TW202134309A - Photo/moisture curable resin composition, adhesive for electronic components, method for producing electronic component, and cured body - Google Patents

Abstract

A photo/moisture curable resin composition according to the present invention contains a radically polymerizable compound, a moisture curable urethane resin and a photopolymerization initiator; the moisture curable urethane resin contains a moisture curable urethane resin that has a polyester skeleton; and if a load of 0.04 MPa is applied to a photocured product thereof obtained by means of ultraviolet light irradiation of 1,000 mJ/cm2, the thickness change ratio before and after the application of load is 50% or less.

Description

Light and moisture curable resin composition, adhesive for electronic parts, manufacturing method of electronic parts, and hardened body

The present invention relates to a light and moisture curable resin composition, an adhesive for electronic parts, a method for manufacturing electronic parts using the adhesive for electronic parts, and a cured body of the light and moisture curable resin composition.

In recent years, liquid crystal display elements, organic EL display elements, etc. have been widely used as display elements with characteristics such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is generally used for sealing of liquid crystal or light-emitting layer, bonding of various members such as substrates, optical films, and protective films. However, in today's era, mobile devices with various display components such as mobile phones and portable game consoles are becoming more and more popular. The miniaturization of display components is the most concerned topic. As a method of miniaturization, the narrow margin of the image display unit is implemented ( Hereinafter also referred to as narrow-edge design). However, in a narrow-edge design, a photo-curable resin composition is sometimes coated on a portion that cannot be reached by light. As a result, there is a problem of insufficient curing of the photo-curable resin composition applied to a portion that cannot be reached by light. . In this regard, the following operation was also carried out, that is, a photothermosetting resin composition was used as a resin composition that can be cured sufficiently even when applied to a part that cannot be reached by light, and both photocuring and thermal curing were used, but There is a possibility that heating at high temperatures may have adverse effects on components.

In addition, in recent years, electronic components such as semiconductor wafers have been required to be highly integrated and miniaturized. For example, an operation is performed to bond a plurality of thin semiconductor wafers through an adhesive layer to form a laminated body of semiconductor wafers. Such a semiconductor wafer laminate is manufactured by, for example, the following method: after coating an adhesive on a semiconductor wafer, laminating another semiconductor wafer through the adhesive, and then hardening the adhesive; and holding it at regular intervals An adhesive is filled between the semiconductor wafers, and then the adhesive is cured. Similarly, in the narrow-edge design, a method to completely harden the applied adhesive after semi-hardening is also studied. Therefore, it has been studied to use light moisture curable resin composition as an adhesive in the bonding of electronic parts such as the lamination of small semiconductor chips and display elements with narrow-edge design.

For example, Patent Document 1 discloses a light-moisture-curable resin composition and an adhesive for electronic parts that have flexibility of the cured product and excellent reliability in a high-temperature and high-humidity environment. Prior art literature Patent literature

Patent Document 1: International Publication No. 2016/076407

[The problem to be solved by the invention]

However, in the bonding of small electronic parts or narrow-edge design, sometimes not only bonding strength is required, but also durability of bonding force is required. Specifically, electronic parts such as semiconductor wafers and display elements are sometimes exposed to a high temperature of about 80°C during their assembly steps and use due to external heating or heat generated by the electronic parts themselves during operation. In addition, electronic components may also be exposed to low temperatures below 0°C depending on the use environment. On the other hand, when the dissimilar materials are bonded to each other by an adhesive, since the thermal expansion coefficients of the dissimilar materials are different from each other, if the temperature changes as described above, the adhesive may occur during the assembly process and use. Greater strain. If such strain occurs repeatedly, the adhesive will be partially broken, etc. and the adhesive strength of the adhesive will decrease. Therefore, it is sometimes required to suppress the decrease of the adhesive force by stress relaxation and improve the durability of the adhesive force even after the repeated strain occurs.

Furthermore, in recent years, even when electronic parts such as semiconductor chips, display elements, etc. are exposed to high temperatures due to external heating or the heat of the electronic parts themselves during operation, sufficient adhesive force for firmly bonding the electronic parts is required .

In the light and moisture curable resin composition disclosed in Patent Document 1, since a cured product with moderate flexibility can be obtained, it is excellent in stress relaxation and has adhesive durability. However, in the light and moisture curable resin composition disclosed in Patent Document 1, there is a problem that the adhesive force at high temperature is insufficient.

Therefore, the subject of the present invention is to provide a light and moisture curable resin composition and an adhesive for electronic parts that are excellent in both durability of adhesive force and sufficient adhesive force at high temperature. [Technical means to solve the problem]

As a result of intensive research, the inventors have conducted research on moisture-curable urethane resins to improve the high-temperature adhesion of conventional light and moisture-curable resin compositions. Furthermore, the inventors of the present invention found that by blending a moisture-curable urethane resin having a polyester skeleton as the moisture-curable urethane resin, the high-temperature adhesive force can be greatly improved. On the other hand, the inventors of the present invention found the problem that when a moisture-curable urethane resin having a polyester skeleton is used as the moisture-curable urethane resin, sufficient adhesive durability cannot be obtained. Therefore, the inventors of the present invention have conducted intensive studies and found that by setting the thickness change rate before and after the load is applied to the cured product in the light-cured state to 50% or less, it is possible to achieve both high-temperature adhesive strength and adhesive strength at a high level. The durability, thus completing the present invention.

式（1）中，R表示氫原子、甲基、及乙基之任一者，l為整數0～5，m為整數1～500，n為整數1～10。 [6]如上述[4]所記載之光與濕氣硬化性樹脂組成物，其中，上述聚醚多元醇係選自由聚丙二醇、四氫呋喃化合物之開環聚合化合物、及具有甲基作為取代基之四氫呋喃化合物之開環聚合化合物所組成之群中之至少1種。 [7]如上述[4]所記載之光與濕氣硬化性樹脂組成物，其中，上述聚醚多元醇為聚丙二醇。 [8]如上述[1]或[2]所記載之光與濕氣硬化性樹脂組成物，其中，上述具有聚酯骨架之濕氣硬化性胺酯樹脂於分子內具有聚醚骨架。 [9]如上述[1]至[8]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光與濕氣硬化性樹脂組成物進而包含間隔粒子。 [10]如上述[1]至[9]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，100質量%之上述光與濕氣硬化性樹脂組成物中，自由基聚合性化合物之含量為3質量%以上。 [11]如上述[1]至[10]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光聚合起始劑為具有醯基膦氧化物（acylphosphine oxide）系骨架之化合物、或具有α-胺基烷基苯酮（α-aminoalkylphenone）系骨架之化合物。 [12]如上述[1]至[11]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光硬化之狀態之硬化物於25℃之儲存彈性模數為10 kPa以上。 [13]如上述[1]至[12]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，藉由將上述光硬化之狀態之硬化物於23℃、50RH%之環境下靜置3日而獲得之硬化物於25℃之儲存彈性模數為1 MPa以上。 [14]如上述[1]至[13]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述具有聚酯骨架之濕氣硬化性胺酯樹脂係藉由使1分子中具有2個以上羥基之聚酯多元醇、與1分子中具有2個以上異氰酸基之聚異氰酸酯化合物進行反應而獲得。 [15]如上述[14]所記載之光與濕氣硬化性樹脂組成物，其中，上述聚酯多元醇為選自由鄰苯二甲酸、對苯二甲酸、間苯二甲酸、及己二酸所組成之群中之至少1種多元羧酸、與選自由1,6-己二醇及1,4-丁二醇所組成之群中之至少1種多元醇之酯。 [16]如上述[1]至[15]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述自由基聚合性化合物包含(甲基)丙烯酸化合物。 [17]如上述[16]所記載之光與濕氣硬化性樹脂組成物，其中，上述(甲基)丙烯酸化合物包含單官能之(甲基)丙烯酸化合物。 [18]如上述[17]所記載之光與濕氣硬化性樹脂組成物，其中，上述(甲基)丙烯酸化合物進而包含多官能之(甲基)丙烯酸化合物。 [19]如上述[18]所記載之光與濕氣硬化性樹脂組成物，其中，上述多官能之(甲基)丙烯酸化合物之含量相對於自由基聚合性化合物總量，為1質量%以上50質量%以下。 [20]如上述[17]至[19]之至少任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述單官能之(甲基)丙烯酸化合物為(甲基)丙烯酸酯化合物。 [21]如上述[1]至[20]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光與濕氣硬化性樹脂組成物100質量%中，上述自由基聚合性化合物之含量為50質量%以下。 [22]如上述[1]至[21]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光與濕氣硬化性樹脂組成物100質量%中，上述濕氣硬化性胺酯樹脂之含量為45質量%以上95質量%以下。 [23]如上述[1]至[22]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光與濕氣硬化性樹脂組成物100質量%中，上述具有聚酯骨架之濕氣硬化性胺酯樹脂之含量為25質量%以上95質量%以下。 [24]如上述[1]至[23]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述光與濕氣硬化性樹脂組成物中之上述光聚合起始劑之含量相對於自由基聚合性化合物及濕氣硬化性胺酯樹脂之合計量100質量份，為0.01質量份以上10質量份以下。 [25]如上述[1]至[24]中任一項所記載之光與濕氣硬化性樹脂組成物，其中，上述厚度變化率為5%以上。 [26]一種電子零件用接著劑，其由上述[1]至[25]中任一項所記載之光與濕氣硬化性樹脂組成物構成。 [27]一種電子機器之製造方法，其包括如下步驟：對上述[26]所記載之電子零件用接著劑進行加熱；及 將上述電子零件用接著劑塗佈於電子零件。 [28]一種方法，其係使用上述[26]所記載之電子零件用接著劑，將電子零件彼此、或電子零件與其他構件接著。 [29]一種硬化體，其係上述[1]至[25]中任一項所記載之光與濕氣硬化性樹脂組成物之硬化體。 [30]一種電子機器，其具備上述[29]所記載之硬化體。 [發明之效果]That is, the present invention provides the following [1] to [30]. [1] A light and moisture-curable resin composition comprising a radical polymerizable compound, a moisture-curable urethane resin, and a photopolymerization initiator, the moisture-curable urethane resin having a polyester skeleton Moisture-curing urethane resin. ^{When a load of 0.04 MPa is applied to a cured product that is photo-cured by irradiating 1000 mJ/cm 2} of ultraviolet rays, the thickness change rate before and after the load is 50% or less. [2] The light and moisture curable resin composition described in [1] above has a viscosity of 3000 Pa·s or less at 25°C and 1 rpm. [3] The light and moisture-curable resin composition as described in [1] or [2], wherein the moisture-curable urethane resin further includes a moisture-curable urethane resin having a polyether skeleton. [4] The light and moisture curable resin composition as described in [3] above, wherein the moisture curable urethane resin having a polyether skeleton is a polyether polyether resin having two or more hydroxyl groups per molecule Alcohol is obtained by reacting with a polyisocyanate compound having two or more isocyanate groups in one molecule. [5] The light and moisture curable resin composition as described in [4] above, wherein the polyether polyol has a structure represented by the following formula (1).

