TWI902797B - Light and moisture curing resin compositions, adhesives for electronic components, cured products, and electronic components. - Google Patents

Abstract

The photo- and moisture-curing resin composition of this invention comprises a free radical polymerizable compound (A), a moisture-curing resin (B), and a photopolymerization initiator (C). When photocured by irradiation with 1000 mJ/ ^cm² ultraviolet light, its storage modulus (G') at 25°C is 250 kPa or more, and its tanδ at 75°C is 1.0 or more.

Description

Light and moisture curing resin compositions, adhesives for electronic components, cured products, and electronic components.

This invention relates to a light and moisture-curing resin composition, an adhesive for electronic components, a cured material, and electronic components.

In recent years, there has been a growing demand for high integration and miniaturization in electronic components such as semiconductor chips. For example, multiple thin semiconductor chips are sometimes bonded together using an adhesive layer to create a semiconductor chip stack. Furthermore, with the increasing prevalence of mobile devices with integrated display components, a common method for miniaturizing display components is to narrow the bezels of the image display section (hereinafter also referred to as "narrow bezel design"). In these applications, with the development of miniaturization or narrow bezel design, there are attempts to use photo- and moisture-curing adhesives to replace double-sided tape.

As a photo- and moisture-curing adhesive, for example, Patent 1 discloses a photo- and moisture-curing resin composition containing a free radical polymerizable compound, a moisture-curing amine ester resin, and a photoradical polymerization initiator, wherein the moisture-curing amine ester resin contains a moisture-curing amine ester resin with a weight average molecular weight of 2000 or more. Furthermore, Patent 2 discloses a reactive hot-melt adhesive composition comprising an amine ester prepolymer, an (meth)acrylic acrylate amine ester having (meth)acrylic groups, and a photopolymerization initiator. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Application Publication No. 2016-074781 Patent Document 2: Japanese Patent Application Publication No. 2019-006854

[The problem the invention aims to solve]

However, light and moisture-curing adhesives do not exhibit adhesion (initial adhesion) immediately after application, unlike double-sided tape. Therefore, it takes time for the components to bond together, which presents a workability problem. For example, in patents 1 and 2, although it is stated that a certain level of adhesion is exhibited after irradiation, the initial adhesion is sometimes insufficient.

Therefore, the problem of this invention is to provide a light and moisture-curing resin composition that exhibits excellent adhesion immediately after light curing, thereby improving workability and other properties. [Technical Means for Solving the Problem]

The inventors have conducted intensive research and found that by keeping the storage modulus (G') of the photocured photocurable and moisture-curable resin composition within a certain range at 25°C and the tanδ at 75°C, the above-mentioned problems can be solved, and the following invention has been completed. That is, the present invention provides the following [1] to [ ²⁵ ]. [1] A photocurable and moisture-curable resin composition comprising a free radical polymerizable compound (A), a moisture-curable resin (B) and a photopolymerization initiator (C), and when photocured by irradiation with ultraviolet light of 1000 mJ/cm2, its storage modulus (G') at 25°C is 250 kPa or more, and its tanδ at 75°C is 1.0 or more. [2] In the light and moisture-curing resin composition described in [1] above, when a glass plate is pressed at 0.08 MPa for 120 seconds after being coated on an aluminum substrate with a line width of 1.0 mm and irradiated with ultraviolet light of 1000 mJ/ ^cm2 to achieve light curing, if the average width of the bonding portion on the glass plate side is set to a and the average width of the bonding portion on the aluminum substrate side is set to b, then a/b is 0.58 or more and 0.99 or less. [3] In the light and moisture-curing resin composition described in [1] or [2] above, the moisture-curing resin (B) includes a moisture-curing amine ester resin. [4] The light and moisture-curing resin composition as described in [3] above, wherein the moisture-curing amine resin is a moisture-curing amine resin having at least one of a polycarbonate backbone, a polyether backbone, and a polyester backbone. [5] The light and moisture-curing resin composition as described in [3] or [4] above, wherein the moisture-curing amine resin is a moisture-curing amine resin having a polycarbonate backbone. [6] The light and moisture-curing resin composition as described in any of [1] to [5] above, wherein the weight average molecular weight of the moisture-curing resin (B) is 7500 or more and 24000 or less. [7] The photo- and moisture-curing resin composition described in any of [1] to [6] above, wherein the free radical polymeric compound (A) comprises a monofunctional free radical polymeric compound. [8] The photo- and moisture-curing resin composition described in [7] above, wherein, relative to 100 parts by mass of the free radical polymeric compound (A), it comprises 90 or more parts by mass of a monofunctional free radical polymeric compound. [9] The photo- and moisture-curing resin composition described in [7] or [8] above, wherein the monofunctional free radical polymeric compound comprises a nitrogen-containing compound. [10] The photo- and moisture-curing resin composition described in [9] above, wherein the monofunctional free radical polymeric compound comprises a chain-like nitrogen-containing compound. [11] The photo- and moisture-curing resin composition as described in [9] or [10] above, wherein the monofunctional free radical polymeric compound comprises a nitrogen-containing compound having a cyclic structure. [12] The photo- and moisture-curing resin composition as described in [11] above, wherein the mass ratio (cyclic/chain) of the nitrogen-containing compound having a cyclic structure to the nitrogen-containing compound having a chain structure is 0.1 or more and 2.0 or less. [13] The photo- and moisture-curing resin composition as described in any one of [9] to [12] above, wherein the content of the nitrogen-containing compound as a monofunctional free radical polymeric compound is 10 or more and 95 or less, relative to 100 parts by mass of the free radical polymeric compound (A). [14] The photo- and moisture-curing resin composition as described in any of [9] to [13] above, wherein the monofunctional free radical polymeric compound comprises, in addition to the nitrogen-containing compound, a monofunctional (meth)acrylate compound. [15] The photo- and moisture-curing resin composition as described in [14] above, wherein the monofunctional (meth)acrylate compound is selected from at least one of the group consisting of alkyl (meth)acrylates, (meth)acrylates with alicyclic structures, and (meth)acrylates with aromatic rings. [16] In the photo- and moisture-curing resin composition described in [15] above, the total content of alkyl methacrylate, methacrylate with an alicyclic structure, and methacrylate with an aromatic ring is 5 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of the free radical polymerizable compound (A). [17] In the photo- and moisture-curing resin composition described in any of [1] to [16] above, the mass ratio (B/A) of the moisture-curing resin (B) to the free radical polymerizable compound (A) is 30/70 or more and 90/10 or less. [18] In the photo- and moisture-curing resin composition described in any of [1] to [17] above, it further includes a filler (D). [19] The photo- and moisture-curing resin composition described in any of [1] to [18] above, wherein the photopolymerization initiator (C) is selected from benzophenone compounds, acetophenone compounds, alkylphenone photopolymerization initiators, acetophosphine oxide compounds, titanium thiocenes compounds, oxime ester compounds, benzoin ether compounds, and 9-oxosulfur At least one of the groups formed. [20] The light and moisture-curing resin composition described in any of [1] to [19] above has an initial adhesion of 0.25 MPa or more. [21] The light and moisture-curing resin composition described in any of [1] to [20] above has a final adhesion of 2.0 MPa or more. [22] The light and moisture-curing resin composition described in any of [1] to [21] above has a viscosity of 35 Pa·s or more and 600 Pa·s or less, as measured using a tapered viscometer at 25°C and 5.0 rpm. [23] An adhesive for electronic components, comprising a photo- and moisture-curing resin composition as described in any of [1] to [22] above. [24] A cured material, which is a cured product of a photo- and moisture-curing resin composition as described in any of [1] to [22] above. [25] An electronic component comprising the cured material described in [24] above. [Effects of the Invention]

According to the present invention, a light and moisture-curing resin composition is provided that exhibits excellent adhesion even immediately after light curing, thereby improving workability and other properties.

The present invention will now be described in detail with reference to the embodiments. <Photocurable and Moisture-Curing Resin Composition> The photocurable and moisture-curing resin composition of the present invention comprises a free radical polymerizable compound (A), a moisture-curing resin (B), and a photopolymerization initiator (C). Regarding the photocurable and moisture-curing resin composition of the present invention, when photocured by irradiation with 1000 mJ/ ^cm² ultraviolet light, its storage modulus (G') at 25°C is 250 kPa or higher, and its tanδ at 75°C is 1.0 or higher. If the storage modulus (G') at 25°C and tanδ at 75°C of the photocurable resin composition of this invention, after photocuring as described above, are both above a certain value, then when appropriate pressure is applied immediately after photocuring, a certain amount of collapse will occur, making it easy to bond to the substrate, and it will also exhibit a certain cohesive force even when shear stress is applied. Therefore, the bonding force (initial bonding force) immediately after photocuring can be made excellent.

[Storage Modulus (G')] The storage modulus (G') of the light- and moisture-curing resin composition of this invention, measured at 25°C after light curing as described above, is 250 kPa or higher. If the storage modulus (G') at 25°C is lower than 250 kPa, the bulk strength after light curing decreases, making it difficult to improve initial adhesion. From the viewpoint of improving bulk strength to improve initial adhesion, the storage modulus (G') at 25°C is preferably 350 kPa or higher, more preferably 500 kPa or higher, further preferably 600 kPa or higher, and even more preferably 700 kPa or higher. From the perspective that it readily exhibits a certain degree of adhesion immediately after light curing, the storage modulus (G') at 25°C is preferably 4000 kPa or less, more preferably 3500 kPa or less, further preferably 3000 kPa or less, and even more preferably 2500 kPa or less.

[tanδ] Regarding the photocurable resin composition of this invention, when measured using a dynamic viscoelasticity measuring device at 1 Hz under photocuring conditions caused by irradiation with 1000 mJ/ ^cm² ultraviolet light, its tanδ at 75°C is 1.0 or higher. If the tanδ at 75°C is less than 1.0, the photocured photocurable resin composition is prone to springback and does not easily collapse when compressed, thus making it difficult to improve initial adhesion. From the viewpoint of improving initial adhesion, a tanδ at 75°C is preferably 1.05 or higher, more preferably 1.1 or higher, and even more preferably 1.2 or higher. Furthermore, from the viewpoint of preventing excessive collapse during compression that would reduce the initial adhesion, the tanδ at 75°C is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.6 or less.

