Energy ray-curable resin composition, coating liquid, resin film-forming film, and method for producing laminate

Abstract

Provided are: an energy-ray-curable resin composition having desired delayed curing properties and performance stability; a coating liquid and a resin-film-forming film each comprising the energy-ray-curable resin composition; and a method for producing a laminate using the coating liquid or the resin-film-forming film. An energy ray-curable resin composition comprising a compound having two or more (meth) acryloyl groups, a compound having two or more groups containing a beta-dicarbonyl structure, and a nonionic photobase generator.

Description

Technical Field

[0001] The present invention relates to an energy-ray curable resin composition, a coating liquid, a resin film-forming film, and a method for producing a laminate. In particular, it relates to an energy-ray curable resin composition that exhibits desired delayed curing properties and performance stability, a coating liquid and a resin film-forming film containing the energy-ray curable resin composition, and a method for producing a laminate using the coating liquid or the resin film-forming film. Background Art

[0002] A resin composition that is cured by energy rays such as ultraviolet rays (energy-ray-curable resin composition) is, for example, a liquid composition that is changed (cured) into a solid composition by irradiation with energy rays. Since there is no need to dry the liquid, the energy-ray-curable resin composition can be used for various purposes such as bonding, coating, printing, medical treatment, and beauty.

[0003] However, since the curing reaction occurs when energy rays reach the components contained in the composition, when the composition has a complicated shape or is thick, there are regions that are difficult for energy rays to reach, resulting in insufficient curing.

[0004] Patent document 1 discloses a UV-curable resin composition, which contains: at least one selected from poly (meth) acrylate and polyvinyl ether, a compound having a thiol group, a photopolymerization initiator that generates a free radical reaction, and an organic compound that absorbs ultraviolet light and emits light. Patent document 1 discloses that by using the UV-curable resin composition, sufficient curing is performed even in a light-shielding portion or a deep portion that is difficult for energy rays to reach.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2023 / 038001 Summary of the invention

[0008] 1. Technical issues to be resolved

[0009] As described above, the energy-ray curable resin composition can be used for bonding purposes. For example, when the energy-ray curable resin composition is used to bond adherends that do not transmit energy rays, if the energy-ray curable resin composition is completely covered by the adherend, the energy rays will not completely reach the energy-ray curable resin composition. Therefore, even if the ultraviolet curable resin composition disclosed in Patent Document 1 is used, it will not be fully cured, and it is likely that a hard bonding portion cannot be obtained.

[0010] Therefore, it is considered to apply an energy ray-curable resin composition to an adherend that does not transmit energy rays, irradiate the adherend with energy rays, and then bond the adherends together.

[0011] However, curing by free radical reaction ends the reaction immediately after energy ray irradiation. Therefore, even if adherends are to be bonded together after energy ray irradiation, there is a problem that bonding cannot be performed because no adhesiveness remains on the irradiated surface due to the end of the curing reaction.

[0012] Therefore, a composition is sought that does not immediately complete the curing reaction after irradiation with energy rays, but rather slowly undergoes a curing reaction, that is, a composition having delayed curing properties. Furthermore, in addition to such delayed curing properties after irradiation with energy rays, it is also required that the energy ray-curable resin composition has stable curing performance (performance stability) in the state before irradiation with energy rays, and does not unexpectedly undergo a curing reaction with the passage of time (over time).

[0013] The present invention is made in view of such actual situation, and its purpose is to provide an energy-ray-curable resin composition having the desired delayed curing property and performance stability, a coating liquid and a resin film-forming film containing the energy-ray-curable resin composition, and a method for manufacturing a laminate using the coating liquid or the resin film-forming film.

[0014] (II) Technical solution

[0015] The scheme of the present invention is as follows.

[0016] [1] An energy-ray-curable resin composition comprising: a compound having two or more (meth)acryloyl groups, a compound having two or more groups containing a β-dicarbonyl structure, and a nonionic photobase generator.

[0017] [2] The energy-ray-curable resin composition according to [1], wherein the group containing a β-dicarbonyl structure is a group containing a β-ketoester structure.

[0018] [3] The energy-ray-curable resin composition according to [2], wherein the group containing a β-ketoester structure is a group containing an acetoacetate structure.

[0019] [4] The energy-ray-curable resin composition according to any one of [1] to [3], wherein the nonionic photobase generator has a group having a structure represented by the following formula:

[0020] [Chemical formula 1]

[0021]

[0022] In the formula, Rv, Rw, Rx, Ry and Rz are organic groups.

[0023] [5] A coating liquid comprising the energy-ray-curable resin composition according to any one of [1] to [4].

[0024] [6] The coating liquid according to [5], wherein the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is 80 parts by mass or more per 100 parts by mass of the solid content of the coating liquid.

[0025] [7] A resin film-forming film formed from the energy-ray-curable resin composition according to any one of [1] to [4].

[0026] [8] The resin film forming film according to [7], wherein the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is 30 parts by mass or more in 100 parts by mass of the resin film forming film.

[0027] [9] A method for producing a laminate, comprising:

[0028] A step of applying the coating liquid described in [5] or [6] to at least one of the first adherend and the second adherend;

[0029] After the coating liquid is applied, the step of irradiating the coating liquid or the dried coating liquid with energy rays; and

[0030] A step of bonding a first adherend and a second adherend together via the coating liquid to form a laminate after irradiating the energy ray.

[0031]

[10] A method for producing a laminate, comprising:

[0032] a step of attaching the resin film-forming film according to [7] or [8] to at least one of a first adherend and a second adherend; and

[0033] After the resin film forming film is attached, the step of irradiating the resin film forming film with energy rays;

[0034] A step of bonding a first adherend and a second adherend together via a resin film forming film to form a laminate after irradiating the energy ray.

[0035]

[11] The method for producing a laminate according to [9] or

[10] , wherein at least one of the first adherend and the second adherend is an adherend that blocks energy rays.

[0036] (III) Beneficial effects

[0037] According to the present invention, there can be provided an energy-ray-curable resin composition having desired delayed curing properties and performance stability, a coating liquid and a resin film-forming film containing the energy-ray-curable resin composition, and a method for manufacturing a laminate using the coating liquid or the resin film-forming film. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a schematic cross-sectional view of an example of the resin film forming sheet according to the present embodiment.

[0039] Figure 2 This is a schematic cross-sectional view of an example of the composite sheet for forming a resin film according to the present embodiment.

[0040] Description of Reference Numerals

[0041] 1: Sheet for forming a resin film; 10: Film for forming a resin film; 21: First release film; 22: Second release film; 2: Composite sheet for forming a resin film; 10: Film for forming a resin film; 4: Adhesive sheet (support sheet) DETAILED DESCRIPTION

[0042] Hereinafter, the present invention will be described in detail based on specific embodiments with reference to the drawings. First, main terms used in this specification will be described.

[0043] The workpiece refers to a plate-like body formed by singulating the resin film forming film possessed by the resin film forming sheet involved in the present embodiment after being attached. The resin film forming film is attached to the back of the workpiece. As the workpiece, there can be listed a circular wafer (including a case with an oriented plane), a square strip (long strip substrate) that implements panel-level packaging and mold resin sealing, etc., among which, from the perspective of easily obtaining the effect of the present invention, a wafer is preferred. As a wafer, for example, it can be a semiconductor wafer such as a silicon wafer, a gallium arsenide wafer, a silicon carbide wafer, a gallium nitride wafer, an indium phosphide wafer, etc.; an insulator wafer such as a glass wafer, a lithium tantalate wafer, a lithium niobate wafer, etc.; in addition, it can also be a reconstructed wafer composed of a resin and a semiconductor for making a fan-out package, etc. From the perspective of easily obtaining the effect of the present invention, as a wafer, a semiconductor wafer or an insulator wafer is preferred, and a semiconductor wafer is more preferred.

[0044] The singulation of a workpiece refers to dividing the workpiece together with the circuit to obtain a singulated workpiece. For example, when the workpiece is a wafer, the singulated workpiece is a chip, and when the workpiece is a strip (long strip substrate) that has been subjected to panel-level packaging or mold resin sealing, the singulated workpiece is a semiconductor package.

[0045] The "front surface" of a workpiece refers to a surface on which a circuit, an electrode, etc. are formed, and the "back surface" of a workpiece refers to a surface on which no circuit, etc. are formed. The electrode may be a convex electrode such as a bump.

[0046] "Main surface" refers to a surface that is larger in area than other surfaces among the surfaces constituting a plate-like body. Usually, a plate-like body has two main surfaces and side surfaces other than the two main surfaces, and the two main surfaces are opposite to each other. In a workpiece, the "front" and "back" are main surfaces.

[0047] “(Meth)acrylate” is used as a term representing both “acrylate” and “methacrylate”, and the same applies to other similar terms.