In formula (1), R represents any one of a hydrogen atom, a methyl group, and an ethyl group, l is an integer of 0-5, m is an integer of 1 to 500, and n is an integer of 1-10. [6] The light and moisture curable resin composition described in [4] above, wherein the polyether polyol is selected from the group consisting of polypropylene glycol, ring-opening polymer compounds of tetrahydrofuran compounds, and those having a methyl group as a substituent At least one of the group consisting of the ring-opening polymer compound of the tetrahydrofuran compound. [7] The light and moisture curable resin composition as described in [4] above, wherein the polyether polyol is polypropylene glycol. [8] The light and moisture curable resin composition according to the above [1] or [2], wherein the moisture curable urethane resin having a polyester skeleton has a polyether skeleton in the molecule. [9] The light and moisture curable resin composition according to any one of the above [1] to [8], wherein the light and moisture curable resin composition further includes spacer particles. [10] The light and moisture curable resin composition according to any one of [1] to [9] above, wherein 100% by mass of the light and moisture curable resin composition is radically polymerized The content of the sexual compound is 3% by mass or more. [11] The light and moisture curable resin composition according to any one of [1] to [10] above, wherein the photopolymerization initiator has an acylphosphine oxide skeleton Compounds, or compounds with α-aminoalkylphenone (α-aminoalkylphenone) skeleton. [12] The light and moisture curable resin composition according to any one of [1] to [11] above, wherein the cured product in the light-cured state has a storage elastic modulus at 25°C of 10 kPa above. [13] The light and moisture curable resin composition as described in any one of [1] to [12] above, wherein the cured product in the light-cured state is exposed to an environment of 23°C and 50RH% The storage elastic modulus of the hardened product obtained by letting it stand for 3 days at 25°C is 1 MPa or more. [14] The light and moisture curable resin composition according to any one of [1] to [13] above, wherein the moisture curable urethane resin having a polyester skeleton is obtained by making one molecule It is obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. [15] The light and moisture curable resin composition as described in [14] above, wherein the polyester polyol is selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, and adipic acid An ester of at least one polycarboxylic acid in the group consisting of and at least one polyhydric alcohol selected from the group consisting of 1,6-hexanediol and 1,4-butanediol. [16] The light and moisture curable resin composition according to any one of [1] to [15] above, wherein the radically polymerizable compound includes a (meth)acrylic compound. [17] The light and moisture curable resin composition according to the above [16], wherein the (meth)acrylic compound includes a monofunctional (meth)acrylic compound. [18] The light and moisture curable resin composition according to the above [17], wherein the (meth)acrylic compound further includes a polyfunctional (meth)acrylic compound. [19] The light and moisture curable resin composition as described in [18] above, wherein the content of the polyfunctional (meth)acrylic compound is 1% by mass or more with respect to the total amount of radically polymerizable compounds 50% by mass or less. [20] The light and moisture curable resin composition according to at least any one of [17] to [19] above, wherein the monofunctional (meth)acrylic compound is a (meth)acrylate compound . [21] The light and moisture curable resin composition according to any one of the above [1] to [20], wherein in 100% by mass of the light and moisture curable resin composition, the radical polymerization The content of the sexual compound is 50% by mass or less. [22] The light and moisture curable resin composition according to any one of the above [1] to [21], wherein in 100% by mass of the light and moisture curable resin composition, the moisture curable The content of the urethane resin is 45% by mass or more and 95% by mass or less. [23] The light and moisture curable resin composition according to any one of [1] to [22], wherein in 100% by mass of the light and moisture curable resin composition, the polyester The content of the moisture-curable urethane resin in the skeleton is 25% by mass or more and 95% by mass or less. [24] The light and moisture curable resin composition according to any one of the above [1] to [23], wherein the photopolymerization initiator in the light and moisture curable resin composition is The content is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture curable urethane resin. [25] The light and moisture curable resin composition according to any one of [1] to [24] above, wherein the thickness change rate is 5% or more. [26] An adhesive for electronic parts, which is composed of the light and moisture curable resin composition described in any one of [1] to [25] above. [27] A method of manufacturing an electronic device, comprising the steps of: heating the adhesive for electronic parts described in [26] above; and applying the adhesive for electronic parts to the electronic parts. [28] A method of using the adhesive for electronic parts described in [26] above to bond electronic parts to each other or electronic parts to other members. [29] A cured body which is a cured body of the light and moisture curable resin composition described in any one of [1] to [25] above. [30] An electronic device comprising the hardened body described in [29] above. [Effects of Invention]

In the present invention, it is possible to provide a light and moisture curable resin composition that is excellent in both durability of adhesive force and sufficient adhesive force at high temperature, and an adhesive for electronic parts.

Hereinafter, the present invention will be described in detail. [Light and moisture curable resin composition] The light and moisture curable resin composition of the present invention contains a radical polymerizable compound, a moisture curable urethane resin, and a photopolymerization initiator. /cm ² of the cured product in the state of UV light curing, when a load of 0.04 MPa is applied, the thickness change rate before and after the load is 50% or less.

In the light and moisture-curable resin composition of the present invention, the moisture-curable urethane resin includes a moisture-curable urethane resin having a polyester skeleton. The light and moisture curable resin composition of the present invention can improve the adhesive force under high temperature environment by including a urethane prepolymer having a polyester skeleton. In addition, the light and moisture curable resin composition of the present invention has a thickness change rate of 50% or less before and after the load is applied to the cured product in the light-cured state, which has good stress relaxation properties and can improve the durability of adhesive force. For example, even if it is repeatedly placed in a high temperature environment and a low temperature environment, it can maintain a certain adhesive force. The thickness change rate before and after load application is preferably 45% or less, more preferably 40% or less. In addition, from the viewpoint of easy improvement of the adhesive force at high temperature, the thickness change rate is preferably 5% or more, and more preferably 10% or more.

(The rate of change in thickness of the cured product in the light-cured state) The cured product in the light-cured state refers to a cured product in a state where the light and moisture-curable resin composition is light-cured without being cured by moisture. In addition, the thickness change rate before and after the load is applied to the cured product in the light-cured state may be measured in the following procedure. <The rate of change in the thickness of the cured product in the light-cured state> Using a dispensing device, the light and moisture-curable resin composition has a line width of 1.0±0.1 mm, a length of 25±0.2 mm, and a thickness of 0.4±0.1 mm coating on polycarbonate substrate (length 50 mm, width 25 mm, thickness 2 mm). Within 1 minute after the coating is completed, use a UV-LED lamp to irradiate 1000 mJ/cm ² of ultraviolet rays to light-harden the light and moisture-curable resin composition. Furthermore, the wavelength of the UV-LED lamp can be appropriately selected according to the absorption wavelength of the contained photopolymerization initiator, for example, the wavelength of 365 nm can be used. Immediately after irradiated with ultraviolet rays, in an environment of 25°C, overlay a glass substrate of the same size as the polycarbonate substrate on the cured product in a light-cured state, and place a 100 g weight on it for 10 seconds to correct The entire hardened product in the light-hardened state is subjected to a load of 0.04 MPa for 10 seconds. Immediately after light irradiation and after the applied load, use a digital microscope to measure the thickness of the central part of the cured product in a light-hardened state, and measure the thickness change rate (%) in the following way. Thickness change rate (%) = (thickness just after light irradiation-thickness after applying load)/(thickness just after light irradiation)×100

(Storage elastic modulus of hardened material in light hardened state) The storage elastic modulus of the cured product in the light-cured state of the light and moisture-curable resin composition of the present invention at 25°C is, for example, 2 kPa or more, preferably 10 kPa or more, more preferably 15 kPa or more, and more preferably Above 20 kPa. By setting the storage elastic modulus of the cured product in the light-cured state at 25°C to the above lower limit, it is easy to adjust the thickness change rate of the cured product in the light-cured state within a specific range. In addition, from the viewpoint of improving the initial adhesion, the upper limit of the storage elastic modulus of the cured product in the light-cured state at 25° C. is preferably 200 kPa or less, more preferably 100 kPa or less.

