Energy ray-curable resin composition, coating liquid, resin film formation film, and method for producing laminated body

Abstract

To provide an energy ray-curable resin composition having desired delay curability and performance stability, a coating liquid and a resin film formation film containing the same, and a method for producing a laminated body using the coating liquid or resin film formation film.SOLUTION: An energy ray-curable resin composition has a compound having two or more (meth)acryloyl groups, a compound having two or more groups including β-dicarbonyl structures, and a nonionic photobase generator.SELECTED DRAWING: Figure 1

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, the present invention relates to an energy ray curable resin composition exhibiting desired delayed curing properties and performance stability, a coating liquid and a resin film-forming film containing the same, and a method for producing a laminate using the coating liquid or the resin film-forming film. [Background technology]

[0002] A resin composition that is cured by energy rays such as ultraviolet rays (energy ray curable resin composition) is, for example, a composition that changes (cures) from a liquid composition to a solid composition by irradiation with energy rays. Since the process of drying the liquid is unnecessary, the energy ray curable resin composition is used for various applications such as adhesion, coating, printing, medical treatment, and beauty treatment.

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

[0004] Patent Document 1 discloses an ultraviolet-curable resin composition containing at least one selected from poly(meth)acrylate and polyvinyl ether, a compound having a thiol group, a photopolymerization initiator that causes a radical reaction, and an organic compound that absorbs ultraviolet light and emits light. Patent Document 1 discloses that the use of this ultraviolet-curable resin composition allows sufficient curing even in light-shielded areas and deep areas where energy rays are difficult to reach. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2023 / 038001 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, the energy ray curable resin composition is used for adhesion purposes. For example, when the energy ray curable resin composition is used to bond adherends that do not transmit energy rays, if the adherends are completely covered with the energy ray curable resin composition, there will be many areas of the energy ray curable resin composition where the energy rays do not reach at all. Therefore, even if the ultraviolet ray curable resin composition disclosed in Patent Document 1 is used, there is a high possibility that it will not be cured sufficiently and a hard adhesive joint will not be obtained.

[0007] In view of this, it has been considered to apply an energy ray-curable resin composition to adherends that are impermeable to energy rays, irradiate the adherends with energy rays, and then bond the adherends to each other.

[0008] However, in curing using radical reactions, the reaction is completed immediately after irradiation with energy rays, and therefore, even if adherends are to be bonded together after irradiation with energy rays, there is a problem that the curing reaction is completed and no tack remains on the irradiated surface, making it impossible to bond the adherends together.

[0009] Therefore, there is a demand for a composition in which the curing reaction proceeds slowly, i.e., a composition having delayed curing properties, rather than a composition in which the curing reaction is completed immediately after the energy ray irradiation. Furthermore, in addition to such delayed curing properties after the energy ray irradiation, the energy ray curable resin composition is required to have stable curing performance (performance stability) without unintentionally progressing the curing reaction with the passage of time (aging) in the state before the energy ray irradiation.

[0010] The present invention has been made in consideration of such circumstances, and aims 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 same, and a method for producing a laminate using the coating liquid or the resin film-forming film. [Means for solving the problem]

[0011] The aspects of the present invention are as follows.

[0012] [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 non-ionic photobase generator.

[0013] [2] The energy ray-curable resin composition according to [1], wherein the group containing a β-dicarbonyl structure is a group containing a β-keto ester structure.

[0014] [3] The energy ray-curable resin composition according to [2], wherein the group containing a β-keto ester structure is a group containing an acetoacetate structure.

[0015] [4] The energy ray-curable resin composition according to any one of [1] to [3], wherein the nonionic photobase generator has a group including a structure represented by the following formula: [ka] In the formula, Rv, Rw, Rx, Ry and Rz are organic groups.

[0016] [5] A coating liquid comprising the energy ray-curable resin composition according to any one of [1] to [4].

[0017] [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.

[0018] [7] A resin film formed from the energy ray-curable resin composition according to any one of [1] to [4].

[0019] [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 non-ionic photobase generator is 30 parts by mass or more in 100 parts by mass of the resin film-forming film.

[0020] [9] A step of applying the coating liquid according to [5] or [6] to at least one of a first adherend and a second adherend; A step of irradiating the coating liquid or the dried coating liquid with energy rays after applying the coating liquid; and a step of laminating the first adherend and the second adherend via the coating liquid to form a laminate after the energy ray irradiation.

[0021]

[10] 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; A step of irradiating the resin film-forming film with energy rays after attaching the resin film-forming film; and after the energy ray irradiation, bonding the first adherend and the second adherend via the resin film-forming film to form a laminate.

[0022]

[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. Effect of the Invention

[0023] According to the present invention, it is possible 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 same, and a method for producing a laminate using the coating liquid or the resin film-forming film. [Brief description of the drawings]

[0024] [Figure 1]FIG. 1 is a schematic cross-sectional view of an example of the sheet for resin film formation according to this embodiment. [Diagram 2] FIG. 2 is a schematic cross-sectional view of an example of the composite sheet for resin film formation according to this embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings based on specific embodiments. First, the main terms used in this specification will be explained.

[0026] The work refers to a plate-shaped body to which the resin film forming film provided in the resin film forming sheet according to this embodiment is attached and then divided into individual pieces. The resin film forming film is attached to the back surface of the work. Examples of the work include a circular wafer (including a case having an orientation flat), a rectangular panel level package, and a strip (rectangular substrate) with molded resin sealing, among which a wafer is preferred from the viewpoint of easily obtaining the effects of the present invention. The wafer may be, for example, a semiconductor wafer such as a silicon wafer, a gallium arsenide wafer, a silicon carbide wafer, a gallium nitride wafer, or an indium phosphide wafer, or an insulator wafer such as a glass wafer, a lithium tantalate wafer, or a lithium niobate wafer, or may be a reconstructed wafer made of a resin and a semiconductor used in the manufacture of a fan-out package or the like. From the viewpoint of easily obtaining the effects of the present invention, a semiconductor wafer or an insulator wafer is preferred, and a semiconductor wafer is more preferred.

[0027] Singulation of a work refers to dividing the work into individual circuits to obtain individual work pieces. For example, if the work is a wafer, the individual work pieces are chips, and if the work is a panel level package or a strip (rectangular substrate) sealed with molded resin, the individual work pieces are semiconductor packages.

[0028] The "front surface" of a workpiece refers to the surface on which circuits, electrodes, etc. are formed, and the "back surface" of a workpiece refers to the surface on which no circuits, etc. are formed. The electrodes may be convex electrodes such as bumps.

[0029] The term "principal surface" refers to a surface that is larger in area than the other surfaces among the surfaces that constitute a plate-like body. Usually, a plate-like body has two principal surfaces and other side surfaces, and the two principal surfaces face each other. In the case of a workpiece, the "front surface" and the "rear surface" are the principal surfaces.

[0030] "(Meth)acrylate" is used as the term to refer to both "acrylate" and "methacrylate," and similar terms.

[0031] The term "energy rays" refers to ultraviolet rays, electron beams, etc., and is preferably ultraviolet rays.

[0032] Unless otherwise specified, "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC). Measurements using this method are performed, for example, using a high-speed GPC device "HLC-8120GPC" manufactured by Tosoh Corporation, connected in this order to high-speed columns "TSK guard column HXL-H", "TSK Gel GMHXL", and "TSK Gel G2000 HXL" (all manufactured by Tosoh Corporation), under the following conditions: column temperature: 40°C, flow rate: 1.0 mL / min, and a differential refractometer as the detector.

