TW202346393A - Light-moisture curable resin composition, adhesive agent for electronic component, and adhesive agent for display element - Google Patents

Abstract

This light-moisture curable resin composition contains a radical polymerizable compound, a moisture-curable resin, and a photo-radical polymerization initiator. The photo-radical polymerization initiator has two or more reaction starting points per molecule.

Description

Light and moisture curable resin compositions, adhesives for electronic parts and adhesives for display elements

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

In recent years, electronic devices such as televisions, PCs, and smartphones have been required to be highly integrated and miniaturized. Therefore, the frame of a display element (hereinafter also referred to as a "monitor") tends to become narrower. In response to this trend, it is considered that the use of adhesives as a means of bonding electronic components and liquid crystal cells has become mainstream instead of the double-sided tape that has been used previously. Among the adhesives, the light- and moisture-curable adhesive described in Patent Document 1, for example, is particularly attractive from the viewpoint of workability or final adhesive strength. Prior technical literature patent documents

Patent Document 1: International Publication No. 2021/230372

[Problem to be solved by the invention]

However, conventional light- and moisture-hardening adhesives do not show sufficient adhesion (initial adhesion) immediately after the parts are joined like tape, so it sometimes takes several hours before it develops. Set or save the process. Therefore, there is a problem that the efficiency of the steps becomes poor and it is difficult to realize automatic steps. Here, an object of the present invention is to provide a light- and moisture-curable resin composition that can exhibit high adhesive force immediately after bonding and can improve workability and step efficiency. [Technical means to solve the problem]

The present inventors conducted in-depth research and found a solution to the above-mentioned problems through the following light- and moisture-curable resin composition containing a radical polymerizable compound, thereby completing the present invention. , moisture-curable resin and photo-radical polymerization initiator. The above-mentioned photo-radical polymerization initiator has more than two reaction starting points in the molecule. The present invention provides the following [1] to [24].

[1] A light and moisture curable resin composition, which includes a radical polymerizable compound, a moisture curable resin and a photo radical polymerization initiator. The photo radical polymerization initiator has two The above reaction starting point. [2] The light- and moisture-curable resin composition according to [1], wherein the photoradical polymerization initiator has a structure derived from a bifunctional or higher aromatic isocyanate compound. [3] The light and moisture curable resin composition according to [1] or [2], wherein the molecular weight of the photo radical polymerization initiator is 500 or more. [4] The light- and moisture-curable resin composition according to any one of [1] to [3], wherein the photoradical polymerization initiator has an urethane bond in the molecule. [5] The light and moisture curable resin composition according to any one of [1] to [4], wherein in the above-mentioned photo radical polymerization initiator, at least one reaction starting point is an acetophenone type . [6] The light- and moisture-curable resin composition according to [5], which has two or more acetophenone type reaction starting points. [7] The light and moisture curable resin composition according to any one of [1] to [6], wherein the content of the photo radical polymerization initiator is the amount of the light and moisture curable resin. The total amount of substances is 0.5 mass% or more and 10 mass% or less. [8] The light and moisture curable resin composition according to any one of [1] to [7], wherein the monofunctional radical polymerizable compound in the light and moisture curable resin composition is The content is 90 parts by mass or more based on 100 parts by mass of the radically polymerizable compound. [9] The light- and moisture-curable resin composition according to any one of [1] to [8], which contains a nitrogen-containing compound as the monofunctional radical polymerizable compound. [10] The light- and moisture-curable resin composition according to [9], wherein the nitrogen-containing compound contains a nitrogen-containing compound having a cyclic structure. [11] The light- and moisture-curable resin composition according to [9] or [10], wherein the nitrogen-containing compound includes a chain nitrogen-containing compound. [12] The light- and moisture-curable resin composition according to [11], which contains monofunctional urethane (meth)acrylate as the chain nitrogen-containing compound. [13] The light- and moisture-curable resin composition according to any one of [9] to [12], wherein the content of the nitrogen-containing compound is 10 parts by mass relative to 100 parts by mass of the radically polymerizable compound. above. [14] The light and moisture curable resin composition according to any one of [1] to [13], wherein the light and moisture curable resin composition contains a moisture curing acceleration catalyst. [15] The light- and moisture-curable resin composition according to any one of [1] to [14], wherein the moisture-curable resin is a moisture-curable polyurethane resin and a hydrolyzable silicone-based resin. Any of them. [16] The light- and moisture-curable resin composition according to [15], wherein the moisture-curable polyurethane resin is a moisture-curable polyurethane resin having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton. At least any one of them. [17] The light- and moisture-curable resin composition according to any one of [1] to [16], wherein the moisture-curable resin has a weight average molecular weight of 7,500 to 24,000. [18] The light and moisture curable resin composition according to any one of [1] to [17], wherein the moisture curable resin in the light and moisture curable resin composition is smaller than the moisture curable resin in the light and moisture curable resin composition. The weight ratio of the above-mentioned radically polymerizable compound is 30/70 or more and 90/10 or less. [19] The light and moisture curable resin composition according to any one of [1] to [18], wherein the storage elastic modulus of the light and moisture curable resin composition is 0.1 MPa or more 5 Below MPa. [20] An adhesive for electronic parts consisting of the light- and moisture-curable resin composition according to any one of [1] to [19]. [21] An adhesive for display elements consisting of the light- and moisture-curable resin composition according to any one of [1] to [19]. [22] A cured body of the light- and moisture-curable resin composition described in any one of [1] to [19]. [23] A use of the light- and moisture-curable resin composition described in any one of [1] to [19] for electronic parts. [24] A use of the light- and moisture-curable resin composition according to any one of [1] to [19] for a display element. [Effects of the invention]

According to the present invention, it is possible to provide a light- and moisture-curable resin composition that can exhibit high adhesive force immediately after bonding and can improve workability and step efficiency.

Hereinafter, the present invention will be described in detail with reference to embodiments. [Light and moisture curable resin composition] Contains radically polymerizable compounds, moisture-hardening resin and photoradical polymerization initiator.

＜Photoradical polymerization initiator＞ The light- and moisture-curable resin composition of the present invention contains a photoradical polymerization initiator having two or more reaction starting points in the molecule. By including such a photo-radical polymerization initiator, the light- and moisture-curable resin composition can exhibit high adhesion (initial adhesion) immediately after photo-curing. Therefore, a high adhesive force can be expressed immediately after being bonded with the photocured curable resin composition, and workability and step efficiency can be improved. Furthermore, the reason why a higher adhesion force can be exhibited immediately after photohardening is not clear, but it is presumed that the reason is that, for example, the photoradical polymerization initiator is incorporated into the polymer chain just after photohardening. High molecular weighting proceeds rapidly, and cohesion increases immediately after photohardening.

The photoradical polymerization initiator is not particularly limited as long as it has two or more reaction starting points in the molecule. Examples of the reaction starting point include: benzophenone type, acetophenone type, and acyl oxidation Phosphine type, titanocene type, oxime ester type, benzoin ether type, 9-oxosulfide𠮿 (thioxanthone) type, etc. Among these, the acetophenone type is preferred. The photoradical polymerization initiator may also contain two or more reaction starting points in one molecule.

In a preferred embodiment of the present invention, as mentioned above, the photoradical polymerization initiator has more than two reaction starting points in the molecule, and at least one reaction starting point is an acetophenone type. By using at least one reaction starting point in the photoradical polymerization initiator as an acetophenone type, the initial adhesive strength of the light- and moisture-curable resin composition can be improved, and workability and step efficiency can be improved. In addition, the acetophenone type has an acetophenone skeleton having at least the following structure, and generates free radicals by irradiation with ultraviolet rays or the like to become a reaction starting point.

The photoradical polymerization initiator preferably has two or more acetophenone type reaction starting points, and further preferably has two acetophenone type reaction starting points. By having multiple acetophenone type reaction starting points, the photoradical polymerization initiator will be easily incorporated into the polymer chain just after photohardening, and the initial adhesion force will be easily improved.

Furthermore, the photoradical polymerization initiator used in the present invention preferably has an amine ester bond in the molecule. By using a photoradical polymerization initiator having an amine ester bond in the molecule, the initial adhesive strength of the light- and moisture-curable resin composition can be easily improved.

The photoradical polymerization initiator preferably has a structure derived from a bifunctional or higher aromatic isocyanate compound. Aromatic isocyanate compounds having two or more functionalities have excellent reactivity, so they can be easily synthesized as photoradical polymerization initiators. Furthermore, the aromatic isocyanate compound having two or more functionalities may be a polyisocyanate compound reacted with a hydroxyacetophenone compound as described below, or may be a polyisocyanate compound used when synthesizing an urethane prepolymer.

The photoradical polymerization initiator used in the present invention is preferably a compound having an acetophenone skeleton and a hydroxyl group (hereinafter, also referred to as a hydroxyacetophenone compound) and a compound containing an isocyanate group (hereinafter, also referred to as a hydroxyacetophenone compound). The reaction product of isocyanate-containing compounds). When reacting an isocyanate-containing compound with a hydroxyacetophenone compound, the moles of the isocyanate group (NCO) in the isocyanate-containing compound and the hydroxyl group (ОH) in the hydroxyacetophenone compound are It is sufficient to react the isocyanate group and the hydroxyl group after setting the ratio to [NCO]/[OH]=1/1.

