TW201934712A - Curable resin composition, cured article, electronic components and assembly components - Google Patents

Abstract

The curable resin composition of this invention has, in predetermined adhesion testing, adhesive strength of at least 6 kgf/cm2 at 80 DEG C, adhesive strength not exceeding 3.5 kgf/cm2 at 120 DEG C, and the ratio of the volume at 120 DEG C to the volume at 25 DEG C does not exceed 1.2.

Description

Curable resin composition, hardened body, electronic parts, and assembled parts

The present invention relates to a hardenable resin composition, a hardened body of a hardenable resin composition, and an electronic part and an assembled part having the hardened body of the hardenable resin composition.

In recent years, electronic components such as semiconductor wafers have been required to be highly integrated and miniaturized. For example, a plurality of thinner semiconductor wafers may be bonded via an adhesive layer to form a laminated body of a semiconductor wafer. Further, in the modern age in which mobile devices with display elements are widespread, the image display portion has been narrowed as a means of miniaturizing the display elements (hereinafter, also referred to as "narrow edge design"). In the narrow-edge design, a technique such as using a dispenser or the like and performing a bonding with a thin line width adhesive is required.
In the design of bonding or narrow edges of such small electronic components, high bonding strength is usually required. For example, it is known to use a radical polymerizable compound, a moisture-curable amine ester, and photo radical polymerization as disclosed in Patent Document 1. The light moisture-curable resin composition of the initiator and the filler is used as the adhesive.

Moreover, in the manufacture of the electronic component and the image display unit described above, it is desirable to easily remanufacture, and a re-adhesive property called rework characteristics is required for the adhesive. Therefore, the adhesive may be required to have a characteristic that the adhesive force is reduced under certain conditions such as heating.
For example, in Patent Document 2, as the adhesive agent whose adhesive force is reduced by heating, a curable resin composition in which a mold release agent and a foaming agent are mixed with an amine ester adhesive is known. The adhesive foams the foaming agent by heating, and moves the release agent to the surface of the adhesive layer, thereby reducing the adhesive force to the adherend.
[Prior technical literature]
[Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2016-29186 Patent Document 2: Japanese Patent Application Publication No. 2003-286465

[Problems to be Solved by the Invention]

However, if a foaming agent or the like is used to reduce the adhesive force by volume expansion as in Patent Document 2, the adhesive residue of the adhesive may increase and it may become difficult to peel off the resin. In addition, if the release agent is intended to migrate to the resin interface, the release agent may migrate with time even at low temperatures, which may deteriorate the reliability of the product.

In addition, electronic components such as semiconductor wafers and display elements may be exposed to high temperatures of about 60 to 80 ° C during assembly steps and use due to the heat generated by the electronic components themselves during external heating or operation. Even in such an environment, it has high adhesion. On the other hand, if electronic parts are reworked under high temperature conditions, there is a problem that the electronic parts are damaged. Therefore, it is desirable to perform rework at the lowest possible temperature.
However, conventional adhesives sometimes have difficulty maintaining a high adhesive force during assembly steps and use environments, while lowering the adhesive force sufficiently by low-temperature heating and insufficient reworkability.

Therefore, an object of the present invention is to provide a curable resin composition capable of exhibiting high reworkability without volume expansion even under low-temperature heating while maintaining a high adhesion force in the steps of assembling electronic parts and the use environment. .
[Technical means to solve the problem]

As a result of earnest research, the inventors have found that the above-mentioned problem can be solved by controlling the adhesion force at a specific temperature without using volume expansion, and the following inventions have been completed.
The present invention provides the following [1] to [11].
[1] A curable resin composition having an adhesive force at 80 ° C. of 6 kgf / cm ² or more and an adhesive force at 120 ° C. of 3.5 kgf / cm ² or less in the following adhesion test, and the curability The ratio of the volume of 120 degreeC of the resin composition to the volume of 25 degreeC is 1.2 or less.
＜ Adhesiveness test ＞
The curable resin composition was coated on an aluminum substrate so as to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm, and thereafter, a glass plate was stacked to harden the curable resin composition to The aluminum substrate was bonded to the glass plate to prepare a sample for adhesion test. The prepared adhesive test sample was placed at 80 ° C for 10 minutes and heated to 80 ° C, and the tensile tester was used to stretch at a speed of 5 mm / sec in a shearing direction at 80 ° C. , The strength when the aluminum substrate and the glass plate were peeled was measured to measure the adhesive force at 80 ° C. The adhesive force at 120 ° C was measured in the same manner except that the heating temperature was changed to 120 ° C.
[2] A curable resin composition having an adhesive force at 80 ° C. of 6 kgf / cm ² or more and an adhesive force of 100 ° C. of 4 kgf / cm ² or less in the following adhesion test, and the curability The ratio of the volume of the resin composition at 100 ° C to the volume of 25 ° C is 1.2 or less.
＜ Adhesiveness test ＞
The curable resin composition was coated on an aluminum substrate so as to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm, and thereafter, a glass plate was stacked to harden the curable resin composition to The aluminum substrate was bonded to the glass plate to prepare a sample for adhesion test. The prepared adhesive test sample was placed at 80 ° C for 10 minutes and heated to 80 ° C, and the tensile tester was used to stretch at a speed of 5 mm / sec in a shearing direction at 80 ° C. , The strength when the aluminum substrate and the glass plate were peeled was measured to measure the adhesive force at 80 ° C. The adhesive force at 100 ° C was measured in the same manner except that the heating temperature was changed to 100 ° C.
[3] The curable resin composition according to the above [1] or [2], wherein the ratio of the storage modulus at 80 ° C to the storage modulus at 120 ° C is 1.5 or more, and the storage modulus at 25 ° C The number is 1.0 × 10 ⁵ Pa or more and 1.0 × 10 ⁸ Pa or less.
[4] The curable resin composition according to any one of the above [1] to [3], which contains wax particles.
[5] The curable resin composition according to the above [4], wherein a ratio of an average particle diameter of the wax particles to an average primary particle diameter is 3 or less.
[6] The curable resin composition according to the above [4] or [5], wherein the melting point of the wax particles is 80 ° C or higher and 110 ° C or lower.
[7] The curable resin composition according to any one of the above [4] to [6], wherein the average particle diameter of the wax particles is 100 μm.
[8] A hardened body, which is a hardened body of the curable resin composition according to any one of the above [1] to [7].
[9] An electronic component comprising the hardened body according to the above [8].
[10] An assembly part comprising a first substrate, a second substrate, and the hardened body described in [8], and at least a part of the first substrate is joined to at least a part of the second substrate via the hardened body.
[11] The assembly component according to the above [10], wherein at least one electronic component can be mounted on each of the first substrate and the second substrate.
[Effect of the invention]

According to the present invention, it is possible to provide a hardenable resin composition that exhibits high reworkability without volume expansion even under low-temperature heating while maintaining a high adhesive force in the steps of assembling electronic parts and the use environment.