[0033] The release film is a film that supports the resin film-forming film in a peelable manner. The term "film" is not limited to a specific thickness, and is used to include a sheet.

[0034] Mass ratios in the description of compositions such as energy ray-curable resin compositions are based on the active ingredients (solid content), and do not include the solvent unless otherwise specified.

[0035] (1. Energy Ray-Curable Resin Composition) The energy ray curable resin composition is a composition used 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, an adhesive liquid containing the energy ray curable resin composition is usually applied to one adherend, and the other adherend is attached to the applied surface, and then the adhesive liquid is irradiated with energy rays to cure the adhesive film, thereby forming an adhesive film that bonds the adherends together.

[0036] However, if the adherends to be bonded are ones that do not transmit energy rays, even if the adherends are bonded together and then irradiated with energy rays, the amount of energy rays reaching the coated surface will be zero or extremely small, resulting in a problem that the energy ray-curable resin composition does not cure and the adherends cannot be sufficiently bonded together.

[0037] In order to bond such adherends, there is a method in which an adhesive liquid is applied to one adherend, energy rays are irradiated, and then the other adherend is laminated. In this case, the energy ray curable resin composition is required to have a slow curing reaction after energy ray irradiation (delayed curing). If the resin film is formed by curing immediately after energy ray irradiation, the surface of the cured resin film will not have tack, and the other adherend will not stick even if it is laminated.

[0038] In addition, the energy ray curable resin composition may be used not only immediately after preparation, but also after storage for a certain period of time. However, the energy ray curable resin composition may change over time, and the curing reaction may proceed unintentionally. In this case, the performance of the energy ray curable resin composition may vary depending on the storage period. Therefore, the energy ray curable resin composition is required to have stable curing performance (performance stability) without unintentionally proceeding the curing reaction over time in the state before energy ray irradiation.

[0039] 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 composition shown below. 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 non-ionic photobase generator (C).

[0040] (1.1. Energy Ray-Curable Resin Component (A)) The energy ray curable resin component is a resin component that is cured by irradiation with energy rays, and is a main component that is responsible for film-forming properties, flexibility, etc., and forms 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.

[0041] Examples of the compound having two or more (meth)acryloyl groups include a polymer (p1) having two or more (meth)acryloyl groups and a weight average molecular weight of 80000 to 2000000, and a compound (p2) having two or more (meth)acryloyl groups and a molecular weight of 100 to 80000. The polymer (p1) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

[0042] (1.1.1. Polymer (p1)) An example of the polymer (p1) is an acrylic resin (p1-1) obtained by reacting an acrylic polymer (p11) having two or more functional groups capable of reacting with groups possessed by other compounds with an energy ray-curable compound (p12) having a group reactive with the functional group and a (meth)acryloyl group.

[0043] Examples of functional groups capable of reacting with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, substituted amino groups (groups having a structure in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms), epoxy groups, etc. In this embodiment, the functional group is preferably a hydroxyl group.

[0044] (1.1.2. Acrylic polymers having two or more functional groups (p11)) The acrylic polymer (p11) having two or more functional groups may be, for example, a copolymer of a (meth)acrylic monomer having a functional group and a (meth)acrylic monomer not having a functional group, and may further include a copolymer of a monomer other than the (meth)acrylic monomer (non-(meth)acrylic monomer) in addition to these monomers. By using at least a (meth)acrylic monomer having a functional group as a constituent monomer, the polymer obtained by reacting this becomes an acrylic polymer (p11) having two or more functional groups.

[0045] The acrylic polymer (p11) may be a random copolymer or a block copolymer, and a known method can be used for the polymerization method.

[0046] Examples of the (meth)acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

[0047] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates; non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryloyl skeleton); and the like.

[0048] Examples of the carboxy group-containing monomer 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; and (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

[0049] The (meth)acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.

[0050] The (meth)acrylic monomer having a functional group constituting the acrylic polymer (p11) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0051] Examples of the (meth)acrylic 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, and (meth)acrylic acid. Examples of (meth)acrylic acid alkyl esters include those in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as isononyl, 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 (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate).

[0052] In addition, examples of (meth)acrylic monomers not having a functional group include alkoxyalkyl group-containing (meth)acrylic acid esters such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and derivatives thereof; and (meth)acrylic acid esters having a non-crosslinkable tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

[0053] The (meth)acrylic monomer having no functional group constituting the acrylic polymer (p11) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0054] Examples of the non-(meth)acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0055] The non-(meth)acrylic monomer constituting the acrylic polymer (p11) may be of only one kind, or of two or more kinds. When it is of two or more kinds, the combination and ratio thereof can be selected arbitrarily.

[0056] 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 to the total amount of the structural units constituting the acrylic polymer (p11) is preferably 0.1 to 50 mass%, more preferably 1 to 40 mass%, and particularly preferably 3 to 30 mass%. When the ratio is in such a range, the content of the energy ray curable group in the acrylic resin (p1-1) obtained by reacting the acrylic polymer (p11) with the energy ray curable compound (p12) makes it possible to adjust the degree of curing of the resin film to a preferred range.

[0057] The acrylic polymer (p11) constituting the acrylic resin (p1-1) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0058] (1.1.3. Energy ray curable compounds (p12)) The energy ray curable compound (p12) is preferably a group having one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with a functional group possessed by the acrylic polymer (p11), and more preferably a group having 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.

[0059] The number of (meth)acryloyl groups that the energy ray curable compound (p12) has in one molecule 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 from the energy ray curable resin component and the curing agent. For example, even if the energy ray curable compound (p12) has one (meth)acryloyl group in one molecule, the acrylic polymer (p11) has two or more functional groups as described above, so the resulting polymer (p1-1) is a compound having two or more (meth)acryloyl groups.

[0060] Examples of the energy ray-curable compound (p12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate; Examples of the isocyanate include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate.

[0061] Among these, the energy ray curable compound (p12) is preferably 2-methacryloyloxyethyl isocyanate.

[0062] The energy ray-curable compound (p12) constituting the acrylic resin (p1-1) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0063] In the acrylic resin (p1-1), the content ratio of the energy ray-curable group derived from the energy ray-curable compound (p12) 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 %.

[0064] When the content ratio is within this range, the adhesive strength of the resin film is increased. When the energy ray curable compound (p12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

[0065] The weight average molecular weight (Mw) of the polymer (p1) is preferably from 80,000 to 2,000,000, and more preferably from 300,000 to 1,500,000. The "weight average molecular weight" here is as explained above.

[0066] The energy curable resin composition may contain only one type of polymer (p1), or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0067] In 100 parts by mass of the energy ray-curable resin composition, the content of the polymer (p1) is preferably from 1 to 70 parts by mass, more preferably from 5 to 60 parts by mass, and particularly preferably from 10 to 50 parts by mass.

[0068] (1.1.4.Compound (p2)) The compound (p2) may be, for example, a polyfunctional monomer or oligomer having two or more (meth)acryloyl groups, and is preferably a polyfunctional acrylate compound having two or more (meth)acryloyl groups.

[0069] Examples of polyfunctional acrylate compounds having two or more (meth)acryloyl groups include bifunctional (meth)acrylates having two (meth)acryloyl groups in one molecule, polyfunctional (meth)acrylates having three or more (meth)acryloyl groups in one molecule, and (meth)acrylate oligomers having two or more (meth)acryloyl groups in one molecule.

