TW202313708A - Photo/moisture-curable resin composition, adhesive for electronic components, cured body, and electronic component - Google Patents

Abstract

This photo/moisture-curable resin composition includes a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having at least three isocyanate groups within the molecule thereof.

Description

Light and moisture curable resin composition, adhesive for electronic parts, cured body, and electronic parts

The present invention relates to a light and moisture curable resin composition, an adhesive for electronic parts, a hardened body, and electronic parts.

In recent years, electronic components such as semiconductor chips have been required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor chips are sometimes bonded through an adhesive layer to manufacture a laminate of semiconductor chips. In addition, as various mobile devices with display elements are becoming more and more popular, as a means of miniaturizing display elements, narrower bezels of image display parts (hereinafter, also referred to as "narrow bezel design") are being carried out. In these applications, light and moisture-curing adhesives are being used instead of double-sided tapes in response to miniaturization and narrower frames.

As a light and moisture curable adhesive, for example, Patent Document 1 discloses a light and moisture curable resin composition, which is characterized in that it contains: a radical polymerizable compound, a moisture curable urethane resin , photoradical polymerization initiator, and moisture remover. Here, the water removal agent is blended for the purpose of improving storage stability, etc., and examples include at least one group selected from the group consisting of isocyanate, isothiocyanate, and carbodiimide groups. compound. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2015/111567

[Problem to be Solved by the Invention]

Generally speaking, it is more common to change the light and moisture-curing adhesive into a B-stage state by photocuring, and to make the adherend bond with the light-moisture-curing adhesive in the B-stage state Adhere and bond temporarily, after that, the adherends are formally bonded to each other by moisture hardening. Also, depending on the use environment, it is sometimes required that the light and moisture-curing adhesive can maintain a high adhesive force (final heat-resistant adhesive force) even in a high-temperature environment after formal bonding. For example, when it is used for electronic parts, it may be heated to a high temperature due to the heat emitted by the electronic parts, so it may be necessary to improve the final heat-resistant adhesive force.

However, depending on the composition of the light and moisture curing type adhesive, the final heat-resistant adhesive strength after formal bonding may not be sufficient. For example, since the adhesive force (initial adhesive force) of light and moisture-curing adhesives in the B-stage state immediately after light-curing is often insufficient, it is considered to increase the molecular weight of the prepolymer contained in it, etc. And improve the initial adhesion. However, if the molecular weight of the prepolymer is increased, the block strength of the cured product will decrease, and the final heat-resistant adhesive force will tend to decrease.

Therefore, an object of the present invention is to provide a light and moisture curable resin composition having good heat-resistant adhesive force after moisture curing. [Technical means to solve the problem]

所構成之群中之至少1種。 [22]如上述[1]至[21]中任一項所記載之光與濕氣硬化型樹脂組成物，其中，上述化合物（D）係選自由多異氰酸酯之縮二脲改質物、多異氰酸酯之異氰尿酸酯改質物、多異氰酸酯之多元醇改質物、及聚合MDI所構成之群中之至少1種。 [23]如上述[1]至[22]中任一項所記載之光與濕氣硬化型樹脂組成物，其中，上述化合物（D）係選自由多異氰酸酯之異氰尿酸酯改質物、及聚合MDI所構成之群中之至少1種。 [24]如上述[1]至[23]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0.1 MPa以上。 [25]如上述[1]至[24]中任一項所記載之光與濕氣硬化型樹脂組成物，其最終耐熱接著力為1.0 MPa以上。 [26]如上述[1]至[25]中任一項所記載之光與濕氣硬化型樹脂組成物，其中，相對於上述自由基聚合性化合物（A）與上述濕氣硬化性樹脂（B）之合計100質量份，上述化合物（D）之含量為0.1質量份以上且10質量份以下。 [27]一種電子零件用接著劑，其係由上述[1]至[26]中任一項所記載之光與濕氣硬化型樹脂組成物所構成。 [28]一種硬化體，其係上述[1]至[26]中任一項所記載之光與濕氣硬化型樹脂組成物之硬化體。 [29]一種電子零件，其包含上述[28]所記載之硬化體。 [發明之效果] As a result of intensive studies, the present inventors found that the radical polymerizable compound (A), moisture curable resin (B) and photopolymerization initiator ( In addition to C), the compound (D) which has 3 or more isocyanate groups in a molecule|numerator can solve the said subject, and the following this invention was completed. That is, the present invention provides the following [1] to [29]. [1] A photo- and moisture-curable resin composition comprising: a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and 3 Compound (D) with more than one isocyanate group. [2] The light and moisture curable resin composition according to the above [1], wherein the compound (D) includes a compound having five or more isocyanate groups in a molecule. [3] The light and moisture curable resin composition described in the above [1] or [2], which is coated on an aluminum substrate with a line width of 1.0 mm, and irradiated with ultraviolet rays of 1000 mJ/cm ² to make it light In the hardened state, when the glass plate is pressed 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, Then, a/b is not less than 0.5 and not more than 0.99. [4] The light and moisture curable resin composition as described in any one of [1] to [3] above, wherein the viscosity is measured using a cone-plate viscometer at 25°C and 5.0 rpm. The viscosity is above 40 Pa·s and below 600 Pa·s. [5] The light and moisture curable resin composition according to any one of the above [1] to [4], wherein the moisture curable resin (B) includes a moisture curable urethane resin. [6] The light and moisture curable resin composition according to any one of the above [1] to [5], wherein the moisture curable urethane resin has a polycarbonate skeleton, a polyether skeleton, And at least any moisture-curable urethane resin among the polyester skeletons. [7] The light and moisture curable resin composition according to any one of the above [1] to [6], wherein the moisture curable urethane resin has a polycarbonate skeleton and is moisture curable. Urethane resin. [8] The light and moisture curable resin composition according to any one of [1] to [7] above, wherein the moisture curable resin (B) has a weight average molecular weight of 7,500 to 24,000 . [9] The light and moisture curable resin composition according to any one of [1] to [8] above, wherein the radically polymerizable compound (A) includes a monofunctional radically polymerizable compound. [10] The light and moisture curable resin composition as described in [9] above, which contains 90 parts by mass or more of the monofunctional radically polymerizable compound relative to 100 parts by mass of the radically polymerizable compound (A). . [11] The light and moisture curable resin composition according to the above [9] or [10], wherein the monofunctional radically polymerizable compound contains a nitrogen-containing compound. [12] The light and moisture curable resin composition according to the above [11], wherein the monofunctional radically polymerizable compound includes a chain nitrogen-containing compound. [13] The light and moisture curable resin composition according to the above [11] or [12], wherein the monofunctional radically polymerizable compound includes a cyclic nitrogen-containing compound. [14] The light and moisture curable resin composition as described in [13] above, wherein the mass ratio of the nitrogen-containing compound having a cyclic structure to the nitrogen-containing compound having a chain structure (cyclic/chain) ) is not less than 0.1 and not more than 2.0. [15] The light and moisture curable resin composition as described in any one of the above [11] to [14], wherein, as the monofunctional free Content of the nitrogen-containing compound of a base polymeric compound is 10 mass parts or more and 95 mass parts or less. [16] The light and moisture curable resin composition according to any one of [11] to [15] above, wherein the monofunctional radically polymerizable compound contains, in addition to the nitrogen-containing compound, a monofunctional Functional (meth)acrylate compound. [17] The light and moisture curable resin composition as described in [16] above, wherein the monofunctional (meth)acrylate compound is selected from the group consisting of alkyl (meth)acrylates, alicyclic structure-containing At least one of the group consisting of (meth)acrylates and aromatic ring-containing (meth)acrylates. [18] The light and moisture curable resin composition as described in the above [17], wherein, based on 100 parts by mass of the radical polymerizable compound (A), an alkyl (meth)acrylate, an alicyclic structure The total content of the (meth)acrylate and the (meth)acrylate containing an aromatic ring is 5 mass parts or more and 90 mass parts or less. [19] The light and moisture curable resin composition according to any one of the above [1] to [18], wherein the moisture curable resin (B) is ) The mass ratio (B/A) is not less than 30/70 and not more than 90/10. [20] The light and moisture curable resin composition according to any one of [1] to [19] above, further comprising a filler (E). [21] The light and moisture curable resin composition according to any one of [1] to [20] above, 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-oxothiophene

At least one of the formed group. [22] The light and moisture curable resin composition according to any one of [1] to [21] above, wherein the compound (D) is selected from biuret-modified polyisocyanate, polyisocyanate At least one of the group consisting of modified isocyanurate, polyol modified polyisocyanate, and polymerized MDI. [23] The light and moisture curable resin composition according to any one of [1] to [22] above, wherein the compound (D) is selected from the group consisting of isocyanurate-modified polyisocyanate, and at least one of the group consisting of polymeric MDI. [24] The light and moisture curable resin composition according to any one of the above [1] to [23], which has an initial adhesive force of 0.1 MPa or more. [25] The light and moisture curable resin composition according to any one of [1] to [24] above, which has a final heat-resistant adhesive force of 1.0 MPa or more. [26] The light and moisture curable resin composition according to any one of the above [1] to [25], wherein the radical polymerizable compound (A) and the moisture curable resin ( B) The content of the said compound (D) is 0.1 mass part or more and 10 mass parts or less for 100 mass parts of total. [27] An adhesive for electronic parts comprising the light and moisture curable resin composition described in any one of [1] to [26]. [28] A cured body of the light and moisture curable resin composition described in any one of [1] to [26] above. [29] An electronic component comprising the hardened body described in the above [28]. [Effect of Invention]

According to the present invention, it is possible to provide a light and moisture curable resin composition having good heat-resistant adhesive force after moisture curing.