(hydroxyacetophenone compound) The hydroxyacetophenone compound is not particularly limited, but a compound represented by the following formula (1) is more preferably used.

In the above formula (1), R ¹ represents a substituent, and m represents an integer from 0 to 4. Examples of the substituent represented by R ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), a benzene group having a hydroxyl group The base of ethanol structure, etc. The alkyl group and the alkoxy group are preferably straight chain or branched chain, more preferably straight chain. When R ¹ is an alkyl group or an alkoxy group, the alkyl group or alkoxy group may be unsubstituted or may have a substituent. Examples of the substituent of the alkyl group or alkoxy group include a hydroxyl group or a group having a hydroxyacetophenone structure. Examples of the group having a hydroxyacetophenone structure include a group obtained by removing one hydrogen atom from the benzene ring to which R ¹ is bonded or from R ¹ in the above formula (1). In addition, the portion of the base of the structure obtained by removing one hydrogen atom from the above formula (1) becomes the bonding bond.

R ² to R ⁴ each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkyl group having one hydroxyl group (preferably an alkyl group having 1 to 10 carbon atoms), or Hydroxy. Moreover, R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably straight chain or branched chain, more preferably straight chain. In the above formula (1), at least one of R ¹ to R ⁴ only needs to have a hydroxyl group, but it is preferable that R ⁴ is a group having a hydroxyl group, and more preferably R ⁴ is a hydroxyl group. In the hydroxyacetophenone-containing compound represented by the above formula (1), m is preferably 0 or 1, and m is more preferably 0. Moreover, the hydroxyacetophenone compound is preferably a compound having one hydroxyl group. The compound having one hydroxyl group is preferably one in which R ⁴ is a hydroxyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group, or are bonded to each other to form a ring, and m is 0.

Specific examples of the compound represented by the above formula (1) include compounds represented by the following structural formula.

As the above-mentioned compound, commercially available products can be used, and examples thereof include Оmnirad 184, Оmnirad 1173, Оmnirad 2959, and Оmnirad 127 (all manufactured by IGM Resins B.V.). As the compound represented by the above formula (1), a compound represented by the following structural formula is preferred.

(Containing isocyanato compounds) ((urethane prepolymer)) The isocyanate group-containing compound reacted with the hydroxyacetophenone compound is preferably an urethane prepolymer. Therefore, the photoradical polymerization initiator is preferably the reaction product of a hydroxyacetophenone compound and an urethane prepolymer. The urethane prepolymer can be obtained by reacting a polyol compound having two or more hydroxyl groups per molecule and a polyisocyanate compound having two or more isocyanato groups per molecule. The urethane prepolymer has an isocyanate group in the molecule. The urethane prepolymer may have only 1 isocyanate group per molecule, or may have 2 or more, but the urethane prepolymer preferably has 1 or 2 isocyanate groups per molecule. Better to have 2. The isocyanate group may be provided at the terminal of the urethane prepolymer, preferably at both terminals of the urethane prepolymer.

The reaction between the above-mentioned polyol compound and the polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound as [NCO]/[OH] = 2.0 ~2.5 range. As the polyol compound used as the raw material of the urethane prepolymer, known polyol compounds commonly used in the production of polyurethane can be used. Examples thereof include: polyester polyol, polyether polyol, and polyalkylene. Polyols, polycarbonate polyols, etc. These polyol compounds may be used individually by 1 type, or in combination of 2 or more types.

Therefore, the urethane prepolymer is preferably at least one of the urethane prepolymers having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, and more preferably is an urethane prepolymer having a polycarbonate skeleton or a polyether skeleton. At least any one of the prepolymers is more preferably an urethane prepolymer having a polycarbonate skeleton.

(Urethane prepolymer with polycarbonate backbone) The urethane prepolymer having a polycarbonate skeleton is obtained by using polycarbonate polyol as the polyol compound and introducing a polycarbonate skeleton into the urethane prepolymer. The urethane prepolymer having a polycarbonate skeleton can be produced by, for example, a polycarbonate polyol having two or more hydroxyl groups per molecule and a polyisocyanate compound having two or more isocyanate groups per molecule. obtained by reaction. As the polycarbonate polyol, polycarbonate diol is preferred. Preferable specific examples of the polycarbonate diol include compounds represented by the following formula (2).

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

In formula (2), R is preferably an aliphatic saturated hydrocarbon group. By making R an aliphatic saturated hydrocarbon group, heat resistance can be easily improved. In addition, yellowing due to thermal deterioration is less likely to occur, and the weather resistance is also improved. R consisting of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but from the viewpoint of easily improving stress relaxation or flexibility, a chain structure is preferred. In addition, R in the chain structure may be linear or branched. n is preferably 5 to 200, more preferably 10 to 150, and still more preferably 20 to 50.

In addition, one type of R contained in the polycarbonate polyol constituting the urethane prepolymer may be used alone, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that at least a part is a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms. By containing a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms, stress relaxation or flexibility can be easily improved. When the polycarbonate diol is a compound represented by the above formula (2), the ratio of chain aliphatic saturated hydrocarbon groups having 6 or more carbon atoms relative to all R contained in the polycarbonate diol is preferably 20 moles. It is 100 mol% or more and 100 mol% or less, More preferably, it is 30% or more and 100 mol% or less, More preferably, it is 50% or more and 100 mol% or less.

Specific examples of R may be linear ones such as tetramethylene, pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene, or may be, for example, Branched chains such as methylpentylene such as 3-methylpentylene and methyloctamethylene. Multiple R's in a molecule can be the same or different from each other. Therefore, two or more types of R may be contained in one molecule. In this case, it is preferable to contain two or three types of R in one molecule. For example, polycarbonate polyol may be a copolymer containing R with a carbon number of 6 or less and R with a carbon number of 7 or more in one molecule. In this case, any R may be a chain aliphatic saturated hydrocarbon group. . In addition, R may contain a linear aliphatic saturated hydrocarbon group or a branched aliphatic saturated hydrocarbon group. The R in the polycarbonate polyol can be a combination of branched chain and linear R, or a linear R can be used alone. In addition, polycarbonate polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

As the polyisocyanate compound used as the raw material of the urethane prepolymer, aromatic isocyanate compounds and aliphatic isocyanate compounds can be preferably used. Examples of the aromatic isocyanate compound include diphenylmethane diisocyanate, liquid modified product of diphenylmethane diisocyanate, polymerized MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like. Examples of aliphatic isocyanate compounds include: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, and trans-cyclohexane-1,4 -Diisocyanates, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane Diisocyanate, etc. As the polyisocyanate compound, an aromatic isocyanate compound is preferred, and a bifunctional or higher aromatic isocyanate compound is more preferred. Among the aromatic isocyanate compounds having two or more functionalities, diphenylmethane diisocyanate and modified products thereof are more preferred. The polyisocyanate compound may be used alone or in combination of two or more types.

(urethane prepolymer with polyester skeleton) The urethane prepolymer having a polyester skeleton is obtained by using polyester polyol as the polyol compound and introducing a polyester skeleton into a polyurethane resin. The urethane prepolymer having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups per molecule and a polyisocyanate compound having two or more isocyanate groups per molecule. . Examples of the polyester polyol include polyester polyol obtained by reaction of polycarboxylic acid and polyol, and poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone. wait. Examples of the polycarboxylic acid used as a raw material for polyester polyol include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecanedicarboxylic acid, etc. Among these, phthalic acid or adipic acid is preferred from the viewpoint of making it easier to improve the adhesive force at high temperatures. 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 these, 1,6-hexanediol or 1,4-butanediol is preferred from the viewpoint of making it easier to improve the adhesive force at high temperature. In addition, polyester polyol may be used individually by 1 type, and may be used in combination of 2 or more types.

(Urethane prepolymer with polyether skeleton) The urethane prepolymer having a polyether skeleton is obtained by using a polyether polyol as the polyol compound and introducing a polyether skeleton into the urethane prepolymer. The polyurethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups per molecule and a polyisocyanate compound having two or more isocyanate groups per molecule.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, ring-opened polymers of tetrahydrofuran, ring-opened polymers of 3-methyltetrahydrofuran, and random copolymers of these or their derivatives, or Block copolymer, bisphenol type polyoxyalkylene modified body, etc. Among these, from the viewpoint of easily improving the coatability of the light- and moisture-curable resin composition, polypropylene glycol, a ring-opened polymer of tetrahydrofuran, or a ring-opened polymer of 3-methyltetrahydrofuran is preferred. . Here, the bisphenol-type polyoxyalkylene modification system allows alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to be added to the bisphenol-type molecular skeleton. Polyether polyol obtained from the active hydrogen part. The polyether polyol can be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modified body preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. The bisphenol type is not particularly limited, and examples include A type, F type, S type, etc., and bisphenol A type is preferred. Moreover, as a polyisocyanate compound, the above-mentioned polyisocyanate compound can be used.