[0070] Examples of bifunctional (meth)acrylates 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)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also known as tricyclodecane dimethylol di(meth)acryloyl). acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, and the like are examples.

[0071] Examples of polyfunctional (meth)acrylates having three or more (meth)acryloyl groups in one molecule include tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin 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.

[0072] An example of a (meth)acrylate oligomer having two or more (meth)acryloyl groups in one molecule is a polyfunctional urethane (meth)acrylate oligomer.

[0073] The weight average molecular weight of the compound (p2) is preferably 100 to 80,000, more preferably 100 or more and less than 80,000, further preferably 200 to 30,000, and particularly preferably 300 to 15,000.

[0074] The compound (p2) contained in the energy ray-curable resin composition may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0075] In 100 parts by mass of the energy ray-curable resin composition, the content of the compound (p2) is preferably from 1 to 70 parts by mass, more preferably from 10 to 60 parts by mass, and particularly preferably from 15 to 55 parts by mass.

[0076] 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 setting the content of the energy ray curable resin component (A) within the above range, it is easier to obtain an energy ray curable resin composition that exhibits the desired delayed curing property and performance stability, and it is easier to obtain a resin film with better adhesion to an adherend.

[0077] In this embodiment, it is not preferable that the energy ray curable resin component contains an epoxy resin from the viewpoint of the performance stability of the energy ray curable resin composition. Therefore, it is preferable that the energy ray curable resin component (A) does not substantially contain an epoxy resin. "Substantially does not contain an epoxy resin" means that the content of the epoxy resin is 1 part by mass or less in 100 parts by mass of the energy ray curable resin composition.

[0078] (1.2. Hardener (B)) In this embodiment, a compound (B) having two or more groups containing a β-dicarbonyl structure is used as an auxiliary (curing agent) for curing the energy ray curable resin component (A). The β-dicarbonyl structure is a structure having another carbonyl group at the β-position of a carbonyl group.

[0079] A compound having a group containing a β-dicarbonyl structure undergoes a Michael addition reaction with a compound having a double bond having Michael addition acceptor by abstracting the hydrogen at the α-position with a base.

[0080] In this embodiment, the compound having two or more groups containing a β-dicarbonyl structure has hydrogen of the active methylene portion abstracted (i.e., deprotonated) by a base generated by irradiation of an energy ray to a photobase generator described later. As a result, a carbanion is generated, and the carbanion attacks the double bond site of the (meth)acryloyl group contained in the energy ray curable resin component, causing Michael addition to proceed, and the curing reaction proceeds. Since the curing reaction by this Michael addition has a slower reaction rate than the curing reaction of the (meth)acryloyl group by radicals, the curing reaction does not occur immediately upon irradiation of the energy ray, and 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 according to this embodiment can achieve delayed curability.

[0081] 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, the energy ray curable resin composition becomes a cured product in a form in which these compounds are intricately entangled by addition reaction with multiple compounds, respectively.

[0082] From the viewpoint of delayed curing properties and performance stability, it is preferable that the compound having a group containing a β-dicarbonyl structure does not form a metal complex.

[0083] In this embodiment, the β-dicarbonyl structure is preferably a β-ketoester structure represented by the following formula Y. This makes it easier to obtain a resin film from the energy ray-curable resin composition that has superior adhesion to an adherend.

[0084] [ka] In formula Y, R 1 and R 2 represents an organic group.

[0085] Furthermore, the β-ketoester structure can be represented by R 1 is preferably an acetoacetate structure in which R is a methyl group. A compound having two or more groups containing an acetoacetate structure can be synthesized, for example, from a polyfunctional alcohol and tertiary butyl acetoacetate.

[0086] Specific examples of the compound having a β-ketoester structure include the compounds represented by the following formulas Y-1 to Y-5.

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] 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 at least one 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 setting the content of the compound (B) within the above range, it is easier to obtain an energy ray curable resin composition exhibiting the desired delayed curing property and performance stability, and it is easier to obtain a resin film with better adhesion to the adherend.

[0093] 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 at least one 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 setting 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, a resin film with better adhesion to the adherend is easily obtained.

[0094] (1.3. Photobase Generator) 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 photoanionic polymerization initiator (photo base generator), and is a compound that generates a base by irradiation with energy rays. The generated base advances the deprotonation of 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 advances. 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 described above can be used as a latent curing agent with excellent storage stability.

[0095] Examples of the photobase generator include a photobase generator that does not have an ionic bond in its molecular structure (non-ionic photobase generator (C)) and a photobase generator that has an ionic bond in its molecular structure (ionic photobase generator). In this embodiment, the non-ionic photobase generator (C) is used from the viewpoint of the performance stability of the energy ray-curable resin composition containing the photobase generator.

[0096] Examples of the non-ionic photobase generator include a photobase generator represented by the following general formula (α1).

[0097] [ka]

[0098] In the formula (α1), n ​​represents an integer of 0 to 4. 11 Rα 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 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, 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 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. 1 represents an amino group.

[0099] In formula (α1), n ​​usually represents an integer of 0 to 4, preferably an integer of 1 to 2, and more preferably 2. When n is 2, R 1 The substitution position of is -CHRα on the benzene ring as specified in formula (α1). 12 - and -NO bond position 1 2 When the bonding position with respect to the 2nd position is taken as the bonding position, the 4th and 5th positions are preferred.

[0100] 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 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, and a halogen atom; 11 When there are a plurality of, they may be different from each other.

[0101] Rα in formula (α1) 11Examples of the alkyl group having 1 to 18 carbon atoms represented by include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, and a n-dodecyl group, and an alkyl group having 2 to 6 carbon atoms is preferable.

[0102] Rα in formula (α1) 11 Examples of the alkenyl group having 2 to 18 carbon atoms represented by include a vinyl group, a propenyl group, a 1-butenyl group, an iso-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, a 3-methyl-1-butenyl group, a 2-methyl-2-butenyl group, a 2,2-dicyanovinyl group, a 2-cyano-2-methylcarboxyvinyl group, and a 2-cyano-2-methylsulfonevinyl group.

[0103] Rα in formula (α1) 11 Examples of the alkynyl group having 2 to 18 carbon atoms represented by include an ethynyl group, a 1-propynyl group, and a 1-butynyl group.

[0104] Rα in formula (α1) 11 Examples of the aryl group having 6 to 12 carbon atoms represented by include a phenyl group, a naphthyl group, and a tolyl group, and an aryl group having 6 to 10 carbon atoms is preferable.

[0105] Rα in formula (α1) 11 Examples of the acyl group having 1 to 18 carbon atoms represented by include a formyl group, an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an iso-propylcarbonyl group, an n-butylcarbonyl group, an n-pentylcarbonyl group, an iso-pentylcarbonyl group, a neo-pentylcarbonyl group, a 2-methylbutylcarbonyl group, and a nitrobenzylcarbonyl group.

[0106] Rα in formula (α1) 11 Examples of the aroyl group having 7 to 18 carbon atoms represented by the formula (1) include a benzoyl group, a toluoyl group, a naphthoyl group, and a phthaloyl group.

[0107] Rα in formula (α1) 11 Examples of the alkoxy group having 1 to 18 carbon atoms represented by include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, an n-hexyloxy group, and an n-dodecyloxy group.