Hereinafter, the present invention will be described in detail with reference to embodiments. ＜Light and Moisture Curing Type Resin Composition＞ The light and moisture curable resin composition of the present invention comprises a radically polymerizable compound (A), a moisture curable resin (B), a photopolymerization initiator (C), and three or more isocyanates in the molecule. Acid-based compounds (D).

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). By containing the radically polymerizable compound (A), photocurability is imparted to the light and moisture curable resin composition. Since the photo- and moisture-curable resin composition has photocurability, a certain adhesive force can be imparted only by light irradiation, so that a certain initial adhesive force can be ensured. What is necessary is just to have a radical polymerizable functional group in a molecule|numerator as a radical polymerizable compound (A). As the radical polymerizable functional group, a compound having an unsaturated double bond is suitable, and a (meth)acryl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned.

Among the above, a (meth)acryl group is suitable from the viewpoint of adhesiveness, that is, it is preferable that the radically polymerizable compound (A) contains a compound having a (meth)acryl group. In addition, a compound having a (meth)acryl group may also be referred to as a "(meth)acrylic compound" below. Also, in this specification, "(meth)acryl" refers to acryl or (meth)acryl, "(meth)acryl" refers to acryl or methacryl, and other similar The same is true of the term.

The radically polymerizable compound (A) may include a monofunctional radically polymerizable compound having one radically polymerizable functional group in one molecule, a polyfunctional radically polymerizable compound having two or more radically polymerizable functional groups in one molecule One or both of radical polymerizable compounds, but from the viewpoint of improving the initial adhesive force of the light- and moisture-curable resin composition, it is preferable to include a monofunctional radical polymerizable compound. Moreover, it is more preferable that a radically polymerizable compound (A) contains at least a monofunctional (meth)acrylic-type compound among (meth)acrylic-type compounds as a monofunctional radically polymerizable compound. Furthermore, the monofunctional radically polymerizable compound may be a prepolymer having a repeating unit by polymerization, but generally, a monofunctional monomer not having a repeating unit may be used.

In the light and moisture curable resin composition, the monofunctional radically polymerizable compound may be, for example, 50 to 100 parts by mass relative to 100 parts by mass of the radically polymerizable compound (A). Also, in order to increase the initial adhesive force of the light and moisture curable resin composition, it is preferable that the light and moisture curable resin composition contains more monofunctional radically polymerizable compounds. Specifically, the light and moisture curable resin composition preferably 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), and preferably It contains 95 mass parts or more, More preferably, it contains 100 mass parts.

[Monofunctional radically polymerizable compound] (nitrogen-containing compounds) It is preferable that the radically polymerizable compound (A) contains a nitrogen-containing compound as the monofunctional radically polymerizable compound. By using the nitrogen-containing compound, the initial adhesive force of the light and moisture curable resin composition becomes good. The photo- and moisture-curable resin composition is photocured by irradiating active energy rays such as ultraviolet rays after being applied to an adherend. In this case, photocuring is usually performed in the presence of oxygen as described later. It is presumed that when the radically polymerizable compound (A) contains a nitrogen-containing compound, it is photocured appropriately even in the presence of oxygen, whereby the initial adhesive force becomes favorable.

The nitrogen-containing compound may contain one or both of a chain nitrogen-containing compound and a ring-shaped nitrogen-containing compound, but it is based on the viewpoint of making the initial adhesive force of the light and moisture-curing resin composition better , preferably contains a nitrogen-containing compound having a ring structure, and more preferably uses a chain nitrogen-containing compound and a nitrogen-containing compound having a ring structure in combination.

Examples of nitrogen-containing compounds having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam; N-acryloylmorph Compounds containing a morpholine skeleton such as morpholino; cyclic imide compounds such as N-(meth)acryloxyethylhexahydrophthalimide, etc. Among these, amido group-containing compounds such as N-vinylcaprolactam are more preferable. Furthermore, in this specification, a nitrogen-containing compound having a ring structure is also referred to as a cyclic nitrogen-containing compound, and a radically polymerizable compound containing a nitrogen atom among the atoms constituting the ring itself is referred to as a cyclic nitrogen-containing compound, except for Other nitrogen-containing compounds are chain nitrogen-containing compounds.

Examples of chain nitrogen-containing compounds include dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, (meth)acrylic acid Aminoethyl ester, dimethylaminoethyl (meth)acrylate and other chain amino-containing (meth)acrylates; diacetone acrylamide, N,N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, methacrylamide and other chain (meth)acrylamide compounds; N - Vinyl acetamide and the like.

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

As the monofunctional urethane (meth)acrylate, for example, one obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be used. Examples of (meth)acrylic acid derivatives having a hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono(meth)acrylates of dihydric alcohols such as trihydric alcohols; or mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, etc.

Examples of isocyanate compounds used to obtain urethane (meth)acrylates include alkane monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate; cyclopentane isocyanate, cyclohexane isocyanate, and isophorone Aliphatic monoisocyanate such as cyclic aliphatic monoisocyanate such as monoisocyanate. More specifically, the monofunctional urethane (meth)acrylate is preferably an urethane (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compound with a diol mono(meth)acrylate , As a more suitable specific example thereof, 1,2-ethanediol-1-acrylate 2-(N-butyl carbamate) can be mentioned. The chain-like nitrogen-containing compound is preferably composed of the above-mentioned monofunctional amine ester (meth)acrylate, and it is also preferred to combine the monofunctional amine ester (meth)acrylate with the addition of (meth)acrylic Compounds other than monofunctional amine ester (meth)acrylates such as amide compounds are used in combination.

In the light and moisture curable resin composition, from the viewpoint of improving the initial adhesive force of the light and moisture curable resin composition, with respect to 100 parts by mass of the radically polymerizable compound (A), as a single The content of the nitrogen-containing compound of the functional radical polymerizable compound is preferably at least 10 parts by mass, more preferably at least 30 parts by mass, further preferably at least 50 parts by mass, further preferably at least 60 parts by mass, most preferably at least 75 parts by mass parts by mass or more. In addition, in order to contain an appropriate amount of "radical polymerizable compound (A) other than the nitrogen-containing compound", the content of the nitrogen-containing compound as the monofunctional radical polymerizable compound is preferably 95 parts by mass or less, more preferably Preferably, it is 90 mass parts or less, More preferably, it is 85 mass parts or less.

When the monofunctional radical polymerizable compound contains a chain nitrogen-containing compound and a nitrogen-containing compound with a ring structure, the nitrogen-containing compound with a ring structure in the monofunctional radical polymerizable compound is The mass ratio (cyclic/chain) of nitrogen-containing compounds is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.5, still more preferably from 0.4 to 1.2. By setting the mass ratio of rings/chains within the above range, the initial adhesive force of the light and moisture curable resin composition can be improved.

(Monofunctional radically polymerizable compounds other than nitrogen-containing compounds) The monofunctional radically polymerizable compound contained in the radically polymerizable compound (A) preferably contains compounds other than the above-mentioned nitrogen-containing compounds (hereinafter also referred to as nitrogen-free compounds). When the radically polymerizable compound (A) contains a nitrogen-free compound as the 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 has a radically polymerizable functional group, but is preferably a monofunctional (meth)acrylic compound, and among them, (meth) ) acrylate compounds. As a monofunctional (meth)acrylate compound, the alkyl (meth)acrylate, the (meth)acrylate containing an alicyclic structure, the (meth)acrylate containing an aromatic ring, etc. are mentioned. These may be used alone or in combination of two or more. Among them, one or both of alkyl (meth)acrylate and aromatic ring-containing (meth)acrylate is preferably used. . With respect to 100 parts by mass of the radically polymerizable compound (A), the alkyl (meth)acrylate in the radically polymerizable compound (A), the (meth)acrylate containing an alicyclic structure, and the aromatic ring-containing The total content of (meth)acrylates is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, further preferably at least 15 parts by mass. Moreover, the said content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, still more preferably 40 parts by mass or less, most preferably 25 parts by mass or less.

Examples of the alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate base) isobutyl acrylate, tertiary butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Base) isononyl acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, etc. The carbon number of the alkyl group is 1 ~18 Alkyl (meth)acrylates. Examples of (meth)acrylates containing an alicyclic structure include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3-(meth)acrylate, (meth)acrylates having an alicyclic structure, such as 3,5-trimethylcyclohexyl, isobornyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. Furthermore, the alicyclic structure is a ring structure in which the ring constituting element is composed of carbon atoms. Examples of aromatic ring-containing (meth)acrylates include: phenyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; base) phenoxyethyl acrylate, etc., and phenoxyalkyl (meth)acrylates, etc.

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

烷環之(甲基)丙烯酸酯，可例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，較佳為使用含氧雜環丁烷環之(甲基)丙烯酸酯、或含四氫呋喃環之(甲基)丙烯酸酯中之任一種，亦較佳為併用該等。 As the monofunctional (meth)acrylate compound, other than alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate can also be used. As the (meth)acrylate compound, for example, a cyclic ether group-containing (meth)acrylate can be used. Examples of cyclic ether group-containing (meth)acrylates include epoxy rings, oxetane rings, tetrahydrofuran rings, dioxolane (dioxolane) rings, dioxane rings, and dioxane rings.

