher was considered to be acceptable.

[0252] ◎: Storage modulus is 5.00 kPa or less ○: Storage modulus is greater than 5.00 kPa and less than 50.0 kPa △: Storage modulus is greater than 50.0 kPa and less than 200 kPa ×: Storage modulus is greater than 200 kPa

[0253] [Absorbance evaluation of component (A)] (Preparation of substrate for absorbance evaluation) The unsaturated group-containing polymerizable resin (A) synthesized in the above Synthesis Example was prepared as a 20 wt % PGMEA solution and applied to a quartz glass substrate using a spin coater so that the cured film had a thickness of 1.0 μm. The film was then prebaked on a hot plate at 100° C. for 5 minutes to produce a dry film. The film was then postbaked at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a cured film.

[0254] (Evaluation method) After post-baking, the absorbance of the substrate with the cured resin film at a wavelength of 266 nm was measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), and the results were evaluated according to the following criteria, as shown in Tables 3 and 4. A grade of fair or better was considered to be acceptable.

[0255] (Evaluation criteria) ◎: Absorbance is 1.00 or more ○: Absorbance is 0.80 or more and less than 1.00 △: Absorbance is 0.50 or more and less than 0.80 ×: absorbance is less than 0.50

[0256] [Laser processability (peelability) evaluation] (Preparation of substrates for evaluation of laser processability (peelability)) The adhesive layer-forming compositions shown in Tables 1 and 2 were applied to glass substrate "#1737" using a spin coater so that the film thickness after drying would be 1.0 μm, and the coating was prebaked on a hot plate at 100°C for 5 minutes to produce a coating. Next, the coating was fully cured (postbaked) at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1 to 20 and Comparative Examples 1 to 5.

[0257] (Evaluation method) After the final curing (post-baking), the cured film was irradiated with a laser (laser wavelength: 266 nm) using a flash lamp pumped Nd:YAG Q-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.). 2 The cured film was processed (removed) with a laser energy of 1000 uF, and the amount of film loss in the laser-irradiated area was measured using a non-contact three-dimensional optical interference microscope "WYKO Contour-GT" (manufactured by Bruker Japan). Evaluation was based on the laser irradiation amount required to achieve a film loss of 0.1 μm, and was based on the following criteria. A score of △ or higher was considered to be acceptable.

[0258] ◎: 150 mJ / cm 2 Below this, the film reduction amount is 0.1 μm ○: 150 mJ / cm 2 Super 200mJ / cm 2 Below this, the film reduction amount is 0.1 μm △: 200mJ / cm 2 Super 250mJ / cm 2 Below this, the film reduction amount is 0.1 μm ×:250mJ / cm 2 The amount of film reduction is 0.1 μm at more than 10 ...

[0259] [Evaluation of storage modulus after exposure] (Preparation of sample for evaluating storage modulus after exposure) The curable resin compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after drying would be 30.0 μm, and the applied film was pre-baked using a hot plate at 100°C for 5 minutes to prepare a dried film. The dried film was then collected from the glass substrate, and used as a sample for evaluating the storage modulus.

[0260] (Evaluation method) The collected samples for evaluation of storage modulus were measured using a modular compact rheometer "MCR302" (Anton Paar Japan Co., Ltd.) at a frequency of 10 Hz under an air atmosphere at 23 °C with light of 365 nm wavelength, and the storage modulus after exposure was measured at 500 mJ / cm 2 or 1000mJ / cm 2 The storage modulus after exposure was measured when the cumulative exposure amount reached 1000 times the exposure dose, and the measured values ​​are shown in Tables 1 and 2. The results of evaluation according to the following criteria are shown in Tables 3 and 4. A rating of △ or higher was considered to be acceptable.

[0261] ◎: Storage modulus after exposure is 5.00 MPa or less ○: The storage modulus after exposure is greater than 5.00 MPa and equal to or less than 50.0 MPa △: The storage modulus after exposure is greater than 50.0 MPa and less than 200 MPa ×: The storage modulus after exposure is greater than 200 MPa.

[0262] [Evaluation of the catchability of the adherend] (Preparation of substrate for evaluation of catchability) The curable resin compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after drying would be 3.0 μm, and the substrate was prebaked on a hot plate at 100°C for 5 minutes to prepare a dried film. This dried film was then heated at an i-line irradiance of 30 mW / cm. 2 500mJ / cm 2 or 1000mJ / cm 2 The glass substrate with the dried film was used as a substrate for evaluating the catch property.

[0263] (Evaluation method) A composition for a laser-peelable temporary adhesive layer having the following composition, prepared from the same materials as the compositions listed in Tables 1 and 2, was applied to a synthetic quartz glass substrate serving as a support (holding substrate), and the composition was prebaked to prepare a transfer source substrate with an adherend (μ-LED chip 30 μm × 15 μm) bonded via the resulting laser-peelable temporary adhesive layer. Next, the adherend and the dried film on the substrate for evaluating catch properties were placed facing each other, and the transfer gap between the adherend and the dried film on the substrate for evaluating catch properties was set to 50 μm.