Furthermore, the storage elastic modulus of the cured product in the light-cured state at 25°C can be measured in the following order. <Storage elastic modulus in light-cured state> Place 3 g of light and moisture-curable resin composition in a UV irradiation rheometer (trade name HAAKE MARS 40/60, manufactured by Thermo Fisher Scientific). 30 seconds after the completion of the placement, the UV-LED lamp was used to irradiate ^{the ultraviolet rays of 1000 mJ/cm 2} to make it photohardened. After irradiating ultraviolet rays for 60 seconds, the shear storage elastic modulus was measured under the conditions of 25°C and 50RH% under the condition of frequency F=1.6 Hz. Furthermore, the wavelength of the UV-LED lamp can be appropriately selected according to the absorption wavelength of the contained photopolymerization initiator, for example, the wavelength of 365 nm can be used.

(The storage elastic modulus of the hardened material in the state of light moisture hardening) The storage elastic modulus at 25°C of the light and moisture curable resin composition of the light and moisture curable resin composition of the present invention is preferably 1 MPa or more, more preferably 5 MPa or more, and more preferably 10 MPa or more . By setting the storage elastic modulus of the cured product in the light moisture cured state at 25°C to above the above lower limit, the high-temperature adhesive strength can be further improved. In addition, from the viewpoint of improving the durability of the adhesive force, the storage elastic modulus of the cured product in the light moisture curing state at 25°C is, for example, 700 MPa or less, preferably 100 MPa or less, and more preferably 70 MPa or less .

Furthermore, the storage elastic modulus of the cured product in the light moisture curing state at 25°C can be measured in the following order. <Storage elastic modulus in light and moisture hardened state> Fill the light and moisture hardening resin composition in a Teflon (registered trademark) mold with a width of 3 mm, a length of 30 mm, and a thickness of 1 mm. Within 1 minute after the filling is completed, the curable resin composition is light-cured by ^{irradiating 1000 mJ/cm 2 of ultraviolet rays with a UV-LED lamp.} Furthermore, the wavelength of the UV-LED lamp can be appropriately selected according to the absorption wavelength of the contained photopolymerization initiator, for example, the wavelength of 365 nm can be used. After that, it was allowed to stand for 3 days under an environment of 23°C and 50RH%. The hardened product in the light moisture hardened state is taken out of the mold, and the dynamic viscoelasticity measurement device (manufactured by IT Measurement and Control Co., Ltd., trade name "DVA-200") is used to measure the dynamics in the range of -100°C to 150°C Viscoelasticity, calculate the storage elastic modulus at room temperature (25℃). The measurement conditions were set as the deformation mode as tensile, the set strain was 1%, the measurement frequency was 1 Hz, and the heating rate was 5°C/min.

(Viscosity) The light and moisture curable resin composition of the present invention has a viscosity measured at 25°C and 1 rpm using a cone-plate viscometer, preferably 3000 Pa·s or less, more preferably 2500 Pa·s or less, and more preferably It is 2000 Pa·s or less, more preferably 1500 Pa·s or less, and still more preferably 800 Pa·s or less. By setting the viscosity at 25°C to the upper limit or less, since coating can be carried out at room temperature or can be carried out by heating at a relatively low temperature, the workability during coating is improved. From the viewpoint of suppressing excessive wetting and spreading during coating, the lower limit of the viscosity is preferably 50 Pa·s or more.

As detailed below, the above-mentioned thickness change rate, storage elastic modulus, and viscosity are cured by appropriately changing the types and amounts of components used in radical polymerizable compounds, moisture-curable urethane resins, and light and moisture. The type and amount of each component added to the resin composition are adjusted.

[Free radical polymerizable compound] The light and moisture curable resin composition of the present invention contains a radical polymerizable compound. The light and moisture curable resin composition of the present invention has photocurability by containing a radical polymerizable compound.

((Meth)acrylic compound) The light and moisture curable resin composition of the present invention preferably contains a compound having a (meth)acryloyl group (hereinafter referred to as "(meth)acrylic compound") as a radical polymerizable compound. Furthermore, in this specification, "(meth)acryloyl" means acryloyl or (meth)acryloyl, "(meth)acrylic" means acrylic or methacrylic, and other similar terms The same is true.

Examples of the (meth)acrylic compound include (meth)acrylate compounds, epoxy (meth)acrylates, amine (meth)acrylates, polyester (meth)acrylates, and the like. The (meth)acrylic compound may be monofunctional or polyfunctional. In addition, (meth)acrylic acid amine ester does not have a residual isocyanate group.

Examples of the monofunctional among the above-mentioned (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, etc. (meth) Alkyl acrylate; cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, (meth) ) (Meth)acrylates with alicyclic structure such as isobornyl acrylate and dicyclopentenyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate (Meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; 2-methoxyethyl (meth)acrylate, (meth) Alkoxyalkyl (meth)acrylates such as 2-ethoxyethyl acrylate, 2-butoxyethyl (meth)acrylate, etc.; Methoxyethylene glycol (meth)acrylate, ethoxyethyl Alkoxyethylene glycol (meth)acrylate such as glycol (meth)acrylate; methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Methoxy polyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, ethoxy triethylene glycol (methyl) ) Polyoxyethylene-based (meth)acrylates such as acrylates and ethoxy polyethylene glycol (meth)acrylates.

In addition, the (meth)acrylate compound may have an aromatic ring, and examples thereof include phenylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; Phenoxyalkyl (meth)acrylates such as phenoxyethyl meth)acrylate and the like. Furthermore, it may be a (meth)acrylate having a plurality of benzene rings such as a chlorophyll skeleton and a biphenyl skeleton. Specifically, chlorophyll-type (meth)acrylate, ethoxylated o-phenylphenol acrylate, etc. may be mentioned. Furthermore, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxydiethylene glycol (meth)acrylate, Phenoxy polyoxyethylene-based (meth)acrylates such as nonylphenoxy polyethylene glycol (meth)acrylate and the like.

Furthermore, as the monofunctional (meth)acrylate compound, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alkoxylate (meth)acrylate, and cyclic trimethylolpropane formal ( (Meth) acrylate, 3-ethyl-3-oxocyclobutanyl methyl (meth)acrylate and other (meth)acrylates with heterocyclic structure; N-acryloyloxyethylhexahydroo Phthalic acid imine acrylates such as xylylenedimethine imines; various imidine (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, (meth) 2,2,3,3-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethyl (meth)acrylate Amino ethyl, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-hydroxypropyl phthalate 2- (Meth)acryloxyethyl, (meth)glycidyl acrylate, 2-(meth)acryloxyethyl phosphate, and the like.

Examples of the bifunctional (meth)acrylate compound include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di( Meth) acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylic acid Ester, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A bis(meth) Base) acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid Di(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether glycol bis(methyl) ) Acrylate, polyesterdiol di(meth)acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the tri- or more-functional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, and glycerol tri(meth)acrylate. Base) acrylate, neopentylerythritol tetra(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(methyl) ) Acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate tri(meth)acrylate, propylene oxide addition triglyceride Base) acrylate, tris(meth)acryloyloxyethyl phosphate, di-trimethylolpropane tetra(meth)acrylate, dineopentyl erythritol penta(meth)acrylate, dineopentyl erythritol Alcohol hexa (meth) acrylate and the like.

As said epoxy (meth)acrylate, what made an epoxy compound and (meth)acrylic acid react, etc. are mentioned, for example. Among them, the reaction between the epoxy compound and the (meth)acrylic acid is conventionally carried out in the presence of a basic catalyst. The epoxy (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, but is preferably polyfunctional. As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type ring Oxygen resin, vulcanized epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin , Dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidamine type epoxy resin, alkyl polyol type epoxy resin, rubber modification Qualitative epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin, etc.

Examples of commercially available epoxy (meth)acrylate esters include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBNEXRYL6040, EBNEXDALRICEL63182 Manufacturing), EA-1010, EA-1020, EA-5323, EA-5520, EACHD, EMA-1020 (all manufactured by Shinnakamura Chemical Industry Co., Ltd.), EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL ACRYLATE DA-141, DENACOL ACRYLATE COLLATE DA-314, DENA ACRYLATE DA -911 (all manufactured by Nagase Kasei Co., Ltd.), etc.