Hereinafter, the present invention will be described in detail.
The adhesive force of the curable resin composition of the present invention at 80 ° C. is 6 kgf / cm ² or more, and satisfies any one of the following first requirements or second requirements.
First requirement: The adhesive force at 120 ° C is 3.5 kgf / cm ² or less, and the ratio of the volume of 120 ° C to the volume of 25 ° C of the curable resin composition is 1.2 or less.
Second requirement: The adhesive force at 100 ° C is 4 kgf / cm ² or less, and the ratio of the volume of 100 ° C to the volume of 25 ° C of the curable resin composition is 1.2 or less.
The curable resin composition of the present invention may satisfy any one of the first and second requirements described above, but it is preferable that both of the first and second requirements are satisfied.

The curable resin composition of the present invention can adhere the adherends such as electronic parts, substrates, and the like to each other with a high adhesive force in an assembly step and a use environment by setting the adhesive force at 80 ° C to 6 kgf / cm ² or more. . In addition, by setting the adhesive force at 120 ° C or 100 ° C to 3.5 kgf / cm ² or less or 4 kgf / cm ² or less, the adhesive can be easily peeled off even by heating at a relatively low temperature. The adherend is excellent in reworkability.
On the other hand, if the adhesion force at 80 ° C does not reach 6 kgf / cm ² , or the adhesion force at 100 ° C becomes higher than 4.0 kgf / cm ² , and the adhesion force at 120 ° C becomes higher than 3.5 kgf / In the case of cm ² or the like, neither reworkability or bonding performance will be improved.

From the viewpoint of further improving the bonding performance, the bonding force at 80 ° C is preferably 7 kgf / cm ² or more, and more preferably 8 kgf / cm ² or more. In order to improve the bonding performance, the higher the bonding strength at 80 ° C, the better, but in terms of practicality, it is 25 kgf / cm ² or less, and preferably 20 kgf / cm ² or less.
From the viewpoint of further improving reworkability, the adhesive force at 120 ° C is preferably 3.0 kgf / cm ² or less, and more preferably 2.5 kgf / cm ² or less. In order to improve reworkability, the lower the adhesion force at 120 ° C., the better, but in terms of practicality, it is 0.1 kgf / cm ² or more, and preferably 0.4 kgf / cm ² or more.
Furthermore, from the viewpoint of further improving reworkability, the adhesive force at 100 ° C is preferably 4.0 kgf / cm ² or less, and more preferably 3.0 kgf / cm ² or less. In order to improve the reworkability, the lower the adhesion force at 100 ° C, the better, but in terms of practicality, it is 0.1 kgf / cm ² or more, and preferably 0.5 kgf / cm ² or more.

In addition, if the ratio of the volume of 120 ° C or 100 ° C of the curable resin composition to the volume of 25 ° C is greater than 1.2, volume expansion will occur by heating. For this reason, the adhesive residue of an adhesive may increase and it may become difficult to peel a resin.
The curable resin composition preferably has a small dimensional change due to heating. Therefore, the ratio of the volume of 120 ° C of the curable resin composition to the volume of 25 ° C is preferably 1 or close to 1. Specifically, it is preferably 1.1 or less, and more preferably 1.05 or less. Moreover, it is preferably 0.9 or more, and more preferably 0.95 or more.
From the same viewpoint, the ratio of the volume of the curable resin composition at 100 ° C to the volume of 25 ° C is preferably 1 or close to 1. Specifically, it is preferably 1.1 or less, and more preferably 1.05 or less. Moreover, it is preferably 0.9 or more, and more preferably 0.95 or more.

(Adhesive test)
In the present invention, the adhesion force at 80 ° C, 100 ° C, and 120 ° C is measured by the following adhesion test.
As shown in FIGS. 1 (a) and 1 (b), a curable resin composition 10 is coated on an aluminum substrate 11 so as to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. Then, the glass plate 12 is stacked, the curable resin composition is cured, and the aluminum substrate 11 and the glass plate 12 are bonded to each other to prepare a sample 13 for adhesion test. The prepared adhesive test sample 13 was placed in an 80 ° C environment for 10 minutes and heated to 80 ° C, and the tensile test machine was used in this environment to pull at a speed of 5 mm / sec in the shearing direction S under this environment. The tensile strength was measured when the aluminum substrate 11 and the glass plate 12 were peeled to measure the adhesive force at 80 ° C. In addition, the temperature of the environment (that is, the heating temperature) was changed to 100 ° C. and 120 ° C., respectively, and the adhesive forces at 100 ° C. and 120 ° C. were measured in the same manner.
Here, the curing conditions of the curable resin composition are the same as the curing conditions using the curable resin composition of the present invention as an adhesive, and it is preferable to set the following conditions depending on the curing mechanism.
In the case of a photocurable resin composition, a distribution device is used to coat the aluminum substrate 11 so that the width is 1.0 ± 0.1 mm, the length is 25 ± 2 mm, and the thickness is 0.4 ± 0.1 mm. The substrate 11 and the glass plate 12 were bonded to each other, and 3,000 mJ / cm ² was irradiated with a mercury lamp to perform light curing to prepare a sample 13 for adhesion test.
In the case of a moisture-curable resin composition, a distribution device is used to coat the aluminum substrate 11 with a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. The glass plates 12 were laminated and left to stand for 3 days under conditions of 25 ° C. and 50 RH% to carry out moisture curing to obtain a sample 13 for evaluation of adhesion.
In the case of the light-moisture-curable resin composition, first, the distribution device is used to coat the aluminum substrate 11 with a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. Light curing was performed by irradiating 3000 mJ / cm ² with a mercury lamp. Thereafter, the aluminum substrate 11 and the glass plate 12 were bonded together, and a weight of 100 g was placed, and moisture curing was performed by leaving it at 25 ° C and 50 RH% for 3 days to obtain a sample 13 for adhesion evaluation.
In the case of a thermosetting resin composition, a distribution device is used to coat the aluminum substrate 11 so as to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm, so that the aluminum substrate 11 and the glass plate 12 The samples were bonded and heated at 90 ° C. for 2 hours to prepare a sample 13 for adhesion test.
In this test, an aluminum alloy "AL-6063" was used for the aluminum substrate. As the glass plate, a glass plate washed with ultrasonic waves for 5 minutes was used.

The curable resin composition of the present invention preferably has a ratio of storage modulus at 80 ° C to storage modulus of 120 ° C (hereinafter, also simply referred to as "storage modulus ratio") of 1.5 or more, and a temperature of 25 ° C. The storage modulus is 1.0 × 10 ⁵ Pa or more and 1.0 × 10 ⁸ Pa or less. In the present invention, after the storage modulus at 25 ° C is set to the above range, the storage modulus ratio is set to 1.5 or more, thereby easily adjusting the adhesive forces at 80 ° C, 100 ° C, and 120 ° C to the above range. .