[0108] Rα in formula (α1) 11 Examples of the alkylthio group having 1 to 18 carbon atoms represented by the formula (I) include a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, an iso-butylthio group, a sec-butylthio group, a t-butylthio group, an n-pentylthio group, an iso-pentylthio group, a 2-methylbutylthio group, a 1-methylbutylthio group, a neo-pentylthio group, a 1,2-dimethylpropylthio group, and a 1,1-dimethylpropylthio group.

[0109] Rα in formula (α1) 11 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0110] Rα in formula (α1) 11 Rα is 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 If there are multiple Rα 11 is preferably an alkoxyl group, and all Rα 11 More preferably, is an alkoxy group.

[0111] In formula (α1), Rα 12represents 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.

[0112] Rα in 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 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 represented by Rα in the formula (α1) are as follows: 11 Examples of 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 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 represented by the formula (I) are the same as those represented by the formula (I).

[0113] Rα in formula (α1) 12 is 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, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

[0114] In formula (α1), Xα 1 represents an amino group. Xα in formula (α1) 1 The amino group represented by is a substituted amino group and an unsubstituted amino group (NH 2 The substituted amino group may be either a mono-substituted amino group or a di-substituted amino group.

[0115] In this embodiment, Xα 1 It is preferable that the compound has a group containing a structure represented by the following formula (α1-X).

[0116] [ka] In the formula, Rv, Rw, Rx, Ry and Rz are organic groups. More preferably, Rv is single-bonded to the ester group in the above general formula (α1), and Rw, Rx, Ry and Rz are alkyl groups or cycloalkyl groups, further preferably, Rw, Rx, Ry and Rz are alkyl groups having 3 or less carbon atoms, and particularly preferably, Rw, Rx, Ry and Rz are methyl groups.

[0117] Specific examples of the compound represented by formula (α1) include the following compounds (α1-1) to (α1-8).

[0118] [ka]

[0119] Further, examples of non-ionic photobase generators include coumaric acid-type photobase generators represented by the following general formula (α2), which have better stability as materials and better efficiency in generating a base when irradiated with energy rays.

[0120] [ka]

[0121] In general formula (α2), Rα 21 and Rα 22 Rα are each independently a hydrogen atom or an organic group and may be the same or different. 21 and Rα 22 may be bonded to form a ring structure, and may contain a heteroatom bond. 21 and Rα 22 At least one of Rα is an organic group. 23 and Rα 24Rα are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group, and may be the same or different. 25 , Rα 26 , Rα 27 and Rα 28 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio 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, and may contain a bond of a heteroatom. 29 is a hydrogen atom or an organic group.

[0122] In general formula (α2), Rα 21 and Rα 22 From the viewpoint of the basicity of the generated base, it is preferable that both of the groups are alkyl groups or are bonded to each other to form an alkylene chain having a cyclic structure, and it is most preferable that both of the groups are bonded to each other to form an alkylene chain having a cyclic structure. The number of carbon atoms constituting the alkyl group or alkylene chain is preferably 1 to 20, and more preferably 1 to 8.

[0123] Also, Rα 21 -N-Rα 22 is preferably a group constituting the structure shown in 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 C(said Rα 21 The group containing C)-N, Ry and Rz identical to C in Rα22 More preferably, Rw, Rx, Ry and Rz are an alkyl group or a cycloalkyl group, particularly preferably, Rw, Rx, Ry and Rz are an alkyl group having 3 or less carbon atoms, and most preferably, Rw, Rx, Ry and Rz are a methyl group.

[0124] In general formula (α2), Rα 23 and Rα 24 are preferably a hydrogen atom or an alkyl group, and most preferably both are hydrogen atoms. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 8 carbon atoms.

[0125] In general formula (α2), Rα 25 , Rα 26 , Rα 27 and Rα 28 are preferably hydrogen atoms, alkyl groups, or alkoxy groups, and most preferably all hydrogen atoms. The alkyl groups preferably have 1 to 20 carbon atoms, and more preferably have 1 to 8 carbon atoms. The alkoxy groups preferably have 1 to 20 carbon atoms, and more preferably have 1 to 8 carbon atoms.

[0126] In general formula (α2), Rα 29 is preferably a hydrogen atom or an organic group which is a protecting group that can be removed by irradiation with energy rays and / or heating, and is most preferably a hydrogen atom.

[0127] As the coumaric acid type compound represented by the general formula (α2), the following compounds (α2-1) and (α2-2) are preferred, with (α2-1) being more preferred.

[0128] [ka]

[0129] Furthermore, as the non-ionic photobase generator, a urethane compound (α3)-1 represented by the following general formula is also preferred.

[0130] [ka]

[0131] In addition, as the non-ionic photobase generator, an oxime ester compound is also preferred. As the oxime ester compound, any compound that generates a basic substance upon irradiation with light can be used. In addition, a compound having two oxime ester groups in the molecule can also be preferably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (α4) can be mentioned.

[0132] [ka]

[0133] In general formula (α4), Xα 4 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 with 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 1 to 8 carbon atoms, or a dialkylamino group), a naphthyl group (substituted with 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 1 to 8 carbon atoms, or a dialkylamino group), and Yα 4 , Zα 4 respectively represent 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 with 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 1 to 8 carbon atoms, or a dialkylamino group), a naphthyl group (substituted with 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 1 to 8 carbon atoms, or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group; 4represents a bond or an alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, or 4,2'-styrene-diyl, and n is an integer of 0 or 1.

[0134] In particular, in the general formula (α4), Xα 4 , Yα 4 are each a methyl group or an ethyl group, and Zα 4 is a methyl group or a phenyl group, n is 0, and Arα 4 is preferably a bond, phenylene, naphthylene, thiophene or thienylene.

[0135] Furthermore, preferred carbazole oxime ester compounds include compounds represented by the following general formula (α5).

[0136] [ka]

[0137] In general formula (α5), Rα 51 Rα 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 Rα 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. 53 Rα 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 with a phenyl group, or a benzyl group which may be substituted with an alkoxy group having 1 to 4 carbon atoms. 54 is a nitro group or Xα 5 It represents an acyl group represented by -C(=O)-. Xα 5represents an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula:

[0138] [ka]

[0139] Among the above-mentioned nonionic photobase generators, the coumaric acid type photobase generators represented by the above general formula (α2) are preferred, and the compound represented by (α2-1) is more preferred.

[0140] 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, it is easier to obtain an energy ray-curable resin composition exhibiting the desired delayed curing property and performance stability, and it is easier to obtain a resin film with better adhesion to the adherend.

[0141] The photobase generator can be synthesized as a condensation product by referring to the examples described in, for example, JP-A-2009-80452, JP-A-2011-52214, JP-A-2021-177210, and JP-A-2019-45735.

[0142] (1.4. Filler) In this embodiment, the energy ray curable resin composition may contain a filler (D). By containing a filler, the resin film obtained by curing the energy ray curable resin composition can be more easily adjusted in thermal expansion coefficient, and by bringing this thermal expansion coefficient closer to the thermal expansion coefficient of the adherend, the adhesion reliability of the adherend via the resin film is further improved. In addition, by containing a filler (D) in the energy ray curable resin composition, a hard resin film can be obtained, and the moisture absorption rate of the resin film can be further reduced, and the adhesion reliability of the adherend via the resin film is further improved.

[0143] The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler from the viewpoint of shape stability at high temperatures.

[0144] Examples of preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, etc.; beads of these inorganic fillers that are spherical; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, silica and surface-modified silica are preferred. The surface-modified silica is preferably surface-modified with a coupling agent, and more preferably surface-modified with a silane coupling agent.