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

The (meth)acrylate of an alkane ring may, for example, be cyclic trimethylolpropane formal (meth)acrylate or the like. As the (meth)acrylate containing a cyclic ether group, it is preferable to use any one of (meth)acrylate containing an oxetane ring or (meth)acrylate containing a tetrahydrofuran ring. These are preferably used in combination.

Also, as monofunctional (meth)acrylate compounds, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; (meth)acrylate-2-methoxyethyl, (meth)acrylate-2-ethoxy Alkoxyalkyl (meth)acrylate such as ethyl ethyl ester, 2-butoxyethyl (meth)acrylate, etc.; methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol ( Alkoxyethylene glycol (meth)acrylate such as meth)acrylate; Methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxy Polyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxylated diethylene glycol (meth)acrylate, ethoxylated triethylene glycol (meth)acrylate , Polyoxyethylene-based (meth)acrylates such as ethoxy polyethylene glycol (meth)acrylate, and the like. Moreover, carboxyl group-containing (meth)acrylic compounds, such as acrylic acid and methacrylic acid, etc. can also be used as a monofunctional (meth)acrylic compound.

[Compounds other than monofunctional radically polymerizable compounds] As long as the effects of the present invention are exhibited, the radically polymerizable compound (A) may contain a polyfunctional radically polymerizable compound. As a polyfunctional radically polymerizable compound, a difunctional (meth)acrylate compound, a trifunctional or more (meth)acrylate compound, a difunctional or more amine ester (meth)acrylate, etc. are mentioned.

Examples of bifunctional (meth)acrylate compounds include: 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2- Ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate , polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide addition bis Phenol A di(meth)acrylate, Propylene oxide added bisphenol A di(meth)acrylate, Ethylene oxide added bisphenol F di(meth)acrylate, Di(meth)acrylate di(meth)acrylate Methylol dicyclopentadienyl ester, neopentyl glycol di(meth)acrylate, (meth)acrylate-2-hydroxy-3-(meth)acryloxypropyl ester, carbonate diol diol (meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol Alcohol di(meth)acrylate, etc.

Moreover, as a trifunctional or more functional (meth)acrylate compound, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide added trimethylolpropane tri(meth)acrylic acid ester, propylene oxide added trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, neopentylitol tri(meth)acrylate, Glyceryl tri(meth)acrylate, Propylene oxide added glyceryl tri(meth)acrylate, Tri(meth)acryloxyethyl phosphate, Di-trimethylolpropane tetra(meth)acrylate ester, neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, etc.

As the difunctional or higher urethane (meth)acrylate, for example, one obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be used. Examples of (meth)acrylic acid derivatives having a hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono(meth)acrylates of dihydric alcohols such as trihydric alcohols; mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin; or bis Epoxy (meth)acrylates such as phenol A type epoxy (meth)acrylates, etc.

Examples of isocyanate compounds for obtaining urethane (meth)acrylate include: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate , trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylidine diisocyanate, xylylene diisocyanate Diisocyanate (XDI), Hydrogenated XDI, Lysine Diisocyanate, Triphenylmethane Triisocyanate, Tris(isocyanatophenyl)phosphorothioate, Tetramethylxylylene Diisocyanate, 1,6,11 -Polyisocyanate compounds such as undecane triisocyanate.

In addition, as the isocyanate compound, a chain-extended polyisocyanate compound (modified polyol) obtained by reacting a polyol with an excess of isocyanate compound can also be used. Here, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. wait. 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, and moisture-curable cyanoacrylate resins. Among them, It is preferably any one of a moisture-curable urethane resin and a hydrolyzable silicon group-containing resin, more preferably a moisture-curable urethane resin. These may be used individually by 1 type, and may use 2 or more types together.

(moisture curable urethane resin) Moisture curable urethane resin can be obtained by reacting the polyol compound which has 2 or more hydroxyl groups in 1 molecule, and the polyisocyanate compound which has 2 or more isocyanate groups in 1 molecule. The moisture-curable urethane resin only needs to have isocyanate groups in the molecule, and the isocyanate groups in the molecule react with moisture in the air or in the adherend to harden. Moisture-curable urethane resins may have only one isocyanate group in one molecule, or may have two or more isocyanate groups, but moisture-curable urethane resins preferably have one isocyanate group in one molecule Or 2 isocyanate groups, More preferably, it has 2. Moreover, an isocyanate group is not specifically limited, What is necessary is just to be provided in the terminal of a moisture curable urethane resin, For example, it can be provided in both terminals.

The reaction between the above-mentioned polyol compound and polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound, which is [NCO]/[OH] = range of 2.0 to 2.5". As the polyol compound used as the raw material of the moisture-curable urethane resin, known polyol compounds commonly used in the production of polyurethane can be used, for example, polyester polyol, polyether polyol, polyalkylene Polyols, polycarbonate polyols, 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, and more preferably has a polycarbonate skeleton or a polyether skeleton. At least one of the moisture-curable urethane resins with a skeleton, and more preferably a moisture-curable urethane resin with a polycarbonate skeleton. Since the moisture-curable urethane resin has a polycarbonate skeleton, heat resistance, mechanical strength, etc. become high, and both the initial adhesive force and the final heat-resistant adhesive force tend to be excellent. Furthermore, it is also possible to provide a light and moisture curable resin composition excellent in weather resistance, moisture resistance, etc. of the cured product.

(moisture curable urethane resin with polycarbonate skeleton) In 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 polyol compound. The moisture curable urethane resin having a polycarbonate skeleton can be obtained, for example, by combining a polycarbonate polyol having two or more hydroxyl groups in one molecule and a polyisocyanate having two or more isocyanate groups in one molecule. obtained by reacting compounds. 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. When R is an aliphatic saturated hydrocarbon group, heat resistance becomes favorable easily. Moreover, yellowing etc. are hard to generate|occur|produce due to thermal deterioration etc., and weather resistance becomes favorable also. R composed 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. Also, R in the chain structure may be linear or branched. n is preferably from 5 to 200, more preferably from 10 to 150, and still more preferably from 20 to 50. R is preferably 5-12. In addition, R contained in the polycarbonate polyol constituting the moisture-curable urethane resin may be used alone or in combination of two or more. When two or more are used in combination, at least a part thereof is preferably a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms. The chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms is preferably 6-12 carbon atoms, more preferably 6-10 carbon atoms, and still more preferably 6-8 carbon atoms.

Specific examples of R may be linear chains such as tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc., or For example, it is a branched chain such as methylpentamethylene such as 3-methylpentamethylene, methyloctamethylene, or the like. A plurality of Rs in one molecule may be the same as 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, a polycarbonate polyol may be a copolymer containing R of 6 or less carbon atoms and R of 7 or more carbon atoms in one molecule. In this case, any R may be a chain aliphatic saturated hydrocarbon group. . In addition, R may contain a linear saturated aliphatic hydrocarbon group, or may contain a branched saturated aliphatic hydrocarbon group. As R in the polycarbonate polyol, branched and linear R may be used in combination, and linear R may be used alone. In addition, polycarbonate polyol may be used individually by 1 type, and may use it in combination of 2 or more types.

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, and naphthalene-1,5-diisocyanate. Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1,4 -Diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate isocyanates, etc. As the polyisocyanate compound, aromatic polyisocyanate compounds are preferable from the viewpoint of improving the adhesive force after complete curing among them, and diphenylmethane diisocyanate is more preferable among them. Moreover, from the viewpoint of easily imparting stress relaxation properties, flexibility, etc. to the cured product of the light and moisture curable resin composition, an aliphatic polyisocyanate compound is preferable. A polyisocyanate compound may be used individually or in combination of 2 or more types.

(moisture curable urethane resin with polyester backbone) In the moisture-curable urethane resin having a polyester skeleton, a polyester skeleton is introduced into the urethane resin by using a polyester polyol as the polyol compound. Moisture curable urethane resin having a polyester skeleton can be formed by reacting a polyester polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule get. Examples of the above-mentioned polyester polyols include polyester polyols obtained by reacting polycarboxylic acids and polyhydric alcohols, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. wait. Examples of the polyvalent carboxylic acid used as a raw material for polyester polyol include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid dicarboxylic acid), etc. Among them, phthalic acid or adipic acid is preferable from the viewpoint of improving the adhesive force at high temperature more easily. Examples of the polyols used as raw materials for polyester polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 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 improving the adhesive force at high temperature more easily. Moreover, as a polyisocyanate compound, the above-mentioned polyisocyanate compound can be used. In addition, polyester polyol may be used individually by 1 type, and may use it in combination of 2 or more types.

(moisture curable urethane resin with polyether backbone) In 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 polyol compound. The urethane resin which has a polyether skeleton can be obtained by reacting the polyether polyol which has 2 or more hydroxyl groups in 1 molecule, and the polyisocyanate compound which has 2 or more isocyanate groups in 1 molecule.

