TW202208448A - Photo/moisture-curable resin composition, adhesive for electronic component, cured body and electronic component - Google Patents

Abstract

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

Description

Light- and moisture-curable resin compositions, adhesives for electronic parts, cured products, and electronic parts

The present invention relates to a light-and-moisture-curable resin composition, an adhesive for electronic parts, a cured product, and electronic parts.

In recent years, electronic components such as semiconductor wafers have been increasingly required to be highly integrated and miniaturized. For example, a laminate of semiconductor wafers may be formed by bonding a plurality of thin semiconductor wafers through an adhesive layer. In addition, in today's age when various types of mobile devices with display elements are becoming more common, as a method of miniaturizing display elements, the image display portion is generally narrowed (hereinafter, also referred to as "narrow-edge design"). In these applications, with the development of miniaturization or narrow edge, attempts are being made to use light and moisture-curable adhesives instead of double-sided tapes.

As a light-and-moisture-curable adhesive, for example, Patent Document 1 proposes a light-and-moisture-curable resin composition containing a radically polymerizable compound, a moisture-curable urethane resin, and a photoradical polymerizable polymer. A starting agent, and the moisture-curable urethane resin described above contains a moisture-curable urethane resin having a weight average molecular weight of 2,000 or more. Moreover, in patent document 2, the reactive hot-melt adhesive composition containing a urethane prepolymer, (meth)acrylate urethane which has a (meth)acryloyl group, and a photopolymerization initiator is proposed. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Laid-Open No. 2016-074781 Patent Document 2: Japanese Patent Laid-Open No. 2019-006854

[The problem to be solved by the invention]

However, the light and moisture-curable adhesives do not exhibit sufficient adhesive force (initial adhesive force) immediately after bonding like double-sided tapes, so it takes time to adhere members to each other, and there is a problem in workability. For example, in Patent Documents 1 and 2, although it is indicated that a certain or more adhesive force is exhibited after light irradiation, the initial adhesive force may be insufficient. Moreover, since the adhesive agent described in patent document 2 is a hot-melt adhesive agent, it needs to be heated before application|coating, and workability|operativity deteriorates further.

Therefore, an object of the present invention is to provide a light- and moisture-curable resin composition which exhibits excellent adhesive force immediately after photocuring, and which can improve workability and the like. [Technical means to solve the problem]

所組成之群中之至少一種。 [20]如上述[1]至[19]中任一項所記載之光與濕氣硬化型樹脂組成物，其初始接著力為0.25 MPa以上。 [21]如上述[1]至[20]中任一項所記載之光與濕氣硬化型樹脂組成物，其最終接著力為2.0 MPa以上。 [22]一種電子零件用接著劑，其係由上述[1]至[21]中任一項所記載之光與濕氣硬化型樹脂組成物構成。 [23]一種硬化物，其係上述[1]至[21]中任一項所記載之光與濕氣硬化型樹脂組成物之硬化物。 [24]一種電子零件，其包含上述[23]所記載之硬化物。 [發明之效果]The inventors of the present invention have made diligent studies and found that the above-mentioned problems can be solved by increasing the gel swelling ratio of the photocured light and moisture-curable resin composition and also keeping the viscosity within a certain range. Thus, the following invention has been completed. That is, the present invention provides the following [1] to [24]. [1] A light and moisture curable resin composition comprising a radically polymerizable compound (A), a moisture curable resin (B), and a photopolymerization initiator (C), and obtained by the following (1) - The gel swelling ratio (W1/W2) obtained by the measurement method shown in (4) is 15 or more, and the viscosity measured at 25°C and 5.0 rpm using a cone-plate viscometer is 35 Pa·s or more And 600 Pa·s or less: (1) Apply 1.0 g of light and moisture-curable resin composition to a mold release PET film with a thickness of 1.5 mm, and irradiate 1000 mJ/cm ² of ultraviolet light to photo-harden (2) Peel off the photohardened light and moisture-curable resin composition from the above-mentioned mold release PET film, and immerse it in THF at 25°C for 48 hours; The air-curable resin composition was taken out on a 200-mesh wire mesh, and washed 5 times with new THF, and then the weight (W1) of the gel remaining in the swollen state on the above-mentioned wire mesh was measured; (4) Make the above The swollen gel was dried at 100° C. for 2 hours to volatilize THF, and the weight (W2) of the dried gel was measured to obtain a gel swelling ratio (W1/W2). [2] The light- and moisture-curable resin composition according to the above [1], which is produced by applying it to an aluminum substrate with a line width of 1.0 mm and irradiating it with ultraviolet rays of 1000 mJ/cm ² When the glass plate is press-bonded at 0.08 MPa for 120 seconds in the photohardened state, if the average width of the bonded portion on the glass plate side is a, and the average width of the bonded portion on the aluminum substrate side is referred to as b, Then a/b is 0.58 or more and 0.99 or less. [3] The light- and moisture-curable resin composition according to the above [1] or [2], wherein the moisture-curable resin (B) contains a moisture-curable urethane resin. [4] The light and moisture-curable resin composition according to the above [3], wherein the moisture-curable urethane resin has at least any one of a polycarbonate skeleton, a polyether skeleton, and a polyester skeleton One is moisture-curable urethane resin. [5] The light- and moisture-curable resin composition according to the above [3] or [4], wherein the moisture-curable urethane resin is a moisture-curable urethane resin having a polycarbonate skeleton. [6] The light and moisture curable resin composition according to any one of the above [1] to [5], wherein the moisture curable resin (B) has a weight average molecular weight of 7500 or more and 24000 or less . [7] The light-and-moisture-curable resin composition according to any one of the above [1] to [6], wherein the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound. [8] The light-and-moisture-curable resin composition according to the above [7], which contains 90 parts by mass or more of a monofunctional radically polymerizable compound with respect to 100 parts by mass of the radically polymerizable compound (A). [9] The light and moisture curable resin composition according to the above [7] or [8], wherein the monofunctional radically polymerizable compound contains a nitrogen-containing compound. [10] The light and moisture-curable resin composition according to the above [9], wherein the monofunctional radically polymerizable compound contains a chain nitrogen-containing compound. [11] The light-and-moisture-curable resin composition according to the above [9] or [10], wherein the monofunctional radically polymerizable compound includes a nitrogen-containing compound having a cyclic structure. [12] The light and moisture-curable resin composition according to the above [11], wherein the mass ratio (cyclic/chain) of the nitrogen-containing compound having a cyclic structure to the chain nitrogen-containing compound It is 0.1 or more and 2.0 or less. [13] The light-moisture-curable resin composition according to any one of the above [9] to [12], wherein the amount of the monofunctional free The content of the nitrogen-containing compound of the base polymerizable compound is 10 parts by mass or more and 95 parts by mass or less. [14] The light-and-moisture-curable resin composition according to any one of the above [9] to [13], wherein the monofunctional radically polymerizable compound further contains a monofunctional compound in addition to the nitrogen-containing compound (Meth)acrylate compound. [15] The light- and moisture-curable resin composition according to the above [14], wherein the monofunctional (meth)acrylate compound is selected from the group consisting of alkyl (meth)acrylate, alicyclic structure-containing At least one of the group consisting of (meth)acrylate and aromatic ring-containing (meth)acrylate. [16] The light-and-moisture-curable resin composition according to the above [15], wherein an alkyl (meth)acrylate, an alicyclic structure-containing compound is contained in an amount of 100 parts by mass of the radically polymerizable compound (A). The total content of the (meth)acrylate and the aromatic ring-containing (meth)acrylate is 5 parts by mass or more and 90 parts by mass or less. [17] The light- and moisture-curable resin composition according to any one of the above [1] to [16], wherein the moisture-curable resin (B) is relative to the radically polymerizable compound (A) ) mass ratio (B/A) is 30/70 or more and 90/10 or less. [18] The light and moisture curable resin composition according to any one of the above [1] to [17], which further contains a filler (D). [19] The light- and moisture-curable resin composition according to any one of the above [1] to [18], wherein the photopolymerization initiator (C) is selected from the group consisting of benzophenone-based compounds, Acetophenone-based compounds, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and 9-oxythiocyanate

At least one of the groups formed. [20] The light and moisture-curable resin composition according to any one of the above [1] to [19], wherein the initial bonding force is 0.25 MPa or more. [21] The light and moisture curable resin composition according to any one of the above [1] to [20], wherein the final adhesive force is 2.0 MPa or more. [22] An adhesive for electronic components, comprising the light- and moisture-curable resin composition according to any one of the above [1] to [21]. [23] A cured product, which is a cured product of the light-and-moisture-curable resin composition according to any one of the above [1] to [21]. [24] An electronic component comprising the cured product according to the above [23]. [Effect of invention]

According to the present invention, there is provided a light and moisture-curable resin composition which exhibits excellent adhesive force immediately after photocuring, and which can improve workability and the like.

Hereinafter, the present invention will be described in detail with reference to embodiments. <Light and moisture curable resin composition> The light and moisture-curable resin composition of the present invention includes a radically polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C). The gel swelling ratio (hereinafter, also referred to as "gel swelling ratio (W1/W2)") of the light and moisture-curable resin composition of the present invention after photocuring determined by the following measurement method was 15 Above, and the viscosity measured under the conditions of 25°C and 5.0 rpm using a cone-plate viscometer (hereinafter, also referred to as "25°C viscosity") is 35 Pa·s or more and 600 Pa·s or less. If the gel swelling ratio (W1/W2) of the light and moisture-curable resin composition of the present invention after photocuring as described above increases, the density of the cross-linked structure after photocuring becomes low, and the 25° C. When the viscosity is within a certain range, it also achieves a complementary effect. When a moderate pressure is applied, a certain amount of collapse will occur and it is easy to adhere to the attached body, and even when the shear stress acts, it also exhibits a certain cohesion force. Therefore, the adhesive force (initial adhesive force) immediately after photohardening can be made excellent.