In the present invention, the storage modulus at 25 ° C, 80 ° C, and 120 ° C is measured by the following measurement method.
A hardened body was obtained by pouring a hardening resin composition into a Teflon (registered trademark) mold having a width of 3 mm, a length of 30 mm, and a thickness of 1 mm. Regarding the hardening of the curable resin composition, in the case of light-moisture hardening, the light-curing is performed by irradiating 3000 mJ / cm ² with a mercury lamp, and thereafter, the temperature is controlled by 23 ° C, 50 It is left to stand for 3 days in an RH% environment for moisture hardening. In addition, in the case of photohardenability, the step of moisture hardening is omitted, and in the case of moisture hardenability, the step of photohardening is omitted, and it is performed in the same manner as described above. Furthermore, in the case of thermosetting, it hardens by heating at 90 degreeC for 2 hours.
Using the obtained hardened body, the dynamic viscoelasticity was measured in a range of 40 to 150 ° C by a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., product name "DVA-200"), and the storage modulus at each temperature was determined. . The measurement conditions are as follows: the deformation mode is tensile, the set strain is 1%, the measurement frequency is 1 Hz, and the temperature rise rate is 5 ° C / min.

From the viewpoint of increasing the adhesive force at 80 ° C and decreasing the adhesive force at 100 ° C or 120 ° C, the storage modulus is preferably 1.7 or more, and more preferably 3.0 or more. The upper limit of the storage modulus ratio is not particularly limited, but is, for example, 15 and preferably 10.
In order to easily adjust the adhesive forces at 80 ° C, 100 ° C, and 120 ° C to a desired range, the storage modulus at 25 ° C is more preferably 5.0 × 10 ⁵ Pa or more, and further preferably 3.0 × 10 ⁶ Pa or more. It is more preferably 5.0 × 10 ⁷ Pa or less, and even more preferably 2.0 × 10 ⁷ Pa or less.

[Curable resin]
The curable resin composition of the present invention is preferably any one of thermosetting, photo-curing, and moisture-curing, but preferably has at least one of photo-curing and moisture-curing. If it has photocurability or moisture curability, the curable resin composition can be cured without heating. Therefore, when the curable resin composition is cured, it is possible to prevent damage to the bonding part or the electronic parts around the bonding part due to heating. In addition, the wax particles described below are not heated and melted at the time of hardening, and can be directly present in the hardened material in the form of particles, and easily become those having good reworkability.

Among the moisture-curing properties and light-curing properties, moisture-curing properties are preferred from the viewpoint of adhesion, and light-curing properties are preferred from the viewpoint of curing speed. Furthermore, from the viewpoint of requiring adhesion and curing speed, the curable resin composition is more preferably one having both photo-curing properties and moisture-curing properties, that is, having photo-moisture-curing properties. If the curable resin composition has photo-moisture-hardening properties, for example, a low adhesive force is first given by photo-hardening, and then it is further hardened with moisture by being placed in the air, and then it can be formed to have sufficient strength. The hardening of the adhesive force.

The curable resin composition of the present invention contains a curable resin, but the type of the curable resin used is selected depending on the curing characteristics of the curable resin composition. The curable resin may specifically be any one of a moisture curable resin, a thermosetting resin, and a photocurable resin, but it is preferably at least one selected from the group consisting of a moisture curable resin and a photocurable resin. It is more preferable to contain both a moisture-curable resin and a photo-curable resin.

The content of the curable resin is preferably 50 parts by mass or more with respect to 100 parts by mass of the curable resin composition, more preferably 55 parts by mass or more, and still more preferably 60 parts by mass or more. The content of the curable resin is preferably 97 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 75 parts by mass or less with respect to 100 parts by mass of the curable resin composition. By setting the content of the curable resin within these ranges, it is easy to adjust the storage modulus and storage modulus ratio at 25 ° C to the above-mentioned required ranges.

(Moisture hardening resin)
Examples of the moisture-curable resin include a moisture-curable amine ester resin, a hydrolyzable silane-containing resin, and a moisture-curable cyanoacrylate resin. Among them, a moisture-curable amine ester is preferred. Resin.
The moisture-curable amine ester resin has an amine ester bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture in the air or an adherend to be hardened. The moisture-curable urethane resin may have only one isocyanate group in one molecule, and may have two or more. Among them, an isocyanate group is preferred at both ends of the main chain of the molecule.

The moisture-curable amine ester resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
The reaction between the above-mentioned polyol compound and polyisocyanate compound is usually the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound, that is, [NCO] / [OH] = 2.0 Perform within a range of ~ 2.5.

As the polyol compound used as a raw material of the moisture-curable urethane resin, a well-known polyol compound generally used for producing polyurethane can be used, and examples thereof include polyester polyol, polyether polyol, and polyalkylene polyol. , Polycarbonate polyols, etc. These polyol compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the polyester polyol include a polyester polyol obtained by reacting a polycarboxylic acid and a polyol, and a poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone. Wait.
Examples of the polycarboxylic acid as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecanedicarboxylic acid, and the like.
Examples of the polyol used as a raw material of the polyester polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,5-pentane. Glycol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, and the like.

Examples of the polyether polyol include ethylene glycol, propylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, and random or block copolymers of these or their derivatives. , Bisphenol-type polyoxyalkylene modified body and so on.
Here, the bisphenol-type polyoxyalkylene modification system causes addition reaction of alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to bisphenol-type molecules Polyether polyol obtained from the active hydrogen portion of the backbone. The polyether polyol may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified body is preferably one in which two or more kinds of alkylene oxides are added to both ends of the bisphenol-type molecular skeleton.
The bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and a bisphenol A type is preferred.

Examples of the polyalkylene polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and the like.
Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol, polycarbonate polycyclohexanedimethyl polyol, and the like.

As the polyisocyanate compound that is a raw material of the moisture-curable urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are suitably used.
Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modification of diphenylmethane diisocyanate, polymerized MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, and transcyclohexane-1,4- Diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate Wait.
Among the polyisocyanate compounds, diphenylmethane diisocyanate and a modified product thereof are preferred in terms of low vapor pressure and toxicity and ease of use.
The polyisocyanate compound may be used alone or in combination of two or more kinds.

The moisture-curable amine ester resin is preferably obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyhydric alcohol compound having a structure represented by the following formula (1), a curable resin composition having excellent adhesion and a hardened material having good flexibility and elongation can be obtained, and are compatible with the following radical polymerizable compound Excellent mutual solubility. In addition, it is easy to adjust the storage modulus ratio and the storage modulus at 25 ° C. to the ranges required above.
Among these, a polyether polyol composed of propylene glycol, a ring-opening polymerization compound of a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group is preferably used.

In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group, I is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. I is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5. Furthermore, the case where I is 0 refers to the case where the carbon bonded to R is directly bonded to oxygen.

The hydrolyzable silane group in the above-mentioned hydrolyzable silane group-containing resin reacts with moisture in the air or the adherend to harden.
The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, and may also have two or more. Among them, it is preferable that the both ends of the main chain of the molecule have a hydrolyzable silane group.

The hydrolyzable silyl group is represented by the following formula (2).


In formula (2), R ^{1 is} independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or -OSiR A triorganosiloxy group represented by ² ₃ (R ^{2 is} each independently a hydrocarbon group having 1 to 20 carbon atoms). In Formula (2), X is each independently a hydroxyl group or a hydrolyzable group. Furthermore, in Formula (2), a is an integer of 1-3.