As polyether polyols, for example, polyethylene glycol, polypropylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers of these or their derivatives or Block copolymers, bisphenol-type polyoxyalkylene modified substances, etc. Here, the bisphenol-type polyoxyalkylene modified substance is the combination of alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and the bisphenol-type molecular skeleton. Polyether polyol obtained by addition reaction of active hydrogen moiety. The polyether polyol can be a random copolymer or a block copolymer. The aforementioned bisphenol-type polyoxyalkylene modified substance is preferably one or more than two kinds of alkylene oxides added to both ends of the bisphenol-type molecular skeleton. 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 frame|skeleton contains the thing obtained using the polyol compound which has a structure represented by following formula (2) further. By using a polyol compound having a structure represented by the following formula (2), it is possible to obtain a light- and moisture-curable resin composition with excellent adhesion, and a cured product that is soft and elongated, and becomes compatible with free radicals. Those having excellent compatibility with the polymerizable compound (A). Among them, it is preferable to use a ring-opening polymer compound composed of polypropylene glycol, tetrahydrofuran (THF), Or a polyether polyol composed of a ring-opening polymer compound of tetrahydrofuran such as 3-methyltetrahydrofuran having a substituent such as a methyl group, more preferably a ring-opening polymer compound of polypropylene glycol and tetrahydrofuran (THF). Generally, the ring-opening polymer compound of tetrahydrofuran (THF) compound is polytetramethylene ether glycol. In addition, polyether polyol may be used individually by 1 type, and may use it 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，所謂l為0之情形，係指與R鍵結之碳直接與氧鍵結。 上述之中，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，特佳為甲基。

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, the case where l is 0 means that the carbon bonded to R is directly bonded to oxygen. Among the above, the total of n and l is more preferably 1 or more, further preferably 1-3. Also, R is more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.

The aforementioned moisture-curable urethane resin having a polycarbonate, polyester, or polyether skeleton may have two or more kinds of skeletons in the molecule, for example, may have a polycarbonate skeleton and a polyester skeleton. In this case, polycarbonate polyol and polyester polyol can be used as the said polyol compound used as a raw material. Similarly, a moisture-curable urethane resin having a polyester skeleton and a polyether skeleton can also be used. Also, the moisture-curable urethane resin can use the above-mentioned urethane resin with isocyanate group, but it is not limited to the urethane resin with isocyanate group, such as the hydrolyzable silicon group-containing resin described later. As explained in , it can also be urethane resin containing hydrolyzable silicon group.

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

式（3）中，R ¹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-OSiR ² ₃（R ²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 are independently substituted alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, or a triorganosilyloxy group represented by -OSiR ² ₃ (R ² is each independently a hydrocarbon group having 1 to 20 carbon atoms). Moreover, 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 above-mentioned hydrolyzable group is not particularly limited, for example, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amine group, an amide group, Acid amido group, aminooxy group, mercapto group, etc. Among them, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferred because of their high activity. Moreover, in terms of relatively stable hydrolyzability and easy handling, alkoxy groups such as methoxy and ethoxy are more preferable, and methoxy and ethoxy are still more preferable. Also, from the viewpoint of safety, the compounds desorbed by the reaction are preferably ethanol, ethoxy group of acetone, and isopropenyloxy group, respectively.

1 to 3 of the above-mentioned hydroxyl groups or the above-mentioned hydrolyzable groups can be bonded to one 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.

From the viewpoint of curability, a in the above formula (3) is preferably 2 or 3, particularly preferably 3. Moreover, a is preferably 2 from the viewpoint of storage stability. In addition, as R ¹ in the above formula (3), for example, alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, trimethyl groups, etc. Silaneoxy, chloromethyl, methoxymethyl, etc. Among them, methyl is preferred.

Examples of the aforementioned hydrolyzable silyl groups include methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetyloxy Dimethoxysilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethyl Oxysilyl, (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (ethoxy Dimethoxysilyl, (1-methoxyethyl)dimethoxysilyl, (aminomethyl)dimethoxysilyl, (N,N-dimethylaminomethyl base) dimethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl, (N- (2-Aminoethyl)aminomethyl)dimethoxysilyl, (Acetyloxymethyl)dimethoxysilyl, (Acetyloxymethyl)diethoxysilyl, etc. .

Examples of hydrolyzable silicon group-containing resins include (meth)acrylic resins containing hydrolyzable silicon groups, organic polymers having hydrolyzable silicon groups at or at molecular chain ends, hydrolyzable silicon-containing Base urethane resin, etc. The hydrolyzable silicon group-containing (meth)acrylic resin preferably has a repeating structural unit derived from a hydrolyzable silicon group-containing (meth)acrylate and/or an alkyl (meth)acrylate in the main chain.

Examples of hydrolyzable silyl group-containing (meth)acrylates include: (meth)acrylate-3-(trimethoxysilyl)propyl, (meth)acrylate-3-(triethoxy) Silyl)propyl, (meth)acrylate-3-(methyldimethoxysilyl)propyl, (meth)acrylate-2-(trimethoxysilyl)ethyl, (meth)acrylate -2-(triethoxysilyl)ethyl ester, 2-(methyldimethoxysilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (methoxysilyl) base) triethoxysilyl methyl acrylate, (methyldimethoxysilyl) methyl (meth)acrylate, etc. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-(meth)acrylate Decyl ester, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, etc.

As a method for producing a hydrolyzable silicon group-containing (meth)acrylic resin, specifically, for example, the hydrolyzable silicon group-containing (meth)acrylate system described in International Publication No. 2016/035718 Polymer synthesis methods, etc. The aforementioned organic polymer having a hydrolyzable silyl group at a molecular chain terminal or at a molecular chain terminal position has a hydrolyzable silyl group at least any one of the terminal of the main chain and the terminal of the side chain. The skeleton structure of the said main chain is not specifically limited, For example, a saturated hydrocarbon type polymer, a polyoxyalkylene type polymer, (meth)acrylate type polymer etc. are mentioned.

Examples of the above-mentioned polyoxyalkylene-based polymers include polyoxyethylene-polyoxypropylene copolymers having a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, and polyoxyethylene-polyoxypropylene copolymers. structure, polyoxypropylene-polyoxybutylene copolymer structure, etc. As a method for producing the above-mentioned organic polymer having a hydrolyzable silicon group at the end of the molecular chain or at the end of the molecular chain, specifically, for example, the method described in International Publication No. 2016/035718 that only at the end of the molecular chain or at the end of the molecular chain can be cited. A method for synthesizing an organic polymer having a crosslinkable silicon group at the end of the molecular chain. In addition, as another method for producing the above-mentioned organic polymer having a hydrolyzable silyl group at the end of the molecular chain or at the end of the molecular chain, for example, the reactive silyl group-containing polymer described in International Publication No. 2012/117902 can be cited. A method for synthesizing an oxyalkylene-based polymer, etc.

As a method for producing the above-mentioned hydrolyzable silicon group-containing urethane resin, for example, a method such as the following method can be mentioned: when a polyol compound and a polyisocyanate compound are reacted to produce the urethane resin, and a silicon-containing compound such as a silane coupling agent The method of reacting the compound of the group. Specifically, for example, the synthesis method of the urethane oligomer which has a hydrolyzable silicon group as described in Unexamined-Japanese-Patent No. 2017-48345, etc. are mentioned.

Examples of the aforementioned silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxy Cyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxy Propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldi 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 individually, or may be used in combination of 2 or more types.

Moreover, a 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 first obtaining a moisture-curable amine having an isocyanate group by the method described above. ester resin (raw material urethane resin), and then react the silane coupling agent with the raw material urethane resin. In addition, the details of the moisture-curable urethane resin which has an isocyanate group are as above-mentioned. As the silane coupling agent that reacts with the raw material urethane resin, it may be used as long as it is appropriately selected from the silane coupling agents exemplified above, but from the viewpoint of reactivity with isocyanate groups, it is preferable to use a Silane coupling agent of mercapto or mercapto groups. As a preferred specific example, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, Methyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanic acid Propyltrimethoxysilane, etc.

Furthermore, a moisture curable resin may have a radically polymerizable functional group. As the radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferable, and a (meth)acryl group is more preferable from the viewpoint of reactivity. In addition, the moisture curable resin which has a radically polymerizable functional group is not included in the above-mentioned radically polymerizable compound, but is handled as a moisture curable resin (B). The moisture-curable resin (B) may be appropriately selected from the above-mentioned various resins, and one type may be used alone, or two or more types may be used in combination.

The weight average molecular weight of the moisture curable resin (B) is preferably not less than 7,500 and not more than 24,000. By setting the weight average molecular weight within the above range, it becomes easy to improve the initial adhesive force of the light and moisture curable resin composition. Moreover, final heat-resistant adhesive force also becomes favorable easily by making it below the said upper limit. From these viewpoints, the weight average molecular weight of the moisture curable resin (B) is more preferably at least 7,800, more preferably at least 10,000, still more preferably at least 11,500; more preferably at most 20,000, and 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 measured by gel permeation chromatography (GPC), and is the value calculated|required by polystyrene conversion.

As described above, the moisture-curable resin may be chain-extended so that the weight average molecular weight becomes a certain value or more. For example, among moisture-curable urethane resins, urethane resins having isocyanate groups obtained by reacting polyol compounds and polyisocyanate compounds having two or more isocyanate groups in one molecule (hereinafter also referred to as It is called "raw material urethane resin"), which can also further react with chain extenders. At this time, the chain extender is used under the condition that the chain extender does not react with all the isocyanate groups of the raw material urethane resin, and the usage amount is appropriately adjusted so that the isocyanate groups remain in the moisture-curing amine. in ester resin. Moreover, the chain extender which reacts with a raw material urethane resin may further react with a 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. Moreover, what is necessary is just to use "the polyol compound of the same kind as the polyol compound used for the synthesis raw material urethane resin" as a polyol compound as a chain extender. Therefore, if the polyol compound used to synthesize the raw material urethane resin is polycarbonate polyol, then polycarbonate polyol can also be used as the chain extender. Regarding the amount of the chain extender used, when the total amount of the raw material urethane resin and the chain extender is 100 parts by mass, for example, it is 5 parts by mass to 40 parts by mass, preferably 10 parts by mass to 35 parts by mass. It is not more than 15 parts by mass and not more than 30 parts by mass.