The amine (meth)acrylate can be obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, for example. Among them, in the reaction of the isocyanate compound and the (meth)acrylic acid derivative, a catalyst amount of a tin-based compound or the like may be used as a catalyst. The amine (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, and is preferably bifunctional. As the isocyanate compound used to obtain (meth)acrylate amine ester, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexa Methylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate Isocyanate, toluidine diisocyanate, xylylene diisocyanate (xylylene diisocyanate, XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, Polyisocyanate compounds such as tetramethylxylylene diisocyanate and 1,6,11-undecane triisocyanate. In addition, as the isocyanate compound, a chain-extended polyisocyanate compound obtained by the reaction of a polyol and an excess isocyanate compound can also be used. Among them, examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

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, polyethylene glycol, etc. Mono(meth)acrylate of diol; or mono(meth)acrylate or di(meth)acrylate of triol such as trimethylolethane, trimethylolpropane, glycerin, etc.; or double Epoxy (meth)acrylates such as phenol A type epoxy (meth)acrylates, etc.

Examples of commercially available amine (meth)acrylates include: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411 , EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9270, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by DAICEL-ALLNEXRES), ARTIN UN-H9000, ARTIN UN-H9000, ARTIN UN-H100 1255, ARTRESIN UN-330, ARTRESIN UN-3320HB, ARTRESIN UN-1200TPK, ARTRESIN SH-500B (all manufactured by Nejo Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U- 2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all manufactured by Shinnakamura Chemical Industry Co., Ltd.), AI- 600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), CN-902, CN-973, CN-9021, CN-9782, CN-9833 (all manufactured by ARKEMA), etc.

As said polyester (meth)acrylate, the thing obtained by making a polyester polyol and (meth)acrylic acid react, etc. are mentioned, for example. As the commercially available one among the above-mentioned polyester (meth)acrylates, for example, ARONIX M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M -8060, M-8100, M-8530, M-8560, M-9050 (all manufactured by Toa Synthetic Chemical Industry Co., Ltd.), Doublemer 2015, Doublemer 2231-TF, Doublemer 2319, Doublemer 257, Doublemer 276, Doublemer 284, Doublemer 2019, Doublemer 2232, Doublemer 236, Doublemer 270, Doublemer 278, Doublemer 285, Doublemer 220, Doublemer 2315-100, Doublemer 245, Doublemer 272, Doublemer 278X25, Doublemer 286, Doublemer 2230-TF, Doublemer 2315HM35, Doublemer 246, Doublemer 275 , Doublemer 281, Doublemer 287 (all manufactured by Double Bond Chemical Company), etc.

(Polymer (meth)acrylate) The light and moisture curable resin composition may also contain (meth)acrylate (hereinafter referred to as "polymer (meth)acrylate") having a number average molecular weight of 5000 or more as the (meth)acrylate compound. When the light and moisture curable resin composition contains a polymer (meth)acrylate, it is easy to adjust the above-mentioned thickness change rate within a specific range. The polymer (meth)acrylate is, for example, a compound in which the polymer chain part is a (meth)acrylate compound and has a (meth)acryloyl group at the end. As the (meth)acrylate compound, the above-mentioned ones are used, and the alkyl (meth)acrylate is preferably used. As such a polymer (meth)acrylate, AA-6 (number average molecular weight 6000, manufactured by Toagosei Co., Ltd.), AB-6 (number average molecular weight 6000, manufactured by Toagosei Co., Ltd.), etc. are mentioned, for example. In addition, the upper limit of the number average molecular weight of the polymer (meth)acrylate is not particularly limited, and is, for example, 100,000 or less.

啉、N-羥乙基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N,N-二甲胺基丙基(甲基)丙烯醯胺等(甲基)丙烯醯胺化合物；苯乙烯、α-甲基苯乙烯、N-乙烯基-2-吡咯啶酮、N-乙烯基-ε-己內醯胺等乙烯系化合物等。(Other radical polymerizable compound) As a radical polymerizable compound, other radical polymerizable compounds other than the above can also be used suitably. As other radical polymerizable compounds, for example, N,N-dimethyl(meth)acrylamide, N-(meth)acrylamide

Morpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylamine (Meth)acrylamide compounds such as propyl(meth)acrylamide; styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-hexanone Vinyl compounds such as amides.

In the present invention, the thickness change rate of the cured product in the light-cured state may be set within a specific range by appropriately combining the types or contents of the above-mentioned radically polymerizable compounds. For example, by using a compound having an acryl group as the (meth)acrylic compound, it is easy to improve the reactivity during light irradiation, and it is easy to adjust the thickness change rate of the cured product in a photocured state within a specific range. Also, for example, by using a multifunctional (meth)acrylic compound as the (meth)acrylic compound, it is easy to increase the reactivity during light irradiation, and as a result, it is easy to adjust the thickness change rate of the cured product in the light-cured state to Within a specific range.

As the polyfunctional (meth)acrylic compound, those mentioned above may be appropriately used. Preferably, the polyfunctional (meth)acrylic compound with a molecular weight of 600 or less (hereinafter, described as "polyfunctional (meth)) Acrylic compound X"). Examples of the polyfunctional (meth)acrylic compound X include polyfunctional (meth)acrylates having 6 to 30 carbon atoms, preferably 8 to 20 carbon atoms. In addition, the polyfunctional (meth)acrylate compound X is preferably 2-4 functional, more preferably 2 to trifunctional. If the polyfunctional (meth)acrylic compound X is used, the cohesive force (crosslink density) of the radical polymerizable compound becomes higher after light curing, and the above-mentioned thickness change rate can be further reduced. In addition, the viscosity of the light and moisture curable resin composition before light irradiation decreases, and the coating properties are also improved.

Specific examples of the polyfunctional (meth)acrylic compound X include: 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and triethylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate , Neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, etc. The polyfunctional (meth)acrylic compound X may be used singly, or two or more of them may be used in combination.

The polyfunctional (meth)acrylic compound X and the monofunctional radical polymerizable compound may be used in combination. The content of the polyfunctional (meth)acrylic compound X relative to the total amount of radically polymerizable compounds is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 35% by mass, more preferably 10% by mass % Above 30% by mass.

Moreover, the content of the total amount of polyfunctional (meth)acrylic compounds relative to the total amount of radical polymerizable compounds is, for example, 1% by mass or more and 50% by mass or less, preferably 3% by mass or more and 40% by mass or less.

The content of the radical polymerizable compound in 100% by mass of the light and moisture curable resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and more preferably It is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the content of the radically polymerizable compound is more than the above lower limit, it is easy to adjust the thickness change rate of the cured product in a photocured state within a specific range. Moreover, when the content of the radical polymerizable compound is less than the above upper limit, it is easy to increase the adhesive force at high temperature.

等。其中，就容易將上述光硬化之狀態之硬化物之厚度變化率調整為特定之範圍內之觀點而言，較佳為具有醯基膦氧化物系骨架之化合物、或具有α-胺基烷基苯酮系骨架之化合物。 作為上述光聚合起始劑中之市售者，例如可列舉：IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE379EG、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、LUCIRIN TPO（皆為BASF公司製造）、安息香甲醚、安息香乙醚、安息香異丙醚（皆為東京化成工業公司製造）等。[Photopolymerization initiator] The light and moisture curable resin composition of the present invention contains a photopolymerization initiator. By including a photopolymerization initiator, the light and moisture curable resin composition of the present invention can be given photocurability. As the photopolymerization initiator, for example, acetophenone-based compounds such as benzophenone-based compounds, α-aminoalkylphenones, and α-hydroxyalkylphenones, phosphine oxide-based compounds, and two Titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxysulfur 𠮿

Wait. Among them, from the viewpoint of easy adjustment of the thickness change rate of the cured product in the above-mentioned photocured state within a specific range, a compound having an phosphine oxide-based skeleton or an α-aminoalkyl group is preferred. Phenone is a compound of the skeleton. Examples of commercially available photopolymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, LUCIRIN TPO (all manufactured by BAXIANGSF), Ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photopolymerization initiator in the light and moisture curable resin composition is preferably 0.01 parts by mass or more relative to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture curable urethane resin, more preferably It is 0.5 parts by mass or more, more preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. When the content of the photopolymerization initiator is within this range, the obtained light and moisture curable resin composition has excellent photocurability and storage stability. In addition, by setting it within the above range, the radical polymer compound is moderately cured, and it is easy to adjust the thickness change rate of the cured product in the above-mentioned light-cured state to be within a specific range.

[Moisture hardening urethane resin] The light and moisture-curable resin composition of the present invention contains a moisture-curable urethane resin. By including the moisture-curable urethane resin, the light and moisture-curable resin composition of the present invention has moisture-curable properties. The moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. The reaction between the polyol compound and the polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound, at [NCO]/[OH]=2.0 ～2.5. As the polyol compound used as the raw material of the moisture-curable urethane resin, well-known polyol compounds commonly used in the production of polyurethane can be used. Examples include polyester polyols, polyether polyols, and polyalkylene glycols. Polyol, polycarbonate polyol, etc. These polyol compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

(Moisture hardening urethane resin with polyester skeleton) The light and moisture-curable resin composition of the present invention contains a moisture-curable urethane resin having a polyester skeleton as the moisture-curable urethane resin. By including a moisture-curable urethane resin having a polyester skeleton, the high-temperature adhesion of the light and moisture-curable resin composition can be improved.

