Photo- and moisture-curing resin composition, adhesive for electronic components, cured body, and electronic components

Abstract

A photo / moisture-curable resin composition comprising a radically polymerizable compound (A), a moisture curable resin (B) and a photopolymerization initiator (C), the photo / moisture-curable resin composition having a gel swelling ratio (W1 / W2) of at least 15 as obtained by a prescribed measurement method, and a viscosity of 35-600 Pa·s as measured using a cone and plate viscometer at 25°C and 5.0 rpm.

Description

[Technical Field]

[0001] The present invention relates to a photo- and moisture-curing resin composition, an adhesive for electronic components, a cured product, and an electronic component. [Background technology]

[0002] In recent years, there has been a demand for higher integration and miniaturization of electronic components such as semiconductor chips. For example, multiple thin semiconductor chips are sometimes joined together via an adhesive layer to form a semiconductor chip stack. Also, in today's world where mobile devices with various display elements are widespread, one method of miniaturizing display elements is to narrow the bezel of the image display area (hereinafter also referred to as "narrow bezel design"). In these applications, in order to achieve miniaturization and narrow bezels, attempts are being made to use photo-moisture-curing adhesives instead of double-sided tape.

[0003] As an example of a photo-moisture-curing adhesive, Patent Document 1 discloses a photo-moisture-curing resin composition containing a radical polymerizable compound, a moisture-curing urethane resin, and a photo-radical polymerization initiator, wherein the moisture-curing urethane resin contains a moisture-curing urethane resin with a weight-average molecular weight of 2000 or more. Patent Document 2 also discloses a reactive hot-melt adhesive composition containing a urethane prepolymer, a urethane (meth)acrylate having a (meth)acryloyl group, and a photopolymerization initiator. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-074781 [Patent Document 2] Japanese Patent Publication No. 2019-006854 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, unlike double-sided tape, light-curing adhesives do not exhibit sufficient adhesive strength (initial adhesive strength) immediately after application, resulting in a time-consuming bonding process and poor workability. For example, while Patent Documents 1 and 2 demonstrate that a certain level of adhesive strength is achieved after light irradiation, the initial adhesive strength may not be sufficient. Furthermore, the adhesive described in Patent Document 2 is a hot-melt adhesive, requiring heating before application, which further worsens workability.

[0006] Therefore, the object of the present invention is to provide a photo-moisture-curing resin composition that exhibits excellent adhesive strength immediately after photocuring, thereby improving workability and other properties. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by increasing the gel swelling ratio of the photocured photo-moisture-curable resin composition while keeping the viscosity within a certain range, and have completed the present invention as follows. That is, the present invention provides the following [1] to

[24] . [1] comprising a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C), The gel swelling ratio (W1 / W2) determined by the measurement methods shown in (1) to (4) below is 15 or greater, and A photo- and moisture-curable resin composition whose viscosity, measured using a cone-plate viscometer at 25°C and 5.0 rpm, is between 35 Pa·s and 600 Pa·s. (1) 1.0 g of light- and moisture-curing resin composition is applied to a release PET film to a thickness of 1.5 mm, and 1000 mJ / cm² is applied. 2 It is photocured by irradiating it with ultraviolet light. (2) The photo-cured photo-moisture-curing resin composition is peeled off the release PET film and immersed in THF at 25°C for 48 hours. (3) The photo-cured photo-moisture-curing resin composition after immersion is removed onto a 200-mesh wire mesh, washed five times with fresh THF, and the weight (W1) of the swollen gel remaining on the wire mesh is measured. (4) The swollen gel is dried at 100°C for 2 hours to volatilize the THF, the weight of the dry gel (W2) is measured, and the gel swelling ratio (W1 / W2) is determined. [2] Applied to an aluminum substrate with a line width of 1.0 mm, and 1000 mJ / cm² 2 The photo-moisture-curing resin composition described in [1] above, wherein, after photocuring by irradiation with ultraviolet light, a glass plate is pressed against it at 0.08 MPa for 120 seconds, and the average width of the bonded portion on the glass plate side is a, and the average width of the bonded portion on the aluminum substrate side is b, a / b is 0.58 or more and 0.99 or less. [3] The photo-moisture-curing resin composition according to [1] or [2] above, wherein the moisture-curing resin (B) includes a moisture-curing urethane resin. [4] The photo-moisture-curing resin composition according to [3] above, wherein the moisture-curing urethane resin is a moisture-curing urethane resin having at least one of a polycarbonate skeleton, a polyether skeleton, and a polyester skeleton. [5] The photo-moisture-curing resin composition according to [3] or [4] above, wherein the moisture-curing urethane resin is a moisture-curing urethane resin having a polycarbonate skeleton. [6] The photo-moisture-curing resin composition according to any one of the above [1] to [5], wherein the weight-average molecular weight of the moisture-curing resin (B) is 7,500 or more and 24,000 or less. [7] A photo-moisture-curable resin composition according to any one of the above [1] to [6], wherein the radical polymerizable compound (A) comprises a monofunctional radical polymerizable compound. [8] The photo-moisture-curable resin composition according to [7] above, comprising 90 parts by mass or more of a monofunctional radical polymerizable compound per 100 parts by mass of radical polymerizable compound (A). [9] The photo-moisture-curable resin composition according to [7] or [8] above, wherein the monofunctional radical polymerizable compound comprises a nitrogen-containing compound.

[10] The photo-moisture-curable resin composition according to [9] above, wherein the monofunctional radical polymerizable compound comprises a chain-like nitrogen-containing compound.

[11] The photo-moisture-curable resin composition according to [9] or

[10] above, wherein the monofunctional radical polymerizable compound comprises a nitrogen-containing compound having a cyclic structure.

[12] The photo-moisture-curing resin composition according to

[11] , wherein the mass ratio (cyclic / chain) of the nitrogen-containing compound having a cyclic structure to the chain-like nitrogen-containing compound is 0.1 or more and 2.0 or less.

[13] The photo-moisture-curable resin composition according to any one of the above [9] to

[12] , wherein the content of a nitrogen-containing compound that is a monofunctional radical polymerizable compound is 10 parts by mass or more and 95 parts by mass or less, relative to 100 parts by mass of the radical polymerizable compound (A).

[14] The photo-moisture-curable resin composition according to any one of the above [9] to

[13] , wherein the monofunctional radical polymerizable compound comprises a monofunctional (meth)acrylic acid ester compound in addition to the nitrogen-containing compound.

[15] The photo-moisture-curing resin composition according to

[14] above, wherein the monofunctional (meth)acrylic acid ester compound is at least one selected from the group consisting of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate.

[16] The photo-moisture-curable resin composition according to

[15] above, wherein the total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate is 5 parts by mass or more and 90 parts by mass or less per 100 parts by mass of radical polymerizable compound (A).

[17] The photo-moisture-curing resin composition according to any one of the above [1] to

[16] , wherein the mass ratio (B / A) of the moisture-curing resin (B) to the radical polymerizable compound (A) is 30 / 70 or more and 90 / 10 or less.

[18] A photo-moisture-curing resin composition according to any one of the above [1] to

[17] , further comprising a filler (D).

[19] The photo-moisture-curable resin composition according to any one of the above [1] to

[18] , wherein the photopolymerization initiator (C) is at least one selected from the group consisting of benzophenone compounds, acetophenone compounds, alkylphenone photopolymerization initiators, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthones.

[20] The photocurable moisture-curable resin composition according to any one of [1] to

[19] above, having an initial adhesive strength of 0.25 MPa or more.

[21] The photocurable moisture-curable resin composition according to any one of [1] to

[20] above, having a final adhesive strength of 2.0 MPa or more.

[22] An adhesive for electronic components comprising the photocurable moisture-curable resin composition according to any one of [1] to

[21] above.

[23] A cured product of the photocurable moisture-curable resin composition according to any one of [1] to

[21] above.

[24] An electronic component comprising the cured product according to

[23] above. [Effect of the Invention]

[0008] According to the present invention, there is provided a photocurable moisture-curable resin composition that exhibits excellent adhesive strength even immediately after photocuring and can improve workability and the like. [Brief Description of the Drawings]

[0009] [Figure 1] It is a conceptual diagram showing a method for measuring the internal-external ratio a / b. [Figure 2] It is a schematic diagram showing an adhesion test method, where Fig. 2(a) is a plan view and Fig. 2(b) is a side view. [Modes for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described in detail while referring to embodiments. [Photocurable Moisture-Curable Resin Composition] The photocurable moisture-curable resin composition of the present invention contains a radically polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C). The photocurable moisture-curable resin composition of the present invention has a gel swelling ratio (hereinafter, also referred to as "gel swelling ratio (W1 / W2)") after photocuring, which is obtained by the measurement method described below, of 15 or more, and a viscosity measured using a cone plate viscometer under the conditions of 25°C and 5.0 rpm (hereinafter, also referred to as "25°C viscosity") of 35 Pa·s or more and 600 Pa·s or less. As described above, when the gel swelling ratio (W1 / W2) after photocuring is increased in the photo-cured, the density of the cross-linked structure after photocuring decreases. Combined with the fact that the viscosity at 25°C remains within a certain range, the structure collapses to a certain extent when moderate pressure is applied, making it easier to adhere to the substrate. Furthermore, it exhibits a certain cohesive force even when shear stress is applied. Therefore, it is possible to achieve excellent adhesive strength (initial adhesive strength) immediately after photocuring.