The hydrolyzable group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an alkenyl group, an aryloxy group, a fluorenyloxy group, a ketoximate group, an amine group, an amido group, Amido (acid amide), amineoxy, mercapto and so on. Among them, in terms of high activity, a halogen atom, an alkoxy group, an alkenyloxy group, and a fluorenyloxy group are preferred. In terms of stable hydrolyzability and ease of handling, alkoxy groups such as methoxy and ethoxy are more preferred, and methoxy and ethoxy are more preferred. From the viewpoint of safety, the compounds to be separated by the reaction are ethanol and acetone, and ethoxy and isopropenyloxy are preferred.

The hydroxyl group or the hydrolyzable group may be bonded to one silicon atom in a range of 1 to 3. When two or more of the above-mentioned hydroxyl group or the above-mentioned hydrolyzable group are bonded to one silicon atom, the groups may be the same or different.

From the viewpoint of hardenability, a in the above formula (2) is preferably 2 or 3, and particularly preferably 3. From the viewpoint of storage stability, a is preferably 2.
Examples of R ¹ in the formula (2) include alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and trimethylsilane Oxy, chloromethyl, methoxymethyl and the like. Among them, methyl is preferred.

Examples of the hydrolyzable silyl group include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tri (2-propenyloxy) silyl group, and triethylfluorenylsilyl group. , (Chloromethyl) dimethoxysilyl, (chloromethyl) diethoxysilyl, (dichloromethyl) dimethoxysilyl, (1-chloroethyl) dimethoxy Silyl, (1-chloropropyl) dimethoxysilyl, (methoxymethyl) dimethoxysilyl, (methoxymethyl) diethoxysilyl, (ethoxymethyl) (Diyl) dimethoxysilyl, (1-methoxyethyl) dimethoxysilyl, (aminomethyl) dimethoxysilyl, (N, N-dimethylaminomethyl) Dimethoxysilyl, (N, N-diethylaminomethyl) dimethoxysilyl, (N, N-diethylaminomethyl) diethoxysilyl, (N- (2 -Aminoethyl) aminomethyl) dimethoxysilyl, (ethoxymethyl) dimethoxysilyl, (ethoxymethyl) diethoxysilyl, and the like.

Examples of the hydrolyzable silane-group-containing resin include (meth) acrylic resin containing a hydrolyzable silane group, an organic polymer having a hydrolyzable silane group at a molecular chain end or a molecular chain end portion, and a hydrolyzable silane group. Amine ester resin, etc.
The hydrolyzable silane-containing (meth) acrylic resin preferably has a repeating structural unit derived from the hydrolyzable silane-containing (meth) acrylate and the (meth) acrylate in the main chain. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acrylate" means acrylate or methacrylate, and other similar terms are the same.

Examples of the (meth) acrylate containing a hydrolyzable silyl group include 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (triethoxysilyl) (meth) acrylate. Propyl ester, 3- (methyldimethoxysilyl) propyl (meth) acrylate, 2- (trimethoxysilyl) ethyl (meth) acrylate, 2- (triethyl) (meth) acrylate Oxysilyl) ethyl ester, 2- (methyldimethoxysilyl) ethyl (meth) acrylate, trimethoxysilyl methyl (meth) acrylate, triethoxy (meth) acrylate Silyl methyl ester, (meth) methoxy (methdimethoxysilyl) methyl ester, and the like.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic ring Hexyl ester, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate , N-dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

As a method for producing a hydrolyzable silyl group-containing (meth) acrylic resin, specifically, for example, a hydrolyzable silicon group-containing (meth) acrylate polymer described in International Publication No. 2016/035718 can be cited. Synthesis methods, etc.
The organic polymer having a hydrolyzable silane group at the end of the molecular chain or at the end of the molecular chain has a hydrolyzable silane group in at least one of the end of the main chain and the end of the side chain.
The backbone structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth) acrylate polymers, and the like.

Examples of the polyoxyalkylene-based polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxyethylene copolymer structure, Polyoxyethylene-polyoxybutene copolymer structure polymer.
As a method for producing the above-mentioned organic polymer having a hydrolyzable silane group at a molecular chain terminal or a molecular chain terminal site, specifically, for example, the molecular chain terminal or the molecular chain terminal described in International Publication No. 2016/035718 may be mentioned. Method for synthesizing an organic polymer having a crosslinkable silane group. In addition, as another method for producing the organic polymer having a hydrolyzable silane group at a molecular chain terminal or a molecular chain terminal portion, for example, a reactive silicon group-containing polyoxyalkylene described in International Publication No. 2012/117902 can be mentioned. Synthetic method of base polymer.

Examples of the method for producing the hydrolyzable silane-containing amine ester resin include a method of reacting a polyol compound with a polyisocyanate compound to produce an amine ester resin, and further reacting a silane-containing compound such as a silane coupling agent Wait. Specifically, for example, a method for synthesizing an amine ester oligomer having a hydrolyzable silane group described in Japanese Patent Application Laid-Open No. 2017-48345 can be mentioned.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and β- (3,4-epoxy ring). (Hexyl) -ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethylsilane Oxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethyldimethoxy Silane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3 -Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. Among these, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred. These silane coupling agents may be used alone or in combination of two or more kinds.

Furthermore, the said moisture-curable resin may have a radical polymerizable functional group. As the radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferred, and in particular, a (meth) acrylfluorenyl group is more preferable in terms of reactivity. In addition, a moisture-curable resin having a radically polymerizable functional group is not included in the radically polymerizable compound described below, and is regarded as a moisture-curable resin.

The weight-average molecular weight of the moisture-curable resin is not particularly limited, and a preferred lower limit is 800, and a preferred upper limit is 10,000. By setting the weight-average molecular weight of the moisture-curable resin to be in this range, the obtained curable resin composition does not become too high in cross-linking density when cured, and is more excellent in flexibility, and has good coatability. Become more excellent. A more preferable lower limit of the weight-average molecular weight of the moisture-curable resin is 2000, a more preferable upper limit is 8000, a more preferable lower limit is 2500, and a more preferable upper limit is 6,000. In addition, in this specification, the said weight average molecular weight is the value calculated | required by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column used when measuring the weight average molecular weight based on polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko). Examples of the solvent used in GPC include tetrahydrofuran.

(Photocurable resin)
Examples of the photocurable resin of the present invention include a radical polymerizable compound. The radical polymerizable compound is preferably used in combination with the above-mentioned moisture-curable resin, and by using it in combination, the curable resin composition becomes light-moisture-curable.

The radical polymerizable compound is not particularly limited as long as it is a photopolymerizable radical polymerizable compound, and it is a compound having a radical polymerizable functional group in the molecule. Among them, a compound having an unsaturated double bond as a radical polymerizable functional group is suitable, and particularly, in terms of reactivity, a compound having a (meth) acrylfluorenyl group (hereinafter, also referred to as "(formaldehyde ) Acrylfluorenyl compounds ").