[0048] The "energy ray" refers to ultraviolet rays, electron beams, etc., and ultraviolet rays are preferred.

[0049] Unless otherwise specified, the "weight average molecular weight" refers to a polystyrene conversion value measured by gel permeation chromatography (GPC). The measurement based on such a method is, for example, a device in which high-efficiency chromatographic columns "TSK guard column HXL-H", "TSK Gel GMHXL", and "TSK Gel G2000 HXL" (all manufactured by TOSOH CORPORATION) are sequentially connected to a high-efficiency GPC device "HLC-8120GPC" manufactured by TOSOH CORPORATION, and the detector is used as a differential refractometer under the conditions of a chromatographic column temperature of 40°C and a flow rate of 1.0 mL / min.

[0050] The release film is a film that supports the resin film forming film in a releasable manner. The film is used as a concept including a sheet, and the thickness is not limited.

[0051] The mass ratio in the description of the composition such as the energy-ray curable resin composition is based on the active ingredient (solid content), and does not include the solvent unless otherwise specified.

[0052] (1. Energy-beam curable resin composition)

[0053] The energy-ray-curable resin composition is a composition for forming a resin film on an adherend. The resin film is a cured product of the energy-ray-curable resin composition. For example, when the resin film is an adhesive film, generally, an adhesive liquid containing the energy-ray-curable resin composition is applied to one adherend, another adherend is attached to the applied surface, and then irradiated with energy rays to cure it, thereby forming an adhesive film that adheres the adherends to each other.

[0054] However, if the adherends to be bonded are energy-irradiable adherends, even if the adherends are irradiated with energy rays after bonding, the amount of energy rays reaching the coated surface is 0 or extremely small. As a result, there is a problem that the energy-ray-curable resin composition is not cured and the adherends cannot be sufficiently bonded to each other.

[0055] Therefore, as a method for bonding such adherends, there is a method in which an adhesive solution is applied to one adherend, and then energy rays are irradiated, and then another adherend is bonded. In this case, the energy ray-curable resin composition is required to undergo a slow curing reaction after irradiation with energy rays (delayed curing). This is because if the resin film is formed by curing immediately after irradiation with energy rays, the surface of the resin film as a cured product is not sticky, so even if another adherend is bonded, it will not be bonded.

[0056] In addition, the energy-ray curable resin composition not only has the situation of being used quickly after production, but also has the situation of being used again after being stored for a certain period of time after production. Then, there is also the situation that the energy-ray curable resin composition changes over time and unexpectedly performs a curing reaction. If so, due to the difference in the storage period, the performance of the energy-ray curable resin composition will produce unevenness. Therefore, for the energy-ray curable resin composition, it is required that the curing reaction is not accidentally performed with the passage of time in the state before irradiating the energy ray, and the curing performance is stable (performance stability).

[0057] The energy-ray curable resin composition according to the present embodiment can exhibit the above-mentioned delayed curing property and performance stability by having the following composition. The energy-ray curable resin composition according to the present embodiment is a resin composition containing at least an energy-ray curable resin component (A), a curing agent (B), and a nonionic photobase generator (C).

[0058] (1.1. Energy-beam curable resin component (A))

[0059] The energy-ray-curable resin component is a resin component that is cured by irradiation with energy rays, and is a main component for taking on film-forming properties, flexibility, etc. and forming a hard resin film after curing. In this embodiment, the energy-ray-curable resin component (A) is a compound having two or more (meth)acryloyl groups. The (meth)acryloyl group has an energy-ray-curable carbon-carbon double bond.

[0060] Examples of the compound having two or more (meth)acryloyl groups include a polymer (p1) having two or more (meth)acryloyl groups and having a weight average molecular weight of 80,000 to 2,000,000, and a compound (p2) having two or more (meth)acryloyl groups and having a molecular weight of 100 to less than 80,000. At least a portion of the polymer (p1) may be crosslinked by a crosslinking agent or may not be crosslinked.

[0061] (1.1.1. Polymer (p1))

[0062] As the above-mentioned polymer (p1), for example, an acrylic resin (p1-1) formed by the reaction of an acrylic polymer (p11) and an energy-ray curable compound (p12), wherein the acrylic polymer (p11) has two or more functional groups capable of reacting with groups possessed by other compounds, and the energy-ray curable compound (p12) has a group reactive with the functional group and a (meth)acryloyl group.

[0063] Examples of the functional group that can react with a group possessed by other compounds include hydroxyl, carboxyl, amino, substituted amino (a group having a structure in which one or two hydrogen atoms of an amino group are substituted by a group other than a hydrogen atom), epoxy, etc. In this embodiment, the functional group is preferably a hydroxyl group.

[0064] (1.1.2. Acrylic polymer having two or more functional groups (p11))

[0065] Examples of the acrylic polymer (p11) having two or more functional groups include a polymer obtained by copolymerizing a (meth)acrylic monomer having a functional group and a (meth)acrylic monomer having no functional group, and a polymer obtained by copolymerizing a monomer other than the (meth)acrylic monomer (non-(meth)acrylic monomer) in addition to these monomers. The acrylic polymer (p11) having two or more functional groups is obtained by reacting these monomers using at least a (meth)acrylic monomer having a functional group as a constituent monomer.

[0066] The acrylic polymer (p11) may be a random copolymer or a block copolymer, and a known method may be employed as the polymerization method.

[0067] As a (meth)acrylic monomer which has a functional group, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, an epoxy group-containing monomer etc. are mentioned, for example.

[0068] As a hydroxyl group-containing monomer, a hydroxyalkyl (meth)acrylate, a non-(meth)acrylic unsaturated alcohol (unsaturated alcohol which does not have a (meth)acryloyl skeleton), etc. are mentioned, for example.

[0069] Examples of carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxylalkyl esters such as 2-carboxyethyl methacrylate, and the like.

[0070] The (meth)acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.

[0071] The (meth)acrylic monomer having a functional group constituting the acrylic polymer (p11) may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected.

[0072] Examples of the (meth)acrylic acid monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, Alkyl (meth)acrylates whose alkyl groups are chain structures having 1 to 18 carbon atoms, such as decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmitoyl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearoyl (meth)acrylate), etc.

[0073] In addition, examples of (meth)acrylic monomers having no functional group include (meth)acrylic acid esters containing alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylic acid esters having aromatic groups such as (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinking (meth)acrylamide and its derivatives; (meth)acrylic acid esters having non-crosslinking tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate, and the like.

[0074] The (meth)acrylic monomer having no functional group constituting the acrylic polymer (p11) may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected.

[0075] Examples of the non-(meth)acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0076] The non-(meth)acrylic monomer constituting the acrylic polymer (p11) may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected.

[0077] In the acrylic polymer (p11), the ratio (content) of the amount of the structural unit derived from the (meth)acrylic monomer having a functional group relative to the total amount of the structural units constituting the acrylic polymer (p11) is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio within such a range, in the acrylic resin (p1-1) obtained by the reaction of the acrylic polymer (p11) and the energy-ray curable compound (p12), the content of the energy-ray curable group can be adjusted to a preferred range for the curing degree of the resin film.

[0078] The acrylic polymer (p11) constituting the acrylic resin (p1-1) may be one type or two or more types. When two or more types are used, the combination and ratio thereof can be arbitrarily selected.

[0079] (1.1.3. Energy ray curable compound (p12))

[0080] The energy-ray curable compound (p12) preferably has one or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group possessed by the acrylic polymer (p11), and more preferably has an isocyanate group. For example, when the energy-ray curable compound (p12) contains a group having an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (p11) having a hydroxyl group as a functional group.

[0081] The number of (meth)acryloyl groups in one molecule of the energy-ray curable compound (p12) is not particularly limited, and can be appropriately selected, for example, in consideration of the physical properties and structure of the cured product (i.e., resin film) of the energy-ray curable resin composition formed by the energy-ray curable resin component and the curing agent. In addition, for example, even if the number of (meth)acryloyl groups in one molecule of the energy-ray curable compound (p12) is 1, as described above, since the acrylic polymer (p11) has two or more functional groups, the obtained acrylic resin (p1-1) becomes a compound having two or more (meth)acryloyl groups.

[0082] Examples of the energy-ray-curable compound (p12) include 2-methacryloyloxyethyl isocyanate, methyl-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0083] Acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate;

[0084] Acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, and the like.

[0085] Among these components, the energy ray curable compound (p12) is preferably 2-methacryloyloxyethyl isocyanate.

[0086] The energy-ray-curable compound (p12) constituting the acrylic resin (p1-1) may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected.

[0087] In the acrylic resin (p1-1), the content ratio of the energy-ray curable group derived from the energy-ray curable compound (p12) relative to the content of the functional group derived from the acrylic polymer (p11) is preferably 20 to 120 mol %, more preferably 35 to 100 mol %, and particularly preferably 50 to 90 mol %.