[0011] [Gel swelling ratio (W1 / W2)] As described above, the photo-curable resin composition of the present invention has a gel swelling ratio (W1 / W2) of 15 or more after photocuring. If the gel swelling ratio (W1 / W2) after photocuring is less than 15, the proportion of cross-linked structures increases immediately after photocuring, making it difficult to crush and resulting in poor initial adhesion. From the viewpoint of achieving higher initial adhesion, the gel swelling ratio (W1 / W2) after photocuring is preferably 20 or more, more preferably 25 or more, and even more preferably 30 or more. Furthermore, there is no particular upper limit specified for the gel swelling ratio (W1 / W2) after photocuring; the larger the better, but for example, 80 or less is sufficient. The gel swelling ratio (W1 / W2) after photocuring can be determined by the following measurement method. (1) 1.0 g of light- and moisture-curing resin composition is applied to a release PET film to a thickness of 1.5 mm, and 1000 mJ / cm² is applied. 2 It is photocured by irradiating it with ultraviolet light. (2) The photo-cured photo-moisture-curing resin composition is peeled off the release PET film and immersed in THF at 25°C for 48 hours. (3) The photo-cured photo-moisture-curing resin composition after immersion is removed onto a 200-mesh wire mesh, washed five times with fresh THF, and the weight (W1) of the swollen gel remaining on the wire mesh is measured. (4) The swollen gel is dried at 100°C for 2 hours to volatilize the THF, the weight of the dry gel (W2) is measured, and the gel swelling ratio (W1 / W2) is determined. Furthermore, the details of the method for measuring the gel swelling ratio (W1 / W2) are as described in the examples below. The gel swelling ratio (W1 / W2) can be adjusted within the above range by appropriately selecting the type of radical polymerizable compound. For example, if a large amount of monofunctional radical polymerizable compound is included, the density of the crosslinked structure formed after photocuring will be lower, allowing the gel swelling ratio (W1 / W2) to be increased.

[0012] [Viscosity at 25℃] The 25°C viscosity of the moisture-curing resin composition described above was measured under high shear at 5.0 rpm without photocuring or moisture curing, and is a viscosity that is less affected by fillers. Therefore, if the 25°C viscosity is less than 35 Pa·s, it means that there is a large amount of low molecular weight components contained in the moisture-curing resin (B), etc., and after light irradiation, the moisture-curing resin (B), etc. may seep out at the interface, making it difficult to improve the initial adhesion strength. In other words, if low molecular weight moisture-curing resin (B), etc. seeps out at the interface after light irradiation, slippage is more likely to occur between the substrate and the resin, making it difficult for tackiness to develop and thus difficult to improve the initial adhesion strength. Furthermore, if the 25°C viscosity exceeds 600 Pa·s, the tackiness inherent in the moisture-curing resin (B) becomes difficult to develop, making it difficult to improve the initial adhesion strength and the final adhesion strength described later. Furthermore, if the viscosity at 25°C falls below 35 Pa·s or exceeds 600 Pa·s, problems such as dripping or inability to apply the product at room temperature will occur, reducing workability.

[0013] The viscosity at 25°C of the light- and moisture-curing resin composition is preferably 40 Pa·s or higher, more preferably 45 Pa·s or higher, even more preferably 90 Pa·s or higher, even more preferably 110 Pa·s or higher, and also preferably 500 Pa·s or lower, more preferably 350 Pa·s or lower, and even more preferably 230 Pa·s or lower. Setting the 25°C viscosity within the above range makes it easier to improve workability and initial adhesion. Furthermore, by keeping the value below the above upper limit, it is possible to prevent the molecular weight of the moisture-curable resin (A) from becoming excessively high, which improves the initial adhesive strength, and further improves the adhesive strength through moisture curing, thus improving the final adhesive strength as well. The final adhesive strength refers to the adhesive strength of the photo-moisture-curable resin composition after photo-curing and moisture-curing, and the details will be described later.

[0014] [Internal / external ratio a / b] When the photo- and moisture-curing resin composition of the present invention is applied linearly to an aluminum substrate under predetermined conditions described later, and after photo-curing with UV light, a glass plate is further pressed onto it, it is preferable that the ratio a / b (also called the "inside-outside ratio a / b") is 0.58 or more and 0.99 or less, where a is the average width of the bonded portion on the glass plate side and b is the average width of the bonded portion on the aluminum substrate side. In the photo-moisture-curing resin composition of the present invention, if the internal-to-external ratio a / b is set to 0.58 or higher, the internal-to-external ratio a / b becomes larger than that of conventional photo-moisture-curing resin compositions, making it easier to crush immediately after photocuring, improving adhesion to the interface of the adherend, and increasing the initial adhesive strength to the adherend. Furthermore, by setting the internal-to-external ratio a / b to 0.99 or lower, it is possible to prevent the cohesive force of the photo-moisture-curing resin composition from decreasing or crushing too much immediately after photocuring, thus preventing a decrease in initial adhesive strength. The above-mentioned inner-to-outer ratio a / b is more preferably 0.63 or higher, even more preferably 0.66 or higher, even more preferably 0.95 or lower, and even more preferably 0.93 or lower. Setting the inner-to-outer ratio a / b within these ranges makes it easier to improve the initial adhesion strength.

[0015] In this invention, the internal-to-external ratio a / b is measured as follows. First, as shown in Figure 1(a), a moisture-curing resin composition 10 is applied to the aluminum substrate 11 in a line width of 1.0 mm. Here, the line width does not need to be exactly 1.0 mm; an error of 1.0 ± 0.1 mm is acceptable. Next, as shown in Figure 1(b), 1000 mJ / cm³ is applied to the moisture-curing resin composition 10. 2The moisture-curing resin composition 10 is cured by irradiating it with ultraviolet light. Immediately thereafter (within 10 seconds), as shown in Figure 1(c), the glass plate 12 is placed on top of the moisture-curing resin composition 10, and the glass plate 12 is pressed against the coated area of ​​the moisture-curing resin composition 10 at 0.08 MPa for 120 seconds. After pressing, the width a1 of the bonded portion between the moisture-curing resin composition 10 and the glass plate 12 is measured. The width a1 is measured at 5 points, and the average value is taken as the average width a. The width b1 of the bonded portion between the moisture-curing resin composition 10 and the aluminum substrate 11 is also measured. The width b1 is measured at 5 points, and the average value is taken as the average width b. The inside-outside ratio a / b is calculated from the average widths a and b. It is recommended to use a weight for pressing, and to measure the widths a1 and b1 5 minutes after removing the weight.

[0016] The internal-to-external ratio a / b can be adjusted within the above range by adjusting the type of radical polymerizable compound, etc. For example, if the photo-moisture-curable resin composition contains a large amount of monofunctional radical polymerizable compounds as radical polymerizable compounds, the proportion of cross-linked structures formed after photocuring decreases, so the internal-to-external ratio a / b can be increased. Also, for example, if the photo-moisture-curable resin composition contains a large amount of radical polymerizable compounds with low glass transition temperatures of homopolymers as radical polymerizable compounds, the cured product after photocuring becomes more flexible, so the internal-to-external ratio a / b can be increased. Furthermore, it can also be adjusted by the weight-average molecular weight of the moisture-curable resin (B).

[0017] [Adhesive strength] The photo- and moisture-curable resin composition of the present invention preferably has an initial adhesive strength of 0.25 MPa or higher. Furthermore, the photo- and moisture-curable resin composition of the present invention preferably has a final adhesive strength of 2.0 MPa or higher. Initial adhesive strength refers to the adhesive strength of the photo-moisture-curable resin composition at 25°C immediately after photocuring, while final adhesive strength refers to the adhesive strength after the photo-moisture-curable resin composition has been photocured and then left at 25°C and 50RH% for 24 hours. Details of the measurement methods for initial and final adhesive strength are described in the examples below. If the photo- and moisture-curing resin composition has an initial adhesive strength of 0.25 MPa or higher at 25°C, it allows for temporary bonding of adherends with relatively high adhesive strength immediately after photocuring, improving workability during temporary bonding. Furthermore, if the final adhesive strength is 2.0 MPa or higher, the adherends can be firmly bonded together by permanent bonding through moisture curing after temporary bonding.