The moisture-curable urethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule . Examples of the polyester polyols include polyester polyols obtained by the reaction of polycarboxylic acids and polyols, poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone, etc. . Examples of the above-mentioned polycarboxylic acids used as raw materials for polyester polyols include: phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and amber Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid, etc. Among them, from the viewpoint that it is easy to further increase the adhesive force at high temperatures, phthalic acid, terephthalic acid, isophthalic acid, or adipic acid is preferred. These polyvalent carboxylic acids may be used individually by 1 type, and may use 2 or more types together. Examples of the above-mentioned polyols used as raw materials for polyester polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc. Among them, from the viewpoint that it is easy to further increase the adhesive force at high temperatures, 1,6-hexanediol or 1,4-butanediol is preferred. These polyhydric alcohols may be used individually by 1 type, and may use 2 or more types together.

As the above-mentioned polyisocyanate compound, aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds are suitably used. As the aromatic polyisocyanate compound, for example, diphenylmethane diisocyanate, a liquid modified product of diphenylmethane diisocyanate, polymeric MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, etc. may be mentioned. As the aliphatic polyisocyanate compound, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4- Diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane Isocyanate, etc. Among them, the polyisocyanate compound is preferably diphenylmethane diisocyanate and its modified products from the viewpoint that the adhesive force after complete curing can be improved. The polyisocyanate compound may be used alone or in combination of two or more kinds.

The moisture curable urethane resin having a polyester skeleton may have a polyether skeleton in the molecule. By having a polyether skeleton in the molecule, it is easy to reduce the viscosity of the light and moisture curable resin composition, and it is easy to improve the coatability. The moisture curable urethane resin having a polyether skeleton in the molecule and having a polyester skeleton can be obtained by, for example, a polyester polyol having two or more hydroxyl groups in one molecule, and a polyether having two or more hydroxyl groups in one molecule. The polyol is obtained by reacting with a polyisocyanate compound having two or more isocyanate groups in one molecule. As the polyester polyol, the above-mentioned polyester polyol can be used. In addition, as the polyether polyol, the following polyether polyol can be used.

(Moisture hardening urethane resin with polyether skeleton) The light and moisture-curable resin composition preferably contains, in addition to the moisture-curable urethane resin having a polyester skeleton, a moisture-curable urethane resin having a polyether skeleton as a moisture-curable amine Ester resin. By further including a moisture-curable urethane resin having a polyether skeleton, it is easy to improve the coatability of the light and moisture-curable resin composition. Furthermore, the moisture-curable urethane resin having a polyether skeleton mentioned here is a moisture-curable urethane resin that does not contain a polyester skeleton. The urethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. Examples of polyether polyols include ring-opening polymers of ethylene glycol, propylene glycol, and tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or their derivatives. Bisphenol type polyoxyalkylene (bisphenol type polyoxyalkylene) modified body, etc. Among them, from the viewpoint of easily improving the coatability of the light and moisture curable resin composition, a ring-opening polymer of propylene glycol or 3-methyltetrahydrofuran is preferred. Here, the bisphenol-type polyoxyalkylene modification system makes alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and bisphenol-type molecular skeleton Active hydrogen part of the polyether polyol obtained by the addition reaction. The polyether polyol may be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modification body preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. It does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, A bisphenol A type is preferable. Moreover, as a polyisocyanate compound, the said polyisocyanate compound can be used.

The moisture-curable urethane resin having a polyether skeleton preferably further contains one obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyol compound having a structure represented by the following formula (1), a light and moisture curable resin composition with excellent adhesion and a soft and good elongation cured product can be obtained, and it can be polymerized with free radicals. The compatibility of sex compounds is excellent. In addition, it is easy to adjust the storage elastic modulus within the above-mentioned required range. Among them, a polyether polyol composed of a ring-opening polymer compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymer compound of a tetrahydrofuran compound having a substituent such as a methyl group is preferably used, and propylene glycol is more preferred.

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

In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group, l is an integer of 0-5, m is an integer of 1 to 500, and n is an integer of 1-10. l is preferably 0-4, m is preferably 50-200, and n is preferably 1-5. Furthermore, the so-called case where l is 0 means the case where 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 still more preferably 1-3. Moreover, R is more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

(Other moisture-curing urethane resins) The light and moisture curable resin composition of the present invention may include the moisture curable urethane resin having a polyester skeleton or other moisture curable amines other than the moisture curable urethane resin having a polyether skeleton. Ester resin. As other moisture-curable urethane resins, for example, urethane resins having a polyalkylene skeleton, urethane resins having a polycarbonate skeleton, and the like can be cited.

The urethane resin having a polyalkylene skeleton can be obtained by reacting a polyalkylene polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. . Examples of polyalkylene polyols include polybutadiene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols. Moreover, as a polyisocyanate compound, the said polyisocyanate compound can be used.

The urethane resin having a polycarbonate skeleton can be obtained by reacting a polycarbonate polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. As a polycarbonate polyol, polyhexamethylene carbonate polyol, polycyclohexane dimethylene carbonate polyol, etc. are mentioned, for example. Moreover, as a polyisocyanate compound, the said polyisocyanate compound can be used.

Furthermore, the moisture curable urethane resin may have a radically polymerizable functional group. The radically polymerizable functional group that the moisture curable urethane resin may have is preferably a group having an unsaturated double bond, and particularly in terms of reactivity, it is more preferably a (meth)acryloyl group . In addition, the moisture-curable resin having a radically polymerizable functional group is not included in the above-mentioned radically polymerizable compound, and is treated as a moisture-curable resin.

The weight average molecular weight of the moisture-curable urethane resin is not particularly limited, but is preferably 500 or more, more preferably 1,000 or more, more preferably 10,000 or less, and more preferably 8,000 or less. When the above-mentioned weight average molecular weight is more than the above-mentioned lower limit, it is easy to improve the adhesive force at high temperature. Moreover, when the said weight average molecular weight is below the said upper limit, it is easy to improve coatability.

In addition, in this specification, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC), and the value calculated|required by polystyrene conversion. Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) is used as a column for measuring the weight average molecular weight in terms of polystyrene by GPC. Moreover, as a solvent used in GPC, tetrahydrofuran can be mentioned.

The content of the moisture curable urethane resin in 100% by mass of the light and moisture curable resin composition is preferably 45% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more, and , Preferably 95% by mass or less, more preferably 90% by mass or less. When the content of the moisture curable urethane resin is more than the above lower limit, it is easy to improve the adhesive force at high temperature. When the content of the moisture-curable urethane resin is less than the above upper limit, it is easy to improve the durability of the adhesive force.

The content of the moisture curable urethane resin having a polyester skeleton in 100% by mass of the light and moisture curable resin composition is, for example, 25% by mass or more, preferably 30% by mass or more, more preferably 40% by mass Above, it is more preferably 50% by mass or more, more preferably 95% by mass or less, and more preferably 90% by mass or less. When the content of the moisture-curable urethane resin having a polyester skeleton is more than the above lower limit, it is easy to improve the adhesive force at high temperature. When the content of the moisture-curable urethane resin having a polyester skeleton is less than the above upper limit, it is easy to improve the durability of the adhesive force.

In the case where the light and moisture-curable resin composition includes a moisture-curable urethane resin having a polyester skeleton and other moisture-curable urethane resins, other moisture-curable urethane resins have a higher The mass ratio of the moisture-curable urethane resin content of the ester skeleton (other moisture-curable urethane resin/moisture-curable urethane resin with polyester skeleton) is preferably 5 or less, more preferably 3 or less, Furthermore, it is preferably 0.001 or more, more preferably 0.01 or more. When the mass ratio of the content of the other moisture-curable urethane resin is below the above upper limit, it is easy to improve the adhesive force at high temperature. When the mass ratio of the content of the above-mentioned other moisture-curable urethane resin is below the above-mentioned upper limit, it is easy to improve the durability of the adhesive force. Furthermore, the other moisture-curing urethane resins mentioned here are moisture-curing urethane resins having a polyether skeleton, etc., other than moisture-curing urethane resins having a polyester skeleton. Urethane resin.

The mass ratio (radical polymerizable compound/moisture-curable urethane resin) of the radical polymerizable compound relative to the content of the moisture-curable urethane resin in the light and moisture-curable resin composition is, for example, 0.04 or more, It is preferably 0.1 or more, more preferably 0.2 or more, more preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less.

[Non-reactive polymer] The light and moisture curable resin composition of the present invention may further include a non-reactive polymer. As a non-reactive polymer, acrylic resin, polyolefin resin, etc. are mentioned, for example. When the light and moisture curable resin composition of the present invention contains a non-reactive polymer, it is easy to adjust the thickness change rate of the cured product in a light-cured state within the above-mentioned range. In addition, the acrylic resin is a polymer of polymerizable monomers such as (meth)acrylate.