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, it is 40/60 or more and 80/20 or less, Still more preferably, it is 50/50 or more and 70/30 or less. When the mass ratio is within these ranges, it is possible to impart photocurability and moisture curability in a balanced manner to the light and moisture curable resin composition, and it is easy to adjust both the initial adhesive force and the final heat-resistant adhesive force to desired values. within range.

The light and moisture curable resin composition may also contain resin components other than the radically polymerizable compound (A) and the moisture curable resin (B) as resin components within the range that does not impair the effect of the present invention, for example Resin components such as non-curable thermoplastic resins (for example, acrylic resins, urethane resins, etc.), thermosetting resins, etc. may be contained. Ratio of resin components other than radically polymerizable compound (A) and moisture-curable resin (B) relative to 100 parts by mass of the total amount of radically polymerizable compound (A) and moisture-curable resin (B) For example, it is 50 mass parts or less, Preferably it is 30 mass parts or less, More preferably, it is 10 mass parts or less.

等。 作為上述光聚合起始劑之中之市售者，例如可例舉：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. By containing the photopolymerization initiator, the light and moisture curable resin composition is properly provided with photocurability. Examples of photopolymerization initiators include: benzophenone-based compounds, acetophenone-based compounds, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, oxime Ester compounds, benzoin ether compounds, 9-oxosulfur

wait. As commercially available among the above-mentioned photopolymerization initiators, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF); Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photopolymerization initiator in the photo- and moisture-curable resin composition is preferably at least 0.1 parts by mass and at most 10 parts by mass, 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 setting the content of the photopolymerization initiator within these ranges, the obtained photo- and moisture-curable resin composition is excellent in photocurability and storage stability. Moreover, by setting it as the said range, a photoradical polymerization compound can be hardened suitably, and it becomes easy to make adhesive force favorable.

[Compound (D)] The light and moisture curable resin composition of the present invention contains a compound (D) having three or more isocyanate groups in the molecule (hereinafter, may be abbreviated as compound (D) in some cases). By including the compound (D) in the light and moisture-curing resin composition, a cross-linked structure is formed in the moisture-cured product, so the block strength is increased, and the heat-resistant adhesion after moisture-curing (final heat-resistant adhesion) get improved. Therefore, as described above, for example, even if the molecular weight of the moisture-curable resin (B) is increased, the block strength of the cured product does not decrease, and the final heat-resistant adhesive force can become excellent.

The compound (D) should just be a compound other than the above-mentioned moisture curable resin (B), and it should just have 3 or more isocyanate groups. The compound (D) should just be a compound whose molecular weight (formula weight) is 1500 or less, for example. The compound (D) may, for example, be a modified polyisocyanate obtained by reacting a polyisocyanate compound with another compound. Examples of modified polyisocyanate include biuret-modified polyisocyanate compounds, isocyanurate-modified polyisocyanate compounds, glycerin, and trimethylolpropane; Polyols obtained by addition polymerization of alkylene oxides such as alkylene oxides and polyols obtained by reacting with polyisocyanate compounds as adducts, also known as polymethylene polyphenylenes of polymerized MDI Polyisocyanates, etc. Furthermore, at least a part of the isocyanate groups contained in the compound (D) may be temporarily protected by a blocking agent, a uretdione structure, or the like. In this case, when a light and moisture curable resin composition is used, the isocyanate group contained in the compound (D) is reproduced by dissociation of the blocking agent or cleavage of the uretdione structure.

As a polyisocyanate compound used as a raw material in a modified substance, the monomer which does not have a repeating unit is mentioned. The polyisocyanate compound is preferably a diisocyanate compound, specifically, aromatic isocyanates such as toluene diisocyanate, diphenylmethane diisocyanate (MDI), and 1,5-naphthalene diisocyanate; isophorone diisocyanate; , Hexamethylene Diisocyanate, Trimethyl Hexamethylene Diisocyanate, Hydrogenated MDI, Norbornane Diisocyanate, Xylylene Diisocyanate (XDI), Hydrogenated XDI, Lysine Diisocyanate, Tetramethylbenzene Aliphatic isocyanate compounds such as dimethyl diisocyanate, etc. Also, as the compound (D), other than the above-mentioned modified polyisocyanate can be used, such as triphenylmethane triisocyanate, tris(isocyanatophenyl)phosphorothioate, 1,6,11-undecane Polyisocyanate compounds such as triisocyanate. Among the above, modified polyisocyanate is preferred, and among them, modified isocyanurate and polymerized MDI are more preferred.

In addition, the compound (D) only needs to have 3 or more isocyanate groups, and it may be a compound with 3 isocyanate groups. However, in order to increase the crosslink density and further improve the heat-resistant adhesive force after moisture curing, it is preferably It contains the compound which has 4 or more isocyanate groups, More preferably, it contains the compound which has 5 or more isocyanate groups. The upper limit of the number of isocyanate groups in the compound (D) is not particularly limited, for example, it is 10 or less, preferably 8 or less. Examples of the compound having three isocyanate groups include biuret-modified products, isocyanurate-modified products, and polyol-modified products among the above, and isocyanurate-modified products are preferred. Moreover, polymeric MDI is mentioned as a more suitable specific example of the compound which has 4 or more isocyanate groups.

The compound (D) having 3 or more isocyanate groups can also be a mixture of compounds with different numbers of isocyanate groups. Therefore, the number of isocyanate groups in compound (D) can be determined by the average number of isocyanate groups express. The average number of isocyanate groups in the compound (D) should just be 3 or more, and it is preferably 4 or more, more preferably 5 or more, in order to further improve the heat-resistant adhesive force. The upper limit of the average number of isocyanate groups in the compound (D) is not particularly limited, for example, it is 10 or less, preferably 8 or less, more preferably 6.5 or less.

The content of the compound (D) in the photo- and moisture-curable resin composition is preferably 0.1 parts by mass or more relative to 100 parts by mass in total of the radically polymerizable compound (A) and the moisture-curable resin (B). And 10 parts by mass or less. When it is more than the above-mentioned lower limit value, a sufficient crosslinked structure can be formed in the cured product after moisture curing due to the compound (D), and it becomes easy to improve the final heat-resistant adhesive force. Moreover, by setting it as 10 mass parts or less, it can prevent that the initial stage adhesive force falls by the influence of a compound (D). From these viewpoints, the content of the compound (D) is more preferably 0.2 parts by mass or more with respect to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B), and more preferably It is 0.3 mass parts or more; Moreover, it is more preferable that it is 5 mass parts or less, and it is still more preferable that it is 3 mass parts or less.

The light and moisture curable resin composition may contain a diisocyanate compound having two isocyanate groups in addition to the compound (D) having three or more isocyanate groups in the molecule. As a specific example of the diisocyanate compound used here, the diisocyanate compound illustrated as a raw material in the modified polyisocyanate is mentioned. Regarding the above-mentioned modified polyisocyanate, in the production process, the diisocyanate compound used as the raw material may not react and may remain as an unreacted diisocyanate compound, but such unreacted diisocyanate compound may also be It is blended together with the compound (D) into the light and moisture curable resin composition. For example, polymethylene polyphenyl polyisocyanate (polymeric MDI) having 3 or more isocyanate groups can also be blended with MDI as a diisocyanate compound in light and moisture curable resin compositions middle. Furthermore, the content of the diisocyanate compound in the light and moisture curable resin composition is not particularly limited, for example, it may be less than the content of the compound (D) on a mass basis.

[Filler (E)] The light and moisture curable resin composition of the present invention may also contain a filler (E). By containing the filler (E), the light and moisture curable resin composition of the present invention has more suitable thixotropy, and can fully maintain the shape after coating. What is necessary is just to use a particulate form as a filler. The filler (E) is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Among them, silicon dioxide is preferable because the light and moisture curable resin composition to be obtained has excellent ultraviolet transmittance. In addition, the filler (E) may be subjected to hydrophobic surface treatment such as silanization treatment, alkylation treatment, and epoxidation treatment. The filler (E) may be used alone or in combination of two or more. The content of the filler (E) is preferably at least 1 part by mass and at most 25 parts by mass, more preferably 2 parts by mass, relative to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). It is not less than 20 parts by mass, and more preferably not less than 3 parts by mass and not more than 15 parts by mass.

(moisture hardening accelerator catalyst) The light and moisture-curable resin composition may contain a moisture-curing accelerator that accelerates the moisture-curing reaction of the moisture-curable resin (B). By using the moisture-curing accelerating catalyst, the moisture-curing property of the photo- and moisture-curing resin composition is more excellent, and it becomes easy to improve the adhesive force. Specific examples of the moisture curing acceleration catalyst include amine compounds, metal catalysts, and the like. Examples of amine compounds include compounds having a morpholino skeleton such as bis(methylmorpholino)diethyl ether, 4-morpholinopropylmorpholine, and 2,2'-dimorpholinodiethyl ether; Bis(2-dimethylaminoethyl)ether, 1,2-bis(dimethylamino)ethane and other dimethylamino-containing amine compounds with 2 dimethylamino groups; triethylamine, 1, 4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane, etc. Examples of metal-based catalysts 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; Zirconium acetylpyruvate, copper naphthenate, cobalt naphthenate and other metal compounds.