[0018] For photo- and moisture-curing resin compositions, it is preferable that the initial adhesive strength be 0.4 MPa or higher to further enhance adhesive stability during temporary bonding. While the initial adhesive strength is not particularly limited, it is preferable, for example, to be less than 1.5 MPa to facilitate repositioning during temporary bonding. Furthermore, in order to bond the adherends more firmly after bonding, the final adhesive strength of the light- and moisture-curing resin composition is more preferably 3.5 MPa or higher. The final adhesive strength is not particularly limited, but is preferably 20 MPa or less, or even 10 MPa or less.

[0019] The following provides a more detailed description of each component contained in the light- and moisture-curing resin composition. [Radical polymerizable compound (A)] The photo- and moisture-curable resin composition of the present invention contains a radical polymerizable compound (A). The photo- and moisture-curable resin composition is given photocurability by containing the radical polymerizable compound (A). Because the photo- and moisture-curable resin composition has photocurability, a certain level of adhesive strength can be imparted simply by light irradiation, thus ensuring appropriate initial adhesive strength. The radical polymerizable compound (A) can have a radical polymerizable functional group in its molecule. Suitable radical polymerizable functional groups include compounds having an unsaturated double bond, such as (meth)acryloyl, vinyl, styryl, and allyl groups.

[0020] Of the above, the (meth)acryloyl group is preferred from the viewpoint of adhesion; that is, the radical polymerizable compound (A) preferably contains a compound having a (meth)acryloyl group. The compound having a (meth)acryloyl group will also be referred to as a "(meth)acrylic compound" below. In this specification, "(meth)acryloyl group" means acryloyl group or (meth)acryloyl group, and "(meth)acrylic" means acrylic or methacrylic, and the same applies to other similar terms.

[0021] The radical polymerizable compound (A) may contain either a monofunctional radical polymerizable compound having one radical polymerizable functional group in one molecule, or a polyfunctional radical polymerizable compound having two or more radical polymerizable functional groups in one molecule, or both. However, from the viewpoint of increasing the gel swelling ratio after photocuring and improving the initial adhesion of the photo-moisture-curable resin composition, it is preferable to include a monofunctional radical polymerizable compound. Furthermore, it is more preferable that the radical polymerizable compound (A) contains at least a monofunctional (meth)acrylic compound, which is a (meth)acrylic compound. The monofunctional radical polymerizable compound may be a polymerized prepolymer having repeating units, but it is generally preferable to use a monofunctional monomer that does not have repeating units.

[0022] The photo-moisture-curable resin composition preferably contains a large amount of monofunctional radical polymerizable compound in order to increase the gel swelling ratio after photocuring and improve the initial adhesive strength. Specifically, the photo-moisture-curable resin composition preferably contains 90 parts by mass or more, preferably 95 parts by mass or more, and more preferably 100 parts by mass of monofunctional radical polymerizable compound per 100 parts by mass of radical polymerizable compound (A).

[0023] [Monofunctional radical polymerizable compound] (nitrogen-containing compounds) The radical polymerizable compound (A) preferably contains a nitrogen-containing compound as a monofunctional radical polymerizable compound. Using a nitrogen-containing compound improves the initial adhesion of the photo-moisture-curable resin composition. The photo-moisture-curable resin composition is photocured by irradiating it with active energy rays such as ultraviolet light after being applied to the substrate, and in general, photocuring is often performed in the presence of oxygen, as will be described later. If the radical polymerizable compound (A) contains a nitrogen-containing compound, it is presumed that it will be appropriately photocured even in the presence of oxygen, thereby improving the initial adhesion.

[0024] The nitrogen-containing compound may contain either or both a chain-like nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure. However, from the viewpoint of improving the initial adhesion of the photo-moisture-curing resin composition, it is preferable to include a nitrogen-containing compound having a cyclic structure, and it is even more preferable to use both a chain-like nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure in combination.

[0025] Examples of nitrogen-containing compounds having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam, morpholine skeleton-containing compounds such as N-acryloylmorpholine, and cyclic imide compounds such as N-(meth)acryloyloxyethylhexahydrophthalimide. Among these, amide group-containing compounds such as N-vinylcaprolactam are even more preferred. In this specification, nitrogen-containing compounds having a cyclic structure are also called cyclic nitrogen-containing compounds, and radical polymerizable compounds in which the nitrogen atom is contained in the atoms constituting the ring itself are defined as cyclic nitrogen-containing compounds, while other nitrogen-containing compounds are defined as chain-like nitrogen-containing compounds.

[0026] Examples of chain-like nitrogen-containing compounds include chain-like amino group-containing (meth)acrylates such as dimethylamino(meth)acrylate, diethylamino(meth)acrylate, aminomethyl(meth)acrylate, aminoethyl(meth)acrylate, and dimethylaminoethyl(meth)acrylate; chain-like (meth)acrylamide compounds such as diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, and methacrylamide; and N-vinylacetamide.

[0027] Furthermore, the chain-like nitrogen-containing compound may be a monofunctional urethane (meth)acrylate. By using a monofunctional urethane (meth)acrylate, when a urethane resin, particularly a urethane resin having a polycarbonate skeleton, is used as the moisture-curing resin (B), compatibility with the moisture-curing resin (B) is improved, making it easier to enhance the initial adhesive strength. In addition, since urethane (meth)acrylate is relatively polar, it is easier to increase the adhesive strength to glass.

[0028] Monofunctional urethane (meth)acrylates can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. Examples of (meth)acrylic acid derivatives having the above-mentioned hydroxyl group include mono(meth)acrylates of dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, as well as mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin.

[0029] Examples of isocyanate compounds used to obtain urethane (meth)acrylate include aliphatic monoisocyanates such as alkane monoisocyanates like butane isocyanate, hexane isocyanate, and decane isocyanate, and cyclic aliphatic monoisocyanates like cyclopentane isocyanate, cyclohexane isocyanate, and isophorone monoisocyanate. More specifically, monofunctional urethane (meth)acrylates are preferably obtained by reacting the above-mentioned monoisocyanate compound with a mono(meth)acrylate of a dihydric alcohol, and a preferred specific example is 1,2-ethanediol 1-acrylate 2-(N-butylcarbamate). Among the chain-like nitrogen-containing compounds mentioned above, it is preferable that monofunctional urethane (meth)acrylate be included, and it is also preferable to use monofunctional urethane (meth)acrylate in combination with compounds other than monofunctional urethane (meth)acrylate, such as (meth)acrylamide compounds.

[0030] In a photo-moisture-curable resin composition, the content of a nitrogen-containing compound as a monofunctional radical polymerizable compound relative to 100 parts by mass of radical polymerizable compound (A) is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and most preferably 60 parts by mass or more, from the viewpoint of improving the initial adhesion of the photo-moisture-curable resin composition. Furthermore, the content of the nitrogen-containing compound as a monofunctional radical polymerizable compound is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less, in order to include an appropriate amount of radical polymerizable compound (A) other than the nitrogen-containing compound.

[0031] When a monofunctional radical polymerizable compound contains a linear nitrogen-containing compound and a cyclic nitrogen-containing compound, the mass ratio (cyclic / linear) of the cyclic nitrogen-containing compound to the linear nitrogen-containing compound in the monofunctional radical polymerizable compound is preferably 0.1 to 2.0, more preferably 0.2 to 1.5, and even more preferably 0.4 to 1.2. By keeping the mass ratio of the cyclic / linear compound within the above range, the initial adhesion of the photo-moisture-curable resin composition can be improved.

[0032] (Monofunctional radical polymerizable compounds other than nitrogen-containing compounds) The monofunctional radical polymerizable compound contained in radical polymerizable compound (A) preferably contains compounds other than the nitrogen-containing compounds described above (hereinafter also referred to as nitrogen-free compounds). By including nitrogen-free compounds as monofunctional radical polymerizable compounds in radical polymerizable compound (A), it becomes easier to improve adhesive strength and other properties.

[0033] The nitrogen-free compound is not particularly limited as long as it has a radically polymerizable functional group, but monofunctional (meth)acrylic compounds are preferred, and (meth)acrylic acid ester compounds are more preferred. Examples of monofunctional (meth)acrylic acid ester compounds include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates. These may be used individually or in combination of two or more, but among them, it is preferable to use one or both of alkyl (meth)acrylates and aromatic ring-containing (meth)acrylates. The total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate in the radical polymerizable compound (A) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the radical polymerizable compound (A). Furthermore, the above content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and most preferably 40 parts by mass or less.

[0034] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomiristyl (meth)acrylate, and stearyl (meth)acrylate, among others, which are alkyl (meth)acrylates with 1 to 18 carbon atoms in the alkyl group. Examples of alicyclic structure-containing (meth)acrylates include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentenyl (meth)acrylate, which have an alicyclic structure. Examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenylalkyl (meth)acrylates such as 2-phenylethyl (meth)acrylate, and phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate.