[Gel swelling ratio (W1/W2)] The light and moisture-curable resin composition of the present invention is as described above, and the gel swelling ratio (W1/W2) after photocuring is 15 or more. If the gel swelling ratio (W1/W2) after photocuring is less than 15, the ratio of the crosslinked structure immediately after photocuring increases, so that it is difficult to collapse, and it is difficult to obtain excellent initial adhesion. From the viewpoint of making the initial adhesive force higher, the gel swelling ratio (W1/W2) after photocuring is preferably 20 or more, more preferably 25 or more, and still more preferably 30 or more. In addition, the upper limit of the gel swelling ratio (W1/W2) after photocuring is not particularly limited, and the larger the better, for example, it may be 80 or less. In addition, the gel swelling ratio (W1/W2) after photocuring was calculated|required by the following measuring method. (1) Apply 1.0 g of light and moisture-curable resin composition to a mold release PET film with a thickness of 1.5 mm, and irradiate 1000 mJ/cm ² of ultraviolet light to photo-harden it. (2) The photocured light and moisture-curable resin composition were peeled off from the above-mentioned mold release PET film, and immersed in THF at 25° C. for 48 hours. (3) The light- and moisture-curable resin composition that has been light-cured after dipping is taken out onto a 200-mesh wire mesh, and after being washed 5 times with new THF, the swelling state remaining on the above-mentioned wire mesh is measured. The weight of the gel (W1). (4) The gel in the swollen state was dried at 100° C. for 2 hours to volatilize THF, and the weight (W2) of the gel in the dried state was measured to obtain the gel swelling ratio (W1/W2). In addition, the details of the measuring method of the gel swelling ratio (W1/W2) are as described in the following examples. In addition, the gel swelling ratio (W1/W2) can be adjusted within the above-mentioned range by appropriately selecting the type of the radically polymerizable compound and the like. For example, when a large amount of a monofunctional radically polymerizable compound is contained, the density of the crosslinked structure formed after photocuring becomes low, so that the gel swelling ratio (W1/W2) can be increased.

[Viscosity at 25℃] The 25°C viscosity of the moisture-curable resin composition mentioned above is measured at a high shear of 5.0 rpm in a state where neither light-cured nor moisture-cured, and this viscosity is not easily affected by fillers . Therefore, if the viscosity at 25°C is less than 35 Pa·s, it means that the moisture-curable resin (B) and the like contain more low-molecular-weight components, and the moisture-curable resin (B) and the like ooze out after light irradiation. to the interface, making it difficult to improve the initial adhesion. That is, if the low molecular weight moisture-curable resin (B) etc. oozes out to the interface after irradiation with light, slippage occurs easily with the adherend, and it becomes difficult to express the adhesive force, and it becomes difficult to improve the initial adhesion force. In addition, when the viscosity at 25°C exceeds 600 Pa·s, it is difficult to express the adhesiveness or the like originally possessed by the moisture-curable resin (B), so that it is difficult to improve the initial adhesion force or the final adhesion force described below. In addition, if the viscosity at 25°C is less than 35 Pa·s or exceeds 600 Pa·s, the following defects will occur, for example, dripping occurs, or it cannot be applied at room temperature, which reduces workability.

The viscosity at 25°C of the light and moisture curable resin composition is preferably 40 Pa·s or more, more preferably 45 Pa·s or more, more preferably 90 Pa·s or more, and still more preferably 110 Pa·s or more , and it is preferably 500 Pa·s or less, more preferably 350 Pa·s or less, and still more preferably 230 Pa·s or less. When the viscosity at 25° C. is within the above-mentioned range, the workability and the initial bonding force can be easily improved. Moreover, if it is below the said upper limit, the molecular weight of the moisture-curable resin (A) can be prevented from becoming too high, so the initial adhesion force is easily improved, and the adhesion force becomes sufficiently high by moisture curing. , it is also easy to improve the final adhesion and so on. In addition, the so-called final adhesive force means the adhesive force of the light and moisture-curable resin composition after photocuring and moisture-curing, the details of which will be described below.

[Internal and external ratio a/b] The light- and moisture-curable resin composition of the present invention is preferably applied to an aluminum substrate in a linear form under the following specific conditions, and then photocured by UV, and then press-bonded to a glass plate. If the average width of the bonded portion on the glass plate side is a, and the average width of the bonded portion on the aluminum substrate side is represented by b, a/b (also referred to as "inner/outer ratio a/b") is 0.58 or more and 0.99 or less . Regarding the light and moisture-curable resin composition of the present invention, if the above-mentioned ratio a/b is set to 0.58 or more, compared with the conventional light and moisture-curable resin composition, the ratio a/b of the present invention is When b is large, it is easy to collapse immediately after photohardening, and the adhesion to the interface of the adherend tends to become high, and the initial adhesion force to the adherend tends to become high. In addition, by setting the inside-outside ratio a/b to be 0.99 or less, the cohesion force between the light and the moisture-curable resin composition immediately after photocuring can be prevented from being reduced, or the initial adhesion force can be prevented from being excessively collapsed. The above-mentioned inside-out ratio a/b is more preferably 0.63 or more, more preferably 0.66 or more, and more preferably 0.95 or less, still more preferably 0.93 or less. When the inside-outside ratio a/b is within these ranges, the initial adhesion force can be easily improved.

In the present invention, the internal-internal ratio a/b is measured as follows. First, as shown in FIG. 1( a ), the moisture-curable resin composition 10 is applied on the aluminum substrate 11 with a line width of 1.0 mm. Here, the so-called line width of 1.0 mm does not need to be strictly 1.0 mm, and an error of 1.0±0.1 mm may exist. Next, as shown in FIG.1(b), the ultraviolet-ray of 1000 mJ/cm< ² > is irradiated to the moisture-curable resin composition 10, and the moisture-curable resin composition 10 is hardened. Immediately (within 10 seconds), as shown in FIG. 1( c ), the glass plate 12 is stacked on the moisture-curable resin composition 10 , and the glass plate 12 is press-bonded to the moisture-curable resin composition at 0.08 MPa 10 coating area and hold for 120 seconds. After the pressure-bonding, the width a1 of the portion where the moisture-curable resin composition 10 and the glass plate 12 are bonded is measured. The width a1 was measured at five points, and the average value was taken as the average width a. Furthermore, the width b1 of the portion where the moisture-curable resin composition 10 and the aluminum substrate 11 are bonded was measured. The width b1 was measured at five points, and the average value was taken as the average width b, and the inside-outside ratio a/b was calculated from the average widths a and b. In addition, the crimping system is performed using a weight, and the widths a1 and b1 may be measured 5 minutes after the weight is removed.

The internal and external ratio a/b can be adjusted within the above-mentioned range by adjusting the type of the radically polymerizable compound and the like. For example, when the light- and moisture-curable resin composition contains a large amount of a monofunctional radically polymerizable compound as the radically polymerizable compound, the ratio of the cross-linked structure formed after photocuring is reduced, so that the ratio a/ b becomes larger. Furthermore, for example, in the case where the light- and moisture-curable resin composition contains a large amount of a homopolymer and a radically polymerizable compound having a low glass transition point as a radically polymerizable compound, the cured product after photocuring also becomes Soft, so the ratio a/b can be increased. Furthermore, you may adjust by the weight average molecular weight of moisture-curable resin (B).

[adhesion force] The light and moisture-curable resin composition of the present invention preferably has an initial bonding force of 0.25 MPa or more. In addition, the light and moisture-curable resin composition of the present invention preferably has a final adhesive force of 2.0 MPa or more. In addition, the so-called initial adhesive force means the adhesive force at 25°C immediately after the light and moisture-curable resin composition is photo-cured, and the so-called final adhesive force means the photo-curing of the light and moisture-curable resin composition. , and then placed under the conditions of 25 ° C and 50 RH% for 24 hours, the adhesion strength. The details of the methods for measuring the initial adhesive force and the final adhesive force are as described in the following examples. Regarding the light and moisture-curable resin composition, if the initial bonding force at 25°C is 0.25 MPa or more, the adherends can be temporarily bonded to each other with a relatively high bonding force immediately after photocuring. Workability is improved. Moreover, if the final bonding force is 2.0 MPa or more, the adherends can be firmly bonded to each other by the main bonding by moisture curing after the temporary bonding.

In order to further improve the bonding stability at the time of temporary bonding, it is more preferable that the initial bonding force of the light-moisture-curable resin composition is 0.4 MPa or more. In addition, the initial bonding force is not particularly limited, but may be less than 1.5 MPa, for example, in order to facilitate re-bonding and the like during temporary bonding. Moreover, in order to join the to-be-adhered bodies more firmly after main bonding, it is more preferable that the final bonding force of the light and moisture-curable resin composition is 3.5 MPa or more. In addition, the final adhesive force is preferably as high as possible, and is not particularly limited, for example, it is 20 MPa or less, and may be 10 MPa or less.

Hereinafter, each component contained in the light-and-moisture-curable resin composition will be described in more detail. [Radical Polymerizable Compound (A)] The light and moisture-curable resin composition of the present invention contains a radically polymerizable compound (A). The light-and-moisture-curable resin composition is provided with photocurability by containing the radically polymerizable compound (A). The light- and moisture-curable resin composition has photocurability, and thus a certain adhesive force can be imparted only by irradiating it with light, so that an appropriate initial adhesive force can be ensured. As a radically polymerizable compound (A), what is necessary is just to have a radically polymerizable functional group in a molecule|numerator. A compound which has an unsaturated double bond as a radically polymerizable functional group is suitable, and a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned.

Among the above, from the viewpoint of adhesiveness, a (meth)acryloyl group is preferable, that is, the radically polymerizable compound (A) preferably contains a compound having a (meth)acryloyl group. In addition, the compound which has a (meth)acryloyl group is also called "(meth)acrylic-type compound" below. In addition, in this specification, "(meth)acryloyl" means acryl or (meth)acryloyl, "(meth)acrylic" means acrylic acid or methacrylic acid, and other similar terms are also used. The same is true.

The radically polymerizable compound (A) may include a monofunctional radically polymerizable compound having one radically polymerizable functional group in one molecule, and a polyfunctional radically polymerizable compound having two or more radically polymerizable functional groups in one molecule one or both of the compounds. However, it is preferable to contain a monofunctional radically polymerizable compound from the viewpoint of improving the gel swelling ratio after the above-mentioned photocuring and improving the initial adhesion force of the light and moisture-curable resin composition. Moreover, it is more preferable that the radically polymerizable compound (A) contains at least a monofunctional (meth)acrylic compound which is a (meth)acrylic compound as a monofunctional radically polymerizable compound. Furthermore, the monofunctional radically polymerizable compound may be a polymerized prepolymer having a repeating unit, and a monofunctional monomer having no repeating unit may be generally used.