[0264] (Composition for laser-peelable temporary adhesive layer) (A)'-15:47.6% by mass (B) :32.7% by mass (C)-1:12.3% by mass (D)-1:7.2% by mass (E)-1:0.2% by mass

[0265] The laser (laser wavelength: 266 nm) was applied to the laser peeling adhesive that fixes the adherend using a flash lamp pumped Nd:YAGQ-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.) at a rate of 50 mJ / cm. 2 The adherend was irradiated from the support side, and transferred to the exposed film on the substrate for evaluating catchability. The results were evaluated according to the following criteria: transfer was successful if there was no misalignment, and transfer was unsuccessful if there was misalignment. The results are shown in Tables 3 and 4. The irradiation dose was 500 mJ / cm. 2 The conditions are standard conditions, and the irradiation dose is 500 mJ / cm 2 If the transfer accuracy is good at an irradiation dose of 1000 mJ / cm, it can be said that the curable resin composition has high transfer accuracy of an adherend transferred from another substrate when photocured to form an adhesive layer. 2 The transfer accuracy under the conditions shown is the transfer accuracy when the irradiation amount is changed from the standard condition, and the irradiation amount is 1000 mJ / cm 2 If the transfer accuracy is good, it can be said that the irradiation margin of the transfer accuracy is good.Each evaluation was performed by transferring 20 μ-LED chips, and a score of △ or higher was considered to be pass.

[0266] (Evaluation criteria) ◎: All μ-LEDs are transferred without misalignment (transfer success rate: 100%) ○: The transfer success rate is 90% or more but less than 100% △: The transfer success rate is 80% or more but less than 90% ×: The transfer success rate is less than 80%

[0267] [Table 3]

[0268] [Table 4]

[0269] As is clear from a comparison of the Examples and Comparative Examples shown in Tables 1 to 4, it was found that by using the curable resin composition according to this embodiment, an adhesive layer can be formed that has high transfer accuracy for an adherend transferred from another substrate. Furthermore, because the absorbance of component (A) satisfies the above (Requirement 2), it was found that irradiating light onto the adhesive layer formed from the curable resin composition according to this embodiment makes it easier to transfer the adherend to yet another substrate. [Industrial Applicability]

[0270] The present invention can provide an unsaturated group-containing polymerizable resin and a curable resin composition that can be used in the production of various products. In particular, it can provide an adhesive layer that is suitable for applications in which semiconductor elements are transferred by light irradiation. [Explanation of symbols]

[0271] 100 laminate 101, 102 Adherent 103 Adhesive layer 104 Holding board 201 Original substrate 202 Resins that change and decompose when exposed to light 301 Adhesive layer 302 Substrate to which the adherend is transferred from the holding substrate

Claims

1. A curable resin composition for forming an adhesive layer on a holding substrate that holds an adherend that has been peeled off from an original substrate by irradiating the original substrate with light, the adhesive layer being used to hold the peeled adherend, the curable resin composition comprising: (A) an unsaturated group-containing polymerizable resin; (B) a solvent; Including, a solution of the component (A) is applied to a substrate and then heat-treated at 100°C for 5 minutes to produce a dried film having a storage modulus of 200 kPa or less; the solution of component (A) is applied to a substrate so that the film thickness after curing is 1.0 μm, and the resulting film is heat-treated at 100° C. for 5 minutes and then at 230° C. for 30 minutes, forming a cured film having an absorbance of 0.50 or more for light with a wavelength of 266 nm; Curable resin composition.

2. (C) a polymerizable compound having at least two unsaturated bonds, The component (C) has an acrylic equivalent of 50 g / eq to 1000 g / eq. The curable resin composition according to claim 1.

3. The weight average molecular weight of the component (A) is 1,000 to 40,000, The acid value of the component (A) is 20 mgKOH / g to 200 mgKOH / g. The curable resin composition according to claim 1.

4. (D) an epoxy compound having at least two epoxy groups; The curable resin composition according to claim 1.

5. A holding substrate; An adherend; an adhesive layer formed from the curable resin composition according to any one of claims 1 to 4 and disposed between the holding substrate and the adherend; having Laminate.

6. A step of applying the curable resin composition according to any one of claims 1 to 4 to a surface of a support substrate to form an adhesive layer; a step of placing an original substrate having an adherend attached thereto at a position facing the adhesive layer of the holding substrate; a step of irradiating the original substrate with light to peel off the adherend, and holding the peeled adherend on the adhesive layer; A method for producing a laminate comprising the steps of:

7. curing the adhesive layer of the holding substrate; A method for producing the laminate according to claim 6.

8. providing a laminate according to claim 5; a step of irradiating the adhesive layer of the laminate with light through the holding substrate to peel off the adherend from the holding substrate; having Methods for processing laminates.

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