[0088] By making the content ratio within such a range, the adhesive force of the resin film becomes greater. In addition, when the energy-ray curable compound (p12) is a multifunctional compound (having two or more functional groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

[0089] The weight average molecular weight (Mw) of the polymer (p1) is preferably 80,000 to 2,000,000, and more preferably 300,000 to 1,500,000. The “weight average molecular weight” is as described above.

[0090] The polymer (p1) contained in the energy-ray curable resin composition may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected.

[0091] The content of the polymer (p1) in 100 parts by mass of the energy-ray-curable resin composition is preferably 1 to 70 parts by mass, more preferably 5 to 60 parts by mass, particularly preferably 10 to 50 parts by mass.

[0092] (1.1.4. Compound (p2))

[0093] Examples of the compound (p2) include polyfunctional monomers or oligomers having two or more (meth)acryloyl groups, and polyfunctional acrylate compounds having two or more (meth)acryloyl groups are preferred.

[0094] Examples of the polyfunctional acrylate compound having two or more (meth)acryloyl groups include a difunctional (meth)acrylate having two (meth)acryloyl groups in one molecule, a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule, and a (meth)acrylate oligomer having two or three or more (meth)acryloyl groups in one molecule.

[0095] Examples of the difunctional (meth)acrylate having two (meth)acryloyl groups in one molecule include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (meth)acrylate, and 1,2-dimethylformamide. di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, etc.

[0096] Examples of the polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule include tris(2-(meth)acryloyloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloyloxyethyl)isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0097] As a (meth)acrylate oligomer which has two or three or more (meth)acryloyl groups in one molecule, for example, a polyfunctional urethane (meth)acrylate oligomer can be exemplified.

[0098] The weight average molecular weight of the compound (p2) is preferably 100 or more and less than 80,000, more preferably 200 or more and 30,000 or less, particularly preferably 300 or more and 15,000 or less.

[0099] The compound (p2) contained in the energy-ray curable resin composition may be one kind or two or more kinds. When it is two or more kinds, the combination and ratio thereof can be arbitrarily selected.

[0100] The content of the compound (p2) in 100 parts by mass of the energy-ray-curable resin composition is preferably 1 to 70 parts by mass, more preferably 10 to 60 parts by mass, particularly preferably 15 to 55 parts by mass.

[0101] In 100 parts by mass of the energy-ray curable resin composition, the content of the energy-ray curable resin component (A) is preferably 1 to 70 parts by mass, more preferably 10 to 60 parts by mass, and particularly preferably 15 to 55 parts by mass. By making the content of the energy-ray curable resin component (A) within the above range, an energy-ray curable resin composition showing the desired delayed curing property and performance stability can be more easily obtained, and a resin film having better adhesion to an adherend can be easily obtained.

[0102] In addition, in the present embodiment, from the perspective of the performance stability of the energy-ray curable resin composition, it is not preferred to contain epoxy resin as the energy-ray curable resin component. Therefore, the energy-ray curable resin component (A) preferably does not substantially contain epoxy resin. Substantially not containing epoxy resin means that in 100 parts by mass of the energy-ray curable resin composition, the content of epoxy resin is less than 1 part by mass.

[0103] (1.2. Curing agent (B))

[0104] In this embodiment, as an auxiliary agent (curing agent) for curing the energy-ray curable resin component (A), a compound (B) having two or more groups containing a β-dicarbonyl structure is used. The β-dicarbonyl structure is a structure having another carbonyl group at the β position of the carbonyl group.

[0105] The compound having a group containing a β-dicarbonyl structure is a compound that undergoes Michael addition reaction with a compound having a double bond that is receptive to Michael addition, as the hydrogen at the α-position is abstracted by a base.

[0106] In the present embodiment, the hydrogen of the active methylene part of the compound having two or more groups containing a β-dicarbonyl structure is taken away (i.e., deprotonated) by the base generated by irradiating the photobase generator described later with energy rays. As a result, negative carbon ions are generated, and the negative carbon ions attack the double bond site of the (meth)acryloyl group contained in the energy ray-curable resin component, thereby performing Michael addition and performing a curing reaction. Compared with the curing reaction of the (meth)acryloyl group brought about by free radicals, the reaction rate of the curing reaction brought about by the Michael addition is slower, so it will not be cured immediately due to the irradiation of energy rays, and the curing reaction proceeds slowly. Therefore, by utilizing the energy ray curing reaction using a compound having a (meth)acryloyl group and a compound having a group containing a β-dicarbonyl structure, the energy ray-curable resin composition involved in the present embodiment can achieve delayed curing.

[0107] In addition, the compound having a (meth)acryloyl group has two or more (meth)acryloyl groups, and the compound having a group containing a β-dicarbonyl structure has two or more groups containing a β-dicarbonyl structure. As a result, these compounds undergo addition reactions with a plurality of compounds and are intricately entangled with each other, and the energy-ray-curable resin composition becomes a cured product.

[0108] In addition, from the viewpoint of delayed curing property and performance stability, the compound having a group containing a β-dicarbonyl structure preferably does not form a metal complex.

[0109] In the present embodiment, the β-dicarbonyl structure is preferably a β-ketoester structure represented by the following formula Y. Thereby, the energy-ray-curable resin composition can easily obtain a resin film having more excellent adhesiveness to an adherend.

[0110] [Chemical formula 2]

[0111]

[0112] In formula Y, R 1 and R 2 Represents an organic group.

[0113] Furthermore, the β-ketoester structure is preferably R 1 The compound having two or more groups containing acetoacetate structures can be synthesized from, for example, a polyfunctional alcohol and tert-butyl acetoacetate.

[0114] Specific examples of the compound having a β-ketoester structure include compounds represented by the following formulae Y-1 to Y-5.

[0115] [Chemical formula 3]

[0116]

[0117] [Chemical formula 4]

[0118]

[0119] [Chemical formula 5]

[0120]

[0121] [Chemical formula 6]

[0122]

[0123] [Chemical formula 7]

[0124]

[0125] In 100 parts by mass of the energy-ray curable resin composition, the content of the compound (B) having two or more groups containing a β-dicarbonyl structure is preferably in at least one of the ranges of 5 to 70 parts by mass, 10 to 65 parts by mass, 13 to 60 parts by mass, and 15 to 55 parts by mass. By making the content of the compound (B) within the above range, it is easier to obtain an energy-ray curable resin composition that exhibits the desired delayed curing properties and performance stability, and it is easier to obtain a resin film that has better adhesion to an adherend.

[0126] In 100 parts by mass of the energy-ray-curable resin composition, the total mass of the compound having two or more (meth)acryloyl groups and the compound having two or more groups containing a β-dicarbonyl structure is preferably in at least one of the ranges of 30 to 99.9 parts by mass, 35 to 99.5 parts by mass, 40 to 99 parts by mass, and 80 to 98 parts by mass. By making the total mass of the compound having two or more (meth)acryloyl groups and the compound having two or more groups containing a β-dicarbonyl structure within the above range, it is easy to obtain a resin film having better adhesion to an adherend.

[0127] (1.3. Photobase Generator)

[0128] In this embodiment, the energy-ray-curable resin composition contains a photobase generator as a catalyst for controlling the deprotonation of the compound (B) having two or more groups containing a β-dicarbonyl structure. The photobase generator is also called a photoanion polymerization initiator (Photo base generator), which is a compound that generates a base by irradiation with energy rays. The generated base deprotonates the compound (B) having two or more groups containing a β-dicarbonyl structure, and a Michael addition reaction with a compound having two or more (meth)acryloyl groups is performed. Since the generation of the base can be controlled by irradiation with energy rays, the compound (B) having two or more groups containing a β-dicarbonyl structure can be used as a latent curing agent with excellent storage stability.

[0129] Examples of the photobase generator include a photobase generator having no ionic bond in the molecular structure (nonionic photobase generator (C)) and a photobase generator having an ionic bond in the molecular structure (ionic photobase generator). In the present embodiment, a nonionic photobase generator (C) is used from the viewpoint of performance stability of the energy-ray curable resin composition containing the photobase generator.

[0130] Examples of the nonionic photobase generator include a photobase generator represented by the following general formula (α1).

[0131] [Chemical formula 8]

[0132]

[0133] In formula (α1), n ​​represents an integer of 0 to 4. Rα 11 represents at least one substituent selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, an aromatic acyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group, and a halogen atom. 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, an aromatic acyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group or a halogen atom. Xα 1 It represents amino group.

[0134] In the formula (α1), n ​​is generally an integer of 0 to 4, preferably an integer of 1 to 2, and more preferably 2. In addition, when the benzene ring in the formula (α1) is 12The bonding position of - is set to 1, and -NO 2 When the bonding position is set to 2, Rα when n is 2 11 The substitution positions are preferably the 4-position and the 5-position.

[0135] In formula (α1), Rα 11 represents at least one substituent selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, an aromatic acyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group and a halogen atom. 11 , can be different from each other.

[0136] As Rα of formula (α1) 11 The alkyl group having 1 to 18 carbon atoms represented by alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, and is preferably an alkyl group having 2 to 6 carbon atoms.

[0137] As Rα of formula (α1) 11 Examples of the alkenyl group having 2 to 18 carbon atoms include vinyl, propenyl, 1-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,2-dicyanovinyl, 2-cyano-2-methylcarboxyvinyl and 2-cyano-2-methylsulfonyl.

[0138] As Rα of formula (α1) 11 Examples of the alkynyl group having 2 to 18 carbon atoms include ethynyl, 1-propynyl and 1-butynyl.

[0139] As Rα of formula (α1) 11 Examples of the aryl group having 6 to 12 carbon atoms include phenyl, naphthyl and tolyl, and an aryl group having 6 to 10 carbon atoms is preferred.

[0140] As Rα of formula (α1) 11 Examples of the acyl group having 1 to 18 carbon atoms include formyl, acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, isopentylcarbonyl, neopentylcarbonyl, 2-methylbutylcarbonyl and nitrobenzylcarbonyl.

[0141] As Rα of formula (α1) 11Examples of the aromatic acyl group having 7 to 18 carbon atoms include benzoyl, toluoyl, naphthoyl and phthaloyl.

[0142] As Rα of formula (α1) 11 Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy and n-dodecyloxy.

[0143] As Rα of formula (α1) 11 Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, 2-methylbutylthio, 1-methylbutylthio, neopentylthio, 1,2-dimethylpropylthio and 1,1-dimethylpropylthio.

[0144] As Rα of formula (α1) 11 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0145] As Rα in formula (α1) 11 , preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, further preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group. 11 When at least one Rα 11 is an alkoxy group, more preferably all Rα 11 It is an alkoxy group.

[0146] In formula (α1), Rα 12 It represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a hydroxyl group or a halogen atom.

[0147] As Rα of formula (α1) 12 The alkyl group having 1 to 18 carbon atoms, the alkynyl group having 2 to 18 carbon atoms, the aryl group having 6 to 12 carbon atoms, the acyl group having 1 to 18 carbon atoms, the aromatic acyl group having 7 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the alkylthio group having 1 to 18 carbon atoms and the halogen atom represented by the formula (α1) include 11The alkyl group having 1 to 18 carbon atoms, the alkynyl group having 2 to 18 carbon atoms, the aryl group having 6 to 12 carbon atoms, the acyl group having 1 to 18 carbon atoms, the aroyl group having 7 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the alkylthio group having 1 to 18 carbon atoms and the halogen atom are the same groups and atoms as those represented.

[0148] As Rα in formula (α1) 12 , preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

[0149] In formula (α1), Xα 1 represents an amino group. Xα in formula (α1) 1 The amino group represented by may be a substituted amino group or an unsubstituted amino group (NH 2 The substituted amino group may be any one of a monosubstituted amino group and a disubstituted amino group.

[0150] In this embodiment, Xα 1 It is preferably a group having a structure represented by the following formula (α1-X).

[0151] [Chemical formula 9]

[0152]

[0153] In the formula, Rv, Rw, Rx, Ry and Rz are organic groups. It is more preferred that Rv is single-bonded to the ester group in the general formula (α1), and Rw, Rx, Ry and Rz are alkyl or cycloalkyl groups. It is further preferred that Rw, Rx, Ry and Rz are alkyl groups having 3 or less carbon atoms, and it is particularly preferred that Rw, Rx, Ry and Rz are methyl groups.

[0154] Specific examples of the compound represented by the formula (α1) include the following compounds (α1-1) to (α1-8).

[0155] [Chemical formula 10]

[0156]

[0157] In addition, as nonionic photobase generators, since they have better stability as a material and better efficiency in generating a base by irradiation with energy rays, coumaric acid-type photobase generators represented by the following general formula (α2) can also be cited.

[0158] [Chemical formula 11]

[0159]

[0160] In the general formula (α2), Rα 21 and Rα 22 Each is independently a hydrogen atom or an organic group and may be the same or different. 21 and Rα 22 They can be bonded to form a ring structure or contain heteroatoms. 21 and Rα 22 At least one of Rα is an organic group. 23 and Rα 24 Each is independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphine group, a phosphine group, a phosphono group, a phosphonate group, or an organic group, and may be the same or different. 25 , Rα 26 , Rα 27 and Rα 28 Each is independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfonic group, a sulfonic group, a sulfonic ester group, a phosphine group, an oxygen phosphine group, a phosphonic acid group, a phosphonic ester group, an amino group, an amine group or an organic group, and may be the same or different. 25 , Rα 26 , Rα 27 and Rα 28 Two or more of them may be bonded to form a ring structure, or may contain a heteroatom bond. 29 It is a hydrogen atom or an organic group.

[0161] From the viewpoint of the basicity of the generated base, in the general formula (α2), Rα 21 and Rα 22 Preferably, they are all alkyl groups or groups forming alkylene chains that are bonded to each other to form a cyclic structure, and most preferably, they are groups forming alkylene chains that are bonded to each other to form a cyclic structure. The number of carbon atoms constituting the alkyl group or alkylene chain is preferably 1 to 20, more preferably 1 to 8.

[0162] In addition, Rα 21 -N-Rα 22 Preferably, it is a group that constitutes the structure represented by the above formula (α1-X). In the above formula (α1-X), Rv, Rw, Rx, Ry and Rz are organic groups. More preferably, Rv is single-bonded to the carbonyl group in the above general formula (α2), and the group containing CN, Rw and Rx is Rα 21 , containing C (with the Rα 21 The C in the same C)-N, Ry and Rz are Rα 22More preferably, Rw, Rx, Ry and Rz are alkyl groups or cycloalkyl groups, and particularly preferably, Rw, Rx, Ry and Rz are alkyl groups having 3 or less carbon atoms, and most preferably, Rw, Rx, Ry and Rz are methyl groups.

[0163] In the general formula (α2), Rα 23 and Rα 24 Preferably, it is a hydrogen atom or an alkyl group, and most preferably, both are hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 8.

[0164] In the general formula (α2), Rα 25 , Rα 26 , Rα 27 and Rα 28 Preferably, it is a hydrogen atom, an alkyl group or an alkoxy group, and most preferably, all of them are hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 8. The number of carbon atoms in the alkoxy group is preferably 1 to 20, and more preferably 1 to 8.

[0165] In the general formula (α2), Rα 29 It is preferably a hydrogen atom or an organic group which is a protecting group that can be deprotected by irradiation with energy rays and / or heating, and most preferably a hydrogen atom.

[0166] As the coumaric acid-type compound represented by the general formula (α2), the following compounds (α2-1) and (α2-2) are preferred, and (α2-1) is more preferred.

[0167] [Chemical formula 12]

[0168]

[0169] Furthermore, as the nonionic photobase generator, a carbamate compound (α3)-1 represented by the following general formula is also preferred.

[0170] [Chemical formula 13]

[0171]

[0172] In addition, as a nonionic photobase generator, an oxime ester compound is also preferred. As an oxime ester compound, any compound that generates an alkaline substance by light irradiation can be used. In addition, a compound having two oxime ester groups in the molecule can also be appropriately used, specifically, an oxime ester compound having a carbazole structure represented by the following general formula (α4) can be listed.

[0173] [Chemical formula 14]

[0174]

[0175] In the general formula (α4), Xα4 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (substituted by an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or a dialkylamino group), or a naphthyl group (substituted by an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or a dialkylamino group), Yα 4 , Zα 4 Each of them represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (substituted by an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or a dialkylamino group), a naphthyl group (substituted by an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or a dialkylamino group), an anthracenyl group, a pyridyl group, an oxaquinone group, a benzothiophene group, and Arα 4 It represents a bond or an alkylene group having 1 to 10 carbon atoms, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, thiophene group, anthrylene group, thiophene group, furylene group, 2,5-pyrrole-diyl group, 4,4'-stilbene-diyl group, 4,2'-phenylene-diyl group, and n is an integer of 0 or 1.

[0176] In the general formula (α4), preferably Xα 4 , Yα 4 Methyl or ethyl, Zα 4 is methyl or phenyl, n is 0, Arα 4 is a bond or a phenylene group, a naphthylene group, a thiophene group or a thienylene group.

[0177] Furthermore, preferred carbazole oxime ester compounds include compounds that can be represented by the following general formula (α5).

[0178] [Chemical formula 15]

[0179]

[0180] In the general formula (α5), Rα 51 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. 52 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms. 53It may be linked via an oxygen atom or a sulfur atom and represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a phenyl group, or a benzyl group which may be substituted by an alkoxy group having 1 to 4 carbon atoms. 54 Indicates nitro or Xα 5 -C(=O)- represents an acyl group. 5 It represents an aryl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, a thienyl group, a morpholinyl group, a thiophenyl group, or a structure represented by the following formula.

[0181] [Chemical formula 16]

[0182]

[0183] Among the above-mentioned nonionic photobase generators, the coumaric acid-type photobase generators represented by the above-mentioned general formula (α2) are preferred, and the compounds represented by (α2-1) are more preferred.

[0184] In 100 parts by mass of the energy-ray curable resin composition, the content of the nonionic photobase generator (C) is preferably 0.1 to 10 parts by mass, 0.3 to 8 parts by mass, 0.5 to 6 parts by mass, or 0.7 to 5 parts by mass. By blending the photobase generator in the above ratio, an energy-ray curable resin composition showing the desired delayed curing property and performance stability can be more easily obtained, and a resin film having better adhesion to an adherend can be easily obtained.

[0185] The photobase generator can be synthesized as a condensate with reference to the examples described in, for example, JP-A-2009-80452, JP-A-2011-52214, JP-A-2021-177210, and JP-A-2019-45735.

[0186] (1.4. Filling material)

[0187] In this embodiment, the energy-ray curable resin composition may contain a filler (D). By containing a filler, the adjustment of the thermal expansion coefficient of the resin film obtained by curing the energy-ray curable resin composition becomes easier, and by making the thermal expansion coefficient close to the thermal expansion coefficient of the adherend, the adhesion reliability of the adherend via the resin film is further improved. In addition, by making the energy-ray curable resin composition contain a filler (D), a hard resin film can be obtained, the moisture absorption rate of the resin film is further reduced, and the adhesion reliability of the adherend via the resin film is further improved.

[0188] The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler from the viewpoint of shape stability at high temperatures.

[0189] Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these inorganic fillers, silica and surface-modified silica are preferred. The surface-modified silica is preferably surface-modified by a coupling agent, more preferably surface-modified by a silane coupling agent.

[0190] The average particle size of the filler is preferably 0.02 to 10 μm, 0.05 to 5 μm, or 0.10 to 3 μm.

[0191] By setting the average particle size of the filler within the above range, the handling properties of the energy-ray curable resin composition become better, and as a result, the quality of the energy-ray curable resin composition can be easily stabilized.

[0192] In the present specification, unless otherwise specified, the “average particle size” refers to a particle size (D50) at a cumulative value of 50% in a particle size distribution curve determined by a laser diffraction scattering method.

[0193] The content of the filler when the total weight of the energy-ray curable resin composition is set to 100 parts by weight is preferably determined according to the form of the energy-ray curable resin composition when it is used. For example, in the case of a liquid coating liquid containing an energy-ray curable resin composition, the content of the filler is preferably 0.5 to 60 parts by weight, 1 to 50 parts by weight, 1.5 to 45 parts by weight, or at least one range of 2 to 20 parts by weight. In addition, when a film is formed by forming a resin film formed by an energy-ray curable resin composition, the content of the filler is preferably 15 to 80 parts by weight, 30 to 70 parts by weight, 35 to 65 parts by weight, or at least one range of 40 to 60 parts by weight.

[0194] By setting the lower limit of the content of the filler to the above value, the adhesion reliability is further improved. In addition, by setting the upper limit of the content of the filler to the above value, the handling property of the energy-ray curable resin composition is further improved.

[0195] (1.5. Colorants)

[0196] The energy-ray curable resin composition may contain a colorant (E). When the resin film is used as a protective film described below, since the back surface of a chip or the like as an adherend is concealed, various electromagnetic waves generated in electronic equipment are blocked, and failure of the chip or the like can be reduced.

[0197] As the colorant (E), for example, known colorants such as organic pigments, organic dyes, and inorganic pigments can be used. In the present embodiment, inorganic pigments are preferred.

[0198] As inorganic pigment, for example, carbon black, cobalt pigment, iron pigment, chromium pigment, titanium pigment, vanadium pigment, zirconium pigment, molybdenum pigment, ruthenium pigment, platinum pigment, ITO (indium tin oxide) pigment, ATO (antimony tin oxide) pigment etc. can be listed. Among these inorganic pigments, carbon black is particularly preferably used. According to carbon black, electromagnetic waves of a wider wavelength range can be blocked.

[0199] The amount of the colorant in the energy-ray curable resin composition is not particularly limited, and the content of the colorant when the total weight of the energy-ray curable resin composition is 100 parts by mass is preferably set to any one of 0.01 to 10 parts by mass, 0.03 to 7 parts by mass, and 0.05 to 4 parts by mass. By setting the upper limit of the content of the colorant to the above value, it is easy to improve the energy-ray curability of the energy-ray curable resin composition.

[0200] The average particle size of the colorant (especially carbon black) is preferably 1 to 500 nm, 3 to 100 nm, or 5 to 50 nm. When the average particle size of the colorant is within the above range, it is easy to control the light transmittance within a desired range.

[0201] (1.6. Other additives)

[0202] Within the scope that does not impair the effects of the present invention, the energy-ray-curable resin composition may contain, for example, non-energy-ray-curable film-forming components (for example, non-energy-ray-curable acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins), coupling agents, cross-linking agents, plasticizers, antistatic agents, antioxidants, impurity absorbers, tackifiers, release agents, etc. as other additives.

[0203] On the other hand, from the perspective of performance stability, in this embodiment, it is preferred that substantially no isocyanate compound and substantially no isothiocyanate compound are contained. Substantially no isocyanate compound and substantially no isothiocyanate compound means that in 100 parts by mass of the energy-ray-curable resin composition, the total content of isocyanate compound and isothiocyanate compound is 1 part by mass or less.

[0204] In addition, from the viewpoint of delayed curing property, in the present embodiment, it is preferred that substantially no photoradical initiator is contained. Substantially no photoradical initiator means that the content of the photoradical initiator is 0.1 parts by mass or less in 100 parts by mass of the energy-ray-curable resin composition.

[0205] (2. Form of the energy-beam curable resin composition when used)

[0206] The energy-ray curable resin composition involved in this embodiment can be appropriately selected in the form of use according to the purpose, etc. In this embodiment, it is preferably used in the form of a coating liquid containing the energy-ray curable resin composition. In addition, it is also preferably used in the form of a resin film formed by the energy-ray curable resin composition.

[0207] (2.1. Coating liquid)

[0208] In the present embodiment, the coating liquid containing the energy-ray curable resin composition may be a coating liquid formed of a liquid energy-ray curable resin composition, or may be a coating liquid containing an energy-ray curable resin composition and a solvent.

[0209] From the perspective of delayed curing, the coating liquid is preferably used as an adhesive liquid. The adhesive liquid is applied to the adherend and irradiated with energy rays, thereby initiating a curing reaction of the energy-ray-curable resin composition. As described above, due to the delayed curing, even after irradiation with energy rays, the curing reaction can maintain the viscosity of the irradiated surface, thereby being able to bond adherends to each other.

[0210] In the coating liquid, the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is preferably 80 parts by mass or more, more preferably 85 parts by mass or more, and even more preferably 90 parts by mass or more, in 100 parts by mass of the solid content. Thus, the energy-ray-curable resin composition can easily obtain a resin film having better adhesion to an adherend.

[0211] The solvent may be selected as a solvent that can be used in the form of a coating liquid according to the purpose, etc. Examples thereof include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve.

[0212] When the coating liquid contains a solvent, the solid content concentration of the coating liquid can be set within an arbitrary range according to the application, etc. In the present embodiment, the solid content concentration is preferably 10% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. In addition, the viscosity of the coating liquid can also be set within the range that can be applied to the adherend.

[0213] (2.1.1. Preparation of coating solution)

[0214] The coating liquid containing the energy-ray curable resin composition can be obtained by fully mixing the energy-ray curable resin component (compound having two or more (meth)acryloyl groups), the compound having two or more groups containing a β-dicarbonyl structure (curing agent), the nonionic photobase generator, other additives such as fillers as required, and a solvent. In addition, when the energy-ray curable resin component is a polymer, it is sufficient to polymerize a mixture of monomers constituting the polymer by a known polymerization method such as a free radical polymerization method to obtain the energy-ray curable resin component.

[0215] (2.2. Resin Film Formation Film)

[0216] In the present embodiment, the resin film-forming film formed of the energy-ray-curable resin composition is formed into a resin film by irradiation with energy rays.

[0217] The resin film forming film can be used as a film (protective film forming film) for forming a protective film for protecting the back side of a chip having a circuit on the surface. In addition, it can be used as an adhesive film forming film for bonding adherends to each other. In addition, it can be used as a film for forming a protective film that exposes the top of a convex electrode such as a bump formed on a wafer, etc., and covers and protects the wafer surface and the bottom of the convex electrode. Same as the coating liquid, from the perspective of delayed curing, it is preferably used as an adhesive film forming film. That is, even after the adhesive film forming film is irradiated with energy rays, the viscosity of the irradiated surface can still be maintained, so that adherends can be bonded to each other.

[0218] In 100 parts by mass of the resin film-forming film, the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 40 parts by mass or more. Thus, the energy-ray-curable resin composition can easily obtain a resin film having better adhesion to an adherend.

[0219] The thickness of the resin film forming film is not particularly limited, and is preferably 100 μm or less, 80 μm or less, 60 μm or less, or 45 μm or less. In addition, the thickness of the resin film forming film is preferably 5 μm or more, 10 μm or more, or 13 μm or more. The thickness of the resin film forming film can be arbitrarily selected and set from the above upper limit and lower limit. If the thickness of the resin film forming film is within the above range, the performance of the obtained resin film becomes better.

[0220] The thickness of the resin film forming film refers to the thickness of the entire resin film forming film. For example, the thickness of a resin film forming film composed of a plurality of layers refers to the total thickness of all the layers constituting the resin film forming film.

[0221] The resin film forming film is usually used in the form of a resin film forming sheet or a resin film forming composite sheet.

[0222] The resin film forming sheet 1 according to the present embodiment has Figure 1 The resin film forming film 10 has two opposing main surfaces, namely, the main surface 10a and the main surface 10b. A first release film 21 supporting the resin film forming film 10 is arranged on the main surface 10a, and a second release film 22 supporting the resin film forming film 10 is arranged on the main surface 10b.

[0223] In addition, the composite sheet for resin film formation has a resin film forming film and a support sheet for supporting the resin film forming film. In addition to the release film, the support sheet has a structure capable of supporting the resin film forming film. As the support sheet, an adhesive sheet having a substrate and an adhesive layer can be exemplified.

[0224] Specifically, if Figure 2 As shown, the composite sheet 2 for forming a resin film has the following structure, which comprises: an adhesive sheet 4 formed by laminating an adhesive layer 42 on one surface of a substrate 41 as a support sheet, a resin film forming film 10 laminated on the adhesive layer 42 of the adhesive sheet 4 in a manner that the main surface 10a is in contact with it, and a release film 23 arranged on the main surface 10b of the resin film forming film 10. Furthermore, an adhesive layer for a clamp (not shown) can be arranged on the peripheral portion of the resin film forming film 10. The adhesive layer for a clamp is a layer used to adhere the composite sheet for forming a resin film to a clamp such as an annular frame. In addition, the first release film 21, the second release film 22 and the release film 23 are preferably release films formed by forming a silicone release agent layer on a single surface of a polyethylene terephthalate (PET) film.

[0225] (2.2.1. Production of Resin Film Forming Film)

[0226] The resin film forming film can be manufactured by a known method. For example, it can be manufactured by using the above-mentioned coating liquid. First, the above-mentioned coating liquid is applied to the release surface of the first release film 21 using a coating machine such as a roll coater, a blade coater, a roll knife coater, an air knife coater, a die coater, a rod coater, a gravure coater, or a curtain coater. If necessary, the solvent of the coating liquid is removed by drying to form a resin film forming film on the first release film 21.

[0227] When manufacturing the resin film forming sheet 1 , it can be obtained by further bonding the release surface of the second release film 22 to the exposed surface of the resin film forming film formed on the first release film 21 .

[0228] In addition, when manufacturing the composite sheet 2 for resin film formation, a laminate containing an adhesive sheet and a sheet for resin film formation can be used. The adhesive sheet can be manufactured using a known method. For example, a composition constituting an adhesive layer is prepared, applied to the release surface of the third release film, and dried as needed to form an adhesive layer on the third release film. Then, a substrate is laminated on the exposed adhesive layer to obtain an adhesive sheet having a third release film disposed on the adhesive layer.

[0229] Next, the second release film of the resin film forming sheet is peeled off, and the third release film of the adhesive sheet is peeled off, and the resin film forming film is bonded to the adhesive layer to obtain a composite sheet for resin film formation. In addition, the resin film forming film can be cut and processed into the size of the adherend (e.g., wafer) to be attached or a size close to the adherend as needed at an appropriate time.

[0230] (3. Method for producing laminate)

[0231] As an example of the use of the coating liquid involved in this embodiment, the following method is illustrated: using the coating liquid containing the energy-ray curable resin composition described above, a laminated body having a first adherend and a second adherend laminated via an adhesive film is manufactured. The method for manufacturing the laminated body involved in this embodiment comprises at least the following steps 1 to 3.

[0232] Step 1: A step of applying the coating liquid containing the energy-ray-curable resin composition described above to at least one of the first adherend and the second adherend.

[0233] Step 2: After the coating liquid is applied, a step of irradiating the coating liquid or the dried coating liquid with energy rays.

[0234] Step 3: After irradiation with energy rays, a first adherend and a second adherend are bonded together via a coating liquid to form a laminate.

[0235] In addition, as a method for applying the coating liquid, a known method can be used, for example, a coating method such as a die coater, a curtain coater, a spray coater, a slit coater, a blade coater, a printing method such as screen printing, inkjet printing, a dripping method such as a dispenser, etc.

[0236] When the coating liquid contains a solvent, it may be dried as necessary. The drying conditions may be, for example, a temperature of 50 to 100° C. and a drying time of 30 seconds to 5 minutes.

[0237] In addition, as an example of the use of the resin film forming film, the following method is illustrated: using the resin film forming film (adhesive film forming film) formed by the energy-ray curable resin composition described above, a laminated body having a first adherend and a second adherend laminated via an adhesive film is manufactured. In this case, the method for manufacturing the laminated body involved in this embodiment at least comprises the following steps 1 to 3.

[0238] Step 1: A step of attaching the resin film-forming film formed of the energy-ray-curable resin composition to at least one of a first adherend and a second adherend.

[0239] Step 2: After the resin film forming film is attached, the resin film forming film is irradiated with energy rays.

[0240] Step 3: After irradiation with energy rays, a first adherend and a second adherend are bonded together via a resin film forming film to form a laminate.

[0241] According to steps 1 to 3, no matter which one of the manufacturing methods using the coating liquid and the manufacturing method using the resin film forming film is used, after the energy-ray-curable resin composition contained in the coating liquid or the resin film forming film is irradiated with energy rays, the first adherend and the second adherend are bonded together. Then, after the curing is completed, a laminated body in which the first adherend and the second adherend are laminated via the adhesive film is obtained.

[0242] As described above, the energy-ray curable resin composition involved in this embodiment exhibits delayed curing properties by irradiating energy rays, and viscosity remains on the irradiated surface for a certain period of time after irradiation, so that the first adherend and the second adherend can be well bonded. When a coating liquid or a resin film-forming film containing an energy-ray curable resin composition that does not exhibit delayed curing properties is used, since curing ends immediately after irradiating energy rays, the viscosity disappears before the first adherend and the second adherend are bonded together, and the first adherend and the second adherend cannot be bonded together.

[0243] In particular, even if at least one of the first adherend and the second adherend is an adherend that blocks energy rays, the first adherend and the second adherend can be well bonded, and further, even if both the first adherend and the second adherend are adherends that block energy rays, the first adherend and the second adherend can be well bonded. Examples of the adherend that blocks energy rays include an adherend that reflects energy rays and an adherend that absorbs energy rays.

[0244] In addition, as another example of using the resin film forming film, the following method is exemplified: forming a resin film on a workpiece, singulating the workpiece on which the resin film is formed, and manufacturing a workpiece singulated product with a resin film. The method for manufacturing a workpiece singulated product with a resin film involved in this embodiment has at least the following steps 1 to 3.

[0245] Step 1: A step of attaching a resin film-forming film formed of the energy-ray-curable resin composition to the back surface of a workpiece.

[0246] Step 2: A step of irradiating the attached resin film-forming film with energy rays to form a resin film on the back surface of the workpiece to obtain a workpiece with a resin film.

[0247] Step 3: a step of singulating the workpiece with the resin film to obtain a plurality of singulated workpieces with the resin film.

[0248] In this embodiment, the resin film forming film is preferably a protective film forming film. In addition, the workpiece is preferably a wafer, more preferably a semiconductor wafer. Therefore, the workpiece singulated object with the resin film is preferably a chip with a protective film, more preferably a semiconductor chip with a protective film.

[0249] In the above-mentioned examples of use of the coating liquid and the resin film-forming film, the irradiance and light quantity of the energy ray may be set to conditions under which the energy ray-curable resin composition can be sufficiently cured. For example, the irradiance of the energy ray is set to 30 to 280 mW / cm 2 The amount of energy ray is set to 500 to 5000 mJ / cm 2 That's it.

[0250] (4. Modifications)

[0251] In the above embodiment, the curing reaction is controlled by irradiating the photobase generator with energy rays and using the photobase generator that generates a base, but in addition to irradiating with energy rays, a photobase generator that generates a base by heating can also be used. In addition, the Michael addition reaction generated by the base released by the irradiation with energy rays can be further promoted by adding heating to the irradiation with energy rays. The heating temperature at this time is preferably 50 to 200°C.

[0252] By using such a photobase generator, a curing reaction by irradiation with energy rays or a curing reaction by heating can be selected according to the application, etc., and delayed curing property can be controlled to appropriately cure the energy-ray-curable resin composition.

[0253] As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment at all, It can change in various forms within the scope of this invention.

[0254] Example

[0255] Hereinafter, the present invention will be described in more detail using Examples, but the present invention is not limited to these Examples.

[0256] (Experiment 1)

[0257] In Experiment 1, a coating liquid containing an energy-ray-curable resin composition was prepared and evaluated.

[0258] (Coating liquid containing energy-ray curable resin composition)

[0259] The following components were mixed in the ratios shown in Table 1 (in terms of solid content), diluted with chloroform so that the solid content concentration was 20% by mass, and immediately stirred and mixed for 5 minutes to prepare coating solutions containing energy-ray-curable resin compositions (Examples 1 to 6 and Comparative Examples 1 to 4).

[0260] (A) Energy-beam-curable resin component

[0261] (A-1) Tris-(2-acryloyloxyethyl)isocyanurate

[0262] (A-2) ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., A-9300-1CL, a trifunctional ultraviolet curable compound)

[0263] (A-3) Urethane acrylate oligomer (manufactured by KJ Chemicals CORPORATION, Quick Cure 8100EA70)

[0264] (B) Curing agent

[0265] (B-1): Hexanediol type multifunctional acetoacetate (a compound having the chemical structure of the formula Y-1)

[0266] (B-2): Tricyclodecane dimethanol type multifunctional acetoacetate (compound having the chemical structure of formula Y-2)

[0267] (B-3): trimethylolpropane type multifunctional acetoacetate (compound having the chemical structure of formula Y-3)

[0268] (B-4): Pentaerythritol-type multifunctional acetoacetate (a compound having the chemical structure of the formula Y-4)

[0269] (B-5): dipentaerythritol type multifunctional acetoacetate (compound having the chemical structure of formula Y-5)

[0270] (C) Nonionic photobase generator

[0271] (C-1): Nonionic photobase generator (a compound having the following chemical structure, (E)-N-(bis(dimethylamino)methylene)-3-(2-hydroxyphenyl)acrylamide: (E)-N-(bis(dimethylamino)methylene)-3-(2-hydroxyphenyl)acrylamide)

[0272] [Chemical formula 17]

[0273]

[0274] (C') Ionic photobase generator

[0275] (C'-1): Ionic photobase generator (compound having the following chemical structure)

[0276] [Chemical formula 18]

[0277]

[0278] (D) Filling material

[0279] (D-1): Silica filler (manufactured by JGC Catalysts and Chemicals Ltd., average particle size: 5 μm)

[0280] (D-2): Epoxy-modified spherical silica filler (manufactured by ADMATECHS CO., LTD., SC2050MA, average particle size 0.5 μm)

[0281] (E) Colorant

[0282] (E-1) Black pigment (a pigment obtained by mixing 32 parts by mass of a phthalocyanine-based cyan pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based red pigment (Pigment Red 177) so that the total amount of the three pigments / the amount of styrene acrylic resin=1 / 3 (mass ratio).)

[0283] (F) Compounds having a thiol group

[0284] (F-1): Pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., PEMP)

[0285] (G) Photoradical initiator

[0286] (G-1) 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (manufactured by IGM Resins, Omnirad (registered trademark) 127D)

[0287] (G-2) 2-(Dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (manufactured by IGM Resins, Omnirad (registered trademark) 379)

[0288] (H) Non-energy ray-curable film-forming component

[0289] (H-1): A (meth)acrylate copolymer prepared by copolymerizing 33 parts by mass of n-butyl acrylate, 27 parts by mass of methyl acrylate, 25 parts by mass of 4-acryloylmorpholine and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 700,000, glass transition temperature: 2°C)

[0290] Using the obtained coating liquid, the following measurements and evaluations were performed.

[0291] (Evaluation of delayed curing properties)

[0292] The delayed curing property was evaluated by bonding copper plates together using the coating solution and measuring the shear bond strength after bonding. First, prepare two copper plates with a width of 10 mm, a length of 45 mm, and a thickness of 1.5 mm. Apply the coating solution that has been prepared for 0.5 hours to an area with a width of 10 mm and a length of 5 mm at one end of one side of a copper plate, and dry it at 60°C for 1 minute. After drying, place the copper plates under an illumination of 50 mW / cm 2 , light intensity is 1600mJ / cm 2 The energy rays were irradiated with ultraviolet light of 365nm wavelength. Then, the bonding area was 50mm 2 (i.e., the width is 10 mm and the length is 5 mm) and the area where the two copper plates overlap each other when viewed from above is also only 50 mm 2 In this way, one end of one side of another copper plate is overlapped on the irradiated surface along the length direction, fixed with a clip, and kept at room temperature (23°C) for 1 hour to obtain a test piece with two copper plates bonded with an adhesive film.

[0293] One end of the non-adhesive film in one copper plate of the obtained test piece was fixed by the clamp of the tensile tester, and one end of the non-adhesive film in the other copper plate was fixed by the other clamp of the tensile tester. The test piece was stretched at a tensile speed of 10 mm / min in the longitudinal direction under an environment of 23°C and a relative humidity of 50%, and peeled off in a state where a shear force was loaded on the adhesive film. The stress when the two copper plates were peeled off was taken as the shear bond strength (MPa).

[0294] In addition, two other copper plates were prepared. In addition to setting the light intensity to a weaker 200mJ / cm 2 A test piece was obtained in the same manner as in the above evaluation except that irradiation was performed, and the shear adhesive strength was measured.

[0295] The obtained shear adhesive strength was evaluated based on the following criteria. The results are shown in Table 1.

[0296] ○: The amount of ultraviolet light is 1600 mJ / cm 2 The shear bond strength when irradiated in the manner of 0.6 MPa or more.

[0297] △: When the amount of ultraviolet light is 1600mJ / cm 2 When the dried coating liquid is irradiated in a manner such that the dried coating liquid is solidified and cannot be bonded to another copper plate, the amount of ultraviolet light is 200 mJ / cm 2 When irradiated in the manner of , the coating liquid after drying is not cured and the shear adhesive strength is 0.6 MPa or more.

[0298] ×: When the amount of ultraviolet light is 1600 mJ / cm 2 When the dried coating liquid is irradiated in a manner, the dried coating liquid solidifies and cannot be attached to another copper plate, and the amount of ultraviolet light is a relatively weak 200mJ / cm 2 When irradiation is performed in a manner such as that described above, the dried coating liquid is also solidified and cannot be bonded to another copper plate.

[0299] (Evaluation of performance stability)

[0300] The test pieces were obtained in the same manner as in the evaluation of delayed curing, except that the coating solution prepared 2 hours after production and the coating solution prepared 168 hours after production were used, and the shear bond strength was measured. At this time, the amount of ultraviolet light was 1600 mJ / cm 2. In addition, the coating solution that was prepared 2 hours after production and the coating solution that was prepared 168 hours after production were not stored at room temperature (23°C) but at an accelerated condition of 40°C. This condition takes into account the possibility that the coating solution is exposed to a temperature slightly higher than room temperature during transportation of the coating solution. The shear bond strength change rate shown below was calculated from the measured shear bond strength and the shear bond strength of the test piece obtained using the coating solution that was prepared 0.5 hours after production.

[0301] Shear bond strength change rate 1 (%) = 100 × {(0.5 hour shear bond strength) - (2 hour shear bond strength)} / (0.5 hour shear bond strength)

[0302] Shear bond strength change rate 2 (%) = 100 × {(0.5 hour shear bond strength) - (168 hour shear bond strength)} / (0.5 hour shear bond strength)

[0303] Here, “0.5 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a coating solution that has been prepared for 0.5 hours, “2 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a coating solution that has been prepared for 2 hours, and “168 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a coating solution that has been prepared for 168 hours.

[0304] The obtained shear bond strength change rate was evaluated based on the following criteria.

[0305] ○: Shear bond strength change rate 1 and shear bond strength change rate 2 are both 10% or less, and the curing performance is stable.

[0306] △: The coating liquid was not cured 168 hours after preparation. Although the coating performance was maintained, it could not be cured by ultraviolet irradiation after coating and drying, and could not be bonded to another copper plate, and the shear bond strength could not be measured.

[0307] ×: The coating liquid underwent a curing reaction 168 hours after preparation and solidified before coating, and the performance stability was poor.

[0308] [Table 1]

[0309]

[0310] According to Table 1, the coating liquid of Comparative Example 3, which does not contain a photobase generator but contains a photoradical initiator, is cured even when the amount of light is low, so another copper plate cannot be attached after irradiation with ultraviolet rays. That is, it can be confirmed that Comparative Example 3 does not show delayed curing. In addition, it can be confirmed that since Comparative Examples 1 and 4 contain a compound having a thiol group as a curable component, the performance stability is lacking. It can be confirmed that since Comparative Example 2 contains an ionic photobase generator as a photobase generator, the performance stability is lacking.

[0311] (Experiment 2)

[0312] In Experiment 2, a resin film-forming sheet was prepared in the following manner using a coating liquid containing the following energy-ray-curable resin composition, and the evaluation was performed.

[0313] (Coating liquid containing energy-ray curable resin composition)

[0314] The following components were mixed at the ratios (solid content conversion) shown in Table 2, and diluted with methyl ethyl ketone so that the solid content concentration became 50% by mass to prepare a coating liquid containing an energy-ray-curable resin composition.

[0315] (Production of Resin Film Forming Sheet)

[0316] A first release film (manufactured by LINTEC Corporation, SP-PET382150, 38 μm thick) having a silicone release agent layer formed on one side of a polyethylene terephthalate (PET) film and a second release film (manufactured by LINTEC Corporation, SP-PET 381031, 38 μm thick) having a silicone release agent layer formed on one side of a PET film were prepared.

[0317] After applying the coating liquid containing the energy-ray curable resin composition prepared above to the release surface of the first release film using a blade coater so that the thickness of the final resin film-forming film is 25 μm, the coating liquid was dried at 120° C. for 2 minutes using an oven to form a resin film-forming film formed of the energy-ray curable resin composition. Next, the release surface of the second release film was overlapped on the resin film-forming film, and the two were bonded together to obtain resin film-forming sheets of Example 6F and Comparative Examples 3F and 4F consisting of the first release film, the resin film-forming film (thickness: 25 μm), and the second release film.

[0318] Evaluation of delayed curing property and performance stability was carried out in the same manner as in Experiment 1 except that the obtained resin film forming sheet was used and the resin film forming film in the resin film forming sheet was attached without applying and drying the coating liquid.

[0319] (Evaluation of delayed curing properties)

[0320] First, prepare two copper plates with a width of 10 mm, a length of 45 mm, and a thickness of 1.5 mm. Cut the resin film forming sheet 0.5 hours after the production into a size of 10 mm × 5 mm, peel off the second peeling film (light peeling type peeling film), and stick the exposed resin film forming film on a region with a width of 10 mm and a length of 5 mm at one end of one side of a copper plate, and peel off the first peeling film (heavy peeling type peeling film). The illumination is 50 mW / cm 2 , light intensity is 1600mJ / cm 2 The exposed resin film was irradiated with ultraviolet light of 365 nm wavelength. 2 (i.e., the width is 10 mm and the length is 5 mm), and the area where the two copper plates overlap each other when viewed from above is also only 50 mm. 2 In this way, one end of one side of another copper plate is overlapped on the irradiated surface along the length direction, fixed with a clip, and kept at room temperature (23°C) for 1 hour to obtain a test piece in which two copper plates are bonded with an adhesive film.

[0321] The obtained test pieces were used to measure the shear bond strength in the same manner as in Experiment 1, and the obtained shear bond strength was evaluated according to the following criteria.

[0322] ○: Shear bond strength is 0.6 MPa or more.

[0323] ×: The resin film-forming film was cured by ultraviolet irradiation and could not be bonded to another copper plate.

[0324] (Evaluation of performance stability)

[0325] The same method as the evaluation of delayed curing property was used to obtain test pieces, and the shear bond strength was measured, except that the resin film-forming film that had been produced 2 hours after production and the resin film-forming film that had been produced 168 hours after production were used. 2 . In addition, in the case of the resin film-forming film 2 hours after production and the resin film-forming film 168 hours after production, the resin film-forming film was not stored at room temperature (23°C) but at 40°C as an accelerated condition. This condition takes into account the possibility that the resin film-forming film is exposed to a temperature slightly higher than room temperature during transportation of the resin film-forming film. The shear bond strength change rate shown below was calculated from the measured shear bond strength and the shear bond strength of the test piece obtained using the resin film-forming film 0.5 hours after production.

[0326] Shear bond strength change rate 3 (%) = 100 × {(0.5 hour shear bond strength) - (2 hour shear bond strength)} / (0.5 hour shear bond strength)

[0327] Shear bond strength change rate 4 (%) = 100 × {(0.5 hour shear bond strength) - (168 hour shear bond strength)} / (0.5 hour shear bond strength)

[0328] Here, “0.5 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a resin film formed into a film 0.5 hours after production, “2 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a resin film formed into a film 2 hours after production, and “168 hour shear adhesion strength” means the shear adhesion strength of a test piece obtained by using a resin film formed into a film 168 hours after production.

[0329] The obtained shear bond strength change rate was evaluated according to the following criteria.

[0330] ○: The shear bond strength change rate 3 and the shear bond strength change rate 4 are both 10% or less, and the curing performance is stable.

[0331] △: Although the performance of the resin film-forming film being able to be attached to the copper plate 168 hours after the production was maintained, it was hardened due to ultraviolet irradiation after attachment and could not be attached to another copper plate, and the shear adhesive strength could not be measured.

[0332] ×: Even without ultraviolet irradiation, the resin film-forming film still undergoes a curing reaction and cures before bonding, making it impossible to bond the copper plate, and the performance stability is poor.

[0333] [Table 2]

[0334]

[0335] According to Table 2, the film of Comparative Example 3F, which does not contain a photobase generator but contains a photoradical initiator, is cured by ultraviolet irradiation after being attached to a copper plate, and therefore another copper plate cannot be attached after ultraviolet irradiation. That is, it can be confirmed that Comparative Example 3F does not show delayed curing. In addition, it can be confirmed that Comparative Example 4F lacks performance stability because it contains a compound having a thiol group as a curable component.

[0336] Industrial Applicability

[0337] The energy ray-curable resin composition of the present invention can express desired delayed curing properties and performance stability, and therefore can express sufficient adhesive strength even when adherends are bonded together after being irradiated with energy rays.

Claims

1. An energy-ray-curable resin composition comprising: a compound having two or more (meth)acryloyl groups, a compound having two or more groups containing a β-dicarbonyl structure, and a nonionic photobase generator.

2. The energy-ray-curable resin composition according to claim 1, wherein The group containing a β-dicarbonyl structure is a group containing a β-ketoester structure.

3. The energy-ray-curable resin composition according to claim 2, wherein The group containing a β-ketoester structure is a group containing an acetoacetate structure.

4. The energy-ray-curable resin composition according to any one of claims 1 to 3, wherein The nonionic photobase generator has a group having a structure represented by the following formula: [Chemical formula 1] In the formula, Rv, Rw, Rx, Ry and Rz are organic groups. 5 . A coating liquid comprising the energy-ray-curable resin composition according to claim 1 .

6. The coating solution according to claim 5, wherein In 100 parts by mass of the solid content of the coating liquid, the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is 80 parts by mass or more. 7 . A resin film-forming film, formed from the energy-ray-curable resin composition according to claim 1 .

8. The resin film-forming film according to claim 7, wherein In 100 parts by mass of the resin film-forming film, the total mass of the compound having two or more (meth)acryloyl groups, the compound having two or more groups containing a β-dicarbonyl structure, and the nonionic photobase generator is 30 parts by mass or more.

9. A method for producing a laminate, comprising: A step of applying the coating liquid according to claim 5 or 6 to at least one of the first adherend and the second adherend; After the coating liquid is applied, the step of irradiating the coating liquid or the dried coating liquid with energy rays; and A step of bonding the first adherend and the second adherend together via the coating liquid to form a laminate after irradiating the energy ray.

10. A method for producing a laminate, comprising: A step of attaching the resin film-forming film according to claim 7 or 8 to at least one of a first adherend and a second adherend; After the resin film forming film is attached, a step of irradiating the resin film forming film with energy rays; and A step of bonding the first adherend and the second adherend together via the resin film forming film to form a laminate after irradiating the energy ray.

11. The method for producing a laminate according to claim 9 or 10, wherein: At least one of the first adherend and the second adherend is an adherend that blocks energy rays.

Images