In order to increase the gel swelling ratio after photocuring of the light and moisture curable resin composition and improve the initial adhesion, the light and moisture curable resin composition preferably contains a large amount of a monofunctional radical polymerizable compound. Specifically, the light and moisture curable resin composition preferably contains 90 parts by mass or more of the monofunctional radical polymerizable compound, preferably 95 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (A). part or more, more preferably 100 parts by mass.

[Monofunctional radically polymerizable compound] (nitrogen containing compounds) The radically polymerizable compound (A) preferably contains a nitrogen-containing compound as a monofunctional radically polymerizable compound. By using the nitrogen-containing compound, the initial adhesion of the light and moisture-curable resin composition becomes good. The light and moisture curable resin composition is applied to the adherend, and then irradiated with active energy rays such as ultraviolet rays to be photocured. In this case, generally, it is photocured in the presence of oxygen as follows. . When the radically polymerizable compound (A) contains a nitrogen-containing compound, it is appropriately photohardened even in the presence of oxygen, whereby it can be estimated that the initial adhesion becomes good.

The nitrogen-containing compound may contain one or both of a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, but from the viewpoint of making the initial adhesion of the light and moisture-curable resin composition good , preferably a nitrogen-containing compound having a cyclic structure, more preferably a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure are used in combination.

啉等含

啉骨架之化合物、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺等環狀醯亞胺化合物等。其中，進而較佳為N-乙烯基己內醯胺等含醯胺基之化合物。再者，於本說明書中，具有環狀結構之含氮化合物亦稱為環狀含氮化合物，將氮原子包含在構成環本身之原子中之自由基聚合性化合物作為環狀含氮化合物，其他含氮化合物則作為鏈狀含氮化合物。Examples of the nitrogen-containing compound having a cyclic structure include nitrogen-containing compounds having a lactamide structure such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and the like, and N-propenylidene.

Lin and other containing

Compounds with a morpholine skeleton, cyclic imide compounds such as N-(meth)acryloyloxyethylhexahydrophthalimide, and the like. Among them, compounds containing an amide group such as N-vinyl caprolactam are more preferred. Furthermore, in this specification, a nitrogen-containing compound having a cyclic structure is also referred to as a cyclic nitrogen-containing compound, and a radically polymerizable compound in which a nitrogen atom is contained in an atom constituting the ring itself is a cyclic nitrogen-containing compound, and other Nitrogen-containing compounds are used as chain nitrogen-containing compounds.

Examples of the chain nitrogen-containing compound include dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, and (meth)acrylic acid. Aminoethyl ester, dimethylaminoethyl (meth)acrylate and other chain-like (meth)acrylates containing amino groups, diacetone acrylamide, N,N-dimethylacrylamide, N, N, Chain (meth)acrylamide compounds such as N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, methacrylamide, etc., N -Vinylacetamide etc.

Moreover, as a chain nitrogen-containing compound, a monofunctional urethane (meth)acrylate may be used. By using a monofunctional urethane (meth)acrylate, in the case of using an urethane resin, especially a urethane resin having a polycarbonate skeleton as the moisture-curable resin (B), it is compatible with the moisture-curable resin. The compatibility of (B) becomes good, and it is easy to improve the initial adhesion. Moreover, since the polarity of urethane (meth)acrylate is relatively high, it is easy to improve the adhesive force to glass.

As the monofunctional (meth)acrylate amine ester, for example, a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound can be used to react. As a (meth)acrylic acid derivative which has the said hydroxyl group, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol, etc. are mentioned, for example Mono(meth)acrylate of dihydric alcohol; or mono(meth)acrylate of trihydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, etc.

Examples of isocyanate compounds for obtaining urethane (meth)acrylate include alkane monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate; cyclopentane isocyanate, cyclohexane isocyanate, isophorone monoisocyanate, and the like. Cyclic aliphatic monoisocyanates; and other aliphatic monoisocyanates. More specifically, the monofunctional urethane (meth)acrylate is preferably an urethane (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compound with a mono(meth)acrylate of a dihydric alcohol, A suitable specific example thereof includes 1,2-ethanediol 1-acrylate 2-(N-butylcarbamate) (1,2-ethanediol 1-acrylate 2-(N-butyl carbamate)) . Among them, the chain nitrogen-containing compound preferably contains a monofunctional urethane (meth)acrylate, and it is also preferred that a monofunctional urethane (meth)acrylate, a (meth)acrylamide compound, etc. be removed from the monofunctional Compounds other than urethane (meth)acrylate are used in combination.

From the viewpoint of improving the initial adhesion of the light-moisture-curable resin composition, in the light-moisture-curable resin composition, with respect to 100 parts by mass of the radically polymerizable compound (A), as The content of the nitrogen-containing compound of the monofunctional radically polymerizable compound is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and most preferably 60 parts by mass or more. Moreover, in order to contain the radically polymerizable compound (A) other than the nitrogen-containing compound in an appropriate amount, the above-mentioned content of the nitrogen-containing compound as the monofunctional radically polymerizable compound is preferably 95 parts by mass or less, more preferably 95 parts by mass or less. 90 parts by mass or less, more preferably 85 parts by mass or less.

When the monofunctional radically polymerizable compound has a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, among the monofunctional radically polymerizable compounds, the nitrogen-containing compound having a cyclic structure is relatively The mass ratio (cyclic/chain) of the nitrogen compound is preferably 0.1 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less, and still more preferably 0.4 or more and 1.2 or less. By making the mass ratio of the ring/chain shape within the above-mentioned range, the initial adhesion of the light and moisture-curable resin composition can be improved.

(Monofunctional radical polymerizable compounds other than nitrogen-containing compounds) The monofunctional radically polymerizable compound contained in the radically polymerizable compound (A) preferably contains a compound other than the above-mentioned nitrogen-containing compound (hereinafter, also referred to as a nitrogen-free compound). By making the radically polymerizable compound (A) contain a nitrogen-free compound as a monofunctional radically polymerizable compound, it becomes easy to improve adhesive force and the like.

The nitrogen-free compound is not particularly limited as long as it is a compound having a radically polymerizable functional group, but a monofunctional (meth)acrylic compound is preferable, and among them, a (meth)acrylate compound is more preferable. . As a monofunctional (meth)acrylate compound, an alkyl (meth)acrylate, an alicyclic structure-containing (meth)acrylate, an aromatic ring-containing (meth)acrylate, etc. are mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more types, Among them, it is preferable to use one or both of (meth)acrylic acid alkyl ester and aromatic ring-containing (meth)acrylic acid ester. The total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate in the radically polymerizable compound (A) relative to radical polymerization 100 parts by mass of the synthetic compound (A), preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more. Moreover, the said content becomes like this. Preferably it is 90 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less, Most preferably, it is 40 mass parts or less.

酯、(甲基)丙烯酸二環戊烯酯等具有脂環式結構之(甲基)丙烯酸酯。 作為含芳香環之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸苄酯、(甲基)丙烯酸2-苯基乙酯等(甲基)丙烯酸苯基烷基酯；(甲基)丙烯酸苯氧基乙酯等(甲基)丙烯酸苯氧基烷基酯；等。Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. ) isobutyl acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate The carbon number of alkyl groups such as isononyl acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, and stearyl (meth)acrylate is 1 to 18 The (meth)acrylic acid alkyl ester. Examples of (meth)acrylates containing an alicyclic structure include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and 3,3,5 (meth)acrylates. -Trimethylcyclohexyl ester, (meth)acrylic acid iso

(meth)acrylate having an alicyclic structure such as dicyclopentenyl (meth)acrylate. Examples of aromatic ring-containing (meth)acrylates include phenylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; ) phenoxyethyl acrylate, etc. (meth) phenoxyalkyl acrylate; etc.

烷環等之(甲基)丙烯酸酯。 作為含環氧環之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸環氧丙酯。作為含氧環丁烷環之(甲基)丙烯酸酯，可列舉(甲基)丙烯酸(3-乙基氧環丁烷-3-基)甲酯。作為含四氫呋喃環之(甲基)丙烯酸酯，可列舉(甲基)丙烯酸四氫呋喃甲酯、四氫呋喃甲醇之(甲基)丙烯酸多聚體酯等。作為含二氧環戊烷環之(甲基)丙烯酸酯，可列舉(甲基)丙烯酸(2-甲基-2-乙基-1,3-二氧環戊烷-4-基)甲酯、(甲基)丙烯酸(2,2-環己基-1,3-二氧環戊烷-4-基)甲酯等。作為具有二

烷環之(甲基)丙烯酸酯，可列舉環狀三羥甲基丙烷縮甲醛(甲基)丙烯酸酯等。 作為含環狀醚基之(甲基)丙烯酸酯，較佳為使用含氧環丁烷環之(甲基)丙烯酸酯、或含四氫呋喃環之(甲基)丙烯酸酯中之任一者，亦較佳為將其等加以併用。As the monofunctional (meth)acrylate compound, those other than alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate can also be used As a compound, for example, a cyclic ether group-containing (meth)acrylate can also be used. Examples of cyclic ether group-containing (meth)acrylates include epoxy rings, oxetane rings, tetrahydrofuran rings, dioxolane rings, dioxolanes

(meth)acrylates of alkane rings and the like. As an epoxy ring-containing (meth)acrylate, glycidyl (meth)acrylate is mentioned, for example. As (meth)acrylate containing an oxetane ring, (3-ethyl oxetane-3-yl) methyl (meth)acrylate is mentioned. As a tetrahydrofuran ring-containing (meth)acrylate, (meth)acrylic acid tetrahydrofuran methyl ester, the (meth)acrylic acid multimer ester of tetrahydrofuran methanol, etc. are mentioned. (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth)acrylate is mentioned as a dioxolane ring-containing (meth)acrylate , (meth)acrylic acid (2,2-cyclohexyl-1,3-dioxolan-4-yl) methyl ester, etc. as having two

Cyclic trimethylolpropane formal (meth)acrylate etc. are mentioned as (meth)acrylate of an alkane ring. As the cyclic ether group-containing (meth)acrylate, it is preferable to use either an oxycyclobutane ring-containing (meth)acrylate or a tetrahydrofuran ring-containing (meth)acrylate. It is preferable to use these etc. together.