[0035] In addition to alkyl (meth)acrylates, alicyclic (meth)acrylates, and aromatic ring (meth)acrylates, other monofunctional (meth)acrylate compounds can also be used. For example, cyclic ether group (meth)acrylates can also be used. Examples of cyclic ether group-containing (meth)acrylates include those having epoxy rings, oxetane rings, tetrahydrofuran rings, dioxolane rings, and dioxane rings. Examples of epoxy ring-containing (meth)acrylates include glycidyl (meth)acrylate. Examples of oxetane ring-containing (meth)acrylates include (3-ethyloxetane-3-yl)methyl (meth)acrylate. Examples of tetrahydrofuran ring-containing (meth)acrylates include tetrahydrofurfuryl (meth)acrylate and tetrahydrofurfuryl alcohol (meth)acrylic acid polymer esters. Examples of dioxolane ring-containing (meth)acrylates include (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate and (2,2-cyclohexyl-1,3-dioxolane-4-yl)methyl (meth)acrylate. Examples of (meth)acrylates having a dioxane ring include cyclic trimethylolpropane formal (meth)acrylate. As the cyclic ether group-containing (meth)acrylate, it is preferable to use either an oxetane ring-containing (meth)acrylate or a tetrahydrofuran ring-containing (meth)acrylate, but it is also preferable to use them in combination.

[0036] In addition, monofunctional (meth)acrylic acid ester compounds may also be used, such as hydroxyalkyl (meth)acrylates including 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; alkoxyalkyl (meth)acrylates including 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 2-butoxyethyl (meth)acrylate; alkoxyethylene glycol (meth)acrylates including methoxyethylene glycol (meth)acrylate and ethoxyethylene glycol (meth)acrylate; methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate. Furthermore, monofunctional (meth)acrylic compounds such as acrylic acid and methacrylic acid, which contain carboxyl, may also be used.

[0037] [Compounds other than monofunctional radical polymerizable compounds] The radical polymerizable compound (A) may contain a polyfunctional radical polymerizable compound as long as it achieves the effects of the present invention. Examples of polyfunctional radical polymerizable compounds include a difunctional (meth)acrylic acid ester compound, a trifunctional or more (meth)acrylic acid ester compound, and a difunctional or more urethane (meth)acrylate.

[0038] Examples of bifunctional (meth)acrylic acid ester compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and poly Examples include propylene glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, and polybutadiene diol di(meth)acrylate.

[0039] Examples of trifunctional or more (meth)acrylic acid ester compounds include trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0040] For example, a urethane (meth)acrylate with two or more functionalities can be obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. Examples of (meth)acrylic acid derivatives having the above-mentioned hydroxyl group include mono(meth)acrylates of dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol; mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; and epoxy(meth)acrylates such as bisphenol A type epoxy(meth)acrylate.

[0041] Examples of isocyanate compounds used to obtain urethane (meth)acrylates include polyisocyanate compounds such as isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tollidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

[0042] Furthermore, as the isocyanate compound, a chain-extended polyisocyanate compound obtained by the reaction of a polyol with an excess isocyanate compound can also be used. Examples of polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. By using these polyisocyanate compounds, polyfunctional urethane (meth)acrylates can be obtained.

[0043] [Moisture-curing resin (B)] Examples of moisture-curing resins (B) used in the present invention include moisture-curing urethane resins, hydrolyzable silyl group-containing resins, and moisture-curing cyanoacrylate resins. Among these, moisture-curing urethane resins and hydrolyzable silyl group-containing resins are preferred, and moisture-curing urethane resins are more preferred. These may be used individually or in combination of two or more.

[0044] (Moisture-curing urethane resin) Moisture-curing urethane resins can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. Moisture-curing urethane resins preferably have isocyanate groups in their molecules, and these isocyanate groups react with moisture in the air or on the adherend to cure. Moisture-curing urethane resins may have only one isocyanate group in one molecule, or two or more, but it is preferable that they have one or two isocyanate groups in one molecule. Furthermore, the isocyanate groups are not particularly limited, but it is preferable that they be provided at the ends of the moisture-curing urethane resin.

[0045] The reaction between the above polyol compound and the polyisocyanate compound is usually carried out in the range of [NCO] / [OH] = 2.0 to 2.5, where the molar ratio of hydroxyl groups (OH) in the polyol compound to isocyanate groups (NCO) in the polyisocyanate compound is in the range of [NCO] / [OH]. As polyol compounds used as raw materials for moisture-curing urethane resins, known polyol compounds commonly used in the production of polyurethanes can be used, such as polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols. These polyol compounds may be used individually or in combination of two or more.

[0046] The moisture-curing urethane resin is preferably at least one of a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, more preferably at least one of a polycarbonate skeleton or a polyether skeleton, and even more preferably a moisture-curing urethane resin having a polycarbonate skeleton. The moisture-curing urethane resin having a polycarbonate skeleton exhibits excellent initial and final adhesive strength. Furthermore, a photo-moisture-curing resin composition with excellent weather resistance, heat resistance, and moisture resistance of the cured product can also be provided.

[0047] (Moisture-curing urethane resin with a polycarbonate backbone) A moisture-curable urethane resin having a polycarbonate skeleton is obtained by introducing a polycarbonate skeleton into a urethane resin by using a polycarbonate polyol as the polyol compound. For example, a moisture-curable urethane resin having a polycarbonate skeleton can be obtained by reacting a polycarbonate polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. As the polycarbonate polyol, polycarbonate diols are preferred, and a preferred specific example of a polycarbonate diol is the compound represented by the following formula (1).

[0048] [ka] In equation (1), R is a divalent carbon-valent hydrogen group having 4 to 16 carbon atoms, and n is an integer from 2 to 500.

[0049] In formula (1), R is preferably an aliphatic saturated hydrocarbon group. Having an aliphatic saturated hydrocarbon group as R tends to improve heat resistance. Furthermore, it reduces the likelihood of yellowing due to thermal degradation, resulting in good weather resistance. R, consisting of an aliphatic saturated hydrocarbon group, may have a chain-like or cyclic structure, but a chain-like structure is preferable from the viewpoint of improving stress relaxation and flexibility. The chain-like structure of R may be linear or branched. n is preferably 5 to 200, more preferably 10 to 150, and even more preferably 20 to 50.

[0050] Furthermore, the R contained in the polycarbonate polyol that constitutes the moisture-curing urethane resin may be used alone or in combination of two or more types. When two or more types are used in combination, it is preferable that at least a portion of them be a chain-like aliphatic saturated hydrocarbon group having 6 or more carbon atoms, and more preferably that at least a portion of them be a chain-like aliphatic saturated hydrocarbon group having 7 or more carbon atoms. The inclusion of chain-like aliphatic saturated hydrocarbon groups having 7 or more carbon atoms makes it easier to improve stress relaxation and flexibility. When the polycarbonate diol is a compound represented by formula (1) above, the proportion of chain-like aliphatic saturated hydrocarbon groups having 7 or more carbon atoms is preferably 20 mol% to 100 mol%, more preferably 30% to 100 mol%, and even more preferably 50% to 100 mol%, relative to R contained in the total polycarbonate diol. The chain-like aliphatic saturated hydrocarbon group having 7 or more carbon atoms preferably has 8 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms.

[0051] Specific examples of R include linear groups such as tetramethylene, pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups, or branched groups such as methylpentylene groups like 3-methylpentylene and methyloctamethylene groups. Multiple R groups in one molecule may be the same or different. Therefore, one molecule may contain two or more types of R, in which case it is preferable to contain two or three types of R. For example, a polycarbonate polyol may be a copolymer containing R with 6 or fewer carbon atoms and R with 7 or more carbon atoms in one molecule, in which case all R groups are preferably linear aliphatic saturated hydrocarbon groups. Furthermore, R may include a linear aliphatic saturated hydrocarbon group or a branched aliphatic saturated hydrocarbon group. In polycarbonate polyols, branched and linear R may be used in combination, or linear R may be used alone. Furthermore, polycarbonate polyols may be used individually or in combination of two or more types.

[0052] Aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds are preferably used as polyisocyanate compounds that serve as raw materials for moisture-curing urethane resins. Examples of aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, and naphthalene-1,5-diisocyanate. Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane, and dicyclohexylmethane diisocyanate. Among the polyisocyanate compounds, aromatic polyisocyanate compounds are preferred from the viewpoint of achieving high adhesive strength after complete curing, and diphenylmethane diisocyanate and its modified products are more preferred. Furthermore, aliphatic polyisocyanate compounds are preferred from the viewpoint of easily imparting stress relaxation properties and flexibility to the cured product of the photo-moisture-curable resin composition. Polyisocyanate compounds may be used individually or in combination of two or more.

[0053] (Moisture-curing urethane resin with a polyester backbone) A moisture-curable urethane resin having a polyester skeleton is obtained by introducing a polyester skeleton into a urethane resin by using a polyester polyol as the polyol compound. A moisture-curable urethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. Examples of the above-mentioned polyester polyols include polyester polyols obtained by the reaction of a polycarboxylic acid with a polyol, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. Examples of polycarboxylic acids used as raw materials for polyester polyols include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and dodecamethylenedicarboxylic acid. Among these, phthalic acid or adipic acid are preferred from the viewpoint of being able to more easily improve adhesive strength at high temperatures. Examples of polyols used as raw materials for polyester polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanediol. Among these, 1,6-hexanediol or 1,4-butanediol are preferred from the viewpoint of being able to more easily improve adhesive strength at high temperatures. Furthermore, polyester polyols may be used individually or in combination of two or more types.