The urethane prepolymer having a polyether skeleton is preferably obtained by using a polyol compound having a structure represented by the following formula (3). By using a polyol compound having a structure represented by the following formula (3), it is possible to obtain a light- and moisture-curable resin composition with excellent adhesion, and a cured product that is soft and has good extensibility, becoming a free radical-resistant resin composition. The polymerizable compound (A) has excellent compatibility. Among them, polypropylene glycol, a ring-opening polymerization compound of a tetrahydrofuran (THF) compound, or a polyether polyol composed of a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group is used, and polypropylene glycol is more preferable. And ring-opening polymer compounds of tetrahydrofuran (THF) compounds. The ring-opening polymerization compound of tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol. Furthermore, one type of polyether polyol may be used alone, or two or more types may be used in combination.

In formula (3), R represents a hydrogen atom, a methyl group or an ethyl group, l is an integer from 0 to 5, m is an integer from 1 to 500, and n is an integer from 1 to 10. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 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, and more preferably 1 to 3. Moreover, R is more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.

The above-mentioned urethane prepolymer having a polycarbonate, polyester, or polyether skeleton may also have two or more kinds of skeletons in the molecule, for example, it may also have a polycarbonate skeleton and a polyester skeleton. In this case, polycarbonate polyol and polyester polyol may be used as the polyol compound used as the raw material. Similarly, urethane prepolymers having polyester skeleton and polyether skeleton can also be used.

((Isocyanate-containing compounds other than urethane prepolymers)) As the isocyanate group-containing compound that reacts with the hydroxyacetophenone compound, one other than the urethane prepolymer may be used, and a polyisocyanate compound other than the urethane prepolymer may also be used. Therefore, the photoradical polymerization initiator may also be the reaction product of a hydroxyacetophenone compound and a polyisocyanate compound. The details of the polyisocyanate compound are as described above. Therefore, a bifunctional or higher aromatic isocyanate compound is preferred, and among these, diphenylmethane diisocyanate and modified products thereof are further preferred.

The photoradical polymerization initiator used in the present invention preferably has a molecular weight of 500 or more. By setting the molecular weight to 500 or more, the initial adhesive strength of the light- and moisture-curable resin composition can be improved. Based on this point of view, the molecular weight of the photoradical polymerization initiator is more preferably 1,000 or more, further preferably 2,000 or more, still more preferably 3,000 or more, further preferably 4,000 or more, and particularly preferably 6,000 or more. Moreover, the upper limit of the molecular weight of the photoradical polymerization initiator is not particularly limited, but from a practical viewpoint, for example, it is preferably 10,000 or less, and more preferably 8,000 or less. Furthermore, regarding the molecular weight, the photoradical polymerization initiator with a molecular weight of less than 1000 can be calculated based on the chemical structure. When there are two or more types of photoradical polymerization initiators with a molecular weight of less than 1000, the average value (weight average molecular weight) may be used as the molecular weight. In addition, a high molecular weight type photoradical polymerization initiator with a molecular weight of 1000 or more means a weight average molecular weight, which is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene conversion. . Furthermore, the weight average molecular weight of the photoradical polymerization initiator can also be calculated based on the weight average molecular weight and the molecular weight of the hydroxyacetophenone compound when the weight average molecular weight of the isocyanate-containing compound such as the urethane prepolymer is known. .

The photoradical polymerization initiator used in the present invention can be obtained by reacting and synthesizing a hydroxyacetophenone compound and an isocyanato group-containing compound using a known method. The reaction between the hydroxyacetophenone compound and the isocyanato group-containing compound can also be carried out in the presence of a catalyst. The catalyst may be an amine compound or the like and is not particularly limited. In addition, the temperature when carrying out the above reaction is preferably 40 to 120°C, more preferably 50 to 100°C. The above reaction can also be performed in a solvent. However, when using a radically polymerizable compound described below, the reaction can also be performed in the presence of a radically polymerizable compound using the radically polymerizable compound as a solvent.

The content of the photoradical polymerization initiator in the light and moisture curable resin composition of the present invention is preferably 0.5 mass% or more and 10 mass% or less, based on the total amount of the light and moisture curable resin composition. More preferably, it is 1.0 mass % or more and 7 mass % or less, and still more preferably, it is 1.5 mass % or more and 5 mass % or less. By setting the content of the photoradical polymerization initiator to be more than the above lower limit, the initial adhesive strength of the light- and moisture-curable resin composition can be effectively improved. Furthermore, by setting the content of the photoradical polymerization initiator to below the above upper limit, the final adhesive strength of the light- and moisture-curable resin composition can be easily improved.

＜Radically polymerizable compound＞ The light- and moisture-curable resin composition of the present invention contains a radically polymerizable compound. The light- and moisture-curable resin composition is provided with photocurable properties by containing a radically polymerizable compound. Since the light- and moisture-curable resin composition has photocurability, it can be given a certain adhesive force just by light irradiation, so it is easy to ensure an appropriate initial adhesive force. In addition, it is possible to achieve a hardness above a certain level by simply irradiating light, and it is easy to ensure operability and the like. Furthermore, by using the above-mentioned photo radical polymerization initiator, the initial adhesive strength can be increased even immediately after photohardening. The radically polymerizable compound only needs to have a radically polymerizable functional group in the molecule. As the radical polymerizable functional group, a compound having an unsaturated double bond is suitable, and examples thereof include: (meth)acrylyl group, vinyl group, styryl group, allyl group, and the like.

Among the above, from the viewpoint of adhesion, a (meth)acrylyl group is more suitable. That is, the radically polymerizable compound preferably contains a compound having a (meth)acrylyl group. In addition, the compound which has a (meth)acrylyl group is also called "(meth)acrylic acid compound" below. Furthermore, in this specification, "(meth)acrylyl" means acrylic group or (meth)acrylyl group, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and other similar terms are also used. Same thing.

The radical polymerizable compound may also include a monofunctional radical polymerizable compound having one radical polymerizable functional group per molecule, and a polyfunctional radical compound having two or more radical polymerizable functional groups per molecule. One or both of the polymerizable compounds, but from the viewpoint of improving the initial adhesive strength of the light- and moisture-curable resin composition, it is preferred to include a monofunctional radical polymerizable compound. Furthermore, the radically polymerizable compound more preferably contains at least a (meth)acrylic acid compound, that is, a monofunctional (meth)acrylic acid compound as a monofunctional radically polymerizable compound. Furthermore, the monofunctional radically polymerizable compound may also be a prepolymer that has been polymerized and has repeating units, but usually a monofunctional monomer without repeating units can be used.

In order to improve the initial adhesion of the light and moisture curable resin composition, the light and moisture curable resin composition preferably contains a large amount of monofunctional radical polymerizable compounds. Specifically, the content of the monofunctional radical polymerizable compound in the light- and moisture-curable resin composition is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, based on 100 parts by mass of the radical polymerizable compound. More preferably, it is 97 parts by mass or more. In addition, the content of the monofunctional radical polymerizable compound may be 100 parts by mass or less.

(Monofunctional radically polymerizable compound) The radically polymerizable compound preferably contains a nitrogen-containing compound as a monofunctional radically polymerizable compound. If a nitrogen-containing compound is used, the adhesion between light and moisture-curable resin composition can be easily improved. The light- and moisture-curable resin composition is applied to the adherend and then irradiated with active energy rays such as ultraviolet rays to be photocured. However, in this case, it is generally photocured in the presence of oxygen as described below. When the radically polymerizable compound contains a nitrogen-containing compound, it is suitably photocured even in the presence of oxygen, and it is estimated that the adhesive force becomes good.

The nitrogen-containing compound may contain one or both of a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, but from the viewpoint of improving the adhesion of the light- and moisture-curable resin composition, it is preferred. To include a nitrogen-containing compound having a cyclic structure, it is more preferred to use a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure in combination.

Examples of nitrogen-containing compounds having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and N-acrylamide. Phenoline etc. contain Phosphine skeleton compounds, cyclic imine compounds such as N-(meth)acryloxyethyl hexahydrophthalimide, etc. Among these, specifically, amide group-containing compounds such as N-vinylcaprolactam are more preferred. Furthermore, in this specification, a nitrogen-containing compound having a cyclic structure is also called a cyclic nitrogen-containing compound, and a radically polymerizable compound in which a nitrogen atom is included in the atoms constituting the ring itself is referred to as a cyclic nitrogen-containing compound. Let other nitrogen-containing compounds be chain nitrogen-containing compounds.

Examples of chain nitrogen-containing compounds include: dimethylamino(meth)acrylate, diethylamino(meth)acrylate, (meth)acrylic acid aminomethyl ester, (meth)acrylic acid amine ethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate and other chain amino-containing (meth)acrylates, diacetone acrylamide, N,N-dimethylacrylamide, N,N-di Ethyl acrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, methacrylamide and other chain (meth)acrylamide compounds, N-vinyl ethyl Amide etc.