The content of the moisture-curing accelerating catalyst is preferably from 0.01 to 8 parts by mass, more preferably from 0.1 to 5 parts by mass, relative to 100 parts by mass of the moisture-curable resin (B). When the content of the moisture curing accelerating catalyst is within the above range, the effect of accelerating the moisture curing reaction becomes excellent without deteriorating the storage stability of the light and moisture curing resin composition. .

(Colorant) The light and moisture curable resin composition of the present invention may also contain a colorant. As a coloring agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. are mentioned. By containing the colorant in the light and moisture curable resin composition, light-shielding properties and the like are also improved. Among them, titanium black is preferable. Since titanium black has the property of "not only fully blocking light of wavelengths in the visible light region, but also transmitting light of wavelengths near the ultraviolet region", it can prevent the photocurability of light and moisture-curable resin compositions from deteriorating. The content of the colorant in the photo- and moisture-curable resin composition is preferably at least 0.05 parts by mass and 8 It is not more than one mass part, more preferably not less than 0.1 mass part and not more than 2 mass parts. When the content of the coloring agent is within these ranges, the adhesiveness of the light and moisture-curable resin composition can be maintained favorably, and appropriate light-shielding properties can be imparted.

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 to the above-mentioned components. In addition, as a coupling agent, a silane coupling agent, a titanate coupling agent, a zirconate coupling agent etc. are mentioned, Among these, a silane coupling agent is preferable. The light and moisture curable resin composition generally does not contain a solvent, but may contain a solvent as needed within the range that does not impair the effect of the present invention.

[Viscosity at 25°C] The light and moisture curable resin composition of the present invention preferably has a viscosity measured at 25°C and 5.0 rpm using a cone-plate viscometer (hereinafter also referred to as "25°C viscosity") of 40 Pa・s or more and 600 Pa・s or less. The 25°C viscosity of the above moisture-curing resin composition is measured under high shear at 5.0 rpm, and the viscosity is not easily affected by fillers. Therefore, if the viscosity at 25°C is 40 Pa·s or more, there is a tendency that the low molecular weight components contained in the moisture curable resin (B) etc. will decrease, and after light irradiation, the moisture curable resin (B) etc. It becomes difficult to bleed out to the interface, and it is easy to improve the initial adhesion. That is, if the low-molecular-weight moisture-curable resin (B) or the like becomes less likely to seep out to the interface after light irradiation, slipping with the adherend is less likely to occur, and adhesive force is more likely to be exhibited, thereby improving the initial adhesive force. Furthermore, in the present invention, by increasing the viscosity at 25°C, the moisture-curable resin composition contains more high-molecular-weight components, and the content of moisture-curable functional groups can be easily reduced. As a result, the block strength after moisture hardening may be lowered, but by containing the above compound (D), the block strength after moisture hardening is increased, and the final heat-resistant adhesive force is also improved. In addition, even if the above-mentioned viscosity at 25°C is 600 Pa·s or less, it is easy to express the inherent adhesiveness and the like of the moisture curable resin (B), and it is easy to improve the initial adhesive force or the final heat-resistant adhesive force. In addition, by setting the viscosity at 25° C. to 40 Pa·s or more and 600 Pa·s or less, abnormalities such as dripping or inability to apply at room temperature are less likely to occur, and workability is improved.

The 25°C viscosity of the light and moisture curable resin composition is more preferably 45 Pa·s or higher, further preferably 90 Pa·s or higher, further preferably 110 Pa·s or higher; more preferably 500 Pa·s s or less, more preferably 350 Pa·s or less, still more preferably 230 Pa·s or less. When the viscosity at 25° C. is within the above range, it becomes easy to improve workability and initial adhesive force. Moreover, if it is below the above-mentioned upper limit, the molecular weight of the moisture curable resin (A) can be prevented from becoming too high, so it becomes easy to increase the initial adhesive force, and further, the adhesive force becomes lower by moisture curing. If it is high enough, it is easy to improve the final heat-resistant adhesion.

[Inside and outside ratio a/b] Under the specific conditions described later, the light and moisture curable resin composition of the present invention is linearly coated on the aluminum substrate, and after it is photocured by UV, and then pressed to the glass plate, the glass plate is When the average width of the bonding portion on the side is a, and the average width of the bonding portion on the aluminum substrate side is b, a/b (also referred to as "inside-outside ratio a/b") is, for example, 0.5 or more and 0.99 or less. In the light and moisture curable resin composition of the present invention, if the above-mentioned internal and external ratio a/b is set to 0.5 or more, the internal and external ratio a/b becomes large, and it becomes easy to collapse immediately after light curing. The higher the adhesiveness, the higher the initial adhesion to the adherend is likely to be. In addition, by setting the internal/external ratio a/b to 0.99 or less, it is possible to prevent the initial adhesive strength from decreasing due to the cohesion of the light and moisture curable resin composition immediately after photocuring, or excessive collapse. The internal and external ratio a/b is more preferably at least 0.58, more preferably at least 0.63, still more preferably at least 0.7, and more preferably at most 0.95, further preferably at most 0.93. When the inside-outside ratio a/b is within these ranges, it is easy to improve the initial adhesive force.

In the present invention, the internal and external ratio a/b is measured as follows. First, as shown in FIG. 1( a ), a moisture-curable resin composition 10 was applied to an 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 there may be an error of 1.0±0.1 mm. Next, as shown in FIG. 1( b ), ultraviolet rays of 1000 mJ/cm ² were irradiated to the moisture-curable resin composition 10 to cure the moisture-curable resin composition 10 . Immediately thereafter (within 10 seconds), the glass plate 12 is superimposed on the moisture-curable resin composition 10 as shown in FIG. The coating area of 10 was crimped for 120 seconds. After the pressure bonding, the width a1 of the bonding portion between the moisture-curing resin composition 10 and the glass plate 12 was measured. The width a1 was measured at 5 points, and the average value thereof was defined as the average width a. Also, the width b1 of the bonding portion between the moisture-curable resin composition 10 and the aluminum substrate 11 was measured. The width b1 was measured at 5 points, and the average value thereof was defined as the average width b, and the inside-outside ratio a/b was calculated from the average widths a and b. Furthermore, crimping is performed using a weight, and after removing the weight, the width a1 and b1 can be measured after 5 minutes.

The internal and external ratio a/b can be adjusted within the above-mentioned range by adjusting the type of radically polymerizable compound and the like. For example, when the photo- and moisture-curable resin composition contains a large amount of monofunctional radically polymerizable compound as the radically polymerizable compound, the ratio of the crosslinked structure formed after photocuring will decrease, so it can be Increase the inside-outside ratio a/b. Also, for example, when the photo- and moisture-curable resin composition contains a large amount of "radical polymerizable compound having a low glass transition point of the homopolymer" as the radical polymerizable compound, the curing after photocuring The material also becomes soft, so the internal and external ratio a/b can be increased. Furthermore, the inside-outside ratio a/b can also be adjusted with the weight average molecular weight of a moisture curable resin (B).

[adherence] The initial adhesive force of the light and moisture curable resin composition of the present invention may be, for example, not less than 0.05 MPa, but is preferably not less than 0.1 MPa. In addition, the final heat-resistant adhesive force of the light and moisture curable resin composition of the present invention is preferably 1.0 MPa or more. Furthermore, the so-called initial adhesive force refers to the adhesive force at 25°C immediately after the light and moisture-curable resin composition is light-cured; the so-called final heat-resistant adhesive force refers to the light- and moisture-curable resin composition. After hardening, and then placed at 25°C, 50 RH% for 24 hours, the adhesive force was measured at 70°C. The details of the measurement methods of the initial adhesive force and the final heat-resistant adhesive force are described in the examples described later.

If the initial adhesive force of the photo- and moisture-curable resin composition at 25°C is above the above-mentioned lower limit value, the adherends can be temporarily bonded to each other with an adhesive force above a certain level immediately after light curing, and the temporary adhesive force can be improved. Timeliness of operation. Also, if the final heat-resistant adhesive force is 1.0 MPa or more, adherends can be firmly bonded to each other even in a high-temperature environment by temporary bonding followed by permanent bonding using moisture hardening.

In order to further improve the adhesion stability during temporary adhesion, the initial adhesion force of the light and moisture curable resin composition is more preferably 0.2 MPa or more. Also, the initial adhesive force is not particularly limited, but the initial adhesive force may be less than 1.5 MPa, for example, in order to allow easy re-bonding during temporary bonding. In addition, in order to more firmly join the adherends after the actual bonding, the final heat-resistant adhesive force of the light and moisture curable resin composition is more preferably 2.0 MPa or more. The higher the final heat-resistant adhesive force, the better, but it is not particularly limited. For example, it is 20 MPa or less, and may be 10 MPa or less.

As a method for producing the light and moisture curable resin composition of the present invention, for example, a radically polymerizable compound (A), a moisture curable resin (B), a photopolymerization initiator ( C), compound (D), and further, a method of mixing other additives such as a filler, a moisture hardening accelerating catalyst, and a coloring agent if necessary. As a mixer, a homodisper, a homomixer, a universal mixer, a planetary mixer, a planetary mixer, a kneader, a three-roll mill, etc. are mentioned, for example.