[0054] (Moisture-curing urethane resin with a polyether skeleton) A moisture-curable urethane resin having a polyether skeleton is obtained by introducing a polyether skeleton into a urethane resin by using a polyether polyol as the polyol compound. A urethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

[0055] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, ring-opened polymers of tetrahydrofuran, ring-opened polymers of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or their derivatives, as well as bisphenol-type polyoxyalkylene modifiers. Among these, polypropylene glycol, ring-opened polymers of tetrahydrofuran, or ring-opened polymers of 3-methyltetrahydrofuran are preferred from the viewpoint of improving the coatability of the photo-moisture-curable resin composition. Here, the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton. The polyether polyol may be a random copolymer or a block copolymer. Preferably, the above bisphenol-type polyoxyalkylene modified product has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. The bisphenol type is not particularly limited, and examples include type A, type F, type S, etc., with bisphenol type A being preferred. Furthermore, the polyisocyanate compounds described above can be used as the polyisocyanate compounds.

[0056] The moisture-curable urethane resin having a polyether skeleton preferably further includes one obtained using a polyol compound having the structure represented by the following formula (2). By using a polyol compound having the structure represented by the following formula (2), a photo-moisture-curable resin composition with excellent adhesion and a cured product that is flexible and has good elongation can be obtained, and it will have excellent compatibility with the radical polymerizable compound (A). In particular, polyether polyols comprising polypropylene glycol, a ring-opening polymerization compound of a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having substituents such as methyl groups are preferred, and polypropylene glycol and a ring-opening polymerization compound of a tetrahydrofuran (THF) compound are more preferred. The ring-opening polymerization compound of a tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol. Furthermore, polyether polyols may be used individually or in combination of two or more types.

[0057] [ka] In formula (2), R represents a hydrogen atom, a methyl group, or an ethyl group, l is an integer from 0 to 5, m is an integer from 1 to 500, and n is an integer from 1 to 10. Preferably, l is from 0 to 4, m is from 50 to 200, and n is from 1 to 5. Note that when l is 0, it means that the carbon bonded to R is directly bonded to oxygen. Of the above, it is more preferable that the sum of n and l is 1 or more, and even more preferable that it is 1 to 3. Furthermore, it is more preferable that R is a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

[0058] The moisture-curing urethane resins having polycarbonate, polyester, or polyether skeletons described above may have two or more skeletons within their molecules; for example, they may have a polycarbonate skeleton and a polyester skeleton. In that case, it is preferable to use polycarbonate polyol and polyester polyol as the polyol compounds used as raw materials. Similarly, moisture-curing urethane resins having a polyester skeleton and a polyether skeleton may also be used. Furthermore, while it is preferable to use a moisture-curing urethane resin containing isocyanate groups as described above, it is not limited to those containing isocyanate groups, and may also be a hydrolyzable silyl group-containing urethane resin, as will be explained later in the section on hydrolyzable silyl group-containing resins.

[0059] (Hydrolyzable silyl group-containing resin) The hydrolyzable silyl group-containing resin used in this invention hardens when the hydrolyzable silyl groups within the molecule react with moisture in the air or on the adherend. A hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group per molecule, or it may have two or more. In particular, it is preferable that the molecule has hydrolyzable silyl groups at both ends of the main chain. Furthermore, the above-mentioned hydrolyzable silyl group-containing resin does not include those having isocyanate groups.

[0060] A hydrolyzable silyl group is represented by the following formula (3). [ka] In formula (3), R 1 Each of these independently comprises an alkyl group having 1 to 20 carbon atoms, which may be substituted, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or -OSiR 2 3(R 2 Each of the three elements is independently a hydrocarbon group having 1 to 20 carbon atoms (represented by the formula (3)). In formula (3), each of the three elements is independently a hydroxyl group or a hydrolyzable group. Furthermore, in formula (3), a is an integer from 1 to 3.

[0061] The above hydrolyzable groups are not particularly limited and include, for example, halogen atoms, alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, ketoxymate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, etc. Among these, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferred due to their high activity. Furthermore, alkoxy groups such as methoxy groups and ethoxy groups are more preferred because they are milder in hydrolysis and easier to handle, with methoxy groups and ethoxy groups being even more preferred. In addition, from the viewpoint of safety, ethoxy groups and isopropenoxy groups are preferred, as the compounds eliminated by the reaction are ethanol and acetone, respectively.

[0062] The above-mentioned hydroxyl groups or hydrolyzable groups can be bonded to one silicon atom in a range of 1 to 3 groups. If two or more of the above-mentioned hydroxyl groups or hydrolyzable groups are bonded to one silicon atom, those groups may be the same or different.

[0063] In formula (3) above, a is preferably 2 or 3 from the viewpoint of curability, and particularly preferably 3. Furthermore, from the viewpoint of storage stability, a is preferably 2. Furthermore, R in equation (3) above 1 Examples include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, trimethylsiloxy groups, chloromethyl groups, and methoxymethyl groups. Among these, methyl groups are preferred.

[0064] Examples of the above hydrolyzable silyl groups include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (dichloromethyl)dimethoxysilyl group, (1-chloroethyl)dimethoxysilyl group, (1-chloropropyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group. Examples include the lyl group, (ethoxymethyl)dimethoxysilyl group, (1-methoxyethyl)dimethoxysilyl group, (aminomethyl)dimethoxysilyl group, (N,N-dimethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, (N-(2-aminoethyl)aminomethyl)dimethoxysilyl group, (acetoxymethyl)dimethoxysilyl group, and (acetoxymethyl)diethoxysilyl group.

[0065] Examples of hydrolyzable silyl group-containing resins include hydrolyzable silyl group-containing (meth)acrylic resins, organic polymers having hydrolyzable silyl groups at the molecular chain ends or molecular chain terminal sites, and hydrolyzable silyl group-containing polyurethane resins. Hydrolyzable silyl group-containing (meth)acrylic resins preferably have repeating structural units in their main chain derived from hydrolyzable silyl group-containing (meth)acrylic acid esters and / or alkyl (meth)acrylic acid esters.

[0066] Examples of hydrolyzable silyl group-containing (meth)acrylic acid esters include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 2-(trimethoxysilyl)ethyl (meth)acrylate, 2-(triethoxysilyl)ethyl (meth)acrylate, 2-(methyldimethoxysilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, triethoxysilylmethyl (meth)acrylate, and (methyldimethoxysilyl)methyl (meth)acrylate. Examples of the alkyl (meth)acrylate esters mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and stearyl (meth)acrylate.

[0067] Specific examples of methods for producing hydrolyzable silyl group-containing (meth)acrylic resins include the synthesis method for hydrolyzable silicon group-containing (meth)acrylic acid ester polymers described in International Publication No. 2016 / 035718. The organic polymer having a hydrolyzable silyl group at the end of the molecular chain or at the end of the molecular chain has a hydrolyzable silyl group at at least one of the ends of the main chain and the ends of the side chains. The skeletal structure of the main chain described above is not particularly limited and examples include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth)acrylic acid ester polymers, and the like.

[0068] Examples of the polyoxyalkylene polymers mentioned above include polymers having a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, or a polyoxypropylene-polyoxybutylene copolymer structure. A specific method for producing the above-mentioned organic polymer having hydrolyzable silyl groups at the molecular chain ends or molecular chain terminal sites is the method for synthesizing organic polymers having crosslinkable silyl groups only at the molecular chain ends or molecular chain terminal sites, as described in International Publication No. 2016 / 035718. Another method for producing the above-mentioned organic polymer having hydrolyzable silyl groups at the molecular chain ends or molecular chain terminal sites is the method for synthesizing reactive silicon group-containing polyoxyalkylene polymers, as described in International Publication No. 2012 / 117902.

[0069] Methods for producing the above-mentioned hydrolyzable silyl group-containing polyurethane resin include, for example, a method in which a silyl group-containing compound, such as a silane coupling agent, is further reacted when a polyol compound and a polyisocyanate compound are reacted to produce a polyurethane resin. Specifically, examples include the method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in Japanese Patent Application Publication No. 2017-48345.

[0070] Examples of the silane coupling agents mentioned above include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane. Among these, γ-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane are preferred. These silane coupling agents may be used individually or in combination of two or more.