Furthermore, as the chain nitrogen-containing compound, monofunctional amine ester (meth)acrylate may be used. By using monofunctional urethane (meth)acrylate, when a polyurethane resin, especially a polyurethane resin having a polycarbonate skeleton, is used as the moisture-curable resin, the compatibility with the moisture-curable resin changes. It is good and easy to improve the adhesion. In addition, urethane (meth)acrylate has relatively high polarity, so it is particularly easy to improve the adhesion to glass.

As the monofunctional amine ester (meth)acrylate, for example, one obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound can be used. Examples of the (meth)acrylic acid derivative having a hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono(meth)acrylate esters of glycols such as trimethylolethane, trimethylolpropane, and glycerol, etc.

Examples of the isocyanate compound used to obtain the urethane (meth)acrylate include alkane monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate, cyclopentane isocyanate, cyclohexane isocyanate, and isophorone Aliphatic monoisocyanates such as cyclic aliphatic monoisocyanates such as monoisocyanates. The monofunctional amine ester (meth)acrylate is more specifically preferably an amine ester (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compound with a diol mono(meth)acrylate. A suitable specific example is 1,2-ethanediol 1-acrylate 2-(N-butylcarbamate). Among the above, the chain nitrogen-containing compound preferably contains a monofunctional amine ester (meth)acrylate, and it is also preferred to use a combination of a monofunctional amine ester (meth)acrylate and a (meth)acrylamide compound. Compounds other than monofunctional amine ester (meth)acrylate.

From the viewpoint of improving the adhesion of the light and moisture curable resin composition, the nitrogen-containing compound that is a monofunctional radical polymerizable compound in the light and moisture curable resin composition is better than the radical polymerizable compound. The content per 100 parts by mass is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, and most preferably 50 parts by mass or more. Furthermore, in order to contain an appropriate amount of a radical polymerizable compound other than a 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 90 parts by mass or less. , more preferably 85 parts by mass or less.

When the monofunctional radical polymerizable compound has a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, the nitrogen-containing compound having a cyclic structure in the monofunctional radical polymerizable compound is smaller than the nitrogen-containing compound having a chain structure. The weight ratio of the nitrogen compound (cyclic/chain) is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.8, further preferably from 0.4 to 1.6. By setting the cyclic/chain weight ratio within the above range, the adhesion between light and moisture-curable resin composition can be improved.

(Monofunctional radical polymerizable compounds other than nitrogen-containing compounds) The monofunctional radical polymerizable compound contained in the radical polymerizable compound preferably contains compounds other than the above-mentioned nitrogen-containing compounds (hereinafter also referred to as nitrogen-free compounds). When the radically polymerizable compound contains a nitrogen-free compound as a monofunctional radically polymerizable compound, the adhesive strength and the like can be easily improved.

The nitrogen-free compound is not particularly limited as long as it has a radically polymerizable functional group, but a monofunctional (meth)acrylic compound is preferred, and a (meth)acrylate compound is more preferred.

Examples of the monofunctional (meth)acrylate compound include: (meth)acrylic acid alkyl ester, alicyclic structure-containing (meth)acrylate, aromatic ring-containing (meth)acrylate, and the like. One type of these may be used alone, or two or more types may be used in combination, but among these, it is preferred to use one or both of (meth)acrylic acid alkyl esters and aromatic ring-containing (meth)acrylic acid esters. . The total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate in the radical polymerizable compound relative to 100 of the radical polymerizable compound The part by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. 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, most preferably 40 parts by mass or less.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) Isobutyl acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth) The carbon number of the alkyl group such as isononyl acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, etc. is 1 to 18 Alkyl (meth)acrylate. Examples of (meth)acrylates containing an alicyclic structure include: (meth)acrylic acid cyclohexyl, (meth)acrylic acid 4-tert-butylcyclohexyl, (meth)acrylic acid 3,3, 5-Trimethylcyclohexyl, isocamphenyl (meth)acrylate, dicyclopentenyl (meth)acrylate and other (meth)acrylates with alicyclic structure. Examples of aromatic ring-containing (meth)acrylates include phenyl alkyl (meth)acrylates such as benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and (meth)acrylic acid esters. ) phenoxyethyl acrylate, etc. (meth)phenoxyalkyl acrylate, etc.

As the monofunctional (meth)acrylate compound, it is also possible to use those other than alkyl (meth)acrylate, (meth)acrylate containing an alicyclic structure, and (meth)acrylate containing an aromatic ring. For example, (meth)acrylate containing a cyclic ether group can also be used. Examples of the (meth)acrylate containing a cyclic ether group include an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a dioxolane ring, and a dioxetane ring. Alkyl ring and other (meth)acrylate. Examples of the epoxy ring-containing (meth)acrylate include glycidyl (meth)acrylate. Examples of the oxetane ring-containing (meth)acrylate include (3-ethyloxetan-3-yl)methyl (meth)acrylate. Examples of the tetrahydrofuran ring-containing (meth)acrylate include tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid polymer ester of tetrahydrofuranmethanol, and the like. Examples of the dioxolane-containing (meth)acrylate include (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate, (2,2-cyclohexyl-1,3-dioxolane-4-yl)methyl methacrylate, etc. as having two Examples of alkyl ring (meth)acrylate include cyclic trimethylolpropane formal (meth)acrylate. As the cyclic ether group-containing (meth)acrylate, it is preferable to use either an oxetane ring-containing (meth)acrylate or a tetrahydrofuran ring-containing (meth)acrylate. It is also preferable to use these together.

Moreover, as the monofunctional (meth)acrylate compound, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxybutyl ester can also be used. , (meth)hydroxyalkyl acrylates such as 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate Alkyl (meth)acrylates such as 2-butoxyethyl acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, etc. Oxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate ) Acrylate, ethyl diglycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, ethoxy triethylene glycol (meth) acrylate, ethoxy polyethylene glycol Polyoxyethylene-based (meth)acrylate such as alcohol (meth)acrylate, etc. Furthermore, as the monofunctional (meth)acrylic compound, carboxyl group-containing (meth)acrylic compounds such as acrylic acid and methacrylic acid can also be used.

(Polyfunctional radical polymerizable compound) The light- and moisture-curable resin composition of the present invention may also contain a polyfunctional radically polymerizable compound as a radically polymerizable compound. Examples of the polyfunctional radical polymerizable compound include bifunctional (meth)acrylate compounds, trifunctional or higher (meth)acrylate compounds, bifunctional or higher amine ester (meth)acrylates, and the like.

Examples of the bifunctional (meth)acrylate compound include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-butanediol di(meth)acrylate. -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2- Ethyl-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 to bisphenol A di(meth)acrylate, ethylene oxide added to bisphenol F di(meth)acrylate, dimethylol dicyclopenta Dialkenyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(meth)acryloxypropyl, carbonate diol diol (meth)acrylate, polyether glycol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene di Alcohol di(meth)acrylate, etc.

Examples of the trifunctional or higher (meth)acrylate compound include trimethylolpropane tri(meth)acrylate and ethylene oxide added trimethylolpropane tri(meth)acrylic acid. Ester, propylene oxide added trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, Glyceryl tri(meth)acrylate, propylene oxide added to glyceryl tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, Neopenterythritol tetra(meth)acrylate, dipenterythritol penta(meth)acrylate, dipenterythritol hexa(meth)acrylate, etc.

Examples of the bifunctional or higher amine ester (meth)acrylate include those obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound. Examples of the (meth)acrylic acid derivative having a hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono(meth)acrylate esters of dihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin and other trihydric alcohols, or Epoxy (meth)acrylate such as bisphenol A type epoxy (meth)acrylate, etc.

Examples of the isocyanate compound used to obtain the urethane (meth)acrylate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. , Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine Diisocyanate, xylylene diisocyanate (XDI), hydrogenated Polyisocyanate compounds such as isocyanate and 1,6,11-undecane triisocyanate.

Furthermore, as the isocyanate compound, a chain-extended polyisocyanate compound obtained by reaction of a polyol and an excess isocyanate compound can also be used. Here, examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. wait. By using these polyisocyanate compounds, polyfunctional amine ester (meth)acrylates can be obtained.

＜Moisture curing resin＞ Examples of the moisture-curable resin used in the present invention include moisture-curable polyurethane resin, hydrolyzable silicone-containing resin, moisture-curable cyanoacrylate resin, and the like. Among them, moisture-curable resins are preferred. Either a polyurethane resin or a hydrolyzable silicone-containing resin, preferably a moisture-curable polyurethane resin. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(Moisture curable polyurethane resin) Moisture-curable polyurethane resin can be produced by using a polyol compound having two or more hydroxyl groups per molecule and a polyisocyanate compound having two or more isocyanate groups per molecule in the same manner as the above-mentioned urethane prepolymer. obtained by reaction. Moisture-curable polyurethane resin only needs to have isocyanate groups in the molecules. The isocyanate groups in the molecules react with moisture in the air or in the adherend to harden. The moisture-curable polyurethane resin may have only one isocyanate group per molecule, or may have two or more isocyanate groups. However, the moisture-curable polyurethane resin preferably has one or two isocyanate groups per molecule. base. In addition, the isocyanate group is not particularly limited as long as it is provided at the terminal of the moisture-curable polyurethane resin.