The method for producing acrylic resin is not particularly limited. For example, it can be produced by solution polymerization, suspension polymerization, bulk polymerization, etc. of polymerizable monomers such as the above-mentioned radical polymerizable compound.

The weight average molecular weight of the acrylic resin is not particularly limited, but is preferably 10,000 or more, and more preferably 50,000 or less. When the above-mentioned weight average molecular weight is more than the above-mentioned lower limit, it is easy to improve the adhesive force at high temperature. Moreover, when the said weight average molecular weight is below the said upper limit, it is easy to improve coatability.

It does not specifically limit as a polyolefin resin, For example, polyethylene, polypropylene, etc. are mentioned. The weight average molecular weight of the polyolefin resin is not particularly limited, but is preferably 10,000 or more, and more preferably 50,000 or less. When the above-mentioned weight average molecular weight is more than the above-mentioned lower limit, it is easy to improve the adhesive force at high temperature. Moreover, when the said weight average molecular weight is below the said upper limit, it is easy to improve coatability.

The content of the non-reactive polymer in 100% by mass of the light and moisture curable resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 45% by mass or less, more preferably It is 40% by mass or less. When the content of the non-reactive polymer is more than the above lower limit, it is easy to improve the adhesive force at high temperature. When the content of the non-reactive polymer is below the above upper limit, it is easy to improve the durability of the adhesive force.

[Spacer particles] The light and moisture curable resin composition of the present invention may also contain spacer particles. When the light and moisture-curable resin composition of the present invention contains spacer particles, it is easy to adjust the thickness change rate of the cured product in a light-cured state within the above-mentioned range.

Examples of the spacer particles include resin particles made of resin, inorganic particles other than metal particles, organic-inorganic hybrid particles, metal particles, and the like. In the present invention, the aforementioned spacer particles are preferably resin particles or organic-inorganic hybrid particles. The aforementioned spacer particles may be core-shell particles having a core and a shell arranged on the surface of the core. The aforementioned core may be an organic core. The above-mentioned housing may be an inorganic housing. From the viewpoint of reducing the stress of the bonding part with the bonded body and maintaining the durability of the adhesive force, spacer particles other than metal particles are preferred, and resin particles and inorganic particles other than metal particles are more preferred. The particles or organic-inorganic mixed particles are more preferably resin particles. If the spacer particles are resin particles, when stress is applied to the adhesive portion, the stress can be alleviated, and the adhesiveness can be maintained at a high level.

From the viewpoint of alleviating the stress of the bonding part with the adherend and maintaining the durability of the adhesive force, the average particle size of the spacer particles is preferably 50 μm or more, more preferably 80 μm or more, and, It is preferably 500 μm or less, and more preferably 400 μm or less.

The above-mentioned average particle diameter represents the number average particle diameter. The average particle size of the aforementioned spacer particles is obtained by observing 50 arbitrary spacer particles with an electron microscope or an optical microscope, and calculating the average value, for example.

From the viewpoint of further improving adhesiveness, the CV value of the particle diameter of the spacer particles is preferably 10% or less, and more preferably 5% or less. The lower limit of the CV value of the particle diameter of the spacer particles is not particularly limited, and it is preferably 1% or more. In addition, the above-mentioned CV value (coefficient of variation) is expressed by the following formula. CV value (%)=(ρ/Dn)×100 ρ: the standard deviation of the particle size of the spacer Dn: the average value of the particle size of the spacer particles

When the light and moisture curable resin composition of the present invention contains spacer particles, from the viewpoint of further improving the stress relaxation properties, in 100% by mass of the light and moisture curable resin composition, the spacer particles The content is preferably 1% by mass or more, more preferably 5% by mass or more. In addition, from the viewpoint of improving coatability, the content of the spacer particles is preferably 20% by mass or less, and more preferably 15% by mass or less. Furthermore, when the light and moisture curable resin composition contains spacer particles, even if the content of the radical polymerizable compound is reduced, the thickness change rate can be reduced. From such a viewpoint, the content of the radical polymerizable compound in 100% by mass of the light and moisture curable resin composition can be set to, for example, 20% by mass or less, or 3% by mass or more and 10% by mass or less. In addition, the mass ratio (radical polymerizable compound/moisture curable urethane resin) may be 0.2 or less, or 0.04 or more and 0.1 or less.

[Filler] The curable resin composition of the present invention may also contain a filler. By containing the filler, the curable resin composition of the present invention tends to have thixotropy, and it is easy to improve the fine line coatability. As the filler, particles in the form of particles may be used. Furthermore, in this specification, filler refers to those whose average particle size of primary particles is less than 1 μm. The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate, and the like. Among them, silicon dioxide is preferred in terms of excellent ultraviolet transmittance of the obtained curable resin composition. In addition, the filler can be subjected to hydrophobic surface treatments such as silicidation treatment, alkylation treatment, and epoxidation treatment. In addition, silica, talc, titanium oxide, etc., have the function of coloring the light and moisture curable resin composition in the same way as the colorants described below. A filler may be used individually by 1 type, and may be used in combination of 2 or more types. The total amount of the filler relative to 100 parts by mass of the light and moisture curable resin composition is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

[Colorant] The light and moisture curable resin composition of the present invention may also contain a coloring agent. As a coloring agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, etc. are mentioned, for example. Among them, titanium black is preferred. In addition, the above-mentioned coloring agent is preferably black, but may have other colors. In addition, the coloring agent is preferably a material having the ability (light-shielding property) to hardly transmit light in the visible light region. Titanium black is a substance that has a higher transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 360 to 450 nm, compared to the average transmittance of light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black has the property of imparting light-shielding properties to light and moisture curable resin composition by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, transmitting light of wavelengths in the vicinity of the ultraviolet region. Therefore, it is easy to impart light-shielding properties, and the photocurability of the light and moisture curable resin composition is maintained well, and the storage elastic modulus after light curing is maintained at a high value. The total amount of the colorant relative to 100 parts by mass of the light and moisture curable resin composition is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

[Moisture Hardening Promotion Catalyst] The light and moisture-curable resin composition of the present invention may also contain a moisture-curing accelerator that promotes the moisture-curing reaction of the moisture-curable urethane resin. By using the moisture hardening accelerating catalyst, the moisture hardening property of the light and moisture hardening resin composition is more excellent, and the adhesive force at high temperature can be further improved. As the moisture hardening accelerating catalyst, specifically, for example, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and stannous octoate; triethylamine, 1,4-diazabicyclo[2.2. 2]Octane, 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane and other amine compounds; zinc octoate, zinc naphthenate and other zinc compounds; zirconium tetraacetylacetone , Copper naphthenate, cobalt naphthenate, etc. With respect to 100 parts by mass of the light and moisture curable resin composition, the content of the moisture hardening accelerating catalyst is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less, and more Preferably, it is 3 parts by mass or less. When the content of the moisture hardening accelerating catalyst is within this range, the storage stability of the light and moisture hardening resin composition is not deteriorated, and the effect of accelerating the moisture hardening reaction is excellent.

[Coupling agent] The light and moisture curable resin composition of the present invention may also contain a coupling agent. By containing the coupling agent, it is easy to improve the adhesive force. As a coupling agent, a silane coupling agent, a titanate type coupling agent, a zirconate type coupling agent, etc. are mentioned, for example. Among them, the silane coupling agent is preferred in terms of its excellent effect of improving adhesiveness. The above-mentioned coupling agents may be used alone or in combination of two or more kinds. Relative to 100 parts by mass of the light and moisture curable resin composition, the content of the coupling agent is preferably 0.05 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 5 parts by mass or less, more preferably 3 parts by mass The following. By setting the content of the coupling agent within these ranges, the storage elastic modulus, etc., will not be affected, and the adhesive force will be improved.

The light and moisture curable resin composition of the present invention can be diluted with a solvent if necessary. When the light and moisture curable resin composition is diluted by a solvent, the mass parts and mass% of the light and moisture curable resin composition are based on the solid content, that is, it means the mass parts and the quality%. In addition, the light and moisture curable resin composition may contain additives such as wax particles and metal-containing particles in addition to the above-mentioned components.

[Manufacturing method of light and moisture curable resin composition] As a method of manufacturing the light and moisture curable resin composition of the present invention, the following methods can be cited: using a mixer, a radical polymerizable compound, a moisture curable urethane resin, a photopolymerization initiator, and a visual Fillers, colorants and other additives blended as needed are mixed. As the mixer, for example, a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer (planetary mixer), a kneader, a three-roll mill, etc. can be cited.

[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 user. Specifically, the light and moisture curable resin composition of the present invention is first cured by light irradiation, for example, in a B-stage state (semi-cured state), and then cured by moisture. It can be completely hardened. Here, when the light and moisture curable resin composition is arranged between the adherends and the adherends are joined, it is applied to an adherend, and thereafter, it is photocured by light irradiation. For example, in a B-stage state, the light and moisture-curable resin composition in the light-cured state is superimposed on another body to be bonded, and the bonded body is temporarily bonded with a moderate adhesive force (initial bonding force). Can. Thereafter, the light and moisture-curable resin composition in the B-stage state is cured completely by using moisture to harden the moisture-curable urethane resin, so that the light and moisture-curable resin composition is overlapped by the light and moisture-curable resin composition. Join the body with sufficient adhesive force.