[0071] Furthermore, the moisture-curing urethane resin may have both isocyanate groups and hydrolyzable silyl groups. It is preferable to first obtain a moisture-curing urethane resin having both isocyanate groups (raw material urethane resin) using the method described above, and then react the raw material urethane resin with a silane coupling agent. The details of the moisture-curable urethane resin having an isocyanate group are as described above. As the silane coupling agent to react with the raw urethane resin, one can be appropriately selected from those listed above, but from the viewpoint of reactivity with the isocyanate group, it is preferable to use a silane coupling agent having an amino group or a mercapto group. Specific examples of preferred silane coupling agents include N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and 3-isocyanatetopropyltrimethoxysilane.

[0072] Furthermore, the moisture-curable resin may have a radical polymerizable functional group. Preferably, the radical polymerizable functional group that the moisture-curable resin may have is a group having an unsaturated double bond, and more preferably, a (meth)acryloyl group from the viewpoint of reactivity. Note that the moisture-curable resin having a radical polymerizable functional group is not included in the radical polymerizable compounds described above, and is treated as moisture-curable resin (B). The moisture-curing resin (B) may be selected from the various resins described above and used alone, or two or more may be used in combination.

[0073] The weight-average molecular weight of the moisture-curable resin (B) is preferably 7500 to 24000. By keeping the weight-average molecular weight within the above range, it becomes easier to increase the initial adhesive strength by setting the internal-to-external ratio a / b and the viscosity at 25°C of the photo-moisture-curable resin composition within a predetermined range. Furthermore, by keeping it below the above upper limit, it becomes easier to achieve good final adhesive strength. From these viewpoints, the weight-average molecular weight of the moisture-curable resin (B) is more preferably 7800 or more, even more preferably 10000 or more, even more preferably 11500 or more, even more preferably 20000 or less, even more preferably 16000 or less, and even more preferably 15000 or less. In this specification, the weight-average molecular weight is determined by measuring it using gel permeation chromatography (GPC) and converting it to polystyrene equivalent.

[0074] As described above, moisture-curing resins may be chain-extended to ensure that their weight-average molecular weight is above a certain value. For example, in the case of moisture-curing urethane resins, a urethane resin having isocyanate groups (hereinafter also referred to as "raw material urethane resin") obtained by reacting a polyol compound with a polyisocyanate compound having two or more isocyanate groups in one molecule may be further reacted with a chain extender. In this case, it is preferable to adjust the amount of chain extender used appropriately so that isocyanate groups remain in the moisture-curing urethane resin, rather than reacting the chain extender with all of the isocyanate groups in the raw material urethane resin. Alternatively, the raw material urethane resin may be reacted with the chain extender that has been reacted with the raw material urethane resin.

[0075] Polyol compounds are preferred as chain extenders used in moisture-curing urethane resins. Details of the polyol compounds are as described above. Furthermore, the polyol compound used as the chain extender should be the same type of polyol compound used to synthesize the raw urethane resin. Therefore, if the polyol compound used to synthesize the raw urethane resin is a polycarbonate polyol, then a polycarbonate polyol should also be used as the chain extender. The amount of chain extender used is calculated based on the total amount of raw urethane resin and chain extender being 100 parts by mass. For example, 5 parts by mass or more and 40 parts by mass or less, preferably 10 parts by mass or more and 35 parts by mass or less, more preferably 15 parts by mass or more and 30 parts by mass or less.

[0076] In a photo-moisture-curing resin composition, the mass ratio (B / A) of the moisture-curable resin (B) to the radical polymerizable compound (A) is preferably 30 / 70 to 90 / 10, more preferably 40 / 60 to 80 / 20, and even more preferably 50 / 50 to 70 / 30. By having the mass ratio within these ranges, the photo-moisture-curing resin composition can be given both photocurability and moisture-curability in a well-balanced manner, and both the initial and final adhesive strengths can be easily adjusted to the desired range.

[0077] The photo-moisture-curing resin composition may contain resin components other than the radical polymerizable compound (A) and the moisture-curing resin (B) as long as the effects of the present invention are not impaired. For example, it may contain resin components such as thermoplastic resins that do not cure (e.g., acrylic resins, urethane resins, etc.) or thermosetting resins. The proportion of resin components other than the radical polymerizable compound (A) and the moisture-curing urethane resin (B) is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total amount of the radical polymerizable compound (A) and the moisture-curing urethane resin (B).

[0078] [Photopolymerization initiator (C)] The photo- and moisture-curable resin composition of the present invention contains a photopolymerization initiator. The inclusion of a photopolymerization initiator appropriately imparts photocurability to the photo- and moisture-curable resin composition. Examples of photopolymerization initiators include benzophenone compounds, acetophenone compounds, alkylphenone photopolymerization initiators, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthones. Examples of commercially available photopolymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF), benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0079] The content of the photopolymerization initiator in the photo-moisture-curable resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the radical polymerizable compound (A). By keeping the photopolymerization initiator content within this range, the resulting photo-moisture-curable resin composition exhibits excellent photocurability and storage stability. Furthermore, maintaining this range allows the photo-radical polymerizable compound to cure properly, making it easier to achieve good adhesive strength.

[0080] [Filler (D)] The photo- and moisture-curing resin composition of the present invention may contain a filler (D). By containing a filler (D), the photo- and moisture-curing resin composition of the present invention will have suitable thixotropy and will be able to sufficiently maintain its shape after application. A particulate filler may be used. As the filler (D), inorganic fillers are preferred, such as silica, talc, titanium dioxide, zinc oxide, and calcium carbonate. Among these, silica is preferred because the resulting photo-moisture-curing resin composition has excellent ultraviolet light transmittance. Furthermore, the filler (D) may be subjected to hydrophobic surface treatments such as silylation, alkylation, or epoxidation. The filler (D) may be used alone or in combination of two or more types. The content of the filler (D) is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 3 to 15 parts by mass, based on 100 parts by mass of the total amount of the radical polymerizable compound (A) and the moisture-curable urethane resin (B).

[0081] (Moisture curing accelerating catalyst) The photo-moisture-curing resin composition may contain a moisture-curing accelerating catalyst that promotes the moisture-curing reaction of the moisture-curing resin (B). By using a moisture-curing accelerating catalyst, the photo-moisture-curing resin composition becomes more moisture-curable and easier to improve in terms of adhesive strength. Examples of moisture-curing accelerating catalysts include amine compounds and metal catalysts. Examples of amine compounds include compounds having a morpholine skeleton such as di(methylmorpholino)diethyl ether, 4-morpholinopropylmorpholine, and 2,2'-dimorpholinodiethyl ether; dimethylamino group-containing amine compounds having two dimethylamino groups such as bis(2-dimethylaminoethyl) ether and 1,2-bis(dimethylamino)ethane; triethylamine, 1,4-diazabicyclo[2.2.2]octane, and 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane. Examples of metal catalysts include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octoate; zinc compounds such as zinc octoate and zinc naphthenate; and other metal compounds such as zirconium tetraacetylacetonate, copper naphthenate, and cobalt naphthenate.

[0082] The content of the moisture curing accelerating catalyst is preferably 0.01 parts by mass to 8 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the moisture-curable urethane resin (B). By having the moisture curing accelerating catalyst content within the above range, an excellent effect of accelerating the moisture curing reaction is achieved without deteriorating the storage stability of the photo-moisture-curable resin composition.

[0083] (Coloring agent) The photo- and moisture-curing resin composition of the present invention may contain a colorant. Examples of colorants include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. The photo- and moisture-curing resin composition also has good light-shielding properties when it contains a colorant. Among these, titanium black is preferred. Titanium black has the property of sufficiently shielding light in the visible light region while transmitting light in the ultraviolet region, thus preventing a decrease in the photocurability of the photo- and moisture-curing resin composition. The colorant content in the photo-moisture-curing resin composition is preferably 0.05 parts by mass to 8 parts by mass, and more preferably 0.1 parts by mass to 2 parts by mass, based on 100 parts by mass of the total amount of the radical polymerizable compound (A) and the moisture-curing urethane resin (B). By keeping the colorant content within this range, the photo-moisture-curing resin composition can be given appropriate light-shielding properties while maintaining good adhesion.

[0084] The photo- and moisture-curing resin composition may contain other additives besides those mentioned above, such as coupling agents, wax particles, ionic liquids, foaming particles, expanding particles, and reactive diluents. Examples of coupling agents include silane coupling agents, titanate-based coupling agents, and zirconate-based coupling agents, with silane coupling agents being preferred among these. The photo-moisture-curing resin composition may be diluted with a solvent as needed. When the photo-moisture-curing resin composition is diluted with a solvent, the parts by mass of the photo-moisture-curing resin composition are based on solid content, i.e., parts by mass excluding the solvent.

[0085] Methods for producing the photo-moisture-curing resin composition of the present invention include mixing a radical polymerizable compound (A), a moisture-curing resin (B), a photopolymerization initiator (C), and other additives such as fillers, moisture-curing accelerators, and colorants, which are added as needed, using a mixer. Examples of mixers include homodispers, homomixers, universal mixers, planetary mixers, planetary agitators, kneaders, and three-roll mixers.