Moreover, as a monofunctional (meth)acrylate compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate can also be used , (meth) 4-hydroxybutyl acrylate and other hydroxyalkyl (meth)acrylates; (meth)acrylate 2-methoxyethyl, (meth)acrylate 2-ethoxyethyl, (meth)acrylate (meth)alkoxyalkyl acrylates such as 2-butoxyethyl acrylate; alkoxyalkyl esters such as methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, etc. oxyethylene glycol (meth)acrylate; methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (methyl) ) acrylate, ethyl carbitol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, ethoxy triethylene glycol (meth) acrylate, ethoxy polyethylene glycol Polyoxyethylene-based (meth)acrylates such as alcohol (meth)acrylates; etc. Moreover, as a monofunctional (meth)acrylic compound, a carboxyl group-containing (meth)acrylic compound, such as acrylic acid and methacrylic acid, can also be used.

[Compounds other than monofunctional radically polymerizable compounds] The radically polymerizable compound (A) may contain a polyfunctional radically polymerizable compound within the range in which the effects of the present invention are exhibited. As a polyfunctional radically polymerizable compound, a bifunctional (meth)acrylate compound, a trifunctional or higher (meth)acrylate compound, a bifunctional or higher (meth)acrylate, etc. are mentioned.

As the bifunctional (meth)acrylate compound, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-butanediol di(meth)acrylate, Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl base-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, 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, dimethylol dicyclopentane Alkenyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-(meth)acrylooxypropyl (meth)acrylate, carbonate glycol di(meth)acrylate Meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol Di(meth)acrylate etc.

Moreover, as a trifunctional or more than trifunctional (meth)acrylate compound, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, , propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, glycerin Tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trimethylolpropane tetra(meth)acrylate, Neopentaerythritol tetra(meth)acrylate, dipeotaerythritol penta(meth)acrylate, dipivalerythritol hexa(meth)acrylate, etc.

As a difunctional or more than (meth)acrylate amine ester, what made the (meth)acrylic acid derivative which has a hydroxyl group and an isocyanate compound react, for example can be used. As a (meth)acrylic acid derivative which has the said hydroxyl group, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol, etc. are mentioned, for example Mono(meth)acrylate of dihydric alcohol; mono(meth)acrylate or di(meth)acrylate of trihydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, etc.; or bisphenol Epoxy (meth)acrylates such as A-type epoxy (meth)acrylates; etc.

烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、硫代磷酸三(異氰酸酯苯基)酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等聚異氰酸酯化合物。As an isocyanate compound for obtaining amine (meth)acrylate, isophorone diisocyanate, 2, 4- toluene diisocyanate, 2, 6- toluene diisocyanate, hexamethylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, normethylene diisocyanate

Alkane diisocyanate, bitoluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethylbenzene Polyisocyanate compounds such as dimethyl diisocyanate and 1,6,11-undecanetriisocyanate.

Moreover, as an isocyanate compound, the chain-extended polyisocyanate compound obtained by the reaction of a polyhydric alcohol and an excess isocyanate compound can also be used. Here, as a polyhydric alcohol, ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate glycol, polyether glycol, polyester glycol, polycaprolactone glycol, etc. are mentioned, for example . By using these polyisocyanate compounds, polyfunctional urethane (meth)acrylates can be obtained.

[Moisture-curable resin (B)] Examples of the moisture-curable resin (B) used in the present invention include moisture-curable urethane resins, hydrolyzable silicon group-containing resins, moisture-curable cyanoacrylate resins, and the like. Among them, preferred are Any one of the moisture-curable urethane resin and the resin containing a hydrolyzable silicon group is more preferably a moisture-curable urethane resin. These etc. may be used individually by 1 type, and may use 2 or more types together.

(Moisture-curable urethane resin) The moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. Moisture-curable urethane resin can have an isocyanate group in the molecule, and the isocyanate group in the molecule reacts with moisture in the air or the adherend to harden. The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups, and the moisture-curable urethane resin preferably has one or more in one molecule. 2 isocyanato groups. Moreover, an isocyanate group is not specifically limited, It can be provided in the terminal of a moisture-curable urethane resin.

In the reaction between the above-mentioned polyol compound and polyisocyanate compound, the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound is usually [NCO]/[OH]=2.0～2.5 within the scope. As the polyol compound used as the raw material of the moisture-curable urethane resin, well-known polyol compounds generally used in the production of polyurethane can be used, for example, polyester polyol, polyether polyol, polyalkylene polyol , polycarbonate polyol, etc. These polyol compounds may be used alone or in combination of two or more.

The moisture-curable urethane resin is preferably at least any one of moisture-curable urethane resins having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, more preferably a polycarbonate skeleton, or a polyester skeleton. At least any one of the moisture-curable urethane resins having an ether skeleton, and more preferably a moisture-curable urethane resin having a polycarbonate skeleton. The moisture-curable urethane resin is excellent in both the initial adhesive force and the final adhesive force by having a polycarbonate skeleton. Furthermore, it is also possible to provide a light- and moisture-curable resin composition excellent in weather resistance, heat resistance, moisture resistance, etc. of the cured product.

(Moisture-curable urethane resin with polycarbonate skeleton) Regarding the moisture-curable urethane resin having a polycarbonate skeleton, a polycarbonate skeleton is introduced into the urethane resin by using a polycarbonate polyol as the above-mentioned polyol compound. The moisture-curable urethane resin having a polycarbonate skeleton can be prepared by, for example, a polycarbonate polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. obtained by the reaction. As polycarbonate polyol, polycarbonate diol is preferable, and the compound represented by following formula (1) is mentioned as a preferable specific example of polycarbonate diol.

式（1）中，R為碳數4～16之二價烴基，n為2～500之整數。

In formula (1), R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 2 to 500.

In formula (1), R is preferably an aliphatic saturated hydrocarbon group. R is an aliphatic saturated hydrocarbon group, whereby the heat resistance can be easily improved. Moreover, yellowing etc. are hard to generate|occur|produce by thermal deterioration etc., and weather resistance also becomes favorable. R consisting of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but preferably has a chain structure from the viewpoint of easily improving stress relaxation properties and flexibility. In addition, R of the chain structure may be linear or branched. n is preferably 5-200, more preferably 10-150, still more preferably 20-50.

Moreover, about R contained in the polycarbonate polyol which comprises a moisture-curable urethane resin, it may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, at least a part is preferably a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms, more preferably at least a part is a chain aliphatic saturated hydrocarbon group having 7 or more carbon atoms. By including a chain-like aliphatic saturated hydrocarbon group having 7 or more carbon atoms, it is easy to improve stress relaxation properties and flexibility. When the polycarbonate diol is a compound represented by the above formula (1), the ratio of the chain aliphatic saturated hydrocarbon group having 7 or more carbon atoms is preferably 20 relative to R contained in the entire polycarbonate diol. Molar % or more and 100 mol % or less, more preferably 30 mol % or more and 100 mol % or less, still more preferably 50 mol % or more and 100 mol % or less. The chain aliphatic saturated hydrocarbon group having 7 or more carbon atoms is preferably 8 or more and 12 or less carbon atoms, and more preferably 8 or more and 10 or less carbon atoms.

Specific examples of R may be straight-chain such as tetramethylene, pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene, and for example, may be Branched chains such as methyl pentylene such as 3-methyl pentylene and methyl octamethylene. A plurality of Rs in one molecule may be the same or different from each other. Therefore, two or more kinds of R may be contained in one molecule, and in this case, two or three kinds of R are preferably contained in one molecule. For example, the polycarbonate polyol may be a copolymer containing R with 6 or less carbon atoms and R with 7 or more carbon atoms in one molecule, and in this case, either R may be a chain-like aliphatic saturated hydrocarbon group. Moreover, R may contain a linear aliphatic saturated hydrocarbon group, and may contain a branched aliphatic saturated hydrocarbon group. Regarding R in the polycarbonate polyol, branched and linear R may be used in combination, or linear R may be used alone. In addition, a polycarbonate polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

烷二異氰酸酯、反式環己烷-1,4-二異氰酸酯、異佛酮二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化二苯基甲烷二異氰酸酯、環己烷二異氰酸酯、雙(異氰酸基甲基)環己烷、二環己基甲烷二異氰酸酯等。 作為聚異氰酸酯化合物，其中，自可提高完全硬化後之接著力之觀點而言，較佳為芳香族聚異氰酸酯化合物，其中更佳為二苯基甲烷二異氰酸酯及其改質物。又，自容易對光與濕氣硬化性樹脂組成物之硬化物賦予應力緩和性、柔軟性等之觀點而言，較佳為脂肪族聚異氰酸酯化合物。 聚異氰酸酯化合物可單獨使用，亦可組合兩種以上而使用。As the polyisocyanate compound used as the raw material of the moisture-curable urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are suitably used. Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, a liquid modified product of diphenylmethane diisocyanate, polymerized MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like. Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate,

Alkane diisocyanate, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanate) methyl) cyclohexane, dicyclohexylmethane diisocyanate, etc. Among them, as the polyisocyanate compound, an aromatic polyisocyanate compound is preferable from the viewpoint that the adhesive force after complete hardening can be improved, and among them, diphenylmethane diisocyanate and a modified product thereof are more preferable. Moreover, an aliphatic polyisocyanate compound is preferable from the viewpoint of easily imparting stress relaxation properties, flexibility, etc. to the cured product of the light and moisture-curable resin composition. The polyisocyanate compound may be used alone or in combination of two or more.