Also, as described above, the molecular weight of moisture curable resins such as moisture curable urethane resins may be increased by chain extenders. In this case, for example, the moisture-curable resin (B) is obtained by reacting a raw material resin such as a raw material urethane resin with a chain extender in advance, and thereafter, it can be mixed with a radically polymerizable compound ( A), photopolymerization initiator (C), compound (D) and other raw materials are mixed. Also, by mixing the raw material resin, the chain extender, and the radically polymerizable compound (A), and heating the mixture as necessary, the chain extender and the raw material resin can be reacted to synthesize a moisture curable compound (A). Resin (B). In this case, a mixture of the moisture curable resin (B) and the radically polymerizable compound (A) is obtained, so the photopolymerization initiator (C) and the compound (D) can also be added to the mixture, and then depending on Other additives that need to be blended 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 used as a hardened body after curing. Specifically, as the light and moisture curable resin composition of the present invention, first, it is photocured by light irradiation, for example, becomes a B-stage state (semi-cured state), and then it is cured by moisture , so that it can be completely hardened. Here, in the case where the adherends are bonded after disposing the light and moisture curable resin composition between the adherends, it is applied on an adherend, and thereafter, After irradiating to make it photohardenable, such as in a B-stage state, another adherend is superimposed on the light and moisture curable resin composition in the photohardened state, so that the adherends can be moderately bonded. The force (initial sticking force) is temporarily followed. Thereafter, the light and moisture curable resin composition in the B-stage state is completely cured due to the moisture curable resin being cured by moisture, so that the adherend that overlaps the light and moisture curable resin composition is formally Then, join with sufficient adhesive force.

The application of the light and moisture curable resin composition to the adherend can be performed, for example, by a dispensing device, and is not particularly limited. The light to be irradiated at the time of photocuring is not particularly limited as long as it hardens the radically polymerizable compound, but ultraviolet rays are preferred. In addition, after photocuring, the light and moisture curable resin composition needs to be left in the air for a certain period of time when it is completely cured by moisture. The application of the light and moisture curable resin composition to the adherend is not particularly limited, and it may be performed at around normal temperature, specifically, at a temperature of about 10 to 35°C. By making the 25 degreeC viscosity of the light and moisture curable resin composition of this invention into the said specific range, even if it coats near normal temperature, it can apply|coat easily, and dripping does not generate|occur|produce. Moreover, since the light and moisture curable resin composition of the present invention exhibits an initial adhesive force of a certain value or more immediately after light irradiation, temporary adhesion can be performed immediately after light curing, resulting in good workability.

The light and moisture curable resin composition of the present invention is preferably used as an adhesive for electronic parts. That is, the present invention also provides an adhesive for electronic parts comprising the above-mentioned light and moisture curable resin composition. Therefore, the above-mentioned adherend is preferably various electronic parts constituting electronic equipment. Examples of various electronic components constituting electronic equipment include: various electronic components provided on display elements and constituting electronic circuits; substrates on which the above-mentioned electronic components are mounted, housings constituting electronic equipment, semiconductor chips, and the like. Also, the material of the adherend may be any of metal, glass, plastic, and the like. 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), a box shape, a case shape, etc. .

As described above, the light and moisture curable resin composition of the present invention is preferably used for bonding electronic parts constituting an electronic device to each other. In addition, the light and moisture curable resin composition of the present invention is also preferably used for bonding electronic parts and other parts. With these constitutions, electronic parts have the hardened body of the present invention. In addition, the light and moisture curable resin composition of the present invention is used in the interior of electronic equipment, etc., for example, to obtain assembly parts by bonding substrates to substrates. The assembled part thus obtained has a first substrate, a second substrate, and the hardened body 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 hardened body. Furthermore, it is preferable that at least one electronic component constituting an electronic circuit is mounted on each of the first substrate and the second substrate.

In addition, the light and moisture curable resin composition of the present invention is preferably used for narrow frame applications. For example, in various display devices such as mobile phone display devices such as smartphones, an adhesive is applied to a narrow rectangular frame (i.e., narrow frame) substrate, and the display panel is mounted through the adhesive. For touch panels and the like, the light and moisture curable resin composition of the present invention may be used as the adhesive. 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 is used in the application of semiconductor wafers, for example, bonding semiconductor wafers to each other. [Example]

The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

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 the comparative example was measured by gel permeation chromatography (GPC), and was calculated|required by polystyrene conversion. The GPC measurement system used Shodex KF-806L (manufactured by Showa Denko) as a column. In addition, tetrahydrofuran (THF) was used as a solvent and a mobile phase. Furthermore, the measurement conditions of GPC were a flow rate of 1.0 mL/min and a measurement temperature of 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 (A) and a moisture curable resin (B) as a sample. In this mixture, the peak of the radically polymerizable compound (A) appears on the low-molecular-weight side, and the peak of the moisture-curable resin (B) appears on the high-molecular-weight side. Therefore, moisture curing can be calculated from the peak on the high-molecular-weight side. The weight average molecular weight of the resin (B).

(Inside-outside ratio a/b) The inside-outside ratio a/b was measured by the method described in the manual. In addition, the aluminum substrate and the glass plate used aluminum alloy "A6063S" with a size of 2 mm x 25 mm x 60 mm, and a glass plate with a smooth surface that was ultrasonically cleaned for 5 minutes, respectively. The coating of the moisture-curing resin composition is carried out at room temperature (25°C) using the "SHOTMASTER 300SX" manufactured by Musashi High-Tech Co., Ltd. mm, length 25 mm, and thickness 0.4±0.1 mm, apply it linearly to the aluminum substrate. Next, 1000 mJ/cm ² of ultraviolet light with a wavelength of 405 nm was irradiated at 1000 mW to the applied light and moisture curable resin composition with a linear LED irradiator (manufactured by HOYA Co., Ltd.). The crimping of the glass plate to the aluminum substrate was performed using a weight as a weight, and the widths a1 and b1 were measured 5 minutes after the weight was removed. The widths a1 and b1 after crimping were measured by observing the crimping surface from the side of the glass plate using a microscope.

(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.

(Initial Adhesion) As shown in Figure 2(a) and (b), use the above-mentioned dispensing device, at room temperature (25°C), light and moisture curable resin composition 20 to have a width of 1.0±0.1 mm, length 25 mm, and thickness 0.4±0.1 mm, coated on the aluminum substrate 21. Then, it was photocured by irradiating 1000 mJ/cm ² of ultraviolet rays with a wavelength of 405 nm at 1000 mW with a linear LED irradiator (manufactured by HOYA Co., Ltd.). Thereafter, the glass plate 22 was bonded to the aluminum substrate 21 through the photocuring light and moisture-curing resin composition 20, and was pressed with a weight at 0.08 MPa for 120 seconds to obtain a sample 23 for adhesiveness evaluation. . Thereafter, in an environment of 25°C, using a tensile tester (“tensile compression tester SVZ-50NB”, manufactured by Imada Seisakusho), stretched at a speed of 10 mm/min in the shearing direction S, and measured aluminum The maximum stress when the substrate 21 and the glass plate 22 were peeled off was taken as the initial adhesive force. In addition, it was performed within 150 seconds from the end of photocuring to the start of the tensile test. The initial adhesion was evaluated based on the following evaluation criteria. A: 0.2 MPa or more B: 0.1 MPa or more and less than 0.2 MPa C: less than 0.1 MPa

(Ultimate Heat Resistance Adhesion) In the same way as the initial adhesion, the glass plate was bonded to the aluminum substrate through photocuring light and a moisture-curing resin composition. Thereafter, the samples for adhesiveness evaluation were obtained by leaving at 25° C. and 50 RH% for 24 hours to harden with moisture. Using the sample for adhesive evaluation, except that the ambient temperature was changed from 25°C to 70°C, in the same way as the method of measuring the initial adhesive force, the sample was stretched in the shear direction to measure the peeling of the aluminum substrate and the glass plate. The maximum stress is used as the final heat-resistant adhesive force. A: Above 2.0 MPa B: More than 1.0 MPa and less than 2.0 MPa C: Less than 1.0 MPa

The urethane resin raw material used in each Example and a comparative example was produced by the following method. [Synthesis Example 1] (PC urethane resin raw material) Polycarbonate diol as a polyol compound (compound represented by formula (1), 90 mol% of R is 3-methylpentamethylene, 10 mol% is hexamethylene, Kuraray Corporation 100 parts by mass, trade name "Kuraraypolyol C-1090"), and 0.01 part by mass of dibutyltin dilaurate were placed in a 500 mL capacity separable flask. The inside of the flask was stirred and mixed under vacuum (20 mmHg or less) at 100° C. for 30 minutes. Thereafter, the pressure was set at normal pressure, and 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name "Pure MDI") was put in as a polyisocyanate compound, and stirred at 80° C. for 3 hours to react, thereby obtaining Moisture-curing 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) Put 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-3000") as a polyol compound, and 0.01 part by mass of dibutyltin dilaurate into a 500 mL capacity separable in the flask. The inside of the flask was stirred and mixed under vacuum (20 mmHg or less) at 100° C. for 30 minutes. Thereafter, the pressure was set at normal pressure, and 17.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name "Pure MDI") was put in as a polyisocyanate compound, and stirred at 80° C. for 3 hours to react, thereby obtaining Moisture curable urethane resin with polyether backbone 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 acrylic acid B. Acrylic acid B is what mixed each compound by the blending ratio of Table 2. As the moisture-curing resin (PC-L25), the raw material of PC urethane resin and PC polyol were sequentially added to acrylic acid B in the mass ratio listed in Table 3 to obtain a mixture. 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 reacts with a part of the urethane resin raw material to synthesize a moisture-curing urethane resin that has been chain-extended and has isocyanate groups at both ends. Thus, a mixture of acrylic acid B (radically polymerizable compound) and moisture-curing urethane resin is obtained. In the obtained mixture of acrylic acid B and moisture curable urethane resin, according to the blending in Table 5, add polyfunctional isocyanate a, photopolymerization initiator, and filler and then mix them to obtain light and moisture Hardening type resin composition. With respect to the obtained light and moisture curable resin composition, the viscosity at 25° C., the inside-outside ratio a/b, the initial adhesive force, and the final heat-resistant adhesive force were measured.