Furthermore, the storage modulus (G') at 25°C and tanδ at 75°C can be adjusted by the type, molecular weight, and dosing amount of the moisture-curing resin (B), or the type or dosing amount of the free radical polymerizing compound (A). For example, increasing the molecular weight of the moisture-curing resin (B) tends to increase the storage modulus (G') at 25°C. Also, if the free radical polymerizing compound (A) contains a large amount of homopolymer with a larger tanδ at 75°C, the aforementioned tanδ of the light- and moisture-curing resin composition tends to increase. Furthermore, if a large amount of monofunctional monomer is incorporated as the free radical polymerizing compound (A), the aforementioned tanδ tends to increase. Furthermore, if the molecular weight of the moisture-curing resin (B) is kept within a certain range, then tanδ is easily kept within that specific range.

Furthermore, the storage modulus (G') and tanδ of the light- and moisture-curing resin composition can be measured as follows. The light- and moisture-curing resin composition is coated onto a viscoelasticity measuring fixture, and irradiated with ultraviolet light at 1000 mJ/ ^cm² using a 1000 mW UV-LED lamp to light-cur it, thereby preparing an evaluation sample. Within 30 seconds of irradiation, the evaluation sample is placed in a dynamic viscoelasticity measuring device, and the storage modulus (G') and tanδ are measured under conditions of 10–100°C, heating rate = 5°C/min, frequency F = 1 Hz, and shear mode.

[25°C Viscosity] The light- and moisture-curing resin composition of this invention preferably has a viscosity (hereinafter also referred to as "25°C viscosity") of 35 Pa·s or higher and 600 Pa·s or lower, measured using a tapered viscometer at 25°C and 5.0 rpm. The 25°C viscosity of the moisture-curing resin composition mentioned above refers to that measured at a high shear rate of 5.0 rpm in a state where neither light curing nor moisture curing has occurred, and this viscosity is not easily affected by fillers. Therefore, if the 25°C viscosity is 35 Pa·s or higher, the low molecular weight components contained in the moisture-curing resin (B) tend to decrease, and after irradiation, the moisture-curing resin (B) is less likely to penetrate to the interface, thus easily improving the initial adhesion. In other words, if low-molecular-weight moisture-curing resins (B) do not readily penetrate to the interface after irradiation, slippage between the resin and the substrate is less likely to occur, resulting in stronger adhesion and improved initial bonding strength. Furthermore, even when the viscosity at 25°C is below 600 Pa·s, the inherent adhesive properties of the moisture-curing resin (B) are readily observed, thereby easily improving the initial bonding strength or the final bonding strength described below. Furthermore, by setting the viscosity at 25°C to 35 Pa·s or higher and 600 Pa·s or lower, defects such as dripping or inability to be applied at room temperature are less likely to occur, thus improving workability.

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, more preferably 90 Pa·s or higher, more preferably 110 Pa·s or higher, and even more preferably 500 Pa·s or lower, more preferably 350 Pa·s or lower, and even more preferably 230 Pa·s or lower. Maintaining the viscosity at 25°C within the above range facilitates improved workability and initial adhesion. Furthermore, setting it below the above upper limit prevents the molecular weight of the moisture-curing resin (A) from becoming excessively high, thus facilitating improved initial adhesion. Furthermore, by achieving sufficiently high adhesion through moisture curing, the final adhesion is also easily improved. Furthermore, the term "final adhesion" refers to the adhesion between light-cured and moisture-cured resin compositions after both light curing and moisture curing, as detailed below.

[Inner/Outer Ratio a/b] The photocurable and moisture-curable resin composition of this invention, when linearly coated on an aluminum substrate under specific conditions and photocured using UV light before being pressed onto a glass plate, has an a/b ratio (also referred to as the "inner/outer ratio a/b") of 0.58 or higher and 0.99 or lower. Regarding the light- and moisture-curing resin composition of this invention, if the aforementioned internal-to-external ratio a/b is set to 0.58 or higher, compared to conventional light- and moisture-curing resin compositions, the internal-to-external ratio a/b of this invention is larger. This results in a tendency for the resin to collapse immediately after light curing, leading to higher interfacial adhesion to the substrate and higher initial adhesion to the substrate. Furthermore, by setting the internal-to-external ratio a/b to 0.99 or lower, it is possible to prevent the light- and moisture-curing resin composition from weakening its cohesive force or collapsing excessively after light curing, thus preventing a decrease in initial adhesion. The aforementioned inner-outer ratio a/b is preferably 0.63 or higher, more preferably 0.66 or higher, and even more preferably 0.95 or lower, and further preferably 0.93 or lower. Keeping the inner-outer ratio a/b within these ranges facilitates an increase in initial adhesion.

In this invention, the internal/external ratio a/b is measured as follows. First, as shown in FIG1(a), a moisture-curing resin composition 10 is coated on an aluminum substrate 11 with a line width of 1.0 mm. Here, the line width of 1.0 mm does not need to be strictly 1.0 mm, and an error of 1.0 ± 0.1 mm is allowed. Then, as shown in FIG1(b), the moisture-curing resin composition 10 is irradiated with ultraviolet light of 1000 mJ/ ^cm2 to cure the moisture-curing resin composition 10. Then, immediately (within 10 seconds), as shown in Figure 1(c), the glass plate 12 is overlapped onto the moisture-curing resin composition 10, and the glass plate 12 is pressed onto the coating area of the moisture-curing resin composition 10 at 0.08 MPa and held for 120 seconds. After pressing, the width a1 of the interface between the moisture-curing resin composition 10 and the glass plate 12 is measured. The width a1 is measured at 5 locations, and the average value is taken as the average width a. Also, the width b1 of the interface between the moisture-curing resin composition 10 and the aluminum substrate 11 is measured. Width b1 is measured at 5 locations, and the average value is taken as the average width b. The inner-outer ratio a/b is calculated based on the average widths a and b. Furthermore, the pressing is performed using a weight. Widths a1 and b1 are measured 5 minutes after the weight is removed.

The internal-to-external ratio a/b can be adjusted to fall within the aforementioned range by changing the type of free radical polymerizable compound. For example, when the light- and moisture-curing resin composition contains a large number of monofunctional free radical polymerizable compounds, the ratio of cross-linked structures formed after photocuring decreases, thus increasing the internal-to-external ratio a/b. Furthermore, when the light- and moisture-curing resin composition contains a large number of homopolymers with low glass transition points, the cured product becomes softer after photocuring, thus increasing the internal-to-external ratio a/b. Moreover, it can also be adjusted by the weight-average molecular weight of the moisture-curing resin (B).

[Adhesion] The photocurable resin composition of this invention preferably has an initial adhesion of 0.25 MPa or more. Furthermore, the photocurable resin composition of this invention preferably has a final adhesion of 2.0 MPa or more. Furthermore, the initial adhesion refers to the adhesion at 25°C immediately after photocuring the photocurable resin composition, and the final adhesion refers to the adhesion after photocuring the photocurable resin composition and then placing it at 25°C and 50% RH for 24 hours. Details regarding the methods for measuring the initial and final adhesion are described in the following embodiments. Regarding light- and moisture-curing resin compositions, if the initial adhesion strength at 25°C is 0.25 MPa or higher, the substrates can be temporarily bonded together immediately after light curing with a relatively high adhesion strength, improving workability during temporary bonding. Furthermore, if the final adhesion strength is 2.0 MPa or higher, the substrates can be firmly bonded together through formal bonding performed via moisture curing after temporary bonding.

To further improve the bonding stability during temporary bonding, the light- and moisture-curing resin composition preferably has an initial adhesion strength of 0.4 MPa or higher. While there is no particular limitation on the initial adhesion strength, it may be less than 1.5 MPa, for example, to facilitate easy re-bonding during temporary bonding. Furthermore, to ensure a more secure bond between the substrates after formal bonding, the light- and moisture-curing resin composition preferably has a final adhesion strength of 3.5 MPa or higher. A higher final adhesion strength is preferred, and there is no particular limitation; for example, it may be 20 MPa or less, or even 10 MPa or less.

The components contained in the photo- and moisture-curing resin composition are described in more detail below. [Free Radical Polymerizing Compound (A)] The photo- and moisture-curing resin composition of this invention contains a free radical polymerizing compound (A). The photo- and moisture-curing resin composition is endowed with photocurability by containing the free radical polymerizing compound (A). Because the photo- and moisture-curing resin composition possesses photocurability, it can be endowed with a certain bonding force simply by irradiating it with light, thus ensuring appropriate initial bonding force. As a free radical polymerizing compound (A), it is sufficient that the molecule contains a free radical polymerizing functional group. Suitable compounds are those with unsaturated double bonds as functional groups for free radical polymerization, such as (meth)acryl, vinyl, styrene, and allyl.

From a continuum perspective, the (meth)acrylic group is preferred, meaning that the free radical polymerizable compound (A) is preferably a compound containing a (meth)acrylic group. Furthermore, compounds containing a (meth)acrylic group are also referred to hereinafter as "(meth)acrylic acid compounds." In this specification, "(meth)acrylic" means acrylonitrile or (meth)acrylic acid, and "(meth)acrylic acid" means acrylic acid or methacrylic acid, and so on.

The free radical polymerizable compound (A) may include one or both of the following: a monofunctional free radical polymerizable compound having one free radical polymerizable functional group per molecule, and a polyfunctional free radical polymerizable compound having two or more free radical polymerizable functional groups per molecule. However, from the viewpoint of increasing the tanδ after photocuring and improving the initial adhesion of the photocurable and moisture-curable resin composition, it is preferable to include a monofunctional free radical polymerizable compound. Furthermore, the free radical polymerizable compound (A) is more preferably a monofunctional (meth)acrylic acid compound that is a (meth)acrylic acid compound. Moreover, the monofunctional free radical polymerizable compound may be a polymerized prepolymer having repeating units, and monofunctional monomers without repeating units are generally used.