Here, the light irradiated during photocuring is not particularly limited as long as it is light for curing the radical polymerizable compound, and ultraviolet rays are preferred. In addition, when the light and moisture curable resin composition is completely cured by moisture after light curing, it can be left in the atmosphere for a specific time.

The light and moisture curable resin composition of the present invention is preferably used as an adhesive for electronic parts. Therefore, the adherend is not particularly limited, and it 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, semiconductor wafers, and the like. As the material of the bonded body, it can be any of metal, glass, plastic, etc. In addition, the shape of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod) shape, a box shape, and a shell shape.

Since the adhesive agent for electronic parts mentioned above contains the moisture curable urethane resin which has a polyester skeleton, it may be difficult to apply|coat using a dispensing apparatus etc. at normal temperature. Therefore, an example of a method of manufacturing an electronic device using the adhesive for electronic parts is a method of manufacturing an electronic device including the steps of heating the adhesive for electronic parts, and using the heated electronic parts The step of applying the adhesive to the electronic parts. Furthermore, the temperature in the above heating step is, for example, 130°C or lower, preferably 100°C or lower, more preferably 80°C or lower, and more preferably 30°C or higher.

As described above, the light and moisture curable resin composition of the present invention is preferably used for bonding electronic parts constituting electronic equipment to each other. In addition, the light and moisture curable resin composition of the present invention is preferably also used for joining electronic parts and other parts. With these configurations, the electronic component has 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, for example, to bond a substrate and a substrate to obtain an assembled part. 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 joined to at least a part of the second substrate through the hardened body. Furthermore, it is preferable that the first substrate and the second substrate each have at least one electronic component mounted thereon. [Example]

The present invention is further described in detail through examples, but the present invention is not limited by these examples.

In this example, the measurement and evaluation of various physical properties were performed in the following manner.

<The rate of change in thickness in the light-cured state> Under an environment of 25°C, using a dispensing device, the light and moisture curable resin compositions obtained in the examples and comparative examples have a line width of 1.0±0.1 mm, length of 25±0.2 mm, and thickness of 0.4±0.1 mm are coated on polycarbonate substrate (length 50 mm, width 25 mm, thickness 2 mm). Furthermore, the light and moisture curable resin compositions obtained in Examples 1, 2, 5-8 and Comparative Example 1 were heated at 50°C for 1 hour and then coated. The light and moisture curable resin compositions obtained in Example 3 were combined with The moisture-curable resin composition was heated at 120°C for 1 hour and then applied. The light and moisture-curable resin composition obtained in Example 4 and Comparative Example 2 was applied at room temperature. Within 1 minute after the coating is completed, use UV-LED (wavelength 365 nm) to irradiate 1000 mJ/cm ² of ultraviolet rays to light-cur the light and moisture-curable resin composition. Measure the thickness immediately after irradiating ultraviolet rays as the thickness before applying the load. Overlay a glass substrate of the same size as the polycarbonate substrate on the hardened object in the light-hardened state, and place a 100 g weight on it for 10 seconds, thereby applying a load of 0.04 MPa to the hardened object in the light-hardened state 10 seconds. As the thickness after the applied load, the thickness of the cured product in the light-cured state is measured, and the thickness change rate (%) is measured as follows. Thickness change rate (%) = (thickness just after light irradiation-thickness after applying load)/(thickness just after light irradiation)×100 Furthermore, the thickness of the hardened object in the light-hardened state is measured by a digital microscope (Trade name "KH-7800", manufactured by HIROX Corporation) Observe and measure.

<The storage elastic modulus of the cured product in the light-cured state> Place 3 g of the light and moisture-curable resin composition in a UV irradiation rheometer (trade name HAAKE MARS 40/60, manufactured by Thermo Fisher Scientific). 30 seconds after the completion of the placement, the UV-LED lamp was used to irradiate ^{the ultraviolet rays of 1000 mJ/cm 2} to make it photohardened. After irradiating ultraviolet rays for 60 seconds, the shear storage elastic modulus was measured under the conditions of 25°C and 50RH% under the condition of frequency F=1.6 Hz. Furthermore, UV-LED lamps use those with a wavelength of 365 nm.

<The storage elastic modulus of the cured product in the state of light moisture curing> The light and moisture curable resin compositions obtained in the examples and comparative examples were filled with a width of 3 mm, a length of 30 mm, and a thickness of 1 mm Teflon (registered trademark) mold. Within 1 minute after the filling is completed, the curable resin composition is light-cured by ^{irradiating 1000 mJ/cm 2} of ultraviolet rays using a UV-LED (wavelength 365 nm). After that, it was cured by moisture (full curing) by standing at 23°C and 50RH% for 3 days. A dynamic viscoelasticity measuring device (manufactured by IT Measurement and Control Co., Ltd., trade name "DVA-200") was used to measure the dynamic viscoelasticity in the range of -100°C to 150°C using the obtained hardened body, and the room temperature (25 ℃) storage elastic modulus. The measurement conditions are that the deformation mode is tensile, the set strain is 1%, the measurement frequency is 1 Hz, and the heating rate is 5°C/min.

＜Viscosity＞ Using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22"), the composition of each light and moisture curable resin obtained in the examples and comparative examples was measured at 25°C at a rotation speed of 1 rpm The viscosity of things.

<High temperature adhesion (adhesive strength at 100°C)> As shown in Figure 1 (a) and (b), each light and moisture curable resin composition 10 obtained in the examples and comparative examples has a width of 0.4 Coated on the glass plate 11 in a manner of ±0.05 mm, a length of 25±2 mm, and a thickness of 0.2±0.05 mm. Within 1 minute after the coating is completed, the curable resin composition 10 is photocured by ^{irradiating 1000 mJ/cm 2} of ultraviolet rays using a UV-LED (wavelength 365 nm). Thereafter, by overlapping the glass plates 12, and placing a weight of 100 g thereon for 10 seconds, a load of 0.04 MPa is applied to the cured product in the light-cured state for 10 seconds. After that, the weight of 100 g was removed, and it was left in an environment of 23° C. and 50 RH% for 3 days to make it moisture hardened (full hardening), and a sample 13 for evaluation was produced. In an environment of 100°C and 50%RH, the produced evaluation sample 13 was stretched in the shear direction S at a speed of 12 mm/sec using a tensile testing machine, and the glass plate 11 and the glass plate 12 were peeled off. The strength is measured at 100°C. Based on the measured adhesive force, the following evaluation criteria are used for evaluation. A: 35 N or more B: 20 N or more and less than 35 N C: less than 20 N

＜Stress relaxation (cold and heat cycle test)＞ Except that the glass plate 11 was changed to a polycarbonate plate, a sample 13 for evaluation was produced in the same manner as in the evaluation of the high-temperature adhesiveness described above. The sample for evaluation was subjected to 1000 cycles of a heating and cooling cycle test, and the heating and cooling cycle test was repeated at -40°C for 30 minutes and 80°C for 30 minutes. For each evaluation sample before the cold and heat test and after the cold and heat test, the polycarbonate plate is stretched at a speed of 12 mm/sec in the shear direction S under 25°C and 50%RH environment. And the strength when peeling off the glass plate 12, and the adhesive force at 25 degreeC was measured. Based on the adhesive force before the thermal cycle test and the adhesive force after the thermal cycle test, the stress relaxation properties of the light moisture curable resin composition were evaluated according to the following evaluation criteria. [Evaluation criteria] A: (Adhesive force after cooling and heating cycle)/(Adhesive force before cooling and heating cycle) ≧0.8 B: 0.8＞(Adhesive force after cooling and heating cycle)/(Adhesive force before cooling and heating cycle) ≧0.6 C: 0.6＞(Adhesive force after cooling and heating cycle)/(Adhesive force before cooling and heating cycle) ≧0.4 D: 0.4> (adhesive force after cold and heat cycle)/(adhesive force before cold and heat cycle)

＜Coatability＞ Using an air dispenser (ML-5000XII, manufactured by Musashi High-Tech Co., Ltd.), the light and moisture curable resin compositions obtained in the examples and comparative examples were evaluated at room temperature, 50°C, and 120°C. Coatability. As an evaluation method, each light and moisture curable resin composition was filled in a 10 mL syringe (manufactured by Musashi High-Tech Co., Ltd.), and then placed in an oven set to each temperature for 1 hour, and then evaluated under the following standard ejection conditions Can thin line coating be carried out. Parts used: Precision nozzle HN-0.4N (manufactured by Musashi High-Tech Co., Ltd., inner diameter 0.40 mm) Spray pressure: 0.3 MPa [Evaluation criteria] 1: Can be coated at room temperature 2: Can be coated at 50℃ 3: Can be coated at 120°C

The moisture curable urethane resin used in each example and comparative example was produced according to the following synthesis examples 1 to 4. The moisture-curable urethane resin 1 having a polyester skeleton was produced according to Synthesis Example 1 below. [Synthesis Example 1] 100 parts by mass of polyester polyol (condensation product of adipic acid and 1,6-hexanediol with an alcohol at the end) as a polyol compound, and 0.01 parts by mass of dibutyltin dilaurate Put it into a separable flask with a capacity of 500 mL, and mix under vacuum (below 20 mmHg) at 100°C for 30 minutes. After that, it was set to normal pressure, 30 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Shoji Co., Ltd., trade name "Pure MDI") as a polyisocyanate compound was added, and the reaction was stirred at 80°C for 3 hours to obtain a polyester containing Moisture-curing urethane resin 1 (weight average molecular weight 5000) of the skeleton.