(Moisture-curable urethane resin with polyester skeleton) The moisture-curable urethane resin having a polyester skeleton is obtained by using a polyester polyol as the above-mentioned polyol compound and introducing a polyester skeleton into the urethane resin. The moisture-curable urethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. As said polyester polyol, the polyester polyol obtained by the reaction of polyvalent carboxylic acid and polyol, the poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone, for example, can be mentioned. Alcohol etc. As the above-mentioned polyvalent carboxylic acid as a raw material of polyester polyol, for example, phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid can be mentioned. acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid Wait. Among them, phthalic acid or adipic acid is preferable from the viewpoint of more easily improving the adhesive force at high temperature. As the above-mentioned polyol as a raw material of polyester polyol, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc. Among them, 1,6-hexanediol or 1,4-butanediol is preferable from the viewpoint of more easily improving the adhesive force at high temperature. In addition, a polyester polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

(Moisture-curable urethane resin with polyether skeleton) Regarding the moisture-curable urethane resin having a polyether skeleton, a polyether skeleton is introduced into the urethane resin by using a polyether polyol as the above-mentioned polyol compound. The urethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers of derivatives thereof and the like. Or block copolymer, bisphenol type polyoxyalkylene modified body, etc. Among them, polypropylene glycol, a ring-opening polymer of tetrahydrofuran, or a ring-opening polymer of 3-methyltetrahydrofuran are preferable from the viewpoint of easily improving the coatability of the light- and moisture-curable resin composition. Here, the bisphenol-type polyoxyalkylene modification system performs alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) on the active hydrogen part of the bisphenol-type molecular skeleton. ) polyether polyol obtained by addition reaction. The polyether polyol may be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modified body preferably has one or more types of alkylene oxides added to both ends of the bisphenol-type molecular skeleton. Although it does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, Preferably it is a bisphenol A type. Moreover, as a polyisocyanate compound, the above-mentioned polyisocyanate compound can be used.

It is preferable that the moisture-curable urethane resin which has a polyether skeleton further contains the thing obtained by using the polyol compound which has the structure represented by following formula (2). By using a polyol compound having a structure represented by the following formula (2), a light- and moisture-curable resin composition excellent in adhesion and a hardened product with good flexibility and extensibility can be obtained, and the resin composition can be polymerized with radicals. The compatibility of the compound (A) becomes excellent. Among them, a polyether polyol composed of a ring-opening polymerized compound of polypropylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerized compound of a tetrahydrofuran compound having a substituent such as a methyl group is preferably used, and a polyether polyol is more preferable. Ring-opening polymerization compound of propylene glycol and tetrahydrofuran (THF) compounds. The ring-opening polymer compound of tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol. In addition, a polyether polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

式（2）中，R表示氫原子、甲基、或乙基，l為0～5之整數，m為1～500之整數，n為1～10之整數。l較佳為0～4，m較佳為50～200，n較佳為1～5。再者，於l為0之情形時，意指與R鍵結之碳直接與氧鍵結在一起。 上述中，n與l之合計更佳為1以上，進而較佳為1～3。又，R更佳為氫原子、甲基，尤佳為甲基。

In formula (2), R represents a hydrogen atom, a methyl group, or an ethyl group, l is an integer of 0-5, m is an integer of 1-500, and n is an integer of 1-10. l is preferably 0-4, m is preferably 50-200, and n is preferably 1-5. Furthermore, when l is 0, it means that the carbon bonded to R is directly bonded to oxygen. In the above, the total of n and l is more preferably 1 or more, and still more preferably 1 to 3. Moreover, R is more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

The above-mentioned moisture-curable urethane resin having a polycarbonate, polyester, or polyether skeleton may have two or more skeletons in the molecule, for example, a polycarbonate skeleton and a polyester skeleton. In this case, polycarbonate polyol and polyester polyol can be used as the above-mentioned polyol compound used as a raw material. Similarly, moisture-curable urethane resin or the like having a polyester skeleton and a polyether skeleton can also be used. In addition, as the moisture-curable urethane resin, one containing an isocyanate group can be used as described above, but it is not limited to one containing an isocyanate group. As explained in the following resin containing a hydrolyzable silicon group, a water-containing resin may also be used. Degradable silicone-based urethane resin.

(with hydrolyzable silicone-based resin) The hydrolyzable silicon group-containing resin used in the present invention reacts with the hydrolyzable silicon group in the molecule and the moisture in the air or the adherend to harden. The resin containing a hydrolyzable silicon group may have only one hydrolyzable silicon group in one molecule, or may have two or more hydrolyzable silicon groups. Among them, it is preferable to have hydrolyzable silicon groups at both ends of the main chain of the molecule. In addition, the resin which has an isocyanate group is not included as said resin containing a hydrolyzable silicon group.

式（3）中，R¹ 分別獨立地為可經取代之碳數1以上且20以下之烷基、碳數6以上且20以下之芳基、碳數7以上且20以下之芳烷基、或-OSiR² ₃ （R² 分別獨立地為碳數1以上且20以下之烴基）所表示之三有機矽烷氧基。又，式（3）中，X分別獨立地為羥基或水解性基。進而，式（3）中，a為1～3之整數。The hydrolyzable silicon group is represented by the following formula (3).

In formula (3), R ¹ is each independently a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or -OSiR ² ₃ (R ² is each independently a hydrocarbon group having 1 or more and 20 or less carbon atoms) triorganosiloxane alkoxy group. In addition, in formula (3), X is each independently a hydroxyl group or a hydrolyzable group. Furthermore, in Formula (3), a is an integer of 1-3.

The hydrolyzable group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, and an acid. amide group, amineoxy group, sulfhydryl group, etc. Among them, from the viewpoint of high activity, a halogen atom, an alkoxy group, an alkenyloxy group, and an alkenyloxy group are preferable. Moreover, from the viewpoint of stable hydrolyzability and easy handling, alkoxy groups such as a methoxy group and an ethoxy group are more preferable, and a methoxy group and an ethoxy group are still more preferable. Moreover, from the viewpoint of safety, it is preferable that the compounds to be removed by the reaction are ethanol, ethoxy group of acetone, and isopropenyloxy group, respectively.

The said hydroxyl group or the said hydrolyzable group may bond 1-3 pieces with respect to 1 silicon atom. When two or more of the above-mentioned hydroxyl groups or the above-mentioned hydrolyzable groups are bonded to one silicon atom, these groups may be the same or different.

About a in said Formula (3), 2 or 3 are preferable from the viewpoint of self-hardening property, and 3 is especially preferable. Moreover, from the viewpoint of storage stability, a is preferably 2. In addition, examples of R ¹ in the above formula (3) include alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and trimethylsilane. oxy, chloromethyl, methoxymethyl, etc. Among them, a methyl group is preferable.

Examples of the hydrolyzable silicon group include methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, and triacetoxysilyl. Silyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethoxy Silyl, (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (ethoxy Methyl)dimethoxysilyl, (1-methoxyethyl)dimethoxysilyl, (aminomethyl)dimethoxysilyl, (N,N-dimethylaminomethyl) base) dimethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl, ( N-(2-Aminoethyl)aminomethyl)dimethoxysilyl, (acetoxymethyl)dimethoxysilyl, (acetoxymethyl)diethoxysilyl Base et al.

Examples of the resin containing a hydrolyzable silicon group include (meth)acrylic resin containing a hydrolyzable silicon group, an organic polymer containing a hydrolyzable silicon group at the end of the molecular chain or at the terminal portion of the molecular chain, and a hydrolyzable silicon group. Polyurethane resin, etc. The hydrolyzable silicon group-containing (meth)acrylic resin preferably has a repeating structural unit derived from the hydrolyzable silicon group-containing (meth)acrylate and/or (meth)acrylate alkyl ester in the main chain.

Examples of (meth)acrylates containing hydrolyzable silicon groups include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl) (meth)acrylates Propyl ester, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 2-(trimethoxysilyl)ethyl (meth)acrylate, 2-(triethyl)(meth)acrylate Oxysilyl)ethyl ester, 2-(methyldimethoxysilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, triethoxy (meth)acrylate Silyl methyl ester, (meth)acrylate (methyldimethoxysilyl) methyl ester, etc. Examples of the above-mentioned alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, ring (meth)acrylate Hexyl ester, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate , n-dodecyl (meth)acrylate, stearyl (meth)acrylate, etc.

Specific examples of the method for producing a hydrolyzable silicon group-containing (meth)acrylic resin include the hydrolyzable silicon group-containing (meth)acrylate-based polymer described in International Publication No. WO 2016/035718. synthetic methods, etc. The organic polymer having a hydrolyzable silicon group at the end of the molecular chain or at the end of the molecular chain has a hydrolyzable silicon group at at least any one of the end of the main chain and the end of the side chain. Although the skeleton structure of the said main chain is not specifically limited, For example, a saturated hydrocarbon type polymer, a polyoxyalkylene type polymer, a (meth)acrylate type polymer etc. are mentioned.

Examples of the above-mentioned polyoxyalkylene-based polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, Polyoxypropylene-polyoxybutylene copolymer structure polymers, etc. Specific examples of the method for producing an organic polymer having a hydrolyzable silicon group at the end of the molecular chain or at the end of the molecular chain include the method described in International Publication No. WO 2016/035718 only at the end of the molecular chain or at the end of the molecular chain. A method for synthesizing an organic polymer with a cross-linkable silicon group at the end. Further, as another method for producing the organic polymer having a hydrolyzable silicon group at the end of the molecular chain or at the end of the molecular chain, for example, the reactive silicon group-containing polyoxane described in International Publication No. WO 2012/117902 can be mentioned. Synthetic method of base polymer, etc.

As a method for producing the above-mentioned hydrolyzable silicon group-containing polyurethane resin, for example, a method such as a method in which a polyol compound and a polyisocyanate compound are reacted to produce a polyurethane resin, and a silicon group-containing compound such as a silane coupling agent is further allowed to be reaction. Specifically, for example, the synthesis method of the urethane oligomer having a hydrolyzable silicon group described in JP-A No. 2017-48345 can be mentioned.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, and β-(3,4-epoxy) Cyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloyloxy Propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethine Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane Silane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. Among them, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.

In addition, the moisture-curable urethane resin may have both an isocyanate group and a hydrolyzable silicon group. The moisture-curable urethane resin having both an isocyanate group and a hydrolyzable silicon group is preferably produced by the following method: First, the moisture-curable amine having an isocyanate group is obtained by the above method ester resin (raw material urethane resin), and further react the silane coupling agent with the raw material urethane resin. Furthermore, the details of the moisture-curable urethane resin having an isocyanate group are as described above. As the silane coupling agent which reacts with the raw material urethane resin, it may be appropriately selected and used from those listed above. From the viewpoint of reactivity with an isocyanate group, it is preferable to use an amine group or Silane coupling agent of mercapto group. Preferred specific examples include N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyl Dimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanato Propyltrimethoxysilane, etc.

Furthermore, the moisture-curable resin may have a radically polymerizable functional group. The radically polymerizable functional group which the moisture-curable resin can have is preferably a group having an unsaturated double bond, and in view of reactivity, a (meth)acryloyl group is particularly preferable. In addition, the moisture-curable resin which has a radically polymerizable functional group is not included in the said radically polymerizable compound, but is handled as a moisture-curable resin (B). The moisture-curable resin (B) may be appropriately selected from among the various resins described above and used alone, or two or more may be appropriately selected and used in combination.