[0086] Furthermore, as mentioned above, moisture-curing resins such as moisture-curing urethane resins may have their molecular weight increased by using chain extenders. In such cases, for example, a moisture-curing resin (B) can be obtained by pre-reacting a raw material resin, such as a raw material urethane resin, with a chain extender, and then mixing it with other raw materials such as a radical polymerizable compound (A) as described above. Alternatively, a moisture-curable resin (B) may be synthesized by mixing the raw material resin, a chain extender, and a radical polymerizable compound (A), and then heating the mixture as needed to react the chain extender with the raw material resin. In this case, a mixture of the moisture-curable resin (B) and the radical polymerizable compound (A) is obtained, and a photopolymerization initiator (C) and other additives as needed are added to this mixture to obtain a photo-moisture-curable resin composition.

[0087] <Method of using photo-moisture-curing resin composition> The photo- and moisture-curable resin composition of the present invention is cured and used as a cured body. Specifically, the photo- and moisture-curable resin composition of the present invention is first photo-cured by light irradiation to, for example, a B-stage state (partially cured state), and then cured with moisture to achieve full curing. Here, when the photo-moisture-curable resin composition is placed between adherends to join them, it is preferable to apply it to one adherend, then photo-cur it by light irradiation to, for example, a B-stage state, and then place the other adherend on top of the photo-cured photo-moisture-curable resin composition to temporarily bond the adherends with an appropriate adhesive force (initial adhesive force). Subsequently, the photo-moisture-curable resin composition in the B-stage state is fully cured by curing the moisture-curable urethane resin with moisture, and the adherends that were placed on top of each other via the photo-moisture-curable resin composition are permanently bonded and joined with sufficient adhesive force.

[0088] The photo- and moisture-curable resin composition can be applied to the substrate, for example, by a dispenser, but is not particularly limited. The light used for photocuring is not particularly limited as long as it is light that cures radical polymerizable compounds, but ultraviolet light is preferred. Furthermore, when the photo- and moisture-curable resin composition is to be fully cured by moisture after photocuring, it can be left in the atmosphere for a predetermined time. The application of the photo- and moisture-curing resin composition to the substrate is not particularly limited, but it is preferable to do so at or near room temperature, specifically at a temperature of about 10 to 35°C. Since the viscosity of the photo- and moisture-curing resin composition of the present invention is within the predetermined range at 25°C, it can be easily applied even when applied at or near room temperature, and dripping does not occur. Furthermore, the photo- and moisture-curing resin composition of the present invention exhibits an initial adhesive strength of a certain value or higher immediately after light irradiation, allowing for immediate temporary bonding after photocuring, resulting in excellent workability.

[0089] The photo- and moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic components. That is, the present invention also provides an adhesive for electronic components comprising the above-mentioned photo- and moisture-curable resin composition. Therefore, the adherend described above is preferably various electronic components that constitute an electronic device. Examples of various electronic components that constitute an electronic device include various electronic components provided on a display element, a substrate on which electronic components are attached, and semiconductor chips. Furthermore, the material of the adherend can be any of metal, glass, plastic, etc. In addition, the shape of the adherend is not particularly limited and can be, for example, film, sheet, plate, panel, tray, rod, box, or housing.

[0090] As described above, the photo- and moisture-curable resin composition of the present invention is preferably used to bond electronic components that constitute electronic devices. Furthermore, the photo- and moisture-curable resin composition of the present invention is also preferably used to bond electronic components to other components. With these configurations, the electronic components will have a cured body of the present invention. Furthermore, the photo- and moisture-curable resin composition of the present invention can be used, for example, to bond substrates together to obtain an assembled component inside electronic equipment. The assembled component thus obtained comprises a first substrate, a second substrate, and a cured body of the present invention, wherein at least a portion of the first substrate is bonded to at least a portion of the second substrate via the cured body. Preferably, at least one electronic component is attached to each of the first and second substrates.

[0091] Furthermore, the photo- and moisture-curing resin composition of the present invention is preferably used in narrow bezel applications. For example, in various display devices such as mobile phone display devices for smartphones, an adhesive is applied to a narrow rectangular frame-shaped (i.e., narrow bezel) base, and display panels, touch panels, etc., are assembled via the adhesive. The photo- and moisture-curing resin composition of the present invention is preferably used as the adhesive. Moreover, the photo- and moisture-curing resin composition of the present invention is preferably used in semiconductor chip applications. In semiconductor chip applications, the photo- and moisture-curing resin composition of the present invention is, for example, used to bond semiconductor chips together. [Examples]

[0092] The present invention will be described in more detail by reference to examples, but the present invention is not limited in any way by these examples.

[0093] The following measurements and evaluations of various physical properties were performed. (Weight-average molecular weight) The weight-average molecular weight of the moisture-curable resin (B) in each example and comparative example was measured by gel permeation chromatography (GPC) and determined in terms of polystyrene conversion. For the GPC measurement, Shodex KF-806L (manufactured by Showa Denko KK) was used as the column. Also, tetrahydrofuran (THF) was used as the solvent and mobile phase. Further, the measurement conditions for GPC were a flow rate of 1.0 ml / min and a measurement temperature of 40°C.

[0094] In each example and comparative example, the above weight-average molecular weight was measured using a mixture of the radically polymerizable compound and the moisture-curable resin (B) as a sample. In this mixture, a peak of the radically polymerizable compound appears on the low molecular weight side and a peak of the moisture-curable resin (B) appears on the high molecular weight side. Therefore, the weight-average molecular weight of the moisture-curable resin (B) can be determined from the peak on the high molecular weight side.

[0095] (Viscosity at 25°C) The viscosity at 25°C was measured using a cone and plate viscometer (trade name TVE-35, manufactured by Toki Sangyo Co., Ltd.) under the conditions of 5.0 rpm and 25°C.

[0096] (Ratio of inside to outside a / b) The ratio of inside to outside a / b was measured by the method described in the specification. As the aluminum substrate and glass plate, an aluminum alloy "A6063S" with a size of 2 mm × 25 mm × 60 mm and a glass plate with a smooth surface that had been ultrasonically cleaned for 5 minutes were used, respectively. The application of the moisture-curable resin composition was carried out at room temperature (25°C) using "SHOTMASTER300SX" manufactured by Musashi Engineering Co., Ltd., a dispensing device, and linearly applied to the aluminum substrate so that the width was 1.0 ± 0.1 mm, the length was 25 mm, and the thickness was 0.4 ± 0.1 mm. Next, for the applied photo-moisture-curable resin composition, ultraviolet light with a wavelength of 405 nm was irradiated at 1000 mJ / cm by a line-type LED irradiator (manufactured by HOYA Corporation, 1000 mW). 2The glass plate was irradiated. The glass plate was pressed against the aluminum substrate using weights, and the widths a1 and b1 were measured 5 minutes after the weights were removed. The widths a1 and b1 after pressing were measured by observing the pressed surface from the glass plate side using a microscope.

[0097] (Gel swelling ratio (W1 / W2)) The gel swelling ratio (W1 / W2) was measured using the method described in the specification. The release PET film used was "PET38×1-C" (manufactured by Nippa Co., Ltd.). The coated photo-moisture-curing resin composition was treated with 405nm wavelength ultraviolet light at a rate of 1000mJ / cm² using a line-type LED irradiator (manufactured by HOYA Corporation, 1000mW). 2 Irradiation was performed. Immersion in THF was carried out using 30 ml of THF in a glass bottle, while gently stirring. As the 200 mesh wire mesh, "Brass 200 mesh (wire diameter 50 μm, mesh opening 77 μm)" (manufactured by Mesh Co., Ltd.) was used. The photo-cured photo-moisture-curing resin composition after immersion was washed five times using fresh 5 ml of THF. The swollen gel was dried by standing it in a constant temperature oven set to 100°C for 2 hours. In the above operations, all THF used was dried THF.