Examples of the (meth) acrylfluorenyl compound include (meth) acrylate compounds, epoxy (meth) acrylates, and (meth) acrylates. The amine (meth) acrylate is one which does not have a residual isocyanate group.

The (meth) acrylate compound may be monofunctional, bifunctional, or trifunctional or higher.
Examples of the monofunctional group in the (meth) acrylate compound include phthalimide acrylates such as N-propenyloxyethylhexahydrophthalimide, and various (formaldehyde) (Meth) acrylate, imine acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Tert-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, ( Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristoyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isomethacrylate (meth) acrylate Fluorenyl ester, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2-hydroxybutyl ester, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (meth) acrylate Butoxyethyl, methoxyethylene (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, phenoxy (meth) acrylate Ethyl ester, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (methyl ) 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethyl (meth) acrylate Aminoethyl, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloxyethyl phosphate, and the like.

Examples of the bifunctional group in the (meth) acrylate compound include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylic acid Ester, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide addition Bisphenol A di (meth) acrylate, propylene oxide addition to bisphenol A di (meth) acrylate, ethylene oxide addition to bisphenol F di (meth) acrylate, dimethylol bicyclo Pentadienyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isotricyanate di (meth) acrylate, (meth) acrylic acid 2- Hydroxy-3- (meth) acrylic acid oxypropyl ester, carbonate diol di (meth) acrylate, Ether glycol di (meth) acrylate, polyester glycol di (meth) acrylate, polycaprolactone glycol di (meth) acrylate, polybutadiene glycol di (meth) acrylate Wait.

Examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (methyl). Acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate , Ethylene oxide addition isotricyanate tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, phosphate tri (meth) acrylate Ethoxyethyl ester, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol Alcohol hexa (meth) acrylate and the like.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid. Here, the reaction of the epoxy compound and (meth) acrylic acid can be performed in the presence of a basic catalyst or the like according to a conventional method. The epoxy (meth) acrylate may be monofunctional or polyfunctional such as difunctional.
Examples of the epoxy compound used as a raw material for synthesizing the aforementioned epoxy (meth) acrylate include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenolic novolac type epoxy resin, o-cresol novolac type ring Oxygen resin, dicyclopentadiene-phenol novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy Resin, rubber modified epoxy resin, glycidyl ester compound, bisphenol A episulfide resin, etc.

As the marketers of the aforementioned epoxy (meth) acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYDRexcel63182 are all manufactured by ExecryDrycel63182 ), EA-1010, EA-1020, EA-5323, EA-5520, EACHD, EMA-1020 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (both manufactured by Nagase Kasei Co., Ltd.), etc.

As the (meth) acrylic acid amine ester, for example, an isocyanate compound and a (meth) acrylic acid derivative having a hydroxyl group can be used. Here, in the reaction between the isocyanate compound and the (meth) acrylic acid derivative, a tin-based compound or the like in a catalyst amount can be used as a catalyst. The (meth) acrylic acid amine may be monofunctional or polyfunctional such as difunctional.
Examples of the isocyanate compound used to obtain the (meth) acrylic acid amine ester include, for example, isophorone diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, and hexamethylene Diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, dihydrazine Toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) phosphorothioate, tetramethylbenzene diisocyanate Methyl diisocyanate, 1,6,11-undecane triisocyanate, etc.
Further, as the isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excess of the isocyanate compound can also be used. Here, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Wait.

Examples of the (meth) acrylic acid derivative having the above-mentioned hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono (meth) acrylates of diols; or mono (meth) acrylates or di (meth) acrylates of triols such as trimethylolethane, trimethylolpropane, and glycerol; or bis Epoxy (meth) acrylate such as phenol A epoxy (meth) acrylate and the like.

As a marketer of the aforementioned (meth) acrylic acid amine esters, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Synthesis), EBCRYL230, EBCRYL270, EBCRYL4858, EBCRYL8402 can be cited. , EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYLin all, EBECRYLinRecommences, EBECRYLinc220, KEBRMYLinc2, KEB -9000A, ArtresinUN-7100, ArtresinUN-1255, ArtresinUN-330, ArtresinUN-3320HB, ArtresinUN-1200TPK, ArtresinSH-500B (all manufactured by Gensang Industrial Corporation), 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 are new Nakamura Chemical Industries Corporation Manufacturing), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA -306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.

As the radically polymerizable compound, other radically polymerizable compounds other than those described above may be appropriately used. Examples of other radically polymerizable compounds include N, N-dimethyl (meth) acrylamide, N- (meth) acryl, morpholine, and N-hydroxyethyl (meth) acryl Amine, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. ( Methacrylamide compounds, vinyl compounds such as styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and the like.

In the curable resin composition, when used in combination with the moisture-curable resin described above, the mass ratio of the content of the radical polymerizable compound to the content of the moisture-curable resin (radical polymerizable compound / moisture curing) It is preferably 1/9 or more and 9 or less, more preferably 3/7 or more and 7/3 or less, and still more preferably 1/2 or more and 2 or less. By setting such a mass ratio, it is possible to improve the curing speed and improve the adhesion of the curable resin composition.

It is preferable that the said radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from a viewpoint of adjusting hardenability. By containing the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound, the obtained curable resin composition becomes the one which is more excellent in hardenability and viscosity. The polyfunctional radically polymerizable compound is preferably difunctional or trifunctional, and more preferably difunctional.

When the radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound, the content of the polyfunctional radically polymerizable compound is relative to that of the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound. The total amount of the sexual compound is 100 parts by mass, preferably 2 parts by mass or more, and more preferably 45 parts by mass or less. When the content of the polyfunctional radically polymerizable compound is within this range, the obtained curable resin composition becomes more excellent in curability and viscosity. The content of the polyfunctional radical polymerizable compound is more preferably 20 parts by mass or more, and still more preferably 40 parts by mass or less.

In the present invention, it is preferred to use at least one selected from the group consisting of epoxy (meth) acrylate and amine (meth) acrylate as a radical polymerizable compound.
Further, at least one selected from the group consisting of epoxy (meth) acrylate and amine (meth) acrylate is preferably used in combination with a (meth) acrylate compound. By using these two or more compounds in combination, it is easy to adjust the storage modulus and storage modulus ratio at 25 ° C to the above-mentioned ranges.
From the viewpoint that it is easy to adjust the storage modulus and storage modulus ratio at 25 ° C within the above range, at least one selected from the group consisting of epoxy (meth) acrylate and (meth) acrylate The ratio (mass ratio) of the content to the content of the (meth) acrylate compound is preferably 0.2 or more. The mass ratio is more preferably 0.35 or more, and more preferably 0.4 or more. The quality is more preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.
In addition, at least one selected from the group consisting of epoxy (meth) acrylate and amine (meth) acrylate may be monofunctional or polyfunctional, but more preferably polyfunctional. On the other hand, the (meth) acrylate compound is preferably monofunctional. Further, at least one selected from the group consisting of epoxy (meth) acrylate and amine (meth) acrylate is preferably amine (meth) acrylate.