[0145] 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.

[0146] By setting the average particle size of the filler within the above range, the energy ray curable resin composition can be more easily handled, and as a result, the quality of the energy ray curable resin composition tends to be stable.

[0147] In this specification, unless otherwise specified, the term "average particle size" refers to the particle size (D50) at an integrated value of 50% in a particle size distribution curve determined by a laser diffraction scattering method.

[0148] The content of the filler when the total weight of the energy ray curable resin composition is 100 parts by mass is preferably determined according to the form of the energy ray curable resin composition when used. For example, in the case of a liquid coating liquid containing the energy ray curable resin composition, the content of the filler is preferably at least one of 0.5 to 60 parts by weight, 1 to 50 parts by weight, 1.5 to 45 parts by weight, and 2 to 20 parts by weight. In addition, in the case of a resin film-forming film made of the energy ray curable resin composition, the content of the filler is preferably at least one of 15 to 80 parts by weight, 30 to 70 parts by weight, 35 to 65 parts by weight, and 40 to 60 parts by weight.

[0149] By setting the lower limit of the filler content within the above range, the adhesive reliability is further improved, and by setting the upper limit of the filler content within the above range, the handleability of the energy ray-curable resin composition is further improved.

[0150] (1.5. Colorants) The energy ray curable resin composition may contain a colorant (E). When the resin film is used as a protective film described later, the back surface of the adherend such as a chip is concealed by the resin film, and various electromagnetic waves generated in electronic devices can be blocked, thereby reducing malfunction of the chip.

[0151] As the colorant (E), for example, known ones such as organic pigments, organic dyes, inorganic pigments, etc. In this embodiment, inorganic pigments are preferred.

[0152] Examples of inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide)-based pigments, and ATO (antimony tin oxide)-based pigments. Among these, it is particularly preferable to use carbon black. Carbon black can block electromagnetic waves in a wide wavelength range.

[0153] 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 at least one of the ranges 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.

[0154] The average particle size of the colorant (particularly 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.

[0155] (1.6. Other Additives) The energy ray-curable resin composition may contain other additives, such as a non-energy ray-curable film-forming component (e.g., a non-energy ray-curable acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, or a saturated polyester resin), a coupling agent, a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, a gettering agent, a tackifier, a release agent, and the like, within the range not impairing the effects of the present invention.

[0156] On the other hand, in the present embodiment, from the viewpoint of performance stability, it is preferable that the composition does not substantially contain an isocyanate compound and does not substantially contain an isothiocyanate compound. "Substantially not containing an isocyanate compound" and "substantially not containing an isothiocyanate compound" mean that the total content of the isocyanate compound and the isothiocyanate compound is 1 part by mass or less in 100 parts by mass of the energy ray curable resin composition.

[0157] In addition, in the present embodiment, from the viewpoint of delayed curing, it is preferable that the composition is substantially free of a photoradical initiator. The term "substantially free of a 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.

[0158] (2. Form of Energy Ray-Curable Resin Composition During Use) The form of the energy ray curable resin composition according to the present embodiment can be appropriately selected depending on the application. In the present embodiment, it is preferable to use it as a coating liquid containing the energy ray curable resin composition. It is also preferable to use it as a resin film-forming film made of the energy ray curable resin composition.

[0159] (2.1. Coating solution) In this embodiment, the coating liquid containing the above-mentioned energy ray curable resin composition may be a coating liquid made of a liquid energy ray curable resin composition, or may be a coating liquid containing the energy ray curable resin composition and a solvent.

[0160] From the viewpoint of delayed curing, the coating liquid is preferably used as an adhesive liquid. The adhesive liquid is applied to an adherend, and the adhesive liquid is irradiated with energy rays, thereby initiating a curing reaction of the energy ray curable resin composition. As described above, this curing reaction is delayed curing, so that even after irradiation with energy rays, the tack of the irradiated surface is maintained, and the adherends can be bonded to each other.

[0161] 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, per 100 parts by mass of solid content. This makes it easier to obtain a resin film with better adhesion to the adherend from the energy ray-curable resin composition.

[0162] The solvent may be selected from those usable as a coating liquid depending on the application, etc. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, cyclohexane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloromethane, etc., alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, etc., ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, etc., esters such as ethyl acetate, butyl acetate, etc., and cellosolve-based solvents such as ethyl cellosolve, etc.

[0163] When the coating liquid contains a solvent, the solid content of the coating liquid may be set to any range depending on the application, etc. In this embodiment, the solid content 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. The viscosity of the coating liquid may also be set to any range within the range that allows application to the adherend.

[0164] (2.1.1. Preparation of coating solution) The coating liquid containing the energy ray curable resin composition is obtained by thoroughly mixing an energy ray curable resin component (a compound having two or more (meth)acryloyl groups), a compound having two or more groups containing a β-dicarbonyl structure (curing agent), a non-ionic photobase generator, and, if necessary, other additive components such as a filler, and a solvent. When the energy ray curable resin component is a polymer, the mixture of monomers constituting the polymer may be polymerized by a known polymerization method such as a radical polymerization method to obtain the energy ray curable resin component.

[0165] (2.2. Resin film forming film) In this embodiment, the resin film formed from the above-mentioned energy ray-curable resin composition forms a resin film by irradiation with energy rays.

[0166] The resin film-forming film may be used as a film (protective film-forming film) for forming a protective film for protecting the back surface of a chip having a circuit or the like on its surface. It may also be used as an adhesive film-forming film for bonding adherends together. It may also be used as a film for forming a protective film that exposes the upper part of a convex electrode such as a bump formed on a wafer or the like and covers and protects the wafer surface and the lower part of the convex electrode. As with the coating liquid, it is preferably used as an adhesive film-forming film from the viewpoint of delayed curing. That is, even after the adhesive film-forming film is irradiated with energy rays, the tack of the irradiated surface is maintained, so that adherends can be bonded together.

[0167] 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. This makes it easier for the energy ray-curable resin composition to obtain a resin film with better adhesion to the adherend.

[0168] The thickness of the resin film-formed film is not particularly limited, but is preferably 100 μm or less, 80 μm or less, 60 μm or less, or 45 μm or less. The thickness of the resin film-formed film is preferably 5 μm or more, 10 μm or more, or 13 μm or more. The thickness of the resin film-formed film can be arbitrarily selected and set from the above upper and lower limit values. When the thickness of the resin film-formed film is within the above range, the performance of the obtained resin film becomes better.

[0169] The thickness of the resin film-formed film means the thickness of the entire resin film-formed film. For example, the thickness of a resin film-formed film composed of multiple layers means the total thickness of all layers constituting the resin film-formed film.

[0170] The resin film forming film is usually used in the form of a sheet for resin film formation or a composite sheet for resin film formation.

[0171] The sheet for resin film formation 1 according to this embodiment has a configuration shown in Fig. 1. The resin film-forming film 10 has two opposing main surfaces 10a and 10b. A first release film 21 supporting the resin film-forming film 10 is disposed on the main surface 10a, and a second release film 22 supporting the resin film-forming film 10 is disposed on the main surface 10b.

[0172] The composite sheet for resin film formation has a resin film-forming film and a support sheet that supports the resin film-forming film. The support sheet is other than a release film and has a configuration that can support the resin film-forming film. An example of the support sheet is a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer.