The weight average molecular weight of the moisture-curable resin (B) is preferably 7,500 or more and 24,000 or less. When the weight-average molecular weight is within the above range, the inside-out ratio a/b and the 25°C viscosity of the light-moisture-curable resin composition are within a specific range, so that the initial adhesion can be easily improved. Moreover, by setting it below the said upper limit value, it becomes easy to make final adhesive force favorable. From these viewpoints, the weight average molecular weight of the moisture-curable resin (B) is more preferably 7,800 or more, more preferably 10,000 or more, still more preferably 11,500 or more, and more preferably 20,000 or less, still more preferably It is 16000 or less, more preferably 15000 or less. In addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC).

The moisture-curable resin may be chain-extended so that the weight average molecular weight may be set to a certain value or more as described above. For example, for moisture-curable urethane resins, chain extension can be performed as follows: a polyol compound having an isocyanate group obtained by reacting a polyol compound with a polyisocyanate compound having two or more isocyanate groups in one molecule urethane resin (hereinafter, also referred to as "raw urethane resin"), and a chain extender is further reacted therewith. In this case, as for the chain extender, all the isocyanate groups contained in the raw material urethane resin may not be reacted with the chain extender, but the amount of the chain extender used may be appropriately adjusted so that the isocyanate groups remain in the moisture-curable urethane resin. middle. In addition, the chain extender which has reacted with the raw material urethane resin may be further reacted with the raw material urethane resin.

The chain extender used in the moisture-curable urethane resin is preferably a polyol compound. Details of the polyol compound are as described above. In addition, as for the polyol compound as a chain extender, it is sufficient to use a polyol compound of the same type as the polyol compound used for synthesizing the raw material urethane resin. Therefore, if the polyol compound used for synthesizing the raw material urethane resin is polycarbonate polyol, the chain extender only needs to use polycarbonate polyol. The usage-amount of the chain extender is, for example, 5 parts by mass or more and 40 parts by mass or less, preferably 10 parts by mass or more and 35 parts by mass, when the total amount of the raw material urethane resin and the chain extender is 100 parts by mass. part or less, more preferably 15 parts by mass or more and 30 parts by mass or less.

In the light and moisture-curable resin composition, the mass ratio (B/A) of the moisture-curable resin (B) to the radically polymerizable compound (A) is preferably 30/70 or more and 90/10 or less , more preferably 40/60 or more and 80/20 or less, still more preferably 50/50 or more and 70/30 or less. By making the mass ratio within these ranges, light-curable and moisture-curable resin compositions can be imparted in a well-balanced manner, and it is easy to adjust both the initial adhesive force and the final adhesive force within the desired range. .

The light and moisture-curable resin composition may contain resin components other than the radically polymerizable compound (A) and the moisture-curable resin (B) as resin components within a range that does not impair the effects of the present invention. Resin components such as thermoplastic resins that do not have curability (eg, acrylic resins, urethane resins, etc.), thermosetting resins, and the like may be contained. The ratio of the resin components other than the radically polymerizable compound (A) and the moisture-curable urethane resin (B) relative to the ratio of the radically polymerizable compound (A) and the moisture-curable urethane resin (B) The total amount of 100 parts by mass is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less.

等。 作為上述光聚合起始劑中之市售者，例如可列舉：IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE379EG、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、IRGACURE TPO（均為BASF公司製造）、安息香甲醚、安息香乙醚、安息香異丙醚（均為東京化成工業公司製造）等。[Photopolymerization Initiator (C)] The light and moisture-curable resin composition of the present invention contains a photopolymerization initiator. The light-and-moisture-curable resin composition is appropriately imparted with photocurability by containing a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone-based compounds, acetophenone-based compounds, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, and oximes. Ester-based compounds, benzoin ether-based compounds, 9-oxythiocyanate

Wait. Among the above-mentioned photopolymerization initiators, commercially available ones include, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF), benzoin ether, benzoin ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photopolymerization initiator in the light-and-moisture-curable resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass relative to 100 parts by mass of the radically polymerizable compound (A). part or more and 5 parts by mass or less. By making content of a photopolymerization initiator into these ranges, the photocurability and storage stability of the light-and-moisture-curable resin composition obtained become excellent. Moreover, by making the said content into the said range, a photoradical superposition compound can be hardened suitably, and it becomes easy to make a favorable adhesive force.

[filler (D)] The light and moisture-curable resin composition of the present invention may contain a filler (D). By containing the filler (D), the light and moisture-curable resin composition of the present invention has a suitable thixotropy, and the shape after coating can be sufficiently maintained. As the filler, a particulate one may be used. As a filler (D), an inorganic filler is preferable, for example, silica, talc, titanium oxide, zinc oxide, calcium carbonate, etc. are mentioned. Among them, silicon dioxide is preferable from the viewpoint of obtaining excellent light and moisture-curable resin composition in terms of UV transmittance. Moreover, hydrophobic surface treatment, such as a siliconization process, an alkylation process, and an epoxidation process, may be performed for the filler (D). The filler (D) may be used alone or in combination of two or more. The content of the filler (D) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 100 parts by mass in total of the radically polymerizable compound (A) and the moisture-curable urethane resin (B). It is 2 parts by mass or more and 20 parts by mass or less, and more preferably 3 parts by mass or more and 15 parts by mass or less.

啉基)二乙醚、4-

啉基丙基

啉、2,2'-二

啉基二乙醚等具有

啉骨架之化合物、雙(2-二甲基胺基乙基)醚、1,2-雙(二甲基胺基)乙烷等具有2個二甲基胺基之含二甲基胺基之胺化合物、三乙胺、1,4-二吖雙環[2.2.2]辛烷、2,6,7-三甲基-1,4-二吖雙環[2.2.2]辛烷等。 作為金屬系觸媒，可列舉：二月桂酸二正丁基錫、二乙酸二正丁基錫、辛酸錫（Tin octylate）等錫化合物；辛酸鋅（Zinc octylate）、環烷酸鋅等鋅化合物；四乙醯丙酮酸鋯、環烷酸銅、環烷酸鈷等其他金屬化合物。(Moisture Hardening Acceleration Catalyst) The light and moisture hardening type resin composition may contain a moisture hardening accelerator which accelerates the moisture hardening reaction of the moisture hardening resin (B). By using the moisture curing accelerator, the moisture curing properties of the light and moisture curing resin composition become more excellent, and it is easy to improve the adhesive force. Specific examples of the moisture curing accelerator include amine-based compounds, metal-based catalysts, and the like. As the amine compound, bis(methyl)

olinyl) diethyl ether, 4-

olinylpropyl

Phosphine, 2,2'-di

olinyl diethyl ether, etc. have

Compounds with morphine skeleton, bis(2-dimethylaminoethyl) ether, 1,2-bis(dimethylamino)ethane and other dimethylamino-containing compounds with two dimethylamino groups Amine compounds, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane, and the like. Examples of the metal-based catalyst include: tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octylate; zinc compounds such as zinc octylate and zinc naphthenate; tetraacetate Zirconium pyruvate, copper naphthenate, cobalt naphthenate and other metal compounds.

The content of the moisture curing accelerator is preferably 0.01 part by mass or more and 8 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the moisture-curable urethane resin (B). By making the content of the moisture-hardening accelerating catalyst within the above-mentioned range, the following effects are obtained, which promote the moisture-curing reaction and prevent the storage stability of light and moisture-curable resin compositions from being deteriorated. worse.

(Colorant) The light and moisture-curable resin composition of the present invention may further contain a colorant. Examples of the colorant include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, and the like. The light-and-moisture-curable resin composition contains a colorant, so that light-shielding properties and the like are also improved. Among them, titanium black is preferred. Titanium black has the property of allowing light of wavelengths in the vicinity of the ultraviolet region to penetrate, while sufficiently shielding light of wavelengths in the visible light region, thereby preventing the photocurability of the light and moisture-curable resin composition from decreasing. The content of the colorant in the light-and-moisture-curable resin composition is preferably 0.05 mass with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable urethane resin (B). part or more and 8 parts by mass or less, more preferably 0.1 part by mass or more and 2 parts by mass or less. By making the content of the colorant within these ranges, the adhesiveness between light and the moisture-curable resin composition can be well maintained, and suitable light-shielding properties can be imparted.

In addition to the components described above, the light and moisture curable resin composition may contain other additives such as coupling agents, wax particles, ionic liquids, expanded particles, expanded particles, and reactive diluents. In addition, as a coupling agent, a silane coupling agent, a titanate type coupling agent, a zirconate type coupling agent, etc. are mentioned, Of these, a silane coupling agent is preferable. The light- and moisture-curable resin composition may be diluted with a solvent, if necessary. When the light-and-moisture-curable resin composition is diluted with a solvent, the part by mass of the light-and-moisture-curable resin composition is based on the solid content, that is, the part by mass after the solvent is removed.

Examples of the method for producing the light and moisture-curable resin composition of the present invention include methods such as a method in which the radically polymerizable compound (A), the moisture-curable resin (B), and the photopolymerizable compound are polymerized using a mixer. The starting agent (C), and other additives such as fillers, moisture hardening accelerators, colorants, etc., which are blended as needed, are mixed. As a mixer, a homogenizer, a homogenizer, a universal mixer, a planetary mixer, a planetary mixer, a kneader, a three-roll mill etc. are mentioned, for example.

In addition, as described above, the molecular weight of moisture-curable resins such as moisture-curable urethane resins may be increased by a chain extender. In this case, for example, a raw material resin such as a raw urethane resin can be reacted with a chain extender in advance to obtain a moisture curable resin (B), and then, as described above, this can be mixed with a radically polymerizable compound (A) or the like. Other ingredients are mixed. Alternatively, the raw material resin, the chain extender, and the radically polymerizable compound (A) may be mixed, and if necessary, the mixture may be heated, etc., whereby the chain extender and the raw resin may be reacted to synthesize wet Air-curable resin (B). In this case, a mixture of the moisture-curable resin (B) and the radically polymerizable compound (A) can be obtained, so the photopolymerization initiator (C) can be added to the mixture, and blended as necessary. other additives to obtain a light- and moisture-curable resin composition.