(Thermosetting resin)
The above-mentioned thermosetting resin is not particularly limited, but when the curable resin composition contains the following wax particles, it is preferred that the resin is cured at a temperature below the melting point of the wax particles. The thermosetting resin hardened by using it at a temperature lower than the melting point of the wax particles, the wax particles do not melt or agglomerate during hardening, the average particle diameter of the wax particles in the hardened body, and the average particle diameter / average primary particle diameter are lower than The curable resin composition is the same. In addition, by lowering the curing temperature of the thermosetting resin, it is possible to prevent the electronic parts in the bonding portion or the periphery of the bonding portion from being damaged by heating. The thermosetting resin may be used in combination with other curable resins. For example, the thermosetting resin may be used in combination with the photocurable resin.
Specifically, the thermosetting resin may be any one that is cured by heating to a temperature of 60 ° C. or higher and less than 120 ° C., and more preferably 100 ° C. or lower.
Specific examples of the thermosetting resin include epoxy resin, phenol resin, amine ester resin, unsaturated polyester resin, urea resin, and melamine resin. When the curable resin composition contains a thermosetting resin, a curing catalyst, a curing accelerator, and the like may be appropriately contained so that the thermosetting resin is cured at the above temperature.

(Wax particles)
The curable resin composition of the present invention preferably contains wax particles. The wax particles are waxes that are present in a particulate form in the curable resin composition. The wax particles are melted by heating, thereby making the curable resin composition soft and thereby easily adjusting the storage modulus to a desired range. In addition, by melting the wax, the adhesive force of the curable resin composition is reduced, and since the particles have a particle shape, the contact area with the curable resin becomes large, so that the adhesive force can be further reduced. Therefore, by containing wax particles, the curable resin composition can sufficiently reduce the adhesive force at 100 ° C or 120 ° C, and can easily be adjusted to the above range.
In addition, in this specification, "wax" means the organic substance which is solid at 23 degreeC, and becomes liquid by heating.

The melting point of the wax particles is preferably 80 ° C or higher and 110 ° C or lower. By setting the melting point of the wax particles within the above range, the adhesion force at 80 ° C can be increased while the adhesion force at 100 ° C or 120 ° C can be easily reduced. From the viewpoint of further increasing the adhesion at 80 ° C, the melting point of the wax particles is more preferably 82 ° C or higher. From the viewpoint of further reducing the adhesive force at 100 ° C or 120 ° C, the melting point of the wax particles is more preferably 105 ° C or lower, and even more preferably 100 ° C or lower.
The melting point of the wax particles is set to the temperature at the peak of the endothermic peak in a graph obtained by differential scanning calorimetry. The micro scanning thermal measurement was performed using a micro scanning thermal measurement device (manufactured by TA Iinstruments, DSC Q100). The measurement conditions are as follows:
Plate: Aluminum Airtight Atmosphere: Nitrogen (40 mL / min)
Heating rate: 10 ℃ / min
Sample size: 10 mg

The average particle diameter of the wax particles is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 25 μm or less, and particularly preferably 10 μm or less. The smaller the average particle diameter of the wax particles is, the larger the contact area with the curable resin is, and it is easy to reduce the adhesive force at 100 ° C or 120 ° C. The lower limit of the average particle diameter of the wax particles is not particularly limited, but is practically 0.1 μm, and preferably 0.5 μm.

The ratio of the average particle diameter of the wax particles to the average primary particle diameter (hereinafter, also referred to as "average particle diameter / average primary particle diameter") indicates the degree of aggregation of the wax particles, and the average particle diameter of those that do not aggregate at all. Consistent with the average primary particle diameter, the average particle diameter / average primary particle diameter became 1. In the present invention, if the wax particles are not aggregated, the adhesive force is easily reduced when heated to 100 ° C or 120 ° C. Therefore, from the viewpoint of reducing the adhesive force at 100 ° C and 120 ° C, the average particle diameter / average primary particle diameter is preferably as low as possible, preferably 3 or less, more preferably 2 or less, and even more preferably 1.5 or less. The lower limit of the average particle diameter / average primary particle diameter is 1.

In addition, the average particle diameter of the wax particles contained in the curable resin composition can be obtained by observing the curable resin composition with a scanning electron microscope, measuring the particle diameter of 50 randomly selected particles, and obtaining the average value. . In addition, the wax particles may aggregate a plurality of particles to form one particle. In this case, the particle diameter of each particle refers to the particle diameter (secondary particle diameter) of the aggregate. In addition, the particle diameter is the maximum diameter of each particle.
When measuring the particle diameter of each wax particle, the primary particle diameter of the measured particles was also measured, and the average value was used as the average primary particle diameter to calculate the average particle diameter / average primary particle diameter. In addition, the primary particle diameter of each particle is the same as the particle diameter in the non-agglomerated particles. In the agglomerated particles, the average particle diameter of all the primary particles observed is taken as the primary particle diameter of the particle.

In addition, if the content of the wax particles per unit area of the curable resin composition is increased, it is easier to reduce the adhesive force by heating. Therefore, by making the thickness of the curable resin composition into a larger thickness within a range capable of maintaining the adhesiveness, it is easier to reduce the adhesive force.
Therefore, in order to maintain the thickness of the curable resin composition at a certain level or more during bonding, it is preferable to perform photo-hardening as a pretreatment. That is, when the wax particles are contained, the curable resin composition can be made light-moisture-curable, and light-cured before being adhered to the adherend as described below, thereby ensuring hardening at the time of attaching. The thickness of the resin composition is constant or more, and the adhesive force is easily reduced by heating.

The wax particles may have a functional group capable of reacting with the curable resin. By having a reactive functional group, the wax particles react with the hardening resin when the hardening resin is hardened, and the wax particles are incorporated in the cross-linking of the hardened body. Therefore, when the wax is melted by heating, the cross-linking disintegrates locally, so that the adhesive force at 100 ° C or 120 ° C is more effectively reduced.
For example, in the case where the curable resin composition contains a moisture-curable resin as the curable resin, a functional group that can be reacted includes a hydroxyl group. The wax particle can introduce a functional group to the particle surface, for example. For example, when a hydroxyl group is introduced onto the surface of a wax particle, a wax having a hydroxyl group can be pelletized in advance.