The reaction between the above-mentioned polyol compound and the polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound as [NCO]/[OH] = 2.0 ~2.5 range. As the polyol compound used as the raw material of the moisture-curable polyurethane resin, well-known polyol compounds commonly used in the production of polyurethane can be used. Examples thereof include polyester polyol, polyether polyol, and polyalkylene polyol. , polycarbonate polyols, etc. These polyol compounds may be used individually by 1 type, or in combination of 2 or more types.

The moisture-curable polyurethane resin is preferably at least one of the moisture-curable polyurethane resins having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, and more preferably a moisture-curable polyurethane resin having a polycarbonate skeleton or a polyether skeleton. At least one of the curable polyurethane resins, and more preferably a moisture-curable polyurethane resin having a polycarbonate skeleton. Moisture-curable polyurethane resin has a polycarbonate skeleton and is excellent in both initial adhesive strength and final adhesive strength. Furthermore, it is also possible to provide a light- and moisture-curable resin composition that is excellent in weather resistance, heat resistance, moisture resistance, etc. of the cured product. Moisture-curable polyurethane resin having a polycarbonate skeleton, moisture-curable polyurethane resin having a polyester skeleton, and moisture-curable polyurethane resin having a polyether skeleton can be used as the above-mentioned ones having a polycarbonate skeleton, respectively. Various urethane prepolymers with polyester skeleton and polyether skeleton.

As the polyisocyanate compound used as a raw material of the moisture-curable polyurethane resin, aromatic isocyanate compounds and aliphatic isocyanate compounds can be preferably used. As the aromatic isocyanate compound and the aliphatic isocyanate compound, the same ones described as the raw materials of the above-mentioned urethane prepolymer can be used, preferably a bifunctional or higher aromatic isocyanate compound, more preferably diphenylmethane diisocyanate or Its modifications. The polyisocyanate compound may be used alone or in combination of two or more types.

In addition, the moisture-curable polyurethane resin may be one containing an isocyanate group as described above, but it is not limited to one having an isocyanate group. It may also be a hydrolyzable polyurethane resin as described below for the hydrolyzable silicone-containing resin. Silicone-based polyurethane resin.

(Contains hydrolyzable silicone resin) The hydrolyzable silicone-containing resin used in the present invention is hardened by reaction between the hydrolyzable silicone group in the molecule and the moisture in the air or in the adherend. The hydrolyzable silicon group-containing resin may have only one hydrolyzable silicon group per molecule, or may have two or more hydrolyzable silicon groups. Among them, those having hydrolyzable silicon groups at both ends of the main chain of the molecule are preferred. In addition, those having an isocyanate group are not included as the above-mentioned hydrolyzable silicone-based resin.

The hydrolyzable silicon group is represented by the following formula (4). In formula (4), R ¹ is each independently an optionally substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or -OSiR ² ₃ (R ² is each independently a hydrocarbon group with a carbon number of 1 to 20). Moreover, in formula (4), X is each independently a hydroxyl group or a hydrolyzable group. Furthermore, in formula (4), a is an integer from 1 to 3.

The above-mentioned hydrolyzable group is not particularly limited, and examples thereof include: halogen atom, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, ketoxamate group, amine group, amide group (amide group), Acid amide group, amineoxy group, sulfhydryl group, etc. Among them, in terms of higher activity, a halogen atom, an alkoxy group, an alkenyloxy group, and a acyloxy group are preferred. Moreover, from the viewpoint of stable hydrolyzability and easy handling, an alkoxy group such as a methoxy group or an ethoxy group is more preferred, and a methoxy group or an ethoxy group is still more preferred. Moreover, from the viewpoint of safety, it is preferable that the compounds released by the reaction are the ethoxy group and the isopropyleneoxy group of ethanol and acetone, respectively.

The above-mentioned hydroxyl group or the above-mentioned hydrolyzable group may be bonded in the range of 1 to 3 per 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 hardening properties, a in the above formula (4) is preferably 2 or 3, and particularly preferably 3. Moreover, from the viewpoint of storage stability, a is preferably 2. Furthermore, examples of R ¹ in the above formula (4) include alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and trimethyl. Siloxy, chloromethyl, methoxymethyl, etc. Among them, methyl is preferred.

Examples of the hydrolyzable silicon group include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, and triacetyloxysilyl group. silyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethyl Oxysilyl, (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (ethoxy (methylmethyl)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 the hydrolyzable silicon group-containing resin include hydrolyzable silicon group-containing (meth)acrylic resin, an organic polymer having a hydrolyzable silicon group at the end of the molecular chain or at the end of the molecular chain, and hydrolyzable silicon group-containing polyurethane. 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 (meth)acrylic acid alkyl ester in the main chain.

Examples of the hydrolyzable silicon group-containing (meth)acrylate include: (meth)acrylic acid 3-(trimethoxysilyl)propyl ester, (meth)acrylic acid 3-(triethoxysilyl)propyl Propyl ester, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 2-(trimethoxysilyl)ethyl (meth)acrylate, 2-(triethyl)acrylate Oxysilyl)ethyl ester, (meth)acrylic acid 2-(methyldimethoxysilyl)ethyl ester, (meth)acrylic acid trimethoxysilyl methyl ester, (meth)acrylic acid triethoxy Silyl methyl ester, (meth)acrylic acid (methyldimethoxysilyl) methyl ester, etc. Examples of the (meth)acrylic acid alkyl ester include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate Ester, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, etc.

Specific examples of a method for producing a hydrolyzable silicon group-containing (meth)acrylic resin include the synthesis of a hydrolyzable silicon group-containing (meth)acrylate polymer described in International Publication No. 2016/035718. Methods etc. 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 has a hydrolyzable silicon group at at least one of the end of the main chain and the end of the side chain. The skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth)acrylate polymers, and the like.

Examples of the polyoxyalkylene polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethene structure, and a polyoxyethylene-polyoxypropylene copolymer structure. Polyoxypropylene-polyoxybutylene copolymer structure polymers, etc. As a method for producing the above-mentioned organic polymer having a hydrolyzable silicon group at the molecular chain terminal or molecular chain terminal portion, specifically, for example, the method described in International Publication No. 2016/035718 can be used only at the molecular chain terminal or molecular chain terminal. Method for synthesizing organic polymers with cross-linkable silicon groups at the terminal parts. In addition, as another method of 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, for example, the reactive silicon group-containing polyoxyethylene disclosed in International Publication No. 2012/117902 can be cited. Synthetic methods of alkylene polymers, etc.

An example of a method for producing the hydrolyzable silicon group-containing polyurethane resin is a method of reacting a polyol compound and a polyisocyanate compound to produce a polyurethane resin, and further reacting a silicon group-containing compound such as a silane coupling agent. Specific examples include a method for synthesizing an urethane oligomer having a hydrolyzable silicon group described in Japanese Patent Application Laid-Open No. 2017-48345.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxy Cyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxysilane Propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethyl 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 preferred. These silane coupling agents can be used alone or in combination of two or more.

Moreover, the moisture-curable polyurethane resin may have both an isocyanate group and a hydrolyzable silicone group. The moisture-curable polyurethane resin having both an isocyanate group and a hydrolyzable silicon group is preferably produced in the following manner, that is, first, the moisture-curable polyurethane resin having an isocyanate group is obtained by the above method ( raw material polyurethane resin), and then react the silane coupling agent with the raw material polyurethane resin. In addition, the details of the moisture-curable polyurethane resin having an isocyanate group are as described above. The silane coupling agent that reacts with the raw material polyurethane resin can be appropriately selected and used from those listed above. However, from the viewpoint of reactivity with isocyanate groups, it is preferable to use silane having an amine group or a mercapto group. coupling agent. Preferable specific examples include: 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, the moisture-curable resin may have a radically polymerizable functional group. As a radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferred, and in terms of reactivity, a (meth)acrylyl group is more preferred. In addition, the moisture-curable resin which has a radically polymerizable functional group is not included in the said radically polymerizable compound, but is regarded as a moisture-curable resin. The moisture-curable resin can be appropriately selected from the above various resins and one type can be used alone, or two or more types can be used in combination.

The weight average molecular weight of the moisture curable resin is preferably from 7,500 to 24,000. By setting the weight average molecular weight within the above range, the initial adhesive strength can be easily increased. In addition, by setting it below the above-mentioned upper limit, it is easy to achieve good final adhesion. From these viewpoints, the weight average molecular weight of the moisture-curable resin is more preferably 7,800 or more, further preferably 10,000 or more, further preferably 11,500 or more, and more preferably 20,000 or less, still more preferably 16,000 or less. , further preferably below 15,000. In addition, in this specification, the said weight average molecular weight is measured by gel permeation chromatography (GPC), and it is the value calculated|required by polystyrene conversion.