[0173] Specifically, as shown in FIG. 2, the composite sheet 2 for resin film formation has a configuration including an adhesive sheet 4 formed by laminating an adhesive layer 42 on one side of a substrate 41 as a support sheet, a resin film-forming film 10 laminated so that the main surface 10a is in contact with the adhesive layer 42 of the adhesive sheet 4, and a release film 23 arranged on the main surface 10b of the resin film-forming film 10. Furthermore, a jig adhesive layer (not shown) may be arranged on the periphery of the resin film-forming film 10. The jig adhesive layer is a layer for adhering the composite sheet for resin film formation to a jig such as a ring frame. It is preferable that the first release film 21, the second release film 22, and the release film 23 are all release films formed by forming a silicone-based release agent layer on one side of a polyethylene terephthalate (PET) film.

[0174] (2.2.1. Production of resin film-formed film) The resin film-forming film can be manufactured by a known method. For example, it may be manufactured 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 knife coater, a roll knife coater, an air knife coater, a die coater, a bar 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.

[0175] When producing the sheet for resin film formation 1, the release surface of the second release film 22 is further laminated to the exposed surface of the resin film-forming film formed on the first release film 21, whereby the sheet for resin film formation 1 is obtained.

[0176] In addition, when manufacturing the composite sheet 2 for resin film formation, a laminate including an adhesive sheet and a sheet for resin film formation can be used. The adhesive sheet can be manufactured by a known method. For example, a composition constituting the adhesive layer is prepared, applied to the release surface of the third release film, and dried as necessary to form an adhesive layer on the third release film. Next, a substrate is attached to the exposed adhesive layer to obtain an adhesive sheet in which the third release film is disposed on the adhesive layer.

[0177] Next, the second release film of the sheet for resin film formation is peeled off, the third release film of the adhesive sheet is peeled off, and the resin film-forming film and the adhesive layer are bonded together to obtain a composite sheet for resin film formation. The resin film-forming film may be cut out at an appropriate timing to the size of the adherend (e.g., wafer) to be attached or to a size close to the adherend, if necessary.

[0178] (3. Manufacturing method of laminate) As an example of the use of the coating liquid according to this embodiment, a method of manufacturing a laminate in which a first adherend and a second adherend are laminated via an adhesive film using a coating liquid containing the above-mentioned energy ray curable resin composition will be exemplified. The method of manufacturing the laminate according to this embodiment includes at least the following steps 1 to 3. Step 1: A step of applying a coating liquid containing the above-mentioned energy ray-curable resin composition to at least one of a first adherend and a second adherend. Step 2: After applying the coating liquid, the coating liquid or the dried coating liquid is irradiated with energy rays. Step 3: After the energy ray irradiation, the first adherend and the second adherend are bonded together via the coating liquid to form a laminate.

[0179] The coating liquid can be applied by any known means, including, for example, coating means such as a die coater, curtain coater, spray coater, slit coater, or knife coater, printing means such as screen printing or inkjet printing, or dropping means such as a dispenser.

[0180] In addition, when the coating liquid contains a solvent, it may be dried as necessary. Drying conditions may be, for example, a temperature of 50 to 100° C. and a drying time of 30 seconds to 5 minutes.

[0181] In addition, as an example of the use of the resin film-forming film, a method of manufacturing a laminate in which a first adherend and a second adherend are laminated via an adhesive film using the resin film-forming film (adhesive film-forming film) made of the above-mentioned energy ray curable resin composition will be exemplified. In this case, the manufacturing method of the laminate according to this embodiment includes at least the following steps 1 to 3. Step 1: A step of attaching a resin film-forming film made of the above-mentioned energy ray-curable resin composition to at least one of a first adherend and a second adherend. Step 2: After the resin film forming film is attached, the resin film forming film is irradiated with energy rays. Step 3: After the energy ray irradiation, the first adherend and the second adherend are bonded together via the resin film-forming film to form a laminate.

[0182] In either the production method using a coating liquid or the production method using a resin film-forming film, as is clear from steps 1 to 3, the first adherend and the second adherend are bonded together after the energy ray-curable resin composition contained in the coating liquid or the resin film-forming film is irradiated with energy rays. Then, after curing is completed, a laminate is obtained in which the first adherend and the second adherend are laminated together via the adhesive film.

[0183] As described above, the energy ray curable resin composition according to the present embodiment exhibits delayed curing by energy ray irradiation, so that tack remains on the irradiated surface for a certain period of time after irradiation, and 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 is used, curing is completed immediately after energy ray irradiation, so that tack is lost before the first adherend and the second adherend are bonded together, and the first adherend and the second adherend cannot be bonded together.

[0184] In particular, even when at least one of the first and second adherends is an adherend that blocks energy rays, or even when both the first and second adherends are adherends that block energy rays, the first and second adherends can be well bonded to each other. Examples of adherends that block energy rays include adherends that reflect energy rays and adherends that absorb energy rays.

[0185] In addition, as another example of use of the resin film-forming film, a method of forming a resin film on a workpiece, and dicing the workpiece on which the resin film is formed to produce a resin film-coated workpiece is exemplified. The method of producing a resin film-coated workpiece according to this embodiment includes at least the following steps 1 to 3. Step 1: A step of attaching a resin film-forming film made of the above-mentioned energy ray-curable resin composition to the back surface of a workpiece Process 2: The attached resin film is irradiated with energy rays to form a resin film on the back side of the workpiece, obtaining a workpiece with a resin film. Step 3: A step of dividing the resin-film-coated workpiece into individual pieces to obtain a plurality of resin-film-coated workpiece individual pieces.

[0186] In this embodiment, the resin film-forming film is preferably a protective film-forming film. The work is preferably a wafer, more preferably a semiconductor wafer. Therefore, the resin film-coated workpiece is preferably a chip with a protective film, more preferably a semiconductor chip with a protective film.

[0187] In the above-mentioned examples of the application of the coating liquid and the resin film-forming film, the illuminance and the amount of light of the energy ray may be set to a value that allows the energy ray-curable resin composition to be sufficiently cured. For example, the illuminance of the energy ray is 30 to 280 mW / cm 2 The amount of energy is 500-5000mJ / cm 2 This can be done as follows.

[0188] (4. Modifications) In the above-mentioned embodiment, the curing reaction is controlled by using a photobase generator that generates a base by irradiating the photobase generator with energy rays, but a photobase generator that generates a base by heating in addition to the energy ray irradiation may be used. In addition to the energy ray irradiation, heating may be performed to further promote the Michael addition reaction by the base released by the energy ray irradiation. The heating temperature in this case is preferably 50 to 200°C.

[0189] By using such a photobase generator, a curing reaction caused by irradiation with energy rays or a curing reaction caused by heating can be selected depending on the application, etc., and the delayed curing property can be controlled, thereby making it possible to appropriately cure the energy ray-curable resin composition.

[0190] Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and may be modified in various aspects within the scope of the present invention. EXAMPLES

[0191] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0192] (Experiment 1) In experiment 1, a coating liquid containing an energy ray-curable resin composition was prepared and evaluated.

[0193] (Coating liquid containing energy ray curable resin composition) The following components were mixed in the compounding ratio (solid content equivalent) shown in Table 1, diluted with trichloromethane so that the solid content concentration became 20 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).