Specific examples of the wax particles include olefin-based waxes or paraffin-based waxes such as polypropylene wax, polyethylene wax, microcrystalline wax, and oxidized polyethylene wax; carnauba wax, sasol wax, and montan ester wax. Iso-aliphatic ester waxes; deacidified carnauba wax; saturated fatty acid waxes such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acid waxes such as methacrylic acid, paulownic acid, and valeric acid; stearic acid Alcohols, aralkyl alcohols, behenyl alcohols, carnauba alcohols, wax alcohols, beeswax alcohols and other saturated alcohol-based waxes or aliphatic alcohol-based waxes; polyalcohol-based waxes such as sorbitol; Saturated fatty acids such as amines and laurylamines; saturated fatty acids such as methylenebisstearylamine, ethylidenebisdecylamine, ethylidenebislaurylamine, and hexamethylenebisstearylamine Diammonium series wax; ethylene dioleamide, hexamethylene dioleamide, N, N'-dioleylhexamethylene diamine, N, N'-dioleyl sebacamide, etc. Saturated fluorene-based waxes, m-xylylenestearylamine, N, N'-distearyl-m-xylylenediamine, and other aromatic bis-fluorine-based waxes; vinyl monomers such as styrene and polystyrene Graft modified waxes obtained by graft polymerization of hydrocarbons; partial ester waxes obtained by reacting fatty acids such as behenic acid monoglyceride with polyols; methyl ester waxes having hydroxyl groups obtained by hydrogenating vegetable oils and fats; ethylene Ethylene / vinyl acetate copolymer wax with a high proportion of ingredients; long-chain acrylic acid alkyl ester waxes such as saturated acrylic acid stearyl wax; acrylic aromatic waxes such as benzyl acrylate wax. Among these, olefin-based wax, paraffin-based wax, and sasol wax are preferred.
As the wax particles, a commercially available product may be used, and other than the commercially available product may be used. Moreover, the wax particle of a commercial item can be pulverized etc., and can be set as the wax particle which has a suitable average particle diameter and average particle diameter / average primary particle diameter. For example, wax particles obtained by pulverizing FNP-0090 (manufactured by Nippon Seiki Wax Co., Ltd.) can also be used.

The content of the wax particles is preferably 3 parts by mass or more with respect to 100 parts by mass of the curable resin composition, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. By setting the content of the wax particles to be above these lower limits, the adhesive force at 100 ° C or 120 ° C can be sufficiently reduced.
The content of the wax particles is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of the curable resin composition. By setting the content of the wax particles below these upper limits, the adhesive force at 80 ° C can be sufficiently improved.

(Photo radical polymerization initiator)
When using a radical polymerizable compound in the curable resin composition of the present invention, it is preferable to contain a photoradical polymerization initiator in order to ensure photocurability.
Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9 -Oxanthium magnitude.
Examples of commercially available photoradical polymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, LucirinTPO (all manufactured by BASF), and benzoin methyl ether. , Benzoin ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and so on.

The content of the photo radical polymerization initiator in the curable resin composition is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the radical polymerizable compound. When the content of the photo-radical polymerization initiator is in this range, the obtained curable resin composition becomes excellent in photo-curability and storage stability. The content of the photo-radical polymerization initiator is more preferably 0.1 parts by mass or more and 5 parts by mass or less.

(catalyst)
When the curable resin composition contains a moisture-curable resin, it may contain a catalyst that promotes the moisture-curing reaction of the moisture-curable resin. By using the catalyst, the curable resin composition can be made more excellent in moisture-curing properties, and the adhesive force at 80 ° C can be made higher.
As the catalyst, specifically, for example, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octoate; triethylamine, U-CAT651M (manufactured by San-Apro Ltd), and U-CAT660M ( (Manufactured by San-Apro Ltd), U-CAT2041 (manufactured by San-Apro Ltd), 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diaza Heterobicyclo [2.2.2] amine compounds such as octane; zinc compounds such as zinc octoate, zinc naphthenate; zirconium tetrapyrene pyruvate; copper naphthenate; cobalt naphthenate.
The content of the catalyst is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the curable resin composition. When the content of the catalyst is in this range, the effect of promoting the moisture curing reaction can be further improved without deteriorating the storage stability and the like of the curable resin composition. The content of the catalyst is more preferably 0.2 parts by mass or more and 3 parts by mass or less.

(Filler)
The curable resin composition of the present invention may contain a filler. By containing a filler, the curable resin composition of the present invention has a good thixotropy and can sufficiently maintain the shape after coating. As the filler, it is sufficient to use particles.
The filler is preferably an inorganic filler, and examples thereof include silicon oxide, talc, titanium oxide, zinc oxide, and calcium carbonate. Among these, in terms of the manner in which the obtained curable resin composition is excellent in ultraviolet transmittance, silicon oxide is preferred. In addition, the filler may be subjected to a hydrophobic surface treatment such as a silane treatment, an alkylation treatment, or an epoxidation treatment.
The filler may be used singly or in combination of two or more kinds.
The content of the filler is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the curable resin composition, more preferably 2 parts by mass or more and 15 parts by mass or less, and still more preferably 3 parts by mass or more and 10 parts by mass or less.

The curable resin composition of the present invention may be diluted with a solvent if necessary. When the curable resin composition is diluted with a solvent, the mass part of the curable resin composition is based on the solid content component, that is, the mass part from which the solvent is removed.
The curable resin composition may contain additives such as a light-shielding agent, a colorant, metal-containing particles, and a reactive diluent in addition to the components described above.

The viscosity of the curable resin composition is preferably 50 Pa · s or more and 1000 Pa · s or less. Moreover, the viscosity refers to the viscosity measured at 25 ° C and 1 rpm using a cone-plate viscometer. When the viscosity is within this range, the workability when the curable resin composition is applied to an adherend such as a substrate becomes more excellent. The above viscosity is more preferably 80 Pa · s or more, more preferably 500 Pa · s or less, and even more preferably 400 Pa · s or less. When the viscosity of the curable resin composition is too high, the coating property can be improved by heating during coating.

As a method for producing the curable resin composition of the present invention, for example, a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roller machine may be used. If necessary, a method of mixing wax particles and other additives.
Here, the temperature when mixing various components is not particularly limited, but when wax particles are blended, the melting point of the wax particles is preferably set to less than the melting point of the wax particles, and more preferably 10 ° C or lower than the melting point of the wax particles. By making the temperature at the time of mixing sufficiently lower than the melting point of the wax particles, the wax particles blended as a raw material do not agglomerate or melt during production, etc., and can exist in the same state as the raw material even in the hardening resin composition. . Therefore, it is easy to adjust so that a wax particle may have a required average particle diameter and average particle diameter / average primary particle diameter.

The curing system of the present invention is obtained by curing the above-mentioned curable resin composition. Since the hardened body of the present invention is within the above-mentioned range because the adhesive force at 80 ° C. and the adhesive force at at least one temperature of 100 ° C. and 120 ° C. are within the above-mentioned ranges, as described above, they are excellent in adhesion performance and reworkability.
Each component contained in the hardened body of the present invention is a component contained in the curable resin composition of the present invention and a component that changes due to a chemical reaction or the like when the component is hardened. Therefore, when the curable resin composition has wax particles, the hardened body of the present invention also includes wax particles. Therefore, it is preferable that the curable resin composition is cured without heating, and even when it is heated for curing, it is preferably heated to such an extent that the wax particles do not melt or aggregate. Therefore, the hardened body may contain wax particles having an average particle diameter, an average particle diameter / average primary particle diameter as described above. Furthermore, the hardened body of the present invention may have a storage modulus ratio within the above range and a storage modulus at 25 ° C.

The hardened body of the present invention exhibits the above-mentioned adhesion by hardening the curable resin composition, thereby adhering the adherends to each other. The curing of the curable resin composition may be appropriately performed depending on the type of the curable resin. For example, in the case of photo-hardening, curing is performed by irradiating various kinds of light such as ultraviolet rays, and in the case of moisture-hardening, curing can be performed by leaving it in the air.