The moisture-curable resin may be chain-extended in order to set the weight average molecular weight to a certain value or more as described above. For example, in a moisture-curable polyurethane resin, a chain extender can be further reacted with a polyurethane resin having an isocyanate group. The polyurethane resin having an isocyanate group is obtained by reacting a polyol compound with one molecule. It is obtained by reacting a polyisocyanate compound having two or more isocyanate groups (hereinafter also referred to as "raw material polyurethane resin"). At this time, the chain extender does not react with all the isocyanate groups of the raw material polyurethane resin, but the usage amount is appropriately adjusted so that the isocyanate groups remain in the moisture-curable polyurethane resin. Furthermore, the raw material polyurethane resin may be reacted with a chain extender that reacts with the raw material polyurethane resin.

The chain extender used in moisture-curable polyurethane resin is preferably a polyol compound. Details of the polyol compound are as described above. In addition, the polyol compound used as the chain extender may be the same polyol compound as the polyol compound used for synthesizing the raw material polyurethane resin. Therefore, as long as the polyol compound used to synthesize the raw material polyurethane resin is polycarbonate polyol, the chain extender can also use polycarbonate polyol. When the total amount of the raw material polyurethane resin and the chain extender is 100 parts by mass, the usage amount of the chain extender is, for example, 5 to 40 parts by mass, preferably 10 to 35 parts by mass, and more preferably It is 15 parts by mass or more and 30 parts by mass or less.

In the light- and moisture-curable resin composition, the weight ratio of the moisture-curable resin to the radical polymerizable compound is preferably 30/70 or more and 90/10 or less, more preferably 40/60 or more and 80/20 or less. More preferably, it is 50/50 or more and 70/30 or less. By setting the weight ratio within these ranges, photo-curable and moisture-curable properties can be imparted to the light- and moisture-curable resin composition in a well-balanced manner, making it easy to adjust both the initial adhesive force and the final adhesive force to the desired level. within the range.

The total content of the radically polymerizable compound and the moisture-curable resin in the light- and moisture-curable resin composition is not particularly limited. It is, for example, 50% by mass based on the total amount of the light- and moisture-curable resin composition. Above, preferably 60 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more. By setting the total amount to be equal to or more than the above-mentioned lower limit, it becomes easy to impart appropriate photocurable properties and moisture curable properties to the light- and moisture-curable resin composition. In addition, the above-mentioned total content may be less than 100% by mass. However, in order to appropriately contain other components, it is preferably 99% by mass or less, and more preferably 98% by mass or less.

Within the scope that does not impair the effects of the present invention, the light- and moisture-curable resin composition may also contain resin components other than radically polymerizable compounds and moisture-curable resins as resin components. For example, it may also contain non-curable resin components. Resin components such as thermoplastic resin (for example, acrylic resin, polyurethane resin, etc.), thermosetting resin, etc. The ratio of resin components other than the radically polymerizable compound and the moisture-curable resin is, for example, 50 parts by mass or less, preferably 30 parts by mass or less relative to 100 parts by mass of the total amount of the radically polymerizable compound and the moisture-curable resin. , more preferably 10 parts by mass or less.

＜Filler＞ The light- and moisture-curable resin composition of the present invention may also contain a filler. By containing a filler, the light- and moisture-curable resin composition of the present invention has appropriate thixotropy and can fully maintain its shape after coating. As the filler, particulate ones may be used. As the filler, an inorganic filler is preferred, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate, and the like. Among them, silica is preferred in that the obtained light- and moisture-curable resin composition has excellent ultraviolet transmittance. In addition, the filler may be subjected to hydrophobic surface treatment such as siliconization treatment, alkylation treatment, and epoxy treatment. One type of filler may be used alone, or two or more types may be used in combination. The content of the filler is preferably from 0.1 to 20 parts by mass based on 100 parts by mass of the moisture-curable resin, more preferably from 0.5 to 15 parts by mass, and further preferably from 1 to 10 parts by mass. .

<Moisture Curing Acceleration Catalyst> The light and moisture curing resin composition of the present invention may also contain a moisture curing accelerating catalyst that accelerates the moisture curing reaction of the moisture curing resin. By using a moisture curing accelerating catalyst, the light- and moisture-curable resin composition becomes one with better moisture curing properties, and the adhesive force can be easily improved. Specific examples of the moisture hardening accelerating catalyst include amine-based compounds, metal-based catalysts, and the like. Examples of amine compounds include bis(methyl Phylyl) diethyl ether, 4- linylpropyl Phenoline, 2,2'-bis Phylinyl diethyl ether, bis(2- Oxylinylethyl) ether, etc. have Compounds with phosphine skeleton, bis(2-dimethylaminoethyl) ether, 1,2-bis(dimethylamino)ethane and other dimethylamino-containing amine compounds with 2 dimethylamino groups, tris Ethylamine, 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 octoate, zinc compounds such as zinc octoate and zinc naphthenate, zirconium tetraacetylpyruvate, and naphthenic acid. Copper, cobalt naphthenate and other metal compounds. In the present invention, when using a moisture hardening accelerating catalyst, it is preferable to use an amine compound, and more preferably to use an amine compound having Compounds having a phosphonium skeleton, more preferably bis(2- linylethyl) ether. In addition, these moisture hardening accelerating catalysts can also be used as reaction catalysts in the process of synthesizing the above-mentioned photo-radical polymerization initiator.

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 based on 100 parts by mass of the moisture curable resin. By setting the content of the moisture curing accelerating catalyst within the above range, the storage stability of the light- and moisture-curable resin composition will not be deteriorated, and the effect of accelerating the moisture curing reaction will be excellent.

In addition to the components mentioned above, the light- and moisture-curable resin composition of the present invention may also contain other additives such as coupling agents, wax particles, ionic liquids, foamed particles, expanded particles, and reactive diluents. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, a zirconate coupling agent, and the like. Among these, a silane coupling agent is preferred. The light- and moisture-hardening resin composition can also be diluted with a solvent if necessary. When the light and moisture curable resin composition is diluted with a solvent, the mass part of the light and moisture curable resin composition is based on the solid content, that is, it means the mass part after removing the solvent.

An example of a method for producing the light- and moisture-curable resin composition of the present invention is to use a mixer to mix a photo-radical polymerization initiator, a radical polymerizable compound, and a moisture-curable resin as necessary. Methods for mixing fillers, moisture hardening accelerators, colorants and other additives. Examples of the mixer include a homogeneous disperser, a homogeneous mixer, a universal mixer, a planetary mixer, a planetary stirring device, a kneader, and a three-roller mill.

Furthermore, when the photoradical polymerization initiator is synthesized in the presence of a radical polymerizable compound as described above, it can also be prepared as a mixture of the photoradical polymerization initiator and the radical polymerizable compound.

Furthermore, as mentioned above, the molecular weight of moisture-curable resins such as moisture-curable polyurethane resin may be increased by a chain extender. In this case, for example, the raw material resin such as raw material polyurethane resin may be reacted with a chain extender in advance to obtain a moisture curable resin, and then mixed with other raw materials such as a radically polymerizable compound as described above. Alternatively, the raw resin, a chain extender and a radically polymerizable compound may be mixed, and the mixture may be heated as necessary to react the chain extender with the raw resin to synthesize the moisture curable resin. In this case, a mixture of moisture-curable resin and radical polymerizable compound will be obtained. Therefore, a photopolymerization initiator and other additives can be prepared as necessary to obtain light and moisture curing. Resin composition.

Furthermore, as described above, when the photoradical polymerization initiator is synthesized in the presence of a radically polymerizable compound, the raw material resin and the expansion agent may be added to the mixture of the photoradical polymerization initiator and the radically polymerizable compound. The chain extender and the raw resin are reacted by heating the mixture as necessary to synthesize the moisture curable resin. In this case, a mixture of moisture-curable resin, radical polymerizable compound and photo-radical polymerization initiator will be obtained. Therefore, other ingredients can be added to the mixture and prepared as needed to obtain light and moisture. Gas-curable resin composition.

＜Storage elastic modulus＞ The storage elastic modulus of the light and moisture curable resin composition of the present invention is not particularly limited, but is preferably 0.1 MPa or more and 5 MPa or less, more preferably 0.2 MPa or more and 3 MPa or less, and still more preferably 0.3 MPa or more 2 Below MPa. By setting the storage elastic modulus of the light- and moisture-curable resin composition to be equal to or higher than the above-mentioned lower limit, the strength of the light- and moisture-curable resin composition increases, and the initial adhesive strength and final adhesive strength can be improved. Furthermore, by setting the storage elastic modulus of the light- and moisture-curable resin composition to be equal to or less than the above-mentioned upper limit, a certain degree of flexibility is imparted to the light- and moisture-curable resin composition and the adhesion between the adherends is improved. become good. Furthermore, the above-mentioned storage elastic modulus can be obtained by the measurement method described in the following examples.