In order to improve the tanδ of the photocurable resin composition after photocuring and enhance the initial adhesion, the photocurable resin composition preferably contains a greater amount of monofunctional free radical polymeric compound. Specifically, relative to 100 parts by mass of free radical polymeric compound (A), the photocurable resin composition preferably contains 90 or more parts by mass of monofunctional free radical polymeric compound, more preferably 95 or more parts by mass, and more preferably 100 parts by mass.

[Monofunctional Radical Polymerizing Compound] (Nitrogen-containing Compound) The radical polymerizing compound (A) is preferably a monofunctional radical polymerizing compound containing a nitrogen-containing compound. By using a nitrogen-containing compound, the initial adhesion of the photo- and moisture-curing resin composition is improved. The photo- and moisture-curing resin composition is applied to the substrate and then photocured by irradiation with active energy rays such as ultraviolet light. Generally, it is photocured in the presence of oxygen, as described below. If the radical polymerizing compound (A) contains a nitrogen-containing compound, it is also properly photocured in the presence of oxygen, thereby presumably resulting in good initial adhesion.

The nitrogen-containing compound may contain one or both of a chain-like nitrogen-containing compound and a nitrogen-containing compound with a cyclic structure, but from the viewpoint of improving the initial adhesion of the light and moisture-curing resin composition, it is preferable to contain a nitrogen-containing compound with a cyclic structure, and more preferably, a combination of a chain-like nitrogen-containing compound and a nitrogen-containing compound with a cyclic structure.

Examples of nitrogen-containing compounds with cyclic structures include: N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and other nitrogen-containing compounds with lactamine structures, as well as N-acrylamide. Phosphorus and other substances containing Compounds with a porphyrin skeleton, cyclic amide compounds such as N-(meth)acryloxyethylhexylphenylenedimethylimide, etc. Among these, compounds containing amide groups such as N-vinylcaprolactone are preferred. Furthermore, in this specification, nitrogen-containing compounds having a cyclic structure are also referred to as cyclic nitrogen-containing compounds. Free radical polymerizable compounds in which nitrogen atoms are contained within the atoms constituting the ring itself are considered cyclic nitrogen-containing compounds, while other nitrogen-containing compounds are considered chain nitrogen-containing compounds.

Examples of chain-like nitrogen-containing compounds include: chain-like amino-containing (meth)acrylates such as dimethylamino (meth)acrylate, diethylamino (meth)acrylate, methylamino (meth)acrylate, ethylamino (meth)acrylate, and dimethylamino (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.

Furthermore, as a chain-like nitrogen-containing compound, it can be a monofunctional (meth)acrylate. By using a monofunctional (meth)acrylate, when using amine resins, especially amine resins with a polycarbonate backbone as moisture-curing resin (B), the compatibility with moisture-curing resin (B) becomes better, and the initial adhesion is easily improved. In addition, (meth)acrylate has relatively high polarity, thus easily improving the adhesion to glass.

As a monofunctional (meth)acrylate, for example, it can be prepared by reacting a (meth)acrylate derivative having a hydroxyl group with an isocyanate compound. Examples of the aforementioned (meth)acrylate derivative having a hydroxyl group include: mono(meth)acrylates of diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol; or mono(meth)acrylates of triols such as trihydroxymethylethane, trihydroxymethylpropane, and glycerol; etc.

Examples of isocyanate compounds used to obtain (meth)acrylates include: alkyl monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate; cyclic aliphatic monoisocyanates such as cyclopentane isocyanate, cyclohexane isocyanate, and isoflavone monoisocyanate; and other aliphatic monoisocyanates. More specifically, a (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compounds with a mono(meth)acrylate of a diol is preferred. A suitable example is 1,2-ethanediol 1-acrylate 2-(N-butyl carbamate). The chain-like nitrogen-containing compound preferably includes a monofunctional (meth)acrylate, and more preferably, it combines a monofunctional (meth)acrylate with compounds other than monofunctional (meth)acrylates, such as (meth)acrylamide compounds.

From the viewpoint of improving the initial adhesion of the photo- and moisture-curing resin composition, in the photo- and moisture-curing resin composition, the content of the nitrogen-containing compound, which is a monofunctional free radical polymerizable compound, is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and most preferably 60 parts by mass or more. Furthermore, in order to contain a suitable amount of the free radical polymerizable compound (A) other than the nitrogen-containing compound, the aforementioned content of the nitrogen-containing compound, which is a monofunctional free radical polymerizable compound, is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less.

When the monofunctional radical polymerizable compound has both chain-like nitrogen-containing compounds and cyclic nitrogen-containing compounds, the mass ratio (cyclic/chain) of the cyclic nitrogen-containing compound to the chain-like nitrogen-containing compound is preferably 0.1 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less, and even more preferably 0.4 or more and 1.2 or less. By keeping the cyclic/chain mass ratio within the above range, the initial adhesion of the light- and moisture-curing resin composition can be improved.

(Monofunctional radical polymerizable compounds other than nitrogen-containing compounds) The monofunctional radical polymerizable compound (A) preferably contains compounds other than the nitrogen-containing compounds mentioned above (hereinafter also referred to as nitrogen-free compounds). By including nitrogen-free compounds in the radical polymerizable compound (A) to make it a monofunctional radical polymerizable compound, adhesion is easily improved, etc.

As a nitrogen-free compound, there are no particular restrictions as long as it possesses a free radical polymerizable functional group; however, monofunctional (meth)acrylate compounds are preferred, and (meth)acrylate esters are even more preferred. Examples of monofunctional (meth)acrylate esters include: alkyl (meth)acrylates, (meth)acrylates containing alicyclic structures, and (meth)acrylates containing aromatic rings. One or more of these compounds may be used alone or in combination; preferably, one or both of alkyl (meth)acrylates and (meth)acrylates containing aromatic rings are used. The total content of alkyl (meth)acrylate, alicyclic (meth)acrylate, and aromatic (meth)acrylate in the free 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, relative to 100 parts by mass of the free 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.

Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, isomyristyl methacrylate, stearyl methacrylate, and other alkyl methacrylates with 1 to 18 carbon atoms. Examples of alkyl methacrylates containing an alicyclic structure include: cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, and iso... Esters, dicyclopentenyl methacrylate, and other (meth)acrylates with an alicyclic structure. Examples of (meth)acrylates containing aromatic rings include: benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and other phenylalkyl (meth)acrylates; phenoxyethyl (meth)acrylate and other phenoxyalkyl (meth)acrylates; etc.

As monofunctional (meth)acrylate compounds, compounds other than alkyl (meth)acrylates, alicyclic (meth)acrylates, and aromatic (meth)acrylates can also be used, such as (meth)acrylates containing cyclic ether groups. Examples of (meth)acrylates containing cyclic ether groups include those with epoxy rings, cyclobutane rings, tetrahydrofuran rings, dioxolane rings, and dioxolane rings. (Meth)acrylates containing alkyl rings, etc. Examples of (meth)acrylates containing epoxy rings include glycidyl (meth)acrylate. Examples of (meth)acrylates containing oxycyclobutane rings include (meth)acrylate (3-ethyloxycyclobutane-3-yl)methyl methacrylate. Examples of (meth)acrylates containing tetrahydrofuran rings include (meth)acrylate tetrahydrofuran methyl ester and (meth)acrylate polymers containing tetrahydrofuran methanol. Examples of (meth)acrylates containing dioxocyclopentane rings include (meth)acrylate (2-methyl-2-ethyl-1,3-dioxocyclopentane-4-yl)methyl ester and (meth)acrylate (2,2-cyclohexyl-1,3-dioxocyclopentane-4-yl)methyl ester. As having two Alkyl cyclic (meth)acrylates include cyclic trimethylolpropane acetal (meth)acrylates, etc. As (meth)acrylates containing cyclic ether groups, it is preferred to use either (meth)acrylates containing an oxy-butane ring or (meth)acrylates containing a tetrahydrofuran ring, or preferably a combination of the latter.

Furthermore, as monofunctional (meth)acrylate compounds, the following can also be used: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and other alkoxyalkyl (meth)acrylates; methoxyethylene glycol (meth)acrylate... Acrylic esters, ethoxylated ethylene glycol (meth)acrylates, and other alkoxylated ethylene glycol (meth)acrylates; methoxylated diethylene glycol (meth)acrylates, methoxylated triethylene glycol (meth)acrylates, methoxylated polyethylene glycol (meth)acrylates, ethyl carbitol (meth)acrylates, ethoxylated diethylene glycol (meth)acrylates, ethoxylated triethylene glycol (meth)acrylates, ethoxylated polyethylene glycol (meth)acrylates, and other polyoxyethylene-based (meth)acrylates; etc. Furthermore, as monofunctional (meth)acrylate compounds, carboxyl-containing (meth)acrylate compounds such as acrylic acid and methacrylic acid can also be used.

[Compounds other than monofunctional radical polymerizable compounds] The radical polymerizable compound (A) may contain polyfunctional radical polymerizable compounds within the scope of achieving the effects of this invention. Examples of polyfunctional radical polymerizable compounds include: difunctional (meth)acrylate compounds, trifunctional or higher (meth)acrylate compounds, and difunctional or higher (meth)acrylate amino esters, etc.

Examples of difunctional (meth)acrylate 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, etc. Fiber acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dihydroxymethyl dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-(meth)acrylic acid propyl acrylate, carbonate glycol di(meth)acrylate, polyether glycol di(meth)acrylate, polyester glycol di(meth)acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, etc.

Furthermore, examples of (meth)acrylate compounds with three or more functions include: trihydroxymethylpropane tri(meth)acrylate, ethylene oxide addition trihydroxymethylpropane tri(meth)acrylate, propylene oxide addition trihydroxymethylpropane tri(meth)acrylate, caprolactone-modified trihydroxymethylpropane tri(meth)acrylate, neopentyltetrol tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tri(meth)acryloxyethyl phosphate, di-trihydroxymethylpropane tetra(meth)acrylate, neopentyltetrol tetra(meth)acrylate, dinepentyltetrol penta(meth)acrylate, dinepentyltetrol hexa(meth)acrylate, etc.

As a (meth)acrylate with two or more functional groups, for example, it can be formed by reacting a (meth)acrylate derivative having a hydroxyl group with an isocyanate compound. Examples of the aforementioned (meth)acrylate derivatives having a hydroxyl group include: mono(meth)acrylates of diols 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 triols such as trihydroxymethylethane, trihydroxymethylpropane, and glycerol; or epoxy(meth)acrylates such as bisphenol A type epoxy(meth)acrylates; etc.

Examples of isocyanate compounds used to obtain (meth)acrylates include: isoflavone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, and chlorinated MDI. Polyisocyanate compounds such as alkyl diisocyanate, benzyl diisocyanate, phenyl dimethyl diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tri(isocyanate phenyl) thiophosphate, tetramethylphenyl dimethyl diisocyanate, and 1,6,11-undecane triisocyanate.

Furthermore, as isocyanate compounds, extended-chain polyisocyanate compounds obtained by reacting a polyol with an excess of an isocyanate compound can also be used. Examples of polyols include: ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate glycol, polyether glycol, polyester glycol, and polycaprolactone glycol. By using these polyisocyanate compounds, multifunctional (meth)acrylates can be obtained.

[Moisture-curing resin (B)] The moisture-curing resin (B) used in this invention may include, for example, moisture-curing amine resins, resins containing hydrolyzable silicone groups, and moisture-curing cyanoacrylate resins. Preferably, it is either a moisture-curing amine resin or a resin containing hydrolyzable silicone groups, and more preferably, a moisture-curing amine resin. One or more of these resins may be used alone or in combination.

(Moisture-curing amine resin) Moisture-curing amine 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. The moisture-curing amine resin may contain isocyanate groups within the molecule, and these isocyanate groups react with moisture in the air or in the bonded substrate to cure. The moisture-curing amine resin may have only one isocyanate group per molecule, or it may have two or more isocyanate groups; preferably, it has one or two isocyanate groups per molecule. Furthermore, the isocyanate group is not particularly limited and can be placed at the end of moisture-curing amine ester resins.

The reaction between the aforementioned polyol compounds and polyisocyanate compounds typically takes place within a molar ratio of [NCO]/[OH] of 2.0 to 2.5, where the ratio of the hydroxyl (OH) group in the polyol compound to the isocyanate (NCO) group in the polyisocyanate compound is [NCO]/[OH] = 2.0 to 2.5. Regarding the polyol compounds used as raw materials for moisture-curing urethane resins, well-known polyol compounds commonly used in the manufacture of polyurethanes can be used, such as polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols. These polyol compounds can be used alone or in combination of two or more.

The moisture-curing urethane resin is preferably at least one of a polycarbonate backbone, a polyether backbone, or a polyester backbone, more preferably at least one of a polycarbonate backbone or a polyether backbone, and even more preferably a moisture-curing urethane resin with a polycarbonate backbone. Regarding the moisture-curing urethane resin, the presence of a polycarbonate backbone results in excellent initial and final adhesion. Furthermore, it can provide a light and moisture-curing resin composition with excellent weather resistance, heat resistance, and moisture resistance in the cured product.

(Moisture-curing amine resin with a polycarbonate backbone) Regarding moisture-curing amine resins with a polycarbonate backbone, the polycarbonate backbone is introduced into the amine resin by using a polycarbonate polyol as the aforementioned polyol compound. For example, a moisture-curing amine resin with a polycarbonate backbone 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. Preferably, a polycarbonate diol is used as the polycarbonate polyol. A preferred example of a polycarbonate diol is a compound represented by the following formula (1).

In equation (1), R is a divalent hydrocarbon with 4 to 16 carbon atoms, and n is an integer from 2 to 500.

In formula (1), R is preferably an aliphatic saturated hydrocarbon. The aliphatic saturated hydrocarbon of R facilitates good heat resistance. Furthermore, it is less prone to yellowing due to heat degradation, and its weather resistance is also good. R, composed of an aliphatic saturated hydrocarbon, can have a chain structure or a ring structure, but from the viewpoint of easily achieving good stress mitigation and flexibility, a chain structure is preferred. Furthermore, the chain-structured R can be either a straight chain or a branched chain. n is preferably 5–200, more preferably 10–150, and even more preferably 20–50.

Furthermore, regarding the R contained in the polycarbonate polyol constituting the moisture-curing urethane resin, one type may be used alone, or two or more types may be used in combination. When two or more types are used, it is preferable that at least a portion is a chain-linked aliphatic saturated hydrocarbon with 6 or more carbon atoms, and more preferably that at least a portion is a chain-linked aliphatic saturated hydrocarbon with 7 or more carbon atoms. By including chain-linked aliphatic saturated hydrocarbons with 7 or more carbon atoms, it is easier to improve stress relief or flexibility. When the polycarbonate diol is a compound represented by formula (1) above, the ratio of chain-linked aliphatic saturated hydrocarbons with 7 or more carbon atoms to the total R content of the polycarbonate diol is preferably 20 mol% or more and 100 mol% or less, more preferably 30 mol% or more and 100 mol% or less, and even more preferably 50 mol% or more and 100 mol% or less. The chain-linked aliphatic saturated hydrocarbons with 7 or more carbon atoms are preferably 8 or more and 12 or less, and even more preferably 8 or more and 10 or less.

Specific examples of R can be linear, such as tetramethylene, pentenyl, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene, or branched, such as methylpentyl or methyloctamethylene. Multiple Rs in a molecule can be identical or different. Therefore, a molecule can contain two or more types of R; in such cases, it is preferable to contain two or three types of R. For example, a polycarbonate polyol can be a copolymer containing Rs with 6 or fewer carbon atoms and Rs with 7 or more carbon atoms in one molecule; in this case, any R can be a linear aliphatic saturated hydrocarbon. Furthermore, R can contain linear aliphatic saturated hydrocarbons or branched aliphatic saturated hydrocarbons. Regarding the solvent (R) in polycarbonate polyols, branched and linear R can be used together, or linear R can be used alone. Furthermore, polycarbonate polyols can be used alone or in combination of two or more.

Regarding polyisocyanate compounds used as raw materials for moisture-curing urethane resins, aromatic and aliphatic polyisocyanate compounds are suitable. Examples of aromatic polyisocyanate compounds include: diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, toluene diisocyanate, and naphthalene-1,5-diisocyanate. Examples of aliphatic polyisocyanate compounds include: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and chlorinated polyisocyanate. Alkyl diisocyanate, trans-cyclohexane-1,4-diisocyanate, isoflavone diisocyanate, hydrogenated phenyl dimethyl diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, etc. As polyisocyanate compounds, aromatic polyisocyanate compounds are preferred from the viewpoint of improving adhesion after complete curing, and diphenylmethane diisocyanate and its modified forms are more preferred. Furthermore, aliphatic polyisocyanate compounds are preferred from the viewpoint of readily imparting stress-relieving and flexible properties to the cured products of light- and moisture-curing resin compositions. Polyisocyanate compounds can be used alone or in combination of two or more.

(Moisture-curing amine resin with a polyester backbone) Moisture-curing amine resins with a polyester backbone are produced by incorporating a polyester polyol as the polyol compound into the amine resin. These resins can be obtained by reacting a polyester polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule. Examples of polyester polyols include: polyester polyols obtained by reacting 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-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, decamethylethylene dicarboxylic acid, and dodecamethylene dicarboxylic acid. Among these, phthalic acid or adipic acid is preferred from the viewpoint of more easily improving adhesion 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. From the perspective of more easily improving adhesion at high temperatures, 1,6-hexanediol or 1,4-butanediol are preferred. Furthermore, the polyester polyol can be used alone or in combination of two or more.

(Moisture-curing amine resin with a polyether backbone) Regarding moisture-curing amine resins with a polyether backbone, the polyether backbone is introduced into the amine resin by using a polyether polyol as the aforementioned polyol compound. The amine resin with a polyether backbone 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.

Examples of polyether polyols include: polyethylene glycol, polypropylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these and their derivatives, as well as bisphenol-type polyoxyalkylene modifiers. Among these, from the viewpoint of easily improving the coatability of light- and moisture-curing resin compositions, polypropylene glycol, ring-opening polymers of tetrahydrofuran, or ring-opening polymers of 3-methyltetrahydrofuran are preferred. Here, the bisphenol-type polyoxyalkylene modifier is a polyether polyol obtained by adding an epoxide (e.g., ethylene oxide, propylene oxide, epoxide, isobutane, etc.) to the active hydrogen portion of the bisphenol-type molecular backbone. The polyether polyol can be a random copolymer or a block copolymer. Preferably, the bisphenol-type polyoxyalkylene modified polymer has one or more epoxides added to both ends of the bisphenol-type molecular backbone. The bisphenol type is not particularly limited; types A, F, and S can be included, but bisphenol A is preferred. Furthermore, the above-mentioned polyisocyanate compound can be used as the polyisocyanate compound.

The moisture-curing amine resin having a polyether backbone is preferably obtained by using a polyol compound having the structure represented by formula (2) below. By using a polyol compound having the structure represented by formula (2) below, a light and moisture-curing resin composition with excellent adhesion and a soft and well-ductile cured product can be obtained, and the compatibility with the free radical polymerizable compound (A) becomes excellent. Preferably, it is made of a polyether polyol composed of a ring-opening polymer of polypropylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymer of a tetrahydrofuran compound having substituents such as methyl groups; more preferably, it is a ring-opening polymer of polypropylene glycol and a tetrahydrofuran (THF) compound. The ring-opening polymers of tetrahydrofuran (THF) compounds are generally polytetramethylene ether glycols. Furthermore, polyether polyols can be used alone or in combination of two or more.

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 0 to 4, m is 50 to 200, and n is 1 to 5. Furthermore, when l is 0, it means that the carbon bonded to R is directly bonded to the oxygen. In the above, the sum of n and l is more preferably 1 or more, and even more preferably 1 to 3. Also, R is more preferably a hydrogen atom, a methyl group, and especially preferably a methyl group.

The moisture-curing amine resins described above, having a polycarbonate, polyester, or polyether backbone, may have two or more backbones within the molecule; for example, they may have a polycarbonate backbone and a polyester backbone. In this case, polycarbonate polyols and polyester polyols can be used as the aforementioned polyol compounds as raw materials. Similarly, moisture-curing amine resins having both polyester and polyether backbones can also be used. Furthermore, moisture-curing amine resins, as described above, may contain isocyanate groups, but are not limited to those containing isocyanate groups. As explained in the section on resins containing hydrolyzable silicone groups, they may also be amine resins containing hydrolyzable silicone groups.

(Resins Containing Hydrolyzable Silicon Groups) The hydrolyzable silicone-containing resins used in this invention are hardened by the reaction of intramolecular hydrolyzable silicone groups with moisture in the air or in the bonded matrix. The hydrolyzable silicone-containing resin may have only one hydrolyzable silicone group per molecule, or it may have two or more hydrolyzable silicone groups. Preferably, hydrolyzable silicone groups are present at both ends of the main chain of the molecule. Furthermore, the aforementioned hydrolyzable silicone-containing resins do not include those containing isocyanate groups.

Hydrolyzable silicon groups are represented by the following formula (3). In formula (3), ^R1 is independently a substituted alkyl group having 1 or more carbon atoms and less than 20 carbon atoms, an aryl group having 6 or more carbon atoms and less than 20 carbon atoms, an aralkyl group having 7 or more carbon atoms and less than ₂₀ carbon atoms, or a triorganosilyl group represented by ^-OSiR23 ( ^R2 is independently an alkyl group having 1 or more carbon atoms and less than 20 carbon atoms). Furthermore, in formula (3), X is independently a hydroxyl group or a hydrolyzable group. Moreover, in formula (3), a is an integer from 1 to 3.

The aforementioned hydrolyzable groups are not particularly limited, and examples include: halogen atoms, alkoxy groups, alkenoxy groups, aryloxy groups, acetoxy groups, ketoximate groups, amino groups, acetamino groups, acetamino groups, aminooxy groups, and tanyl groups. From the perspective of higher reactivity, halogen atoms, alkoxy groups, alkenoxy groups, and acetoxy groups are preferred. Furthermore, from the perspective of hydrolytic stability and ease of handling, alkoxy groups such as methoxy and ethoxy groups are more preferred, and methoxy and ethoxy groups are even more preferred. From the perspective of safety, compounds released through the reaction are preferably the ethoxy groups of ethanol and acetone, and the isopropenoxy groups.

The aforementioned hydroxyl group or hydrolyzable group may be bonded to 1 to 3 silicon atoms. When the aforementioned hydroxyl group or hydrolyzable group is bonded to 2 or more silicon atoms, these groups may be the same or different.

Regarding 'a' in the above formula (3), from the viewpoint of hardening properties, it is preferably 2 or 3, and more preferably 3. Furthermore, from the viewpoint of preserving stability, 'a' is preferably 2. Also, as ^R1 in the above formula (3), examples include: methyl, alkyl such as ethyl, cycloalkyl such as cyclohexyl, aryl such as phenyl, aralkyl such as benzyl, trimethylsiloxy, chloromethyl, methoxymethyl, etc. Among these, methyl is preferred.

Examples of hydrolyzable silicone groups include: methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethoxysilyl, (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (ethyl... (N,N-dimethylaminomethyl)dimethoxysilyl, (1-methoxyethyl)dimethoxysilyl, (aminomethyl)dimethoxysilyl, (N,N-dimethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl, (N-(2-aminoethyl)aminomethyl)dimethoxysilyl, (acetoxymethyl)dimethoxysilyl, (acetoxymethyl)diethoxysilyl, etc.

Examples of hydrolyzable silicone resins include: (meth)acrylate resins containing hydrolyzable silicone groups, organic polymers having hydrolyzable silicone groups at the ends or terminal sites of the molecular chain, and polyurethane resins containing hydrolyzable silicone groups. Hydrolyzable silicone (meth)acrylate resins preferably have repeating structural units derived from (meth)acrylates and/or alkyl (meth)acrylates containing hydrolyzable silicone groups in the main chain.

Examples of hydrolyzable silicone-containing (meth)acrylates 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, trimethoxysilyl methyl (meth)acrylate, triethoxysilyl methyl (meth)acrylate, and (methyldimethoxysilyl)methyl (meth)acrylate. Examples of the aforementioned alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate, stearyl methacrylate, etc.

As a method for manufacturing (meth)acrylate resins containing hydrolyzable silicone groups, specifically, examples include the synthesis method of (meth)acrylate polymers containing hydrolyzable silicone groups described in International Publication No. 2016/035718. The aforementioned organic polymers having hydrolyzable silicone groups at the ends or terminal sites of the molecular chain have hydrolyzable silicone groups at at least one location, either at the end of the main chain or at the end of the side chain. The backbone structure of the aforementioned main chain is not particularly limited; examples include saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth)acrylate polymers.

Examples of the aforementioned polyoxyalkylene-based polymers include polymers having polyoxyethylene, polyoxypropylene, polyoxybutene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutene copolymer structures. Specifically, methods for manufacturing the aforementioned organic polymers having hydrolyzable silicon groups at the ends or terminal sites of the molecular chain include, for example, the method for synthesizing organic polymers having crosslinkable silicon groups only at the ends or terminal sites of the molecular chain as described in International Publication No. 2016/035718. Furthermore, other methods for manufacturing the aforementioned organic polymers having hydrolyzable silicone groups at the ends or terminal sites of the molecular chain include, for example, the synthesis method of polyoxyalkylene polymers containing reactive silicone groups as described in International Publication No. 2012/117902.

As a method for manufacturing the aforementioned polyurethane resin containing hydrolyzable silicone groups, examples include methods such as reacting a polyol compound with a polyisocyanate compound to produce the polyurethane resin, and further reacting it with a silicone-containing compound such as a silane coupling agent. Specifically, examples include the method for synthesizing amine oligomers containing hydrolyzable silicone groups as described in Japanese Patent Application Publication No. 2017-48345.

Examples of silane coupling agents include, for example: vinyltrichlorosilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β... N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methylpropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-isocyanopropyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, etc. Among these, γ-methylpropyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, and 3-isocyanopropyltriethoxysilane are preferred. These silane coupling agents can be used alone or in combination of two or more.

Furthermore, moisture-curing amine resins can also possess both isocyanate groups and hydrolyzable silicone groups. Moisture-curing amine resins possessing both isocyanate groups and hydrolyzable silicone groups are preferably manufactured by the following method: First, a moisture-curing amine resin (raw material amine resin) containing isocyanate groups is obtained by the above method, and then a silane coupling agent is reacted with the raw material amine resin. Furthermore, the details of moisture-curing amine resins containing isocyanate groups are as described above. As a silane coupling agent that reacts with the raw material amine ester resin, it is acceptable to select an appropriate one from those listed above. From the viewpoint of reactivity with isocyanate groups, it is preferable to use a silane coupling agent containing an amino or guanylic group. Preferred examples include: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-guanylic propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, etc.

Furthermore, the moisture-curing resin may possess a free radical polymerizable functional group. Preferably, the free radical polymerizable functional group possessed by the moisture-curing resin is a group with an unsaturated double bond; from a reactivity perspective, (meth)acrylic acid is particularly preferred. Moreover, the moisture-curing resin possessing the free radical polymerizable functional group is not included in the above-mentioned free radical polymerizable compounds, but is treated as moisture-curing resin (B). Moisture-curing resin (B) may be appropriately selected from the various resins mentioned above and used alone, or appropriately selected from two or more and used in combination.

The weight-average molecular weight of the moisture-curing resin (B) is preferably 7500 or higher and 24000 or lower. By keeping the weight-average molecular weight within the above range, the storage modulus (G') of the light- and moisture-curing resin composition at 25°C and the tanδ at 75°C are within specific ranges, which easily improves the initial adhesion. Furthermore, by setting it below the above upper limit, the final adhesion is also easily improved. From these points of view, the weight-average molecular weight of the moisture-curing resin (B) is more preferably 7800 or higher, more preferably 10000 or higher, more preferably 11500 or higher, more preferably 20000 or lower, more preferably 16000 or lower, and more preferably 15000 or lower. Furthermore, in this specification, the weight-average molecular weight mentioned above was determined by gel osmosis chromatography (GPC) and calculated using polystyrene conversion.

Moisture-curing resins can be extended to achieve a weight-average molecular weight of a certain value, as described above. For example, for moisture-curing amine resins, extension can be performed as follows: For amine resins containing isocyanate groups (hereinafter also referred to as "raw material amine resins") obtained by reacting a polyol compound with a polyisocyanate compound having two or more isocyanate groups in one molecule, an extension agent is then reacted with it. In this case, the extension agent may not react with all the isocyanate groups present in the raw material amine resin; instead, the amount used is appropriately adjusted so that isocyanate groups remain in the moisture-curing amine resin. Furthermore, chain extenders that have already reacted with the raw material amine ester resin can also further induce the raw material amine ester resin to react with it.

The chain extender used in moisture-curing urethane resins is preferably a polyol compound. Details of the polyol compound are as described above. Furthermore, regarding the polyol compound used as the chain extender, any polyol compound of the same type as the polyol compound used in the synthesis of the urethane resin can be used. Therefore, if the polyol compound used in the synthesis of the urethane resin is a polycarbonate polyol, then a polycarbonate polyol can also be used as the chain extender. Regarding the amount of chain extender used, when the total amount of the urethane resin and the chain extender is set to 100 parts by mass, for example, it should be 5 parts by mass or more and 40 parts by mass, preferably 10 parts by mass or more and 35 parts by mass, and more preferably 15 parts by mass or more and 30 parts by mass.

In light- and moisture-curing resin compositions, the mass ratio (B/A) of the moisture-curing resin (B) to the free radical polymerizable compound (A) is preferably 30/70 or higher and 90/10 or lower, more preferably 40/60 or higher and 80/20 or lower, and even more preferably 50/50 or higher and 70/30 or lower. By keeping the mass ratio within these ranges, light- and moisture-curing resin compositions can be imparted with balanced light-curing and moisture-curing properties, and the initial and final adhesion strengths can be easily adjusted to the desired range.

The light- and moisture-curing resin composition may also contain resin components other than the free radical polymerizable compound (A) and the moisture-curing resin (B) as resin components, to the extent that it does not impair the effects of the invention. For example, it may also contain resin components such as thermoplastic resins that do not have curing properties (e.g., acrylic resins, urethane resins, etc.) and thermosetting resins. Regarding the ratio of resin components other than the free radical polymerizable compound (A) and the moisture-curing urethane resin (B), relative to 100 parts by mass of the total mass of the free radical polymerizable compound (A) and the moisture-curing urethane resin (B), it is, for example, 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less.

[Photopolymerization Initiator (C)] The photopolymerization initiator of this invention contains a photopolymerization initiator. The photopolymerization initiator appropriately imparts photocurability to the photopolymerization initiator. Examples of photopolymerization initiators include: benzophenone compounds, acetophenone compounds, alkyl benzophenone photopolymerization initiators, acetylenol oxide compounds, titanium thiocenes compounds, oxime ester compounds, benzoin ether compounds, and 9-oxosulfur compounds. 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.).

The content of the photopolymerization initiator in the photo- and moisture-curing resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the free radical polymerizable compound (A). By keeping the content of the photopolymerization initiator within these ranges, the photocurability and storage stability of the obtained photo- and moisture-curing resin composition become excellent. Furthermore, by keeping the above content within the above ranges, the photoradical recombination compound is properly cured, and adhesion is easily improved.

[Filler (D)] The photocurable resin composition of this invention may contain filler (D). By containing filler (D), the photocurable resin composition of this invention possesses suitable thixotropy, which sufficiently maintains the shape after coating. As a filler, any particulate form is acceptable. As a filler (D), an inorganic filler is preferred, such as: silica, talc, titanium oxide, zinc oxide, calcium carbonate, etc. Among these, silica is preferred from the viewpoint that the obtained photocurable resin composition exhibits excellent ultraviolet transmittance. Furthermore, hydrophobic surface treatments such as siliconeization, alkylation, and epoxidation can also be applied to filler (D). Filler (D) can be used alone or in combination with two or more other fillers. The content of filler (D) relative to 100 parts by weight of the combined weight of the free radical polymerizable compound (A) and the moisture-curing urethane resin (B) is preferably 1 part by weight or more and 25 parts by weight or less, more preferably 2 parts by weight or more and 20 parts by weight or less, and even more preferably 3 parts by weight or more and 15 parts by weight or less.

(Moisture Curing Promoter Catalyst) Photo- and moisture-curing resin compositions may contain a moisture curing promoter catalyst that promotes the moisture curing reaction of the moisture-curing resin (B). By using a moisture curing promoter catalyst, the moisture curing properties of the photo- and moisture-curing resin composition become superior, and adhesion is easily improved. Specifically, moisture curing promoter catalysts include amine compounds and metal-based catalysts. Examples of amine compounds include: di(methyl...) (Pinyl)diethyl ether, 4- linylpropyl porphyrin, 2,2'-di phyllyl diethyl ether and others have Compounds with a porphyrin skeleton, amine compounds containing two dimethylamino groups such as bis(2-dimethylaminoethyl) ether and 1,2-bis(dimethylamino)ethane, triethylamine, 1,4-diacylbiscyclo[2.2.2]octane, and 2,6,7-trimethyl-1,4-diacylbiscyclo[2.2.2]octane, etc. As metal-based catalysts, examples include: tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octylate; zinc compounds such as zinc octylate and zinc cycloalkylates; and other metal compounds such as zirconium tetraacetate, copper cycloalkylates, and cobalt cycloalkylates.

The content of the moisture-curing promoter relative to 100 parts by weight of the moisture-curing urethane resin (B) is preferably 0.01 parts by weight or more and 8 parts by weight or less, more preferably 0.1 parts by weight or more and 5 parts by weight or less. By keeping the content of the moisture-curing promoter within the above range, the following effect becomes excellent: it promotes the moisture-curing reaction without deteriorating the preservation stability of the light- and moisture-curing resin composition.

(Coloring Agent) The photocurable and moisture-curing resin composition of this invention may also contain a coloring agent. Examples of coloring agents include: iron oxide, titanium black, aniline black, anthocyanin black, fullerene, carbon black, and resin-coated carbon black. The presence of a coloring agent improves the light-blocking properties of the photocurable and moisture-curing resin composition. Titanium black is preferred. While effectively blocking wavelengths in the visible light region, titanium black also allows light of wavelengths near the ultraviolet region to pass through, thus preventing a decrease in the photocurability of the photocurable and moisture-curing resin composition. Regarding the content of colorant in the light- and moisture-curing resin composition, relative to 100 parts by weight of the total mass of the free radical polymerizable compound (A) and the moisture-curing urethane resin (B), it is preferably 0.05 parts by weight or more and 8 parts by weight or less, more preferably 0.1 parts by weight or more and 2 parts by weight or less. By keeping the colorant content within these ranges, the adhesion of the light- and moisture-curing resin composition can be well maintained, and appropriate light-blocking properties can be imparted.

In addition to the components mentioned above, light- and moisture-curing resin compositions may also contain coupling agents, wax particles, ionic liquids, foaming particles, expanding particles, reactive thinners, and other additives. Furthermore, coupling agents include silane coupling agents, titanium-based coupling agents, and zirconate-based coupling agents, with silane coupling agents being preferred. Light- and moisture-curing resin compositions may also be diluted with solvents as needed. When light- and moisture-curing resin components are diluted with solvent, the mass fraction of the light- and moisture-curing resin components is based on the solids content, that is, the mass fraction after solvent removal.

As a method for manufacturing the photo- and moisture-curing resin composition of this invention, the following methods can be used: A free radical polymerizable compound (A), a moisture-curing resin (B), a photopolymerization initiator (C), and, as needed, fillers, moisture-curing accelerators, colorants, and other additives are mixed using a mixer. Examples of mixers include: homogenizers, homogenizing mixers, universal mixers, planetary mixers, planetary stirring devices, kneaders, and three-roll mills.

Furthermore, as mentioned above, sometimes a chain extender is used to increase the molecular weight of moisture-curing resins such as moisture-curing amine ester resins. In this case, for example, the raw material resin such as the amine ester resin can be reacted with the chain extender to obtain the moisture-curing resin (B), and then, as described above, it can be mixed with other raw materials such as the free radical polymerizable compound (A). Alternatively, the process can also be as follows: the raw material resin, the chain extender, and the free radical polymerizable compound (A) can be mixed, and the mixture can be heated as needed to react the chain extender with the raw material resin, thereby synthesizing the moisture-curing resin (B). In this case, a mixture of moisture-curing resin (B) and free radical polymerizable compound (A) can be obtained. A photopolymerization initiator (C), and other additives as needed, can then be added to this mixture to obtain a light- and moisture-curing resin composition.

<Method of Use of Light and Moisture Curing Resin Composition> The light and moisture curing resin composition of this invention is cured and used in the form of a cured product. Specifically, the light and moisture curing resin composition of this invention can be cured as follows: First, it is light-cured by irradiation, for example, to a stage B state (semi-cured state), and then fully cured by using moisture. In the case of bonding the substrates by placing a light- and moisture-curing resin composition between them, the following steps can be taken: the light- and moisture-curing resin composition is applied to one substrate, and then light-cured by irradiation, for example, to a stage B state. Another substrate is then superimposed on the light-cured light- and moisture-curing resin composition, and the substrates are temporarily bonded by an appropriate bonding force (initial bonding force). Then, for the light- and moisture-curing resin composition in stage B, moisture is used to cure the moisture-curing amine resin, thereby completely curing it. This formally bonds the substrates that have been superimposed by the light- and moisture-curing resin composition, and joins the substrates together with sufficient adhesive force.

The application of photocurable resins to substrates is not particularly limited, for example, by using a dispensing device. The light used for photocuring is not particularly limited, as long as it is light that cures free radical polymerizable compounds; ultraviolet light is preferred. Furthermore, when completely curing the photocurable resin using moisture after photocuring, simply leaving it in the atmosphere for a specific time is sufficient. The application of photocurable resins to substrates is not particularly limited and can be performed near room temperature, specifically at temperatures around 10–35°C. The photocurable and moisture-curing resin composition of this invention has a viscosity at 25°C within the specific range described above. Therefore, it can be easily applied even at near room temperature without dripping. Furthermore, the photocurable and moisture-curing resin composition of this invention exhibits an initial adhesion force of a certain value or higher immediately after light irradiation. Therefore, temporary bonding can be performed immediately after light curing, resulting in excellent workability.

The photo- and moisture-curing resin composition of this invention is preferably used as an adhesive for electronic components. That is, this invention also provides an adhesive for electronic components composed of the aforementioned photo- and moisture-curing resin composition. Therefore, the aforementioned bonded object is preferably any electronic component constituting an electronic device. Examples of various electronic components constituting an electronic device include: various electronic components disposed on display elements, substrates for mounting electronic components, semiconductor chips, etc. Furthermore, the material of the bonded object can be any of metal, glass, plastic, etc. Furthermore, the shape of the substrate is not particularly limited; examples include: membrane-like, sheet-like, plate-like, panel-like, tray-like, rod-like, box-like, and shell-like.

As described above, the photo- and moisture-curing resin composition of the present invention is preferably used for bonding electronic components constituting an electronic device to each other. Furthermore, the photo- and moisture-curing resin composition of the present invention is also preferably used for bonding electronic components to other components. With these configurations, the electronic components have the cured material of the present invention. Furthermore, the photo- and moisture-curing resin composition of the present invention is used, for example, in the interior of an electronic device to bond substrates to obtain an assembled component. The assembled component thus obtained has a first substrate, a second substrate, and the cured material of the present invention, with at least a portion of the first substrate bonded to at least a portion of the second substrate via the cured material. Moreover, it is preferable that at least one electronic component is mounted on each of the first and second substrates.

Furthermore, the photo- and moisture-curing resin composition of the present invention is preferably used for narrow-edge applications. For example, in various display devices such as smartphones and other mobile phone display devices, an adhesive is applied to a narrow, square-shaped (i.e., narrow-edge) substrate, and a display panel, touch panel, etc., is assembled using this adhesive. However, the photo- and moisture-curing resin composition of the present invention can be used as this adhesive. Moreover, the photo- and moisture-curing resin composition of the present invention is preferably used for semiconductor chip applications. In semiconductor chip applications, the photo- and moisture-curing resin composition of the present invention is used, for example, to bond semiconductor chips together. Embodiments

The invention is illustrated in more detail by way of examples, but the invention is not limited by such examples.

The determination and evaluation of various physical properties were carried out as follows. (Weight-average molecular weight) The weight-average molecular weight of the moisture-curing resin (B) in each example and comparative example was determined by gel permeation chromatography (GPC) and calculated using polystyrene conversion. A Shodex KF-806L column (manufactured by Showa Denko Corporation) was used as the column for GPC determination. Tetrahydrofuran (THF) was used as the solvent and mobile phase. Furthermore, the determination conditions for GPC were a flow rate of 1.0 ml/min and a measurement temperature of 40°C.

Furthermore, in each embodiment and comparative example, the aforementioned weight-average molecular weight was measured using a mixture of the free radical polymerizable compound and the moisture-curing resin (B) as a sample. Regarding this mixture, a peak for the free radical polymerizable compound appears on the low molecular weight side, while a peak for the moisture-curing resin (B) appears on the high molecular weight side. Therefore, the weight-average molecular weight of the moisture-curing resin (B) can be determined from the peak on the high molecular weight side.

(Viscosity at 25°C) The viscosity at 25°C was measured using a tapered viscometer (trade name TVE-35, manufactured by Toki Sangyo Co., Ltd.) at 5.0 rpm and 25°C.

(Storage modulus (G') at 25°C and tanδ at 75°C) As a dynamic viscoelasticity measuring device, the product name "DVA-200" manufactured by IT Meter and Control Co., Ltd. was used. As a viscoelasticity measuring fixture, a shear test fixture was used. A 0.6 mm × 6 mm × 9 mm light- and moisture-curing resin composition was placed on the viscoelasticity measuring fixture and light-cured by irradiation with ultraviolet light at a wavelength of 405 nm at 1000 mJ/ ^cm² . The light-cured sample was measured according to the method described in the instruction manual.

(Inner/outer ratio a/b) The inner/outer ratio a/b was measured using the method described in the instruction manual. Furthermore, aluminum alloy "A6063S" with dimensions of 2 mm × 25 mm × 60 mm and a smooth glass plate with a surface that had undergone ultrasonic cleaning for 5 minutes were used as the aluminum substrate and glass plate, respectively. The moisture-curing resin composition was applied using a "SHOTMASTER300SX" manufactured by Musashi High Technology Co., Ltd., which served as the dispensing device, at room temperature (25°C), and was applied to the aluminum substrate in a straight line with a width of 1.0 ± 0.1 mm, a length of 25 mm, and a thickness of 0.4 ± 0.1 mm. Next, the applied light and moisture-curing resin composition was irradiated with 405 nm ultraviolet light at a intensity of 1000 mJ/ ^cm² using a linear LED irradiator (manufactured by HOYA Co., Ltd., 1000 mW). When pressing the glass plate onto the aluminum substrate, weights were used as a support, and the widths a1 and b1 were measured 5 minutes after the weights were removed. The widths a1 and b1 after pressing were measured using a microscope by observing the pressing surface from the glass plate side.

(Initial Adhesion) As shown in Figures 2(a) and (b), using the above-described dispensing apparatus, a light- and moisture-curing resin composition 20 was applied to an aluminum substrate 21 at room temperature (25°C) with 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 irradiated at 1000 mJ/ ^cm² using a linear LED irradiator (manufactured by HOYA Co., Ltd., 1000 mW) to perform light curing. Then, a glass plate 22 was bonded to the aluminum substrate 21 using the light-cured light- and moisture-curing resin composition 20, and the coated area was pressed with a weight at 0.08 MPa for 120 seconds to obtain a sample 23 for adhesion evaluation. Then, at 25°C, a tensile testing machine ("Tensile and Compression Testing Apparatus SVZ-50NB", manufactured by Imada Seisakusho) was used to perform a tensile test in the shear direction S at a speed of 10 mm/min. The maximum stress when peeling the aluminum substrate 21 and the glass plate 22 was measured, and the measured maximum stress was taken as the initial adhesion force. Furthermore, the tensile test was conducted within 150 seconds from the end of light curing to the start of the test. The initial adhesion force was evaluated according to the following criteria: A: 0.4 MPa or more; B: 0.25 MPa or more but less than 0.4 MPa; C: less than 0.25 MPa.

(Final Bonding Force) Similar to the initial bonding force determination, a glass plate was bonded to an aluminum substrate using a light-cured, light- and moisture-curing resin composition. Then, it was placed at 25°C and 50% RH for 24 hours to allow moisture curing, thus obtaining a sample for bonding performance evaluation. Using this sample, the sample was stretched in the shear direction, similar to the initial bonding force determination method. The maximum stress upon separation of the aluminum substrate and glass plate was measured, and the measured maximum stress was taken as the final bonding force. A: 3.5 MPa or more B: 2.0 MPa or more but less than 3.5 MPa C: Less than 2.0 MPa

The amine resin raw materials used in each embodiment and comparative example were prepared by the following method. [Synthesis Example 1] (PC amine resin raw material) 100 parts by weight of polycarbonate diol (the compound represented by formula (1), where 90 mol% of R is 3-methylpentyl and 10 mol% is hexamethylene; manufactured by Kuraray Co., Ltd., trade name "Kuraraypolyol C-1090") and 0.01 parts by weight of dibutyltin dilaurate were placed into a 500 mL separable flask. The mixture was stirred at 100°C for 30 minutes under vacuum (below 20 mmHg) in the flask to mix the components. Then, under normal pressure, 50 parts by weight of diphenylmethane diisocyanate (manufactured by Nichiso Corporation, trade name "Pure MDI"), the polyisocyanate compound, were added, and the mixture was stirred at 80°C for 3 hours to react, thereby obtaining a moisture-curing amine resin (PC amine resin raw material) with a polycarbonate backbone and isocyanate groups at both ends. The weight-average molecular weight of the obtained amine resin raw material was 6700.

[Synthesis Example 2] (ET amine ester resin raw material) 100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Co., Ltd., trade name "PTMG-3000") as the polyol compound and 0.01 parts by weight of dibutyltin dilaurate were added to a 500 mL separable flask. The mixture was stirred at 100°C under vacuum (below 20 mmHg) for 30 minutes to mix. Then, under normal pressure, 17.5 parts by weight of diphenylmethane diisocyanate (manufactured by Nichiso Corporation, trade name "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred at 80°C for 3 hours to allow the reaction to proceed, thereby obtaining a moisture-curing amine resin (ET amine resin raw material) with a polyether backbone and isocyanate groups at both ends. The weight average molecular weight of the obtained amine resin raw material was 3500.

[Example 1] As shown in Table 5, 60 parts by weight of each of the raw materials constituting the moisture-curing resin (PC-L25) were added to 40 parts by weight of acrylic resin A. Acrylic resin A was prepared by mixing the compounds according to the admixture ratios shown in Table 2. PC amine resin raw materials and PC polyol were sequentially added to acrylic resin A according to the mass ratios shown in Table 3 to obtain a mixture as the moisture-curing resin (PC-L25). The polycarbonate diol used in Synthesis Example 1 was used as the PC polyol. By stirring the mixture obtained at 50°C, a portion of the PC polyol and urethane resin raw material are reacted to synthesize a moisture-curing urethane resin with extended chains and residual isocyanate groups, resulting in a mixture of acrylic resin A (a free radical polymerizable compound) and the moisture-curing urethane resin. A photopolymerization initiator and a filler are added to the obtained mixture of acrylic resin A and the moisture-curing urethane resin according to the composition in Table 5, and the mixture is further mixed to obtain a light- and moisture-curing resin composition. For the obtained light and moisture-curing resin composition, the viscosity at 25°C, storage modulus (G') at 25°C, tanδ at 75°C, internal/external ratio a/b, initial adhesion, and final adhesion were measured.

[Examples 2-4, 7, 8, Comparative Examples 1, 2] Acrylic resin B was used instead of acrylic resin A, and the moisture-curing resin listed in Tables 3, 4, and 5 was used instead of the moisture-curing resin (PC-L25) as the moisture-curing resin. Otherwise, the process was the same as in Example 1. That is, acrylic resin B was used instead of acrylic resin A, and the ratio and type of the amine resin raw material and polyol added to acrylic resin B were changed to those listed in Tables 3 and 4 to obtain a mixture of acrylic resin B and the moisture-curing amine resin. Otherwise, the process was the same as in Example 1. Furthermore, polytetramethylene ether glycol used in Synthesis Example 2 was used as the ET polyol in Table 4. Furthermore, in Comparative Example 1, only amine resin raw material was added to acrylic resin A without the addition of polyols; therefore, the amine resin raw material was directly used as a moisture-curing resin.

[Examples 5, 9-11, Comparative Examples 3-5] Acrylic resins B-H were used instead of acrylic resin A; otherwise, the procedures were the same as in Example 1. Furthermore, acrylic resins B-H were prepared by mixing the compounds according to the blending ratios recorded in Table 2.

[Example 6] A photopolymerization initiator, filler, and colorant were added to a mixture of acrylic resin B and a moisture-curing urethane resin according to the composition in Table 5, and the mixture was then mixed to obtain a light- and moisture-curing resin composition. All other aspects were performed in the same manner as in Example 5.

The components used in each embodiment and comparative example, other than the moisture-curing amine resin (B), are shown in Table 1 below. [Table 1] Product Name Distributors Compound name Cyclic nitrogen compounds NVC Tokyo Chemical Industry Co., Ltd. N-vinyl-ε-caprolactam Monofunctional acrylates Viscoat#216 Osaka Organic Chemicals Co., Ltd. 1,2-Ethylene glycol 1-acrylate 2-(N-Butylaminocarbamate) Multifunctional acrylates EBECRYL8411 DAICEL-ALLNEX (stock) - Multifunctional acrylates TMPT-A Osaka Organic Chemicals Co., Ltd. Trimethylolpropane triacrylate Monofunctional acrylate a Viscoat#192 Osaka Organic Chemicals Co., Ltd. phenoxyethyl acrylate Monofunctional acrylates b IDAA Osaka Organic Chemicals Co., Ltd. Isodecyl acrylate Monofunctional acrylates C DMAA KJ Chemicals (stock) Dimethylacrylamide Monofunctional acrylates d DEAA KJ Chemicals (stock) Diethylacrylamide Photopolymerization initiator Irgacure TPO BASF Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide filler AEROSIL RY-200S Japan Aerosil (stock) Silica filler Colorant 13M-C Mitsubishi Materials (shares) Titanium Black

The acrylic resins A through H used in the embodiments and comparative examples are shown below. [Table 2] Acrylic resin A (parts by weight) Acrylic resin B (parts by weight) Acrylic resin C (parts by weight) Acrylic resin D (parts by mass) Acrylic resin E (parts by weight) Acrylic resin F (parts by weight) Acrylic resin G (parts by weight) Acrylic resin H (parts by mass) Cyclic nitrogen compounds 30 30 30 30 30 30 30 30 Monofunctional acrylates 35 42 33 twenty four 42 42 42 42 Multifunctional acrylates 0 0 0 0 0.25 0.34 0.42 0.5 Multifunctional acrylates 0 0 15 30 0 0 0 0 Monofunctional acrylate a 7 17.5 13.75 10 17.25 17.16 17.08 17 Monofunctional acrylates b 14 0 0 0 0 0 0 0 Monofunctional acrylates C 14 0 0 0 0 0 0 0 Monofunctional acrylates d 0 10.5 8.25 6 10.5 10.5 10.5 10.5 total 100 100 100 100 100 100 100 100

The moisture-curing resins (B) used in the embodiments and comparative examples are shown in Table 3 below. As mentioned above, the moisture-curing resin (L0) uses amine resin raw materials directly as moisture-curing resin (B). Otherwise, the reaction products of the following amine resin raw materials and polyols are used as moisture-curing resins (B). [Table 3] PC amine ester resin raw material (parts by weight) PC polyols (parts by mass) Moisture-curing resin (PC-L0) 100 0 Moisture-curing resin (PC-L10) 90 10 Moisture-curing resin (PC-L15) 85 15 Moisture-curing resin (PC-L20) 80 20 Moisture-curing resin (PC-L25) 75 25 Moisture-curing resin (PC-L30) 70 30 Moisture-curing resin (PC-L35) 65 35

[Table 4] ET amine ester resin raw material (parts by weight) ET polyols (parts by mass) Moisture-curing resin (ET-L25) 75 25

[Table 5] Implementation Examples Comparative example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 Composition (parts by mass) Acrylic resin A 40 - - - - - - - - - - - - - - - Acrylic resin B - 40 40 40 40 40 40 40 - - - 40 40 - - - Acrylic resin C - - - - - - - - - - - - - 40 - - Acrylic resin D - - - - - - - - - - - - - - 40 - Acrylic resin E - - - - - - - - 40 - - - - - - - Acrylic resin F - - - - - - - - - 40 - - - - - - Acrylic resin G - - - - - - - - - - 40 - - - - - Acrylic resin H - - - - - - - - - - - - - - - 40 Moisture-curing resin (PC-L0) - - - - - - - - - - - 60 - - - - Moisture-curing resin (PC-L10) - 60 - - - - - - - - - - - - - - Moisture-curing resin (PC-L15) - - 60 - - - - - - - - - - - - - Moisture-curing resin (PC-L20) - - - 60 - - - - - - - - - - - - Moisture-curing resin (PC-L25) 60 - - - 60 60 - - 60 60 60 - - 60 60 60 Moisture-curing resin (ET-L25) - - - - - - 60 - - - - - - - - - Moisture-curing resin (PC-L30) - - - - - - - 60 - - - - - - - - Moisture-curing resin (PC-L35) - - - - - - - - - - - - 60 - - - Photopolymerization initiator 0.48 0.48 0.48 0.48 0.48 0.96 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 filler 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Colorant - - - - - 0.3 - - - - - - - - - - Physical properties and evaluation Moisture-curing resin (B) Weight average molecular weight (Mw) 12000 7900 9000 10800 12000 12000 12800 15900 12000 12000 12000 6700 22000 12000 12000 12000 Viscosity of the component [Pa・s] (5.0 rpm) 110 37 44 73 125 132 240 457 130 133 129 19 750 247 499 125 G'@25℃[kPa] 816.1 410.1 344.5 735.2 1613 285.5 484.8 2053 1176 1856 1966 228.5 3281 1153 749.9 2072 Tanδ@75℃ 1.48 1.18 1.06 1.25 1.25 1.20 1.12 1.25 1.09 1.12 1.02 1.08 0.91 0.83 0.63 0.96 Inner/outer ratio [a/b] 0.91 0.94 0.94 0.93 0.88 0.90 0.91 0.68 0.82 0.71 0.63 0.97 0.52 0.55 0.39 0.56 Initial follow-up force [MPa] 0.54 0.27 0.34 0.5 0.65 0.38 0.26 0.62 0.31 0.27 0.25 0.16 0.16 0.10 0.10 0.20 Initial follow-through evaluation A B B A A B B A B B B C C C C C Final pressure [MPa] 5 8.2 6.3 5.6 4.3 4.1 5.2 3.9 4.3 4.1 3.6 8.2 4.1 3.5 2.8 3.5 Final evaluation A A A A A A A A A A A A A B B B

The photo- and moisture-curing resin compositions of Examples 1-11 contain a free radical polymerizable compound (A), a moisture-curing resin (B), and a photopolymerization initiator (C), and have a storage modulus (G') at 25°C and a tanδ at 75°C of specific values or higher, thereby achieving excellent initial adhesion. In contrast, in Comparative Examples 1-5, at least one of the storage modulus (G') at 25°C and the tanδ at 75°C did not reach the specific value, thus failing to achieve good initial adhesion.

10: Moisture-curing resin composition 11: Aluminum substrate 12: Glass plate 20: Light and moisture-curing resin composition 21: Aluminum substrate 22: Glass plate 23: Sample for adhesion evaluation

[Figure 1] is a conceptual diagram illustrating the method for determining the internal-external ratio a/b. [Figure 2] is a schematic diagram illustrating the adhesion test method, with Figure 2(a) being a top view and Figure 2(b) being a side view.

Claims (10)

A photo- and moisture-curing resin composition comprising a free radical polymerizable compound (A), a moisture-curing resin (B), and a photopolymerization initiator (C), wherein the free radical polymerizable compound (A) comprises a monofunctional free radical polymerizable compound, and the moisture-curing resin (B) comprises a moisture-curing amine ester resin, wherein the viscosity measured using a tapered viscometer at 25°C and 5.0 rpm is 35 Pa·s or more and 600 Pa·s or less, and when photocured by irradiation with 1000 mJ/ ^cm² of ultraviolet light, the storage modulus (G') at 25°C is 250 kPa or more, and the tanδ at 75°C is 1.0 or more and 2.0 or less. In the case of the light and moisture curing resin composition of claim 1, when a glass plate is pressed at 0.08 MPa for 120 seconds after the resin is coated on an aluminum substrate with a line width of 1.0 mm and irradiated with ultraviolet light of ¹⁰⁰⁰ mJ/cm² to achieve light curing, if the average width of the bonding portion on the glass plate side is set as a and the average width of the bonding portion on the aluminum substrate side is set as b, then a/b is 0.58 or more and 0.99 or less. The light- and moisture-curing resin composition of claim 1 or 2, wherein the moisture-curing urethane resin is a moisture-curing urethane resin having at least one of a polycarbonate backbone, a polyether backbone, and a polyester backbone. As in the light and moisture-curing resin composition of claim 1 or 2, wherein the weight average molecular weight of the aforementioned moisture-curing resin (B) is 7,500 or more and 24,000 or less. As in the light and moisture-curing resin composition of claim 1 or 2, wherein the aforementioned monofunctional free radical polymeric compound comprises a amide-containing compound as a nitrogen-containing compound having a cyclic structure. For example, the light and moisture curing resin composition of claim 1 or 2, relative to 100 parts by mass of the free radical polymerizable compound (A), includes more than 90 parts by mass of a monofunctional free radical polymerizable compound. The light and moisture-curing resin composition of claim 1 or 2 further includes a filler (D). An adhesive for electronic components, comprising a light- and moisture-curing resin composition of any one of claims 1 to 7. A hardened material, which is a hardened form of the light and moisture-curing resin composition of any one of claims 1 to 8. An electronic component comprising the hardened material of claim 9.