In the case of having photo-hardening property, first, the photo-hardening resin is hardened by irradiating light such as ultraviolet rays to give a lower adhesive force. In this case, the light-curable curable resin composition may have adhesiveness. Then, it is further placed in the air and hardened by moisture to form a hardened material having sufficient adhesion.
To explain in more detail, for example, when two adherends are bonded, first, the curable resin composition of the present invention is applied to one adherend, and thereafter, the curable resin composition is irradiated with light. The medium photo-curable resin is hardened, so that the curable resin composition adheres to an adherend with a lower adhesive force. Then, the other adherend is adhered to one adherend via the light-curable curable resin composition, and then placed in the air, thereby hardening the curable resin composition with moisture, and by Sufficient adhesive force joined the two adherends.

The curable resin composition of the present invention is cured as described above to form a cured body, and then the adhesive force is reduced by heating. Therefore, the adherend can be easily peeled off by heating, and reattachment (rework) of the adherend can be performed.
Here, the heating at the time of rework may be higher than 80 ° C. When the temperature is higher than 80 ° C., the adhesive force of the curable resin composition of the present invention becomes low, so that the adherend can be easily peeled off. The heating during rework is preferably 120 ° C or lower. When the temperature is 120 ° C. or lower, the adherend can be easily peeled off without damaging electronic parts or the like in the bonding part or the periphery of the bonding part. From these viewpoints, the heating temperature during rework is preferably 90 ° C or higher, and more preferably 95 ° C or higher. The temperature is preferably 110 ° C or lower, and more preferably 105 ° C or lower.
Further, when the curable resin composition contains wax particles, the heating during rework is preferably higher than the melting point of the wax particles, and more preferably 10 ° C or higher than the melting point of the wax particles. By heating to a temperature higher than the melting point of the wax particles, the force is appropriately reduced.

The curable resin composition of the present invention is used for, for example, various members (adhered bodies) constituting various electronic devices or electronic parts. Examples of the adherend include various adherends such as metal, glass, and plastic. 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) shape, a box shape, and a frame shape.

For example, the curable resin composition of the present invention is used for the members constituting an electronic component. Thereby, the electronic component has the hardened body of the present invention. In such an electronic component, various members are joined with a high adhesion force by the hardened body of the present invention. In addition, since the hardened body is heated to a low temperature and the adhesive force is reduced, it has excellent reworkability and can be easily re-adhered without damaging the electronic components.

The curable resin composition of the present invention is used in an electronic device or the like, for example, for bonding a substrate to a substrate to obtain an assembled component. The assembled component obtained in this way has a first substrate, a second substrate, and a cured body of the present invention, and at least a portion of the first substrate is joined to at least a portion of the second substrate via the cured body. In addition, it is preferable that the first substrate and the second substrate each have at least one electronic component mounted thereon.
In such an assembled component, the first and second substrates are bonded with a high adhesive force by the hardened body of the present invention. In addition, since the hardened body is heated to a lower temperature and the adhesion force is reduced, the reworkability is excellent, and the electronic components provided on the substrate can be easily reattached without damaging the electronic components provided on the substrate.
[Example]

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

In this embodiment, various physical properties were evaluated as follows.
(Average particle diameter, average particle diameter / average primary particle diameter)
According to the method described in the specification, the average particle diameter of the wax particles contained in the curable resin composition obtained in each Example and Comparative Example, and the ratio of the average particle diameter to the average primary particle diameter (average particle diameter / (Average primary particle diameter) was measured.
(Adherence)
The adhesive forces of 80 ° C, 100 ° C, and 120 ° C of the curable resin composition obtained in each of the examples and comparative examples were measured according to the methods described in the specification.
(Storage modulus)
The storage modulus of the curable resin composition obtained in the examples and comparative examples was measured according to the method described in the specification, and the storage modulus at 25 ° C and the storage modulus at 80 ° C with respect to 120 ° C Ratio of stored modulus.
(Volume ratio)
The volume of the hardenable resin composition at 25 ° C, 100 ° C, and 120 ° C was measured by a laser microscope, and the ratio of the volume of 100 ° C to the volume of 25 ° C of the hardenable resin composition was determined, and 120 ° C. The ratio of the volume to the volume of 25 ° C.

The moisture-curable urethane resin used in each Example and Comparative Example was produced according to the following Synthesis Example 1.
[Synthesis example 1]
As a polyol compound, 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-2000") and 0.01 part by mass of dibutyltin dilaurate were placed in a 500 mL volume. In a separable flask, stir at 100 ° C for 30 minutes under vacuum (less than 20 mmHg) and mix. Thereafter, it was set at normal pressure, and 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "PureMDI") was placed as a polyisocyanate compound, and the mixture was stirred at 80 ° C for 3 hours for reaction to obtain moisture. Curable urethane resin (weight average molecular weight 2700).

The components other than the moisture-curable urethane resin used in each Example and Comparative Example are as follows.
(Radical Polymerizable Compound)
Amyl acrylate: manufactured by Daicel allnex, trade name "EBECRYL8411", bifunctional phenoxyethyl acrylate: manufactured by Kyoeisha Chemical Company, trade name "Light acrylate PO-A", monofunctional lauryl acrylate: Kyoeisha Manufactured by chemical company, trade name "Light acrylate LA", monofunctional (wax particles)
Finely pulverized polyolefin wax (1): FNP-0090 (trade name, manufactured by Nippon Seiki Wax Co., Ltd.) is finely pulverized so that the primary particle size becomes 1 to 10 μm, melting point: 92 ° C
Finely pulverized polyolefin wax (2): Finely pulverized FNP-0090 (trade name, manufactured by Nippon Seiki Wax Co., Ltd.) so that the primary particle diameter becomes 1 to 10 μm and the secondary particle diameter becomes 30 to 200 μm. , Melting point: 92 ° C
Finely pulverized polyolefin wax (3): FNP-0090 (trade name, manufactured by Nippon Seiki Wax Co., Ltd.) is finely pulverized so that the primary particle diameter becomes 100 to 200 μm. Melting point: 92 ° C
(Photo radical polymerization initiator)
2-benzyl-2-dimethylamino-1- (4-portolinylphenyl) -butanone-1 (manufactured by BASF, trade name "IRGACURE369")
(catalyst)
U-CAT 660M (trade name, manufactured by San-Apro Ltd)
(Filler)
Trimethylsilanized silicon oxide (manufactured by Japan Aerosil, trade name "R812", primary particle diameter 7 nm)

[Examples 1 to 3, Comparative Examples 1, 2, 3]
According to the blending ratios described in Table 1, each material was stirred at a temperature of 50 ° C using a planetary stirring device (manufactured by Thinky, "defoaming stirring Taro"), and then uniformly mixed at a temperature of 50 ° C using a ceramic three-roller. The curable resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained.

[Table 1]

As shown in Table 1, in each example, the adhesive force at 80 ° C. can be increased. On the other hand, the adhesive force at 100 ° C. and 120 ° C. can be reduced to improve the adhesion performance, and the reworkability can also be improved. On the other hand, in