<How to use light and moisture curable resin composition> The light and moisture curable resin composition of the present invention is cured and used as a cured product. Specifically, the light and moisture-curable resin composition of the present invention can be cured as follows: first, photo-curing is performed by irradiating light, for example, to a B-stage state (semi-cured state), and then It is fully hardened by hardening with moisture. Here, in the case where the light and the moisture-curable resin composition are arranged between the adherends and the adherends are joined between the adherends, the above-mentioned light and the moisture-curable resin composition can be applied as follows: On an adherend, it is photocured by irradiating light, for example, to a B-stage state, and another adherend is superimposed on the photocured light and the moisture-curable resin composition, using a suitable The bonding force (initial bonding force) causes temporary bonding between the objects to be bonded. Then, with respect to the light and moisture-curable resin composition in the B-stage state, the moisture-curable urethane resin is cured with moisture to be completely cured, so that the light and moisture-curable resin composition can be cured through the light and moisture-curable resin composition. The overlapped bonded bodies are formally bonded, and the bonded bodies are joined with sufficient bonding force.

The application of the light and moisture-curable resin composition to the adherend can be performed, for example, using a dispenser, and is not particularly limited. The light irradiated at the time of photohardening will not be specifically limited as long as it hardens a radically polymerizable compound, Preferably it is an ultraviolet-ray. Moreover, after photocuring the light and moisture-curable resin composition, when it is completely cured with moisture, it may be left to stand in the air for a predetermined period of time. The coating of the light-and-moisture-curable resin composition to the adherend is not particularly limited, and it can be carried out in the vicinity of normal temperature, and specifically, can be carried out at a temperature of about 10 to 35°C. The 25°C viscosity of the light and moisture-curable resin composition of the present invention is within the above-mentioned specific range, so even if it is applied near normal temperature, it can be easily applied without dripping. . In addition, the light and moisture-curable resin composition of the present invention expresses an initial bonding force of a certain value or more immediately after light irradiation, so that temporary bonding can be performed immediately after photocuring, and workability becomes good.

The light and moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic parts. That is, this invention also provides the adhesive agent for electronic components which consists of the said light and moisture curable resin composition. Therefore, it is preferable that the said adherend is various electronic components which comprise an electronic apparatus. As various electronic components which comprise an electronic apparatus, various electronic components provided in a display element, a board|substrate on which electronic components are mounted, a semiconductor chip, etc. are mentioned, for example. Moreover, as a material of the to-be-adhered body, any one of metal, glass, plastic, etc. may be sufficient. Furthermore, the shape of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod-shaped body) shape, a box shape, a case shape, and the like.

As described above, the light and moisture-curable resin composition of the present invention is preferably used for bonding electronic parts constituting electronic equipment to each other. In addition, the light and moisture-curable resin composition of the present invention is preferably used for joining electronic components to other components. With these constitutions, the electronic component has the cured product of the present invention. In addition, the light and moisture-curable resin composition of the present invention is used, for example, in electronic equipment and the like to obtain an assembly by bonding a substrate to a substrate. The assembly thus obtained has the first substrate, the second substrate, and the cured product of the present invention, and at least a part of the first substrate is bonded to at least a part of the second substrate through the cured product. Furthermore, it is preferable that at least one electronic component is mounted on the 1st board|substrate and the 2nd board|substrate, respectively.

In addition, the light and moisture-curable resin composition of the present invention is preferably used for narrow-edge applications. For example, in various display devices such as display devices for mobile phones such as smartphones, an adhesive is coated on a narrow box-shaped (ie, narrow edge) substrate, and display panels, touch panels, etc. are assembled through the adhesive. However, as the adhesive, the light and moisture-curable resin composition of the present invention can be used. Furthermore, the light and moisture-curable resin composition of the present invention is preferably used for semiconductor wafer applications. The light and moisture-curable resin composition of the present invention are used for semiconductor wafer applications, for example, for bonding semiconductor wafers to each other. Example

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples at all.

The measurement and evaluation of various physical properties were performed as follows. (weight average molecular weight) The weight average molecular weight of the moisture-curable resin (B) in each Example and Comparative Example was measured by gel permeation chromatography (GPC), and was calculated|required by polystyrene conversion. In the GPC measurement, Shodex KF-806L (manufactured by Showa Denko Co., Ltd.) was used as a column. In addition, tetrahydrofuran (THF) was used as a solvent and a mobile phase. Further, as the measurement conditions of GPC, the flow rate was 1.0 ml/min, and the measurement temperature was 40°C.

In addition, in each Example and a comparative example, the said weight average molecular weight was measured using the mixture of a radically polymerizable compound and a moisture curable resin (B) as a sample. In this mixture, the peak of the radically polymerizable compound appears on the low molecular weight side, and the peak of the moisture curable resin (B) appears on the high molecular weight side, so the moisture curable resin (B) can be obtained from the peak on the high molecular weight side. the weight average molecular weight.

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

(Internal and external ratio a/b) The internal and external ratio a/b was measured by the method described in the specification. Furthermore, as the aluminum substrate and the glass plate, an aluminum alloy "A6063S" with a size of 2 mm x 25 mm x 60 mm was used, and a glass plate with a smooth surface that was ultrasonically cleaned for 5 minutes was used. The coating of the moisture-curable resin composition was carried out at room temperature (25°C) using "SHOTMASTER300SX" manufactured by Musashi High-Tech Co., Ltd. as a dispensing device, and the width was 1.0±0.1 mm, the length was 25 mm, and the thickness was 1.0±0.1 mm. 0.4±0.1 mm is applied to the aluminum substrate in a straight line. Next, the applied light and moisture-curable resin composition was irradiated with ultraviolet rays having a wavelength of 405 nm at 1000 mJ/cm ² using a linear LED irradiator (manufactured by HOYA Co., Ltd., 1000 mW). When the glass plate was crimped to the aluminum substrate, a weight was used as a weight, and the widths a1 and b1 were measured 5 minutes after the weight was removed. When measuring the widths a1 and b1 after crimping, the crimping surface was observed and measured from the glass plate side using a microscope.

(Gel swelling ratio (W1/W2)) The gel swelling ratio (W1/W2) was measured by the method described in the specification. In addition, "PET38x1-C" (made by Nippa Co., Ltd.) was used as a mold release PET film. The applied light and moisture-curable resin composition was irradiated with ultraviolet rays having a wavelength of 405 nm at 1000 mJ/cm ² using a linear LED irradiator (manufactured by HOYA Co., Ltd., 1000 mW). As for the immersion in THF, 30 ml of THF put into a glass bottle was used, and it was performed while stirring gently. As a 200-mesh wire mesh, "brass 200-mesh (wire diameter 50 μm, mesh 77 μm)" (manufactured by MESH Co., Ltd.) was used. As for the cleaning of the light- and moisture-curable resin composition that has been photocured after dipping, it was performed 5 times using new 5 ml of THF. The drying of the gel in the swollen state was performed by standing in a thermostat set at 100°C for 2 hours. In the above-mentioned operations, all THF was dried THF.

(Initial Adhesion Force) As shown in FIGS. 2( a ) and ( b ), using the above-mentioned dispensing apparatus, on the aluminum substrate 21 , a width of 1.0±0.1 mm, a length of 25 mm, and a thickness of 0.4±0.1 mm were applied The light and moisture-curable resin composition 20 was applied at room temperature (25° C.). Then, photocuring was performed by irradiating ultraviolet rays with a wavelength of 405 nm at 1000 mJ/cm ² using a linear LED irradiator (manufactured by HOYA Co., Ltd., 1000 mW). Then, the glass plate 22 was bonded to the aluminum substrate 21 via the photocured light and the moisture-curable resin composition 20 , and the application area was press-bonded with a weight at 0.08 MPa for 120 seconds to obtain an adhesive for evaluation. Sample 23. Then, in an environment of 25°C, using a tensile tester ("tensile compression tester SVZ-50NB", manufactured by Imada Manufacturing Co., Ltd.) in the shearing direction S at a speed of 10 mm/min, the peeling aluminum was measured. The maximum stress between the substrate 21 and the glass plate 22, and the measured maximum stress is used as the initial bonding force. In addition, it was performed within 150 seconds from the completion of photohardening to the start of the tensile test. The initial bonding force was evaluated according to the following evaluation criteria. A: 0.4 MPa or more B: 0.25 MPa or more and less than 0.4 MPa C: less than 0.25 MPa

(final adhesion) In the same manner as the initial adhesive force, the glass plate was bonded to the aluminum substrate via the photocured light and the moisture-curable resin composition. Then, it was left to stand under the conditions of 25 degreeC and 50RH% for 24 hours, and it was made to moisture harden by it, and the sample for adhesiveness evaluation was obtained. Using the sample for adhesion evaluation, the sample was stretched in the shearing direction in the same way as the method for measuring the initial adhesion force, and the maximum stress when peeling off the aluminum substrate and the glass plate was measured, and the measured maximum stress was used as the final adhesion force. . A: 3.5 MPa or more B: 2.0 MPa or more and less than 3.5 MPa C: less than 2.0 MPa

The urethane resin raw material used in each Example and Comparative Example was produced by the following method. [Synthesis Example 1] (PC urethane resin raw material) 100 parts by mass of polycarbonate diol (a compound represented by formula (1), 90 mol % of R is 3-methylpentylene, and 10 mol % is hexamethylene as a polyol compound; Kuraray polyol C-1090 (trade name: Kuraray polyol C-1090), and 0.01 part by mass of dibutyltin dilaurate were placed in a separable flask having a capacity of 500 mL. The flask was mixed by stirring at 100°C for 30 minutes under vacuum (below 20 mmHg). Then, at normal pressure, 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred and reacted at 80° C. for 3 hours to obtain a Moisture-curable urethane resin with polycarbonate skeleton and isocyanate groups at both ends (PC urethane resin raw material). The weight average molecular weight of the obtained urethane resin raw material was 6700.