＜How to use light and moisture curable resin composition＞ The light- and moisture-curable resin composition of the present invention is cured and used as a cured body. Specifically, the light and moisture curable resin composition of the present invention is first photocured by light irradiation, for example, into a B-stage state (semi-cured state), and then cured by moisture to make it fully curable. Just harden. Here, when the light- and moisture-curable resin composition is disposed between the adherends to join the adherends, it is applied to one adherend and is then photocured by irradiation with light. For example, in the B-stage state, another adherend is overlapped on top of the light and moisture-curable resin composition in the photocured state, and the adherends are temporarily connected with a moderate adhesive force (initial adhesive force). Can. Thereafter, the light and moisture-curable resin composition in the B-stage state are fully cured by curing the moisture-curable polyurethane resin using moisture, thereby blocking the adherend overlapping the light- and moisture-curable resin composition. They are formally connected and joined with sufficient bonding force.

The application of the light- and moisture-curable resin composition to the adherend may be performed, for example, by a dispenser, but is not particularly limited. The light irradiated during photocuring is not particularly limited as long as the radically polymerizable compound is cured, but ultraviolet rays are preferred. In addition, when the light- and moisture-curable resin composition is completely cured by moisture after light curing, it may be left in the atmosphere for a predetermined time. The application of the light- and moisture-curable resin composition to the adherend is not particularly limited, and it may be carried out at a temperature near normal temperature. Specifically, it may be carried out at a temperature of about 10 to 35°C. The light- and moisture-curable resin composition of the present invention exhibits an initial adhesion force above a certain value immediately after light irradiation. Therefore, temporary adhesion can be performed immediately after light curing, and the workability becomes good.

The light- and moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic parts. That is, the present invention also provides an adhesive for electronic parts composed of the above-mentioned light- and moisture-curable resin composition. Therefore, the above-mentioned adherend is preferably various electronic components constituting electronic equipment. Examples of various electronic components constituting electronic equipment include various electronic components provided in display elements, substrates on which electronic components are mounted, and semiconductor wafers. In addition, the material of the adherend may be any one of metal, glass, plastic, etc. Furthermore, the shape of the adherend is not particularly limited, and examples thereof include: film-shaped, sheet-shaped, plate-shaped, panel-shaped, disk-shaped, rod-shaped, box-shaped, shell-shaped, etc. .

As described above, the light- and moisture-curable resin composition of the present invention is preferably used to join electronic components constituting an electronic device. Furthermore, the light- and moisture-curable resin composition of the present invention is preferably also used to join electronic components to other components. With these structures, electronic components 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 bond substrates to substrates to obtain assembled parts. The assembled part obtained in this way 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 via the hardened body. Furthermore, it is preferable that at least one electronic component is mounted on the first substrate and the second substrate respectively.

In addition, the light- and moisture-curable resin composition of the present invention is preferably used for narrow bezel applications. For example, in various display devices such as display devices for mobile phones such as smartphones, an adhesive is applied on a narrow square frame-shaped (ie, narrow frame) base, and a display panel is mounted through the adhesive. For touch panels, etc., 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 semiconductor wafers, for example, for bonding semiconductor wafers to each other. Example

Hereinafter, the present invention will be described in further detail using examples, but the present invention is not limited to these examples.

[physical properties] In each of the Examples and Comparative Examples, the physical properties of the light- and moisture-curable resin composition were evaluated as follows.

<Storage elastic modulus> The light- and moisture-curable resin composition is poured into a Teflon (registered trademark) mold with a width of 3 mm, a length of 30 mm, and a thickness of 1 mm, and is hardened to obtain a hardened product sample. . Furthermore, the hardened product sample was obtained in the following way: using UV-LED (wavelength 365 nm), in an environment of 25°C and 50 RH%, using 3000 mJ/cm ² to light and moisture curable resin composition It is photocured by irradiating ultraviolet rays, and then left in an environment of 25° C. and 50% RH for 72 hours to be moisture cured. Using the obtained hardened material sample, the storage elastic modulus of the hardened material sample at 25°C was measured with a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., trade name "DVA-200"). Furthermore, the measurement conditions are that the deformation mode is tensile, the set strain is 1%, the measurement frequency is 1 Hz, and the temperature rise rate is 5°C/min. Furthermore, when photocuring is performed when measuring the storage elastic modulus, the illumination during photocuring is adjusted within the range of 1000 mW/cm ² . The same applies to the measurement of the initial pressing (PUSH) adhesive force described below.

<Initial Press Adhesion Force> As shown in Figure 1(a), prepare a first substrate 11 of 90 mm×50 mm, a thickness of 5 mm, and a circular hole 11A with a diameter of 12 mm in the center, and a 50 mm×50 mm and a second substrate 12 with a thickness of 5 mm. The first substrate 11 is made of polycarbonate (PC), and the second substrate 12 is made of polycarbonate (PC). Using a dispensing machine to surround the hole 11A of the first substrate 11 as the center, apply the adhesive composition 10 into a circular shape of 25 mm in diameter with a width of 1 mm±0.2 mm and a thickness of 0.4 mm±0.05 mm. . Within 1 minute after the coating is completed, a UV-LED (wavelength 365 nm) is used to irradiate ultraviolet light at 3000 mJ/cm ² to thereby light-harden the adhesive composition 10 . Thereafter, a gap material (not shown) with a height of 0.2 mm and the adhesive composition 10 are interposed, so that the center positions of the first and second substrates 11 and 12 are consistent with each other, and the second substrate 12 is overlapped on the first substrate. 11, and a weight of 1 kg was placed on the second substrate 12 for 50 seconds to press-bond the first and second substrates 11 and 12 through the adhesive composition 10. Immediately after removing the weight of 1 kg (0 minutes later), the obtained measurement sample 13 was arranged so that the first substrate 11 was on the upper side and the second substrate 12 was on the lower side, and was made of stainless steel. In a state where the first substrate 11 is supported, a rod-shaped member 14 having a circular cross-section with a diameter of 10 mm is inserted into the hole 11A. Then, as shown in FIG. 1( b ), the second substrate 12 is pressed vertically downward by the rod-shaped member 14 at a speed of 10 mm/min, and the stress when the second substrate 12 is peeled off from the first substrate 11 is measured, and is set to Initial pressing force (0 minutes). In addition, the initial pressing adhesion force (15 minutes) was measured in the same manner except that a weight of 1 kg was removed and the measurement was performed after letting it stand for 15 minutes. Furthermore, the initial pressing adhesion force (30 minutes) was measured in the same manner except that a weight of 1 kg was removed and the measurement was performed after letting it stand for 30 minutes. Furthermore, in the above-mentioned measurement of the initial press adhesive force, a series of operations from photohardening to measurement of the adhesive force were performed in an environment of 25°C and 50 RH%.

＜Evaluation of final pressing force＞ In the method for measuring the initial pressing adhesion force, the final pressing force is measured in the same way except that after removing the weight of 1 kg and leaving the adhesive composition 10 at 25°C and 50 RH% for 24 hours to allow moisture to harden. Then force. Based on this measured value, the final pressing adhesive force is evaluated. The evaluation criteria are as follows. (Evaluation criteria) A: More than 2 MPa B: 1 MPa or more and 2 MPa or less C: Less than 1 MPa

The polyurethane resin raw materials used in each of the Examples and Comparative Examples were produced according to the methods shown in Synthesis Examples 1 and 2 below. [Synthesis example 1] ＜PC polyurethane resin raw materials＞ For 100 parts by mass of polycarbonate diol (a compound represented by formula (2)) as a polyol compound, 90 mol% of R is 3-methylpentylene and 10 mol% is hexamethylene, (manufactured by Kuraray Co., Ltd., trade name "Kuraray polyol C-1090") and 0.01 parts by mass of dibutyltin dilaurate were placed in a detachable flask with a capacity of 500 mL. Stir and mix in the flask under vacuum (below 20 mmHg) and 100°C for 30 minutes. Thereafter, the pressure was adjusted to normal, 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the mixture was stirred at 70° C. for 6 hours to react, thereby obtaining Polyurethane resin raw material with polycarbonate skeleton and isocyanate groups at both ends (PC polyurethane resin raw material). The weight average molecular weight of the obtained PC polyurethane resin raw material was 6,000.

[Synthesis example 2] ＜PE polyurethane resin raw materials＞ Add 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-3000") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate to a volume of 500 mL. in a separate flask. Stir and mix in the flask under vacuum (below 20 mmHg) and 100°C for 30 minutes. Thereafter, the pressure was adjusted to normal, and 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the mixture was stirred at 80° C. for 3 hours to react, thereby obtaining Polyurethane resin raw material with polyether skeleton and isocyanate groups at both ends (PE polyurethane resin raw material). The weight average molecular weight of the obtained PE polyurethane resin raw material was 2700.

In addition, the photoradical polymerization initiator used in each example was produced according to the method shown in the following synthesis examples 3 to 5. [Synthesis example 3] ＜Photoradical polymerization initiator (A)＞ The PC polyurethane resin raw material obtained in Synthesis Example 1 and 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., product name " Оmnirad 1173") mixture. 5.5 parts by mass of this mixture, 60 parts by mass of a mixture of radically polymerizable compounds 1 to 4 mixed at the ratio described in Table 1, and 1 part by mass of the catalyst were placed in a flask. Thereafter, the PC polyurethane resin raw material and 2-hydroxy-2-methylpropiophenone were reacted at 80° C. for 6 hours to prepare a photoradical polymerization initiator (A). The photoradical polymerization initiator (A) is obtained as a mixture of radically polymerizable compounds 1 to 4 and a catalyst (hereinafter also referred to as initiator-containing acrylic masterbatch (MB-A)). Furthermore, the weight average molecular weight of the photoradical polymerization initiator (A) is 6300, and it has two reaction starting points in the molecule.