[0098] (Initial adhesive strength) As shown in Figures 2(a) and (b), the photo-moisture-curing resin composition 20 was applied to the aluminum substrate 21 at room temperature (25°C) using the dispensing apparatus described above, so that it had a width of 1.0 ± 0.1 mm, a length of 25 mm, and a thickness of 0.4 ± 0.1 mm. Then, ultraviolet light with a wavelength of 405 nm was applied at a rate of 1000 mJ / cm² using a line-type LED irradiator (manufactured by HOYA Corporation, 1000 mW). 2 The resin composition was photocured by irradiation. Subsequently, a glass plate 22 was bonded to an aluminum substrate 21 via the photocured photo-moisture-curing resin composition 20, and pressure was applied using a weight at 0.08 MPa relative to the coating area for 120 seconds to obtain a sample 23 for adhesion evaluation. Subsequently, under a 25°C atmosphere, the aluminum substrate 21 and glass plate 22 were subjected to tensile testing using a tensile testing machine ("Tensile and Compression Testing Apparatus SVZ-50NB," manufactured by Imada Seisakusho) at a speed of 10 mm / min in the shear direction S. The maximum stress at which the aluminum substrate 21 and glass plate 22 peeled off was measured and defined as the initial adhesive strength. The time from the end of photocuring to the start of the tensile test was kept within 150 seconds. The initial adhesive strength was evaluated according to the following evaluation criteria. A: 0.4 MPa or higher B: 0.25 MPa or higher, less than 0.4 MPa C: Less than 0.25 MPa

[0099] (Final adhesive strength) Similar to the initial adhesion measurement method, a glass plate was bonded to an aluminum substrate via a photocured, photo-moisture-curing resin composition. The mixture was then left to moisture-cur at 25°C and 50RH for 24 hours to obtain a sample for adhesion evaluation. Using this sample, the sample was pulled in the shear direction, similar to the initial adhesion measurement method, and the maximum stress at which the aluminum substrate and glass plate separated was measured to determine the final adhesion strength. A: 3.5 MPa or higher B: 2.0 MPa or higher, less than 3.5 MPa C: Less than 2.0 MPa

[0100] The urethane resin raw materials used in each example and comparative example were prepared by the following method. [Synthesis Example 1] (PC urethane resin raw material) 100 parts by mass of polycarbonate diol (a compound represented by formula (1), where 90 mol% of R is a 3-methylpentylene group and 10 mol% is a hexamethylene group, manufactured by Kuraray Co., Ltd., trade name "Kuraraypolyol C-1090") as the polyol compound and 0.01 parts by mass of dibutyltin dilaurate were placed in a 500 mL separable flask. The flask was mixed under vacuum (20 mmHg or less) by stirring at 100 °C for 30 minutes. Then, the pressure was reduced to atmospheric pressure, and 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name "Pure MDI") as the polyisocyanate compound was added and the mixture was reacted by stirring at 80 °C for 3 hours to obtain a moisture-curable urethane resin (PC urethane resin raw material) having a polycarbonate backbone and isocyanate groups at both ends. The weight-average molecular weight of the obtained urethane resin raw material was 6700.

[0101] [Synthesis Example 2] (ET urethane resin raw material) 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-3000") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate were placed in a 500 mL separable flask. The flask was mixed under vacuum (20 mmHg or less) by stirring at 100 °C for 30 minutes. Then, the pressure was reduced to atmospheric pressure, and 17.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name "Pure MDI") as a polyisocyanate compound was added. The mixture was reacted by stirring at 80 °C for 3 hours to obtain a moisture-curable urethane resin (ET urethane resin raw material) having a polyether skeleton and isocyanate groups at both ends. The weight-average molecular weight of the obtained urethane resin raw material was 3500.

[0102] [Example 1] As shown in Table 5, 40 parts by mass of acrylic A were mixed with 60 parts by mass of each raw material constituting the moisture-curing resin (PC-L25). Acrylic A was prepared by mixing each compound in the proportions shown in Table 2. As the moisture-curing resin (PC-L25), the PC urethane resin raw material and PC polyol were added to acrylic A in the proportions shown in Table 3 to obtain a mixture. As the PC polyol, the polycarbonate diol used in Synthesis Example 1 was used. By stirring the resulting mixture at 50°C, a portion of the urethane resin raw material was reacted with PC polyol, synthesizing a moisture-curable urethane resin with extended chains and residual isocyanate groups, thus obtaining a mixture of acrylic A (radical polymerizable compound) and moisture-curable urethane resin. The resulting mixture of acrylic A and moisture-curable urethane resin was further mixed with a photopolymerization initiator and filler according to the formulations in Table 5 to obtain a photo-moisture-curable resin composition. The viscosity at 25°C, gel swelling ratio, inner-to-outer ratio a / b, initial adhesive strength, and final adhesive strength of the obtained photo-moisture-curable resin composition were measured.

[0103] [Examples 2-4, 7, 8, Comparative Examples 1, 2] The procedure was carried out in the same manner as in Example 1, except that acrylic B was used instead of acrylic A, and the moisture-curing resin used instead of the moisture-curing resin (PC-L25) was one of the moisture-curing resins listed in Tables 3, 4, and 5. In other words, the procedure was carried out in the same manner as in Example 1, except that acrylic B was used instead of acrylic A, and the mixing ratio and type of urethane resin raw material and polyol added to acrylic B were changed as shown in Tables 3 and 4 to obtain a mixture of acrylic B and moisture-curable urethane resin. In Table 4, the ET polyol used was polytetramethylene ether glycol, which was used in Synthesis Example 2. In Comparative Example 1, only urethane resin raw material was added to acrylic A, and no polyol was added, so the urethane resin raw material was used as is as a moisture-curable resin.

[0104] [Examples 5, 9-11, Comparative Examples 3-5] The procedure was carried out in the same manner as in Example 1, except that acrylics B to H were used instead of acrylic A. Each of the acrylics B to H was prepared by mixing the compounds according to the proportions shown in Table 2.

[0105] [Example 6] The procedure was carried out in the same manner as in Example 5, except that a photopolymerization initiator, filler, and colorant were added to the mixture of acrylic B and moisture-curable urethane resin obtained according to the formulation in Table 5 and mixed to obtain a photo-moisture-curable resin composition.

[0106] The components other than the moisture-curing urethane resin (B) used in each example and comparative example are shown in Table 1 below. [Table 1]

[0107] The acrylics A to D used in the examples and comparative examples were as follows: [Table 2]

[0108] The moisture-curing resin (B) used in the examples and comparative examples is shown in Table 3 below. As described above, in the case of moisture-curing resin (L0), the urethane resin raw material was used as is as moisture-curing resin (B), while in the other cases, the reaction product of the following urethane resin raw material and polyol was used as moisture-curing resin (B). [Table 3]

[0109] [Table 4]

[0110] [Table 5]

[0111] Each of the photo- and moisture-curable resin compositions in Examples 1 to 10 contained a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C), and exhibited excellent initial adhesion because the gel swelling ratio and viscosity at 25°C were within a predetermined range. In contrast, in Comparative Examples 1 to 5, at least one of the gel swelling ratio and viscosity at 25°C was outside the predetermined range, and therefore good initial adhesion could not be achieved.

Claims

1. It comprises a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C), The radical polymerizable compound (A) includes a monofunctional radical polymerizable compound, The moisture-curing resin (B) includes a moisture-curing urethane resin, The weight-average molecular weight of the moisture-curing resin (B) is 7,500 or more and 20,000 or less. The above-mentioned radical polymerizable compound (A) contains 100 parts by mass of the above-mentioned monofunctional radical polymerizable compound, with a total of 90 parts by mass or more of the above-mentioned monofunctional radical polymerizable compound. The gel swelling ratio (W1 / W2) determined by the measurement methods shown in (1) to (4) below is 15 or more. The viscosity measured using a cone-plate viscometer at 25°C and 5.0 rpm is 35 Pa·s or more and 600 Pa·s or less, and The solution was applied to an aluminum substrate with a line width of 1.0 mm, and then subjected to a concentration of 1000 mJ / cm². ２ A photo-curable resin composition in which, after being photocured by irradiation with ultraviolet light, a glass plate is pressed against it at 0.08 MPa for 120 seconds, and the average width of the bonded portion on the glass plate side is a and the average width of the bonded portion on the aluminum substrate side is b, a / b is 0.58 or more and 0.99 or less. (1) 1.0 g of light- and moisture-curing resin composition is applied to a release PET film to a thickness of 1.5 mm, and 1000 mJ / cm² is applied. ２ It is photocured by irradiating it with ultraviolet light. (2) The photo-cured photo-moisture-curing resin composition is peeled off the release PET film and immersed in THF at 25°C for 48 hours. (3) The photo-cured photo-moisture-curing resin composition after immersion is removed onto a 200-mesh wire mesh, washed five times with fresh THF, and the weight (W1) of the swollen gel remaining on the wire mesh is measured. (4) The swollen gel is dried at 100°C for 2 hours to volatilize the THF, the weight of the dry gel (W2) is measured, and the gel swelling ratio (W1 / W2) is determined.

2. The photo-moisture-curing resin composition according to claim 1, wherein the moisture-curing urethane resin is a moisture-curing urethane resin having at least one of a polycarbonate skeleton, a polyether skeleton, and a polyester skeleton.

3. The photo-moisture-curing resin composition according to claim 1 or 2, wherein the moisture-curing urethane resin is a moisture-curing urethane resin having a polycarbonate skeleton.

4. The photo-moisture-curable resin composition according to any one of claims 1 to 3, wherein the monofunctional radical polymerizable compound comprises a nitrogen-containing compound.

5. The photo-moisture-curing resin composition according to any one of claims 1 to 4, further comprising a filler (D).

6. An adhesive for electronic components comprising a photo- and moisture-curing resin composition according to any one of claims 1 to 5.

7. A cured body of a photo- and moisture-curable resin composition according to any one of claims 1 to 5.

8. An electronic component comprising the cured body described in claim 7.

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