The moisture-curable urethane resin 2 having a polyester skeleton was produced according to Synthesis Example 2 below. [Synthesis example 2] 100 parts by mass of polyester polyol (polyester polyol obtained from adipic acid, 1,6-hexanediol and isophthalic acid as main components) as a polyol compound, aromatic ring The concentration is 15% by mass, the weight average molecular weight is 1000), and 0.01 parts by mass of dibutyltin dilaurate are added to a separable flask with a capacity of 500 mL. Under vacuum (below 20 mmHg), stir at 100°C for 30 minutes to mix. After that, the pressure was set to normal pressure, and 52.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Shoji Co., Ltd., trade name "Pure MDI") as a polyisocyanate compound was added, and stirred at 80°C for 3 hours to react to obtain a polyester containing Moisture-curing urethane resin of the skeleton 2. The weight average molecular weight of the obtained moisture curable urethane resin was 1,500.

The moisture-curable urethane resin 1 having a polyether skeleton was produced according to Synthesis Example 3 below. [Synthesis Example 3] 100 parts by mass of polypropylene glycol (manufactured by Asahi Glass Company, trade name "EXCENOL 2020") as a polyol compound, and 0.01 parts by mass of dibutyltin dilaurate were added to a 500 mL separable flask, and under vacuum ( 20 mmHg or less), stir at 100°C for 30 minutes, and mix. After that, the pressure was set to normal pressure, 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the reaction was stirred at 80°C for 3 hours to obtain a polyether containing Moisture-curing urethane resin 1 (weight average molecular weight 2900) of the skeleton.

The moisture-curable urethane resin 2 having a polyether skeleton was produced according to Synthesis Example 4 below. [Synthesis Example 4] 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-2000") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate are added to a separable volume of 500 mL In a flask, stir under vacuum (below 20 mmHg) at 100°C for 30 minutes to mix. After that, the pressure was set to normal pressure, 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the reaction was stirred at 80°C for 3 hours to obtain a polyether containing Moisture-curing urethane resin 2 (weight average molecular weight 2700) of the skeleton.

啉基苯基)-丁酮-1（2-benzyl-2-dimethylamino-1-（4-morpholinophenyl）-butanone-1）（BASF公司製造，「IRGACURE369」） 偶合劑：3-丙烯醯氧基丙基三甲氧基矽烷，信越化學工業公司製造，「KBM-5103」 填充劑：三甲基矽基化處理二氧化矽（Nippon Aerosil公司製造，「R812」，一次粒徑7 nm） 間隔粒子：樹脂粒子（積水化學工業公司製造，「MICROPEARL GS-L250」，平均粒徑（目錄值）：250.0±12.5 μm，CV值（目錄值）：約7%） 著色劑：鈦黑The components other than the moisture curable urethane resin used in each example and comparative example are as follows. Amino acrylate: manufactured by DAICEL-ALLNEX, "EBECRYL8411", difunctional tetrahydrofurfuryl acrylate: manufactured by Kyoeisha Chemical Co., Ltd., "LIGHT ACRYLATE THF-A", monofunctional stearyl acrylate: manufactured by Sartomer, "SR257 ", monofunctional 3,3,5-trimethylcyclohexyl acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd., "VISCOAT#196", monofunctional 1,6-hexane diacrylate: manufactured by Kyoeisha Chemical Co., Ltd., "LIGHT ACRYLATE 1,6-HX-A", bifunctional trimethylolpropane triacrylate: manufactured by Kyoeisha Chemical Co., Ltd., "LIGHT ACRYLATE TMP-A", trifunctional photopolymerization initiator: 2-benzyl -2-Dimethylamino-1-(4-

(2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1) (manufactured by BASF Corporation, "IRGACURE369") Coupling agent: 3-propenyloxypropyl Trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-5103" Filler: Trimethylsilylated silica (manufactured by Nippon Aerosil, "R812", primary particle size 7 nm) Spacer particles: resin Particles (manufactured by Sekisui Chemical Industry Co., Ltd., "MICROPEARL GS-L250", average particle size (catalog value): 250.0±12.5 μm, CV value (catalog value): about 7%) Coloring agent: titanium black

[Examples 1 to 8, Comparative Examples 1 and 2] According to the blending ratio described in Table 1, the materials were stirred at a temperature of 50°C with a planetary stirring device (manufactured by THINKY, "Defoaming Stirring Taro"), and then at a temperature of 50°C with a ceramic three-roll mill The light moisture curable resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were obtained by uniformly mixing.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Composition (parts by mass) Moisture hardening urethane resin Moisture-curing urethane resin containing polyester skeleton 1 60 45 70 30 30 45 45 60 Moisture-curing urethane resin containing polyester skeleton 2 45 Moisture-curing urethane resin containing polyether skeleton 1 35 20 30 20 20 20 20 35 Moisture-curing urethane resin containing polyether skeleton 2 50 Radical polymerizable compound Amino acrylate 1 6 4 5 6 6 6 1 8 Tetrahydrofurfuryl acrylate 4 18 16 10 25 18 18 18 4 25 Stearyl Acrylate 11 10 20 11 11 11 17 3,3,5-trimethylcyclohexyl acrylate 20 1,6-hexane diacrylate 5 Trimethylolpropane triacrylate 5 Photopolymerization initiator 1 1 1 1 1 1 1 1 1 1 Coupling agent 1 Filler 5 5 5 Spacer particles 10 Colorant 0.1 Physical properties Thickness change rate in light-hardened state 40% 40% 45% 25% 40% 45% 40% 40% 70% 35% Storage elastic modulus at 25℃ in light-hardened state (kPa) 3 20 18 40 25 18 20 20 3 30 Storage elastic modulus of hardened material at 25℃ (MPa) 30 25 600 30 18 25 26 100 30 6 Viscosity (Pa·s) 2500 2000 solid 500 1000 2000 2200 1200 2500 200 Evaluation High temperature adhesion (adhesive strength at 100℃) A B A B B B A B A C Stress relaxation (cold and hot cycle test) A A A A A A A A C A Coatability 2 2 3 1 2 2 2 2 2 1

As shown in the above examples, it can be seen that the light moisture-curable resin composition contains a moisture-curable urethane resin having a polyester skeleton, so that the high-temperature adhesiveness becomes good. In addition, it can be seen that when the thickness change rate becomes 50% or less, the stress relaxation properties become better, and the durability of the adhesive force becomes better.

10: Curable resin composition 11: glass plate 12: glass plate 13: sample S: Shear direction

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

Claims (12)

A light and moisture-curable resin composition comprising a radical polymerizable compound, a moisture-curable urethane resin and a photopolymerization initiator. The moisture-curable urethane resin includes a moisture-curable polyester skeleton When a load of 0.04 MPa is applied to a cured product that is photo-cured by irradiating 1000 mJ/cm ² of ultraviolet rays, the thickness change rate before and after the load is 50% or less. For example, the light and moisture curable resin composition of claim 1 has a viscosity of 3000 Pa·s or less at 25°C and 1 rpm. The light and moisture-curable resin composition of claim 1 or 2, wherein the moisture-curable urethane resin further includes a moisture-curable urethane resin having a polyether skeleton. The light and moisture curable resin composition of claim 1 or 2, wherein the moisture curable urethane resin having a polyester skeleton has a polyether skeleton in the molecule. The light and moisture curable resin composition according to any one of claims 1 to 4, which further includes spacer particles. The light and moisture curable resin composition according to any one of claims 1 to 5, wherein the content of the radical polymerizable compound in 100% by mass of the light and moisture curable resin composition is 3% by mass above. The light and moisture curable resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator is a compound having an acylphosphine oxide skeleton or an α-amine Alkyl alkylphenone (α-aminoalkylphenone) is a compound of the skeleton. The light and moisture curable resin composition according to any one of claims 1 to 7, wherein the storage elastic modulus of the cured product in the light-cured state at 25°C is 10 kPa or more. The light and moisture curable resin composition of any one of claims 1 to 8, which is obtained by leaving the cured product in the light-cured state for 3 days under an environment of 23°C and 50RH% The storage elastic modulus of the hardened material at 25°C is above 1 MPa. An adhesive for electronic parts, which is composed of the light and moisture curable resin composition of any one of claims 1 to 9. A method of manufacturing an electronic machine, comprising the following steps: heating the adhesive for electronic parts of claim 10; and The heated adhesive for electronic parts is applied to the electronic parts. A hardened body which is a hardened body of the light and moisture curable resin composition of any one of claims 1 to 9.

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