[Example 2, 3, 5] It implemented similarly to Example 1 except having used polyfunctional isocyanate b instead of polyfunctional isocyanate a, and having changed the compounding quantity as described in Table 5.

[Example 4] In the obtained mixture of acrylic acid B and moisture curable urethane resin, according to the blending of Table 5, add multifunctional isocyanate b, photopolymerization initiator, filler, and coloring agent and mix, so as to obtain light and The moisture-curable resin composition was carried out in the same manner as in Example 3 except that.

[Example 6] As the moisture curable resin, the moisture curable resin (ET-L25) was used instead of the moisture curable resin (PC-L25) as described in Tables 4 and 5, and it was carried out in the same manner as in Example 3. . That is, as described in Table 4, the urethane resin raw material added to acrylic B, and the blending ratio and types of polyols were changed to obtain a mixture of acrylic B and moisture-curable urethane resin. Example 3 was implemented in the same manner. In addition, as the ET polyol in Table 4, the polytetramethylene ether glycol used in the synthesis example 2 was used.

[Example 7, 8, 9] Except having used acrylic acid C, D, A instead of acrylic acid B, it carried out similarly to Example 3. In addition, acrylic acid C, D, and A were what mixed each compound by the blending ratio of Table 2, respectively.

[Comparative examples 1 to 5] In Comparative Examples 1-5, it implemented similarly to Examples 1, 6-9, respectively, except not blending polyfunctional isocyanate.

[Comparative Example 6] Except having used difunctional isocyanate (MDI) instead of polyfunctional isocyanate, it carried out similarly to Example 1.

COMPARATIVE EXAMPLE 7 It implemented similarly to Example 6 except having used difunctional isocyanate (MDI) instead of polyfunctional isocyanate. [Table 1] Product name dealer Compound name Cyclic Nitrogenous Compounds NVC Tokyo Chemical Industry Co., Ltd. N-vinyl-ε-caprolactam Monofunctional amine ester acrylate Viscoat#216 Osaka Organic Chemical Industry Co., Ltd. 1,2-Ethylene glycol-1-acrylate-2-(N-butylcarbamate) Multifunctional amine ester acrylate EBECRYL8411 DAICEL-ALLNEX (share) - 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 (Shares) Dimethacrylamide Monofunctional Acrylate d DEAA KJ CHEMICALS (Shares) Diethylacrylamide polyfunctional isocyanate a Coronate HX Tosoh Co., Ltd. Polyisocyanate modifier polyfunctional isocyanate b MILLIONATE MR-200 Tosoh Co., Ltd. Polymethylene polyphenyl polyisocyanate Difunctional isocyanate (MDI) MILLIONATE MT Tosoh Co., Ltd. diphenylmethane diisocyanate Photopolymerization initiator Irgacure TPO BASF Corporation Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide filler AEROSIL RY-200S Japan AEROSIL (share) Silica filler Colorant 13M-C Mitsubishi Materials Co., Ltd. Titanium black ※Furthermore, polyfunctional isocyanate a is an isocyanurate modified substance, and it is a compound with 3 isocyanate groups in the molecule. A mixture of polyfunctional isocyanate b-based MDI (difunctional isocyanate) and polymeric MDI (polymethylene polyphenyl polyisocyanate: compound (D)) having 3 or more isocyanate groups, the ratio of MDI is 40% by mass , The ratio of polymerized MDI is 60% by mass. The average number of isocyanate groups in polymerized MDI is 5-6.

Acrylic acids A to D used in Examples and Comparative Examples are as follows. [Table 2] Acrylic acid A (parts by mass) Acrylic acid B (parts by mass) Acrylic acid C (parts by mass) Acrylic acid D (parts by mass) Cyclic Nitrogenous Compounds 30 30 30 30 Monofunctional amine ester acrylate 35 42 33 twenty four Multifunctional amine ester acrylate 0 0 15 30 Monofunctional acrylate a 7 17.5 13.75 10 Monofunctional acrylate b 14 0 0 0 Monofunctional acrylate c 14 0 0 0 Monofunctional Acrylate d 0 10.5 8.25 6 total 100 100 100 100

The moisture curable resin (B) used in the Example and the comparative example is shown in Table 3, 4 below. As mentioned above, the following reaction products of urethane resin raw materials and polyols were used as the moisture curable resin (B). [table 3] PC urethane resin raw material (parts by mass) PC polyol (parts by mass) Moisture curable resin (PC-L25) 75 25

[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 1 2 3 4 5 6 7 Blending (parts by mass) Acrylic A - - - - - - - - 40 - - - - 40 - - Acrylic B 40 40 40 40 40 40 - - - 40 40 - - - 40 40 Acrylic C - - - - - - 40 - - - - 40 - - - - Acrylate D - - - - - - - 40 - - - - 40 - - - Moisture curable resin (PC-L25) 60 60 60 60 60 - 60 60 60 60 - 60 60 60 60 - Moisture curable resin (ET-L25) - - - - - 60 - - - - 60 - - - - 60 polyfunctional isocyanate a 1.2 - - - - - - - - - - - - - - - polyfunctional isocyanate b - 0.6 1.2 1.2 2.4 1.2 1.2 1.2 1.2 - - - - - - - Difunctional isocyanate (MDI) - - - - - - - - - - - - - - 1.2 1.2 Photopolymerization initiator 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 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 12000 12000 12000 12000 12800 12000 12000 12000 12000 12800 12000 12000 12000 12000 12800 Viscosity of the composition [Pa・s] (5.0 rpm) 122 127 124 130 120 229 239 489 112 125 240 247 499 110 129 232 Internal and external ratio (a/b) 0.9 0.88 0.88 0.80 0.90 0.89 0.56 0.38 0.89 0.88 0.91 0.55 0.39 0.90 0.86 0.92 Final heat-resistant adhesion [MPa] 2.8 2.1 3.4 1.9 3.0 2.4 1.5 1.6 2.2 0.7 0.63 0.55 0.52 0.94 0.98 0.81 Final Heat Resistance Adhesion Evaluation A A A B A A B B A C C C C C C C Initial adhesion force [MPa] 0.57 0.61 0.64 0.27 0.6 0.23 0.1 0.07 0.53 0.65 0.26 0.1 0.1 0.53 0.55 0.28 Initial Adhesion Evaluation A A A A A A B C A A A B B A A A

Since the light and moisture curable resin compositions of Examples 1 to 9 contain the radical polymerizable compound (A), the moisture curable resin (B), and the photopolymerization initiator (C), in addition to The compound (D) has more than 3 isocyanate groups in the molecule, so the final heat-resistant adhesive force after moisture curing becomes higher, and it can maintain high adhesive force even in high temperature environments. In contrast, since the light- and moisture-curing resin compositions of Comparative Examples 1 to 5 do not contain the compound (D) having 3 or more isocyanate groups in the molecule, the final heat-resistant adhesive force after moisture curing changes. Low, can not ensure high adhesion in high temperature environment. This tendency also existed in the comparative example 6 and the comparative example 7 which used the diisocyanate compound instead of the compound (D) which has 3 or more isocyanate groups.

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: Samples for Adhesion Evaluation a1: width b1: width S: shearing direction UV: Ultraviolet

[Fig. 1] is a conceptual diagram showing the measurement method of the internal-interior ratio a/b. [Fig. 2] is a schematic view showing the adhesion test method, wherein Fig. 2(a) is a plan view and Fig. 2(b) is a side view.

Claims (12)

A light and moisture curable resin composition comprising a radically polymerizable compound (A), a moisture curable resin (B), a photopolymerization initiator (C), and three or more isocyanates in the molecule Acid-based compounds (D). The light and moisture curable resin composition according to claim 1, wherein the compound (D) includes a compound having 5 or more isocyanate groups in the molecule. Such as the light and moisture curable resin composition of claim 1 or 2, which is coated on an aluminum substrate with a line width of 1.0 mm, and is irradiated with ultraviolet rays of 1000 mJ/cm ² to make it photohardenable. When the plates are bonded 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, then a/b is 0.5 or more and Below 0.99. The light and moisture curable resin composition according to any one of Claims 1 to 3, wherein the viscosity measured under the conditions of 25°C and 5.0 rpm using a cone-plate viscometer is 40 Pa·s or more And below 600 Pa·s. The light and moisture curable resin composition according to any one of claims 1 to 4, wherein the moisture curable resin (B) includes a moisture curable urethane resin. The light and moisture curable resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the moisture curable resin (B) is 7,500 to 24,000. The light and moisture curable resin composition according to any one of claims 1 to 6, wherein the radically polymerizable compound (A) includes a monofunctional radically polymerizable compound. The light and moisture curable resin composition according to claim 7, wherein the monofunctional radical polymerizable compound is contained in 90 parts by mass or more with respect to 100 parts by mass of the radical polymerizable compound (A). The light and moisture curable resin composition according to any one of claims 1 to 8, further comprising a filler (E). An adhesive for electronic parts, which is composed of the light and moisture curable resin composition according to any one of claims 1 to 9. A hardened body, which is a hardened body of the light and moisture curable resin composition according to any one of claims 1 to 10. An electronic component comprising the hardened body of claim 11.

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