[Synthesis Example 4] ＜Photoradical polymerization initiator (B)＞ The PE polyurethane resin raw material obtained in Synthesis Example 2 and 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., product name " Оmnirad 1173") mixture. 5.5 parts by mass of this mixture, 60 parts by mass of a mixture of radically polymerizable compounds 1 to 4 mixed at the ratio described in Table 1, and 1 part by mass of the catalyst were placed in a flask. Thereafter, the PE polyurethane resin raw material and 2-hydroxy-2-methylpropiophenone were reacted at 80° C. for 6 hours to prepare a photoradical polymerization initiator (B). The photoradical polymerization initiator (B) is obtained as a mixture of radically polymerizable compounds 1 to 4 and a catalyst (hereinafter also referred to as initiator-containing acrylic masterbatch (MB-B)). Furthermore, the weight average molecular weight of the photoradical polymerization initiator (B) is 3000, and it has two reaction starting points in the molecule.

[Synthesis Example 5] ＜Photoradical polymerization initiator (C)＞ As a polyisocyanate compound, diphenylmethane diisocyanate (manufactured by Nisso Corporation, trade name "Pure MDI") and 2-hydroxy-2 were prepared so that the molar ratio of isocyanate groups and hydroxyl groups became 1/1. - A mixture of methylpropiophenone (manufactured by IGM Resins B.V., product name "Оmnirad 1173"). 0.9 parts by mass of this mixture, 60 parts by mass of a mixture of radically polymerizable compounds 1 to 4 mixed at a ratio described in Table 1, and 1 part by mass of a catalyst were placed in a flask. Thereafter, the polyisocyanate compound and 2-hydroxy-2-methylpropiophenone were reacted at 80° C. for 6 hours to prepare a photoradical polymerization initiator (C). The photoradical polymerization initiator (C) is obtained as a mixture of radically polymerizable compounds 1 to 4 and a catalyst (hereinafter also referred to as initiator-containing acrylic masterbatch (MB-C)). Furthermore, the molecular weight of the photoradical polymerization initiator (C) is 578, and it has two reaction starting points in the molecule.

[Example 1] 66.5 parts by mass of the starter-containing acrylic masterbatch (MB-A) obtained in Synthesis Example 3, 75 parts by mass of the PC polyurethane resin raw material obtained in Synthesis Example 1, and 25 parts by mass of polycarbonate diol used in Synthesis Example 1 Mass parts are mixed. By stirring the obtained mixture at 50°C, the polyol is reacted with part of the PC polyurethane resin raw material to synthesize a chain-extended moisture-curable polyurethane resin with residual isocyanate groups, thereby obtaining radically polymerizable compounds 1 to 1 4. A mixture of moisture-hardening resin and photoradical polymerization initiator. 3 parts by mass of the filler and 1.5 parts by mass of the additive were added to the obtained mixture, and further mixed to obtain a light- and moisture-curable resin composition. The details of the obtained light and moisture curable resin composition are shown in Table 2.

[Example 2] In addition to using 66.5 parts by mass of the acrylic masterbatch (MB-B) containing the starter obtained in Synthesis Example 4 instead of 66.5 parts by mass of the acrylic masterbatch (MB-A) containing the starter obtained in Synthesis Example 3, Implemented in the same manner as Example 1. The details of the obtained light and moisture curable resin composition are shown in Table 2.

[Example 3] Except that 61.9 parts by mass of the acrylic masterbatch containing the starter (MB-C) obtained in Synthesis Example 5 was used instead of 66.5 parts by mass of the acrylic masterbatch containing the starter (MB-A) obtained in Synthesis Example 3. Implemented in the same manner as Example 1. The details of the obtained light and moisture curable resin composition are shown in Table 2.

[Comparative example 1] As recorded in Table 1, 0.5 parts by mass of the photoradical polymerization initiator (D) and 1 part by mass of the catalyst were mixed into the mixture of radical polymerizable compounds 1 to 4 to prepare an acrylic masterbatch containing the initiator ( MB-D). In the same manner as in Example 1, except that 61.5 parts by mass of the acrylic masterbatch containing the starter (MB-D) was used instead of 66.5 parts by mass of the acrylic masterbatch containing the starter (MB-A) obtained in Synthesis Example 3. implementation. The details of the obtained light and moisture curable resin composition are shown in Table 2.

The components other than the moisture-curable resin and the photoradical polymerization initiator obtained in Synthesis Examples 3 to 5 are as follows.

Radically polymerizable compound 1: diethyl acrylamide Radically polymerizable compound 2: 1,2-ethylene glycol 1-acrylate 2-(n-butylcarbamate) Radically polymerizable compound 3: acrylic acid Phenoxyethyl ester radically polymerizable compound 4: N-vinyl-ε-caprolactam Catalyst: bis(2- Phylinylethyl) ether photoradical polymerization initiator (D): manufactured by BASF, trade name "IRGACURE 369" Filler: trimethylsilylated silica, manufactured by Japan Aerosil Corporation, trade name "R812 ", primary particle size 7 nm. Additive: a mixture of silane coupling agent and antioxidant with a mass ratio of 1:1

[Table 1] MB-A MB-B MB-C MB-D Radically polymerizable compound 1 (parts by mass) 15 15 15 15 Free radical polymerizable compound 2 (mass part) 15 15 15 15 Radically polymerizable compound 3 (parts by mass) 10 10 10 10 Radically polymerizable compound 4 (parts by mass) 20 20 20 20 Photoradical polymerization initiator (A) (mass part) Mw=6300 5.5 Photoradical polymerization initiator (B) (mass part) Mw=3000 5.5 Photoradical polymerization initiator (C) (mass part) Mw=578 0.9 Photoradical polymerization initiator (D) (mass part) Mw=367 0.5 Catalyst (mass parts) 1 1 1 1

The light- and moisture-curable resin compositions obtained in each of the Examples and Comparative Examples are shown in Table 2 below.

[Table 2] Example 1 Example 2 Example 3 Comparative example 1 Composition (mass parts) Moisture hardening resin 100 100 100 100 MB-A 66.5 MB-B 66.5 MB-C 61.9 MB-D 61.5 filler 3 3 3 3 additives 1.5 1.5 1.5 1.5 total 171 171 166.4 166 physical properties Storage elastic modulus of hardened body (MPa) 0.97 0.47 0.66 0.52 Initial pressing force (0 min after crimping, MPa) 0.76 0.64 0.70 0.36 Initial press bonding force (15 minutes after crimping, MPa) 0.77 0.72 0.87 0.44 Initial press bonding force (30 minutes after crimping, MPa) 0.98 1.08 0.93 0.76 Evaluation of final pressing force A B B A

As shown in Table 2, the light- and moisture-curable resin compositions produced in Examples 1 to 3 were all excellent in initial adhesive strength. In contrast, the light- and moisture-curable resin composition produced in Comparative Example 1 had a lower initial adhesive strength.

10: Adhesive composition 11: 1st substrate 11A:hole 12: 2nd substrate 13: Samples for measurement 14: Rod-shaped member

[Fig. 1] is a schematic diagram showing the adhesion test method, Fig. 1(A) is a top view, and Fig. 1(B) is a side view.

Claims (10)

A light- and moisture-curable resin composition, which includes a radically polymerizable compound, a moisture-hardening resin, and a photoradical polymerization initiator. The above-mentioned photoradical polymerization initiator has more than two reactions in the molecule. starting point. The light and moisture curable resin composition according to claim 1, wherein the photo radical polymerization initiator has a structure derived from a bifunctional or higher aromatic isocyanate compound. The light and moisture curable resin composition of claim 1 or 2, wherein the molecular weight of the above-mentioned photo radical polymerization initiator is 500 or more. The light- and moisture-curable resin composition according to any one of claims 1 to 3, wherein the photoradical polymerization initiator has an urethane bond in the molecule. The light and moisture curable resin composition according to any one of claims 1 to 4, wherein in the above-mentioned photo radical polymerization initiator, at least one reaction starting point is acetophenone type. The light- and moisture-curable resin composition according to any one of claims 1 to 5, wherein the content of the above-mentioned photo radical polymerization initiator is 0.5 based on the total amount of the above-mentioned light- and moisture-curable resin composition. More than 10% by mass and less than 10% by mass. The light and moisture curable resin composition according to any one of claims 1 to 6, wherein the content of the monofunctional radical polymerizable compound in the light and moisture curable resin composition is relative to the radical polymerization 100 parts by mass of the chemical compound is 90 parts by mass or more. An adhesive for electronic parts consisting of the light- and moisture-curable resin composition according to any one of claims 1 to 7. An adhesive for display elements consisting of the light- and moisture-curable resin composition according to any one of claims 1 to 7. A cured body of the light- and moisture-curable resin composition according to any one of claims 1 to 7.