[0194] (A) Energy ray curable resin component (A-1) Tris-(2-acryloyloxyethyl)isocyanurate (A-2) ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300-1CL, trifunctional UV-curable compound) (A-3) Urethane acrylate oligomer (KJ Chemicals, Quick cure 8100EA70) (B) Hardener (B-1): Hexanediol-type polyfunctional acetoacetate ester (a compound having the chemical structure of the above formula Y-1) (B-2): Tricyclodecane dimethanol type multifunctional acetoacetate ester (a compound having the chemical structure of the above formula Y-2) (B-3): Trimethylolpropane-type multifunctional acetoacetate ester (a compound having the chemical structure of the above formula Y-3) (B-4): Pentaerythritol-type multifunctional acetoacetate ester (a compound having the chemical structure of the above formula Y-4) (B-5): Dipentaerythritol-type multifunctional acetoacetate ester (a compound having the chemical structure of the above formula Y-5) (C) Non-ionic photobase generator (C-1): Non-ionic photobase generator (a compound having the following chemical structure: (E)-N-(bis(dimethylamino)methylene)-3-(2-hydroxyphenyl)acrylamide) [ka] (C') Ionic Photobase Generator (C'-1): Ionic photobase generator (compound having the following chemical structure) [ka] (D) Filler (D-1): Silica filler (manufactured by JGC Catalysts and Chemicals, average particle size 5 μm) (D-2): Epoxy group-modified spherical silica filler (manufactured by Admatechs Co., Ltd., SC2050MA, average particle size 0.5 μm) (E) Coloring agent (E-1) Black pigment (a pigment obtained by mixing 32 parts by mass of a phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone red pigment (Pigment Red 177), and pigmentizing the mixture such that the total amount of the three pigments / the amount of styrene acrylic resin was 1 / 3 (mass ratio).) (F) Compounds having a thiol group (F-1): Pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals, PEMP) (G) Photoradical initiator (G-1) 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (IGM Resins, Omnirad® 127D) (G-2) 2-(Dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (IGM Resins, Omnirad® 379) (H) Non-energy ray curable film-forming component (H-1): (meth)acrylic acid ester copolymer obtained 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).

[0195] The obtained coating solution was used to carry out the following measurements and evaluations.

[0196] (Evaluation of delayed curing properties) The delayed curing property was evaluated by bonding copper plates together using the coating liquid and measuring the shear adhesive strength after bonding. First, two copper plates measuring 10 mm in width, 45 mm in length, and 1.5 mm in thickness were prepared. The coating liquid that had been prepared 0.5 hours after preparation was applied to an area of ​​10 mm in width and 5 mm in length at one end of one side of one of the copper plates, and dried at 60°C for 1 minute. After drying, ultraviolet rays with a wavelength of 365 nm and an illuminance of 50 mW / cm were applied as energy rays.2 The light intensity is 1600mJ / cm 2 Immediately afterwards, one end of one side of the other copper plate was attached to the irradiated surface so that the bonding area was 50 mm 2 (i.e., width 10 mm, length 5 mm) and the area where the two copper plates overlap when viewed in a plan view is also the same 50 mm 2 The copper plates were overlapped in the lengthwise direction so that they were one piece, fixed with clips, and held at room temperature (23°C) for 1 hour to obtain a test piece in which two copper plates were bonded with an adhesive film.

[0197] One end of one copper plate of the obtained test piece without the adhesive film was fixed with a jig of a tensile tester, and one end of the other copper plate without the adhesive film was fixed with the other jig of the tensile tester, and the test piece was pulled in the length direction at a pulling speed of 10 mm / min in an environment of 23°C and relative humidity of 50%, and peeled off in a manner that a shear force was applied to the adhesive film. The stress when the two copper plates were peeled off was taken as the shear adhesive strength (MPa).

[0198] In addition, two other copper plates were prepared and the light intensity was set to a low level of 200 mJ / cm 2 A test piece was obtained in the same manner as in the above evaluation, except that the irradiation was performed so as to obtain a shear adhesive strength.

[0199] The obtained shear adhesive strength was evaluated according to the following criteria, and the results are shown in Table 1. ○: UV light intensity is 1600mJ / cm 2 When the irradiation was performed so that the shear adhesive strength was 0.6 MPa or more. △: The amount of ultraviolet light for the dried coating liquid is 1600 mJ / cm 2 When the ultraviolet light was irradiated so that the coating liquid after drying solidified and it was not possible to bond the other copper plate, 2 When the coating solution was irradiated so as to achieve the above condition, the coating solution did not solidify after drying, and the shear adhesive strength was 0.6 MPa or more. ×: The amount of ultraviolet light for the dried coating liquid is 1600 mJ / cm 2When the coating solution was irradiated so that the other copper plate could not be bonded to the other copper plate, the amount of ultraviolet light was weak at 200 mJ / cm. 2 Even when the coating solution was irradiated so as to achieve the above condition, the coating solution solidified after drying, and it was not possible to bond the other copper plate to the coating solution.

[0200] (Evaluation of performance stability) Except for using the coating solution that had been prepared 2 hours and the coating solution that had been prepared 168 hours, test pieces were obtained in the same manner as in the evaluation of delayed curing properties, and the shear adhesive strength was measured. The amount of ultraviolet light was 1600 mJ / cm 2 The coating liquids that had been produced for 2 hours and 168 hours were stored at accelerated temperatures of 40°C rather than at room temperature (23°C). This was done in consideration of the possibility that the coating liquid may be exposed to temperatures slightly higher than room temperature during transportation, etc. The shear adhesive strength change rate shown below was calculated from the measured shear adhesive strength and the shear adhesive strength of the test piece obtained using the coating liquid that had been produced for 0.5 hours. Shear adhesive strength change rate 1 (%) = 100 × {(0.5h shear adhesive strength) - (2h shear adhesive strength)} / (0.5h shear adhesive strength) Shear adhesive strength change rate 2 (%) = 100 × {(0.5h shear adhesive strength) - (168h shear adhesive strength)} / (0.5h shear adhesive strength)

[0201] Here, "0.5-h shear adhesive strength" refers to the shear adhesive strength of a test piece obtained using a coating liquid that was prepared 0.5 hours ago, "2-h shear adhesive strength" refers to the shear adhesive strength of a test piece obtained using a coating liquid that was prepared 2 hours ago, and "168-h shear adhesive strength" refers to the shear adhesive strength of a test piece obtained using a coating liquid that was prepared 168 hours ago.

[0202] The obtained rate of change in shear adhesive strength was evaluated according to the following criteria. The results are shown in Table 1. ○: Both the shear adhesive strength change rate 1 and the shear adhesive strength change rate 2 were 10% or less, and the hardening performance was stable. △: The coating solution did not solidify 168 hours after preparation, and the coating performance was maintained, but it solidified when exposed to ultraviolet light after coating and drying, making it impossible to bond the other copper plate and measuring the shear adhesive strength. ×: The coating solution 168 hours after preparation had undergone a curing reaction, solidified before application, and had poor performance stability.

[0203] [Table 1]

[0204] From Table 1, in Comparative Example 3, which does not contain a photobase generator but contains a photoradical initiator, the coating liquid solidified even when the amount of light was small, so it was not possible to attach the other copper plate after ultraviolet irradiation. In other words, it was confirmed that Comparative Example 3 does not exhibit delayed curing properties. In addition, it was confirmed that Comparative Examples 1 and 4 contain a compound having a thiol group as a curable component, so that they lack performance stability. It was confirmed that Comparative Example 2 contains an ion-type photobase generator as a photobase generator, so that they lack performance stability.