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

[Example 1] As described in Table 5, 60 parts by mass of each raw material constituting the moisture-curable resin (PC-L25) was added to 40 parts by mass of the acrylic resin A. Acrylic resin A was obtained by mixing each compound at the mixing ratio described in Table 2. The PC urethane resin raw material and PC polyol were sequentially added to the acrylic resin A according to the mass ratio described in Table 3 to obtain a mixture as a moisture-curable resin (PC-L25). As the PC polyol, the polycarbonate diol used in Synthesis Example 1 was used. By stirring the obtained mixture at 50°C, the PC polyol and a part of the urethane resin raw material were reacted to synthesize a chain-extended moisture-curable urethane resin having isocyanate groups remaining to obtain an acrylic resin A mixture of A (radical polymerizable compound) and moisture-curable urethane resin. To the obtained mixture of acrylic resin A and moisture-curable urethane resin, a photopolymerization initiator and a filler were added according to the composition in Table 5 and further mixed to obtain a light- and moisture-curable resin composition . About the obtained light-and-moisture-curable resin composition, the viscosity at 25 degreeC, the gel swelling ratio, the inside-outside ratio a/b, the initial adhesion force, and the final adhesion force were measured.

[Examples 2 to 4, 7, 8, Comparative Examples 1, 2] Acrylic resin B was used instead of acrylic resin A, and the moisture-curable resin (PC-L25) described in Tables 3, 4, and 5 was used instead of moisture-curable resin (PC-L25). Example 1 was carried out in the same manner. That is, acrylic resin B was used instead of acrylic resin A, and the blend ratio and type of the urethane resin raw material added to acrylic resin B, and polyols were changed to those described in Tables 3 and 4, and acrylic resin B and acrylic resin were obtained. Except for the mixture of the moisture-curable urethane resin, it was carried out in the same manner as in Example 1. In addition, as the ET polyol in Table 4, the polytetramethylene ether glycol used in Synthesis Example 2 was used. In addition, in Comparative Example 1, only the urethane resin raw material was added to the acrylic resin A, and the polyol was not added, so the urethane resin raw material was used as the moisture-curable resin as it was.

[Examples 5, 9 to 11, Comparative Examples 3 to 5] It carried out similarly to Example 1 except having used the acrylic resin B-H instead of the acrylic resin A. In addition, the acrylic resins B to H are obtained by mixing each compound at the mixing ratio described in Table 2, respectively.

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

Components other than the moisture-curable urethane resin (B) used in each Example and Comparative Example are shown in Table 1 below. [Table 1] Product name dealer Compound name Cyclic nitrogen compounds NVC Tokyo Chemical Industry Co., Ltd. N-Vinyl-ε-caprolactam Monofunctional urethane acrylate Viscoat #216 Osaka Organic Chemical Industry Co., Ltd. 1,2-Ethylene glycol 1-acrylate 2-(N-butylcarbamate) Polyfunctional urethane acrylate EBECRYL8411 DAICEL-ALLNEX (Shares) - Multifunctional Acrylate TMPT-A Osaka Organic Chemical Industry Co., Ltd. Trimethylolpropane triacrylate Monofunctional acrylate a Viscoat #192 Osaka Organic Chemical Industry Co., Ltd. Phenoxyethyl acrylate Monofunctional acrylate b IDAA Osaka Organic Chemical Industry Co., Ltd. Isodecyl Acrylate Monofunctional acrylate c DMAA KJ Chemicals (stock) Dimethacrylamide Monofunctional acrylated DEAA KJ Chemicals (stock) Diethylacrylamide photopolymerization initiator Irgacure TPO BASF Corporation Diphenyl(2,4,6-trimethylbenzyl)phosphine oxide filler AEROSIL RY-200S Japan Aerosil (stock) silica filler Colorant 13M-C Mitsubishi Materials (stock) Titanium Black

The acrylic resins A to D used in the examples and comparative examples are as follows. [Table 2] Acrylic resin A (parts by mass) Acrylic resin B (parts by mass) Acrylic resin C (parts by mass) Acrylic resin D (parts by mass) Acrylic resin E (parts by mass) Acrylic resin F (parts by mass) Acrylic resin G (parts by mass) Acrylic resin H (parts by mass) Cyclic nitrogen compounds 30 30 30 30 30 30 30 30 Monofunctional urethane acrylate 35 42 33 twenty four 42 42 42 42 Polyfunctional urethane acrylate 0 0 15 30 0 0 0 0 Multifunctional Acrylate 0 0 0 0 0.25 0.34 0.42 0.5 Monofunctional acrylate a 7 17.5 13.75 10 17.25 17.16 17.08 17 Monofunctional acrylate b 14 0 0 0 0 0 0 0 Monofunctional acrylate c 14 0 0 0 0 0 0 0 Monofunctional acrylated 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-curable resin (B) used in Examples and Comparative Examples is shown in Table 3 below. As described above, the moisture-curable resin (L0) uses the urethane resin raw material as the moisture-curable resin (B) as it is, and other than that, the reaction products of the following urethane resin raw materials and polyols are used as the moisture-curable resin. Air-curable resin (B). [table 3] PC urethane resin raw material (parts by mass) PC polyol (parts by mass) Moisture curable resin (PC-L0) 100 0 Moisture curable resin (PC-L10) 90 10 Moisture curable resin (PC-L15) 85 15 Moisture curable resin (PC-L20) 80 20 Moisture curable resin (PC-L25) 75 25 Moisture curable resin (PC-L30) 70 30 Moisture curable resin (PC-L35) 65 35

[Table 4] ET urethane resin raw material (parts by mass) ET polyol (parts by mass) Moisture curable resin (ET-L25) 75 25

[table 5] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 Composition (parts by mass) Acrylic A 40 - - - - - - - - - - - - - - - Acrylic B - 40 40 40 40 40 40 40 - - - 40 40 - - - Acrylic C - - - - - - - - - - - - - 40 - - Acrylic D - - - - - - - - - - - - - - 40 - Acrylic E - - - - - - - - 40 - - - - - - - Acrylic resin F - - - - - - - - - 40 - - - - - - Acrylic G - - - - - - - - - - 40 - - - - - Acrylic resin H - - - - - - - - - - - - - - - 40 Moisture curable resin (PC-L0) - - - - - - - - - - - 60 - - - - Moisture curable resin (PC-L10) - 60 - - - - - - - - - - - - - - Moisture curable resin (PC-L15) - - 60 - - - - - - - - - - - - - Moisture curable resin (PC-L20) - - - 60 - - - - - - - - - - - - Moisture curable resin (PC-L25) 60 - - - 60 60 - - 60 60 60 - - 60 60 60 Moisture curable resin (ET-L25) - - - - - - 60 - - - - - - - - - Moisture curable resin (PC-L30) - - - - - - - 60 - - - - - - - - Moisture curable 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 Curable 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 composition [Pa·s] (5.0 rpm) 110 37 44 73 125 132 240 457 130 133 129 19 750 247 499 125 Gel swelling ratio (W1/W2) 40.5 38.7 36.6 37.5 31.2 26.7 44.6 30.6 20.8 20 16 60.7 34.1 13.2 9.9 14.7 Inside-out ratio [a/b] 0.91 0.94 0.94 0.93 0.88 0.9 0.91 0.68 0.82 0.71 0.63 0.97 0.52 0.55 0.39 0.56 Initial Adhesion 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 Adhesion Evaluation A B B A A B B A B B B C C C C C Final bonding force [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 Adhesion Evaluation A A A A A A A A A A A A A B B B

The light- and moisture-curable resin compositions of Examples 1 to 10 contain the radically polymerizable compound (A), the moisture-curable resin (B), and the photopolymerization initiator (C), and the gel swelling ratio and The 25°C viscosity is within a specific range, whereby the initial adhesion becomes excellent. On the other hand, in Comparative Examples 1 to 5, since at least any one of the gel swelling ratio and the viscosity at 25° C. was outside the specific range, the initial adhesive force could not be improved.

10: Moisture-curable resin composition 11: Aluminum substrate 12: glass plate 20: Light and moisture curable resin composition 21: Aluminum substrate 22: glass plate 23: Sample for Adhesion Evaluation

Fig. 1 is a conceptual diagram showing a method of measuring the internal-internal ratio a/b. 2( a ) is a plan view and FIG. 2( b ) is a side view.

Claims (10)

A light and moisture curable resin composition comprising a radically polymerizable compound (A), a moisture curable resin (B) and a photopolymerization initiator (C), and obtained by the following (1) to (4) ), the gel swelling ratio (W1/W2) determined by the measurement method shown in Pa·s or less: (1) Apply 1.0 g of light and moisture-curable resin composition to a release PET film with a thickness of 1.5 mm, and irradiate 1000 mJ/cm ² of ultraviolet light to photo-harden; ( 2) The photocured light and moisture-curable resin composition was peeled from the above-mentioned mold release PET film, and immersed in THF at 25°C for 48 hours; (3) The photocured light and moisture after dipping were cured The resin composition was taken out on a 200-mesh wire mesh, and washed with new THF for 5 times, and then the weight (W1) of the gel remaining in the swollen state on the above-mentioned wire mesh was measured; (4) Make the above swollen state The gel was dried at 100° C. for 2 hours to volatilize THF, and the weight (W2) of the dried gel was measured to obtain a gel swelling ratio (W1/W2). The light and moisture-curable resin composition according to claim 1, wherein it is photocured by coating it on an aluminum substrate with a line width of 1.0 mm and irradiating it with ultraviolet rays of 1000 mJ/cm ² . When the glass plate is crimped at 0.08 MPa for 120 seconds, if the average width of the bonding portion on the glass plate side is a and the average width of the bonding portion on the aluminum substrate side is b, a/b is 0.58 Above and below 0.99. The light and moisture-curable resin composition according to claim 1 or 2, wherein the moisture-curable resin (B) contains a moisture-curable urethane resin. The light and moisture-curable resin composition according to any one of claims 1 to 3, wherein the moisture-curable resin (B) has a weight average molecular weight of 7,500 or more and 24,000 or less. The light-and-moisture-curable resin composition according to any one of claims 1 to 4, wherein the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound. The light-and-moisture-curable resin composition according to claim 5, which contains 90 parts by mass or more of the monofunctional radically polymerizable compound with respect to 100 parts by mass of the radically polymerizable compound (A). The light and moisture curable resin composition according to any one of claims 1 to 6, which further comprises a filler (D). An adhesive for electronic parts, comprising the light- and moisture-curable resin composition of any one of claims 1 to 7. A hardened product, which is a hardened product of the light-and-moisture-curable resin composition of any one of claims 1 to 8. An electronic part comprising the hardened product of claim 9.

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