[0205] (Experiment 2) In Experiment 2, a sheet for resin film formation was prepared as follows using a coating liquid containing the following energy ray-curable resin composition, and an evaluation was performed.

[0206] (Coating liquid containing energy ray curable resin composition) The following components were mixed in the compounding ratio (solid content equivalent) shown in Table 2, and diluted with methyl ethyl ketone to a solid content concentration of 50 mass % to prepare a coating liquid containing an energy ray-curable resin composition.

[0207] (Preparation of resin film forming sheet) A first release film (manufactured by Lintec Corporation, SP-PET382150, thickness 38 μm) consisting of a polyethylene terephthalate (PET) film with a silicone-based release agent layer formed on one side thereof, and a second release film (manufactured by Lintec Corporation, SP-PET381031, thickness 38 μm) consisting of a PET film with a silicone-based release agent layer formed on one side thereof were prepared.

[0208] The coating solution containing the energy ray curable resin composition prepared above was applied to the release surface of the first release film by a knife coater so that the thickness of the resin film-forming film finally obtained was 25 μm, and then dried at 120 ° C. for 2 minutes using an oven to form a resin film-forming film made of the energy ray curable resin composition. Next, the release surface of the second release film was overlaid on the resin film-forming film to bond the two together, and the resin film-forming sheets of Example 6F and Comparative Examples 3F and 4F, which consist of the first release film, the resin film-forming film (thickness: 25 μm), and the second release film, were obtained.

[0209] Using the obtained resin film forming sheet, delayed curing properties and performance stability were evaluated in the same manner as in Experiment 1, except that the coating liquid was not applied and dried, and the resin film forming film on the resin film forming sheet was attached.

[0210] (Evaluation of delayed curing properties) First, two copper plates with a width of 10 mm, a length of 45 mm, and a thickness of 1.5 mm were prepared. A resin film forming sheet 0.5 hours after preparation was cut into a size of 10 mm x 5 mm, the second release film (light release type release film) was peeled off, and the exposed resin film forming film was attached to an area of ​​width 10 mm and length 5 mm at one end of one side of one of the copper plates, and the first release film (heavy release type release film) was peeled off. The exposed resin film forming film was irradiated with ultraviolet light having a wavelength of 365 nm at an illuminance of 50 mW / cm. 2 The light intensity is 1600mJ / cm 2 Immediately afterwards, one end of one side of the other copper plate was attached to the irradiated surface so that the bonding area was 50 mm 2(i.e., width 10 mm, length 5 mm) and the area where the two copper plates overlap when viewed in a plan view is also the same 50 mm 2 The copper plates were overlapped in the lengthwise direction so that they were one piece, fixed with clips, and held at room temperature (23°C) for 1 hour to obtain a test piece in which two copper plates were bonded with an adhesive film.

[0211] The shear adhesive strength of the obtained test pieces was measured in the same manner as in Experiment 1, and the obtained shear adhesive strength was evaluated according to the following criteria. The results are shown in Table 2. ○: Shear adhesive strength was 0.6 MPa or more ×: The resin film was solidified by ultraviolet irradiation, and it was not possible to bond the other copper plate.

[0212] (Evaluation of performance stability) Except for using resin film-coated films that had been produced for 2 hours and resin film-coated films that had been produced for 168 hours, test pieces were obtained in the same manner as in the evaluation of delayed curing properties, and the shear adhesive strength was measured. The amount of ultraviolet light was 1600 mJ / cm 2 The resin film-formed film that had been produced for 2 hours and the resin film-formed film that had been produced for 168 hours were stored at an accelerated temperature of 40°C, rather than at room temperature (23°C). This condition took into consideration the possibility that the resin film-formed film may be exposed to a temperature slightly higher than room temperature during transportation, etc. The shear adhesive strength change rate shown below was calculated from the measured shear adhesive strength and the shear adhesive strength of the test piece obtained using the resin film-formed film that had been produced for 0.5 hours. Shear adhesive strength change rate 3 (%) = 100 × {(0.5h shear adhesive strength) - (2h shear adhesive strength)} / (0.5h shear adhesive strength) Shear adhesive strength change rate 4 (%) = 100 × {(0.5h shear adhesive strength) - (168h shear adhesive strength)} / (0.5h shear adhesive strength)

[0213] Here, "0.5 h shear adhesion strength" refers to the shear adhesion strength of a test piece obtained using a resin film-forming film that was produced 0.5 hours ago, "2 h shear adhesion strength" refers to the shear adhesion strength of a test piece obtained using a resin film-forming film that was produced 2 hours ago, and "168 h shear adhesion strength" refers to the shear adhesion strength of a test piece obtained using a resin film-forming film that was produced 168 hours ago.

[0214] The obtained rate of change in shear adhesive strength was evaluated according to the following criteria. The results are shown in Table 2. ○: Both the shear adhesive strength change rate 3 and the shear adhesive strength change rate 4 were 10% or less, and the hardening performance was stable. △: The resin film coated film 168 hours after production maintained its ability to be attached to a copper plate, but solidified when exposed to ultraviolet light after attachment, making it impossible to attach the other copper plate and measuring the shear adhesive strength. ×: The resin film-forming film had such poor performance stability that the curing reaction proceeded even without irradiation with ultraviolet light, solidified before application, and the copper plate could not be applied.

[0215] [Table 2]

[0216] From Table 2, in Comparative Example 3F, which does not contain a photobase generator but contains a photoradical initiator, the film solidified by UV irradiation after being attached to the copper plate, so it was not possible to attach the other copper plate after UV irradiation. That is, it was confirmed that Comparative Example 3F does not exhibit delayed curing. In addition, it was confirmed that Comparative Example 4F lacks performance stability because it contains a compound having a thiol group as a curable component. [Industrial Applicability]

[0217] The energy ray-curable resin composition of the present invention can exhibit the desired delayed curing property and performance stability, and therefore can exhibit sufficient adhesive strength even when an adherend is attached to the composition after irradiation with energy rays. [Explanation of symbols]

[0218] 1...Resin film forming sheet 10...Resin film forming film 21…First release film 22...Second release film 2…Composite sheet for forming resin film 10...Resin film forming film 4...Adhesive sheet (support sheet)

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 non-ionic photobase generator.

2. 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-keto ester structure.

3. 3. The energy ray-curable resin composition according to claim 2, wherein the group containing a β-keto ester structure is a group containing an acetoacetic ester structure.

4. The energy ray-curable resin composition according to claim 1 , wherein the nonionic photobase generator has a group containing a structure represented by the following formula: 【Chemistry 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 liquid according to claim 5, wherein a 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, based on 100 parts by mass of a solid content of the coating liquid.

7. A resin film formed from the energy ray-curable resin composition according to claim 1.

8. The resin film-forming film according to claim 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 non-ionic photobase generator is 30 parts by mass or more in 100 parts by mass of the resin film-forming film.

9. A step of applying the coating liquid according to claim 5 to at least one of a first adherend and a second adherend; a step of irradiating the coating liquid or the dried coating liquid with an energy ray after the coating liquid is applied; and after the energy ray irradiation, bonding the first adherend and the second adherend via the coating liquid to form a laminate.

10. A step of attaching the resin film-forming film according to claim 7 to at least one of a first adherend and a second adherend; A step of irradiating the resin film-forming film with an energy ray after the resin film-forming film is attached; and after the energy ray irradiation, bonding the first adherend and the second adherend via the resin film-forming film to form a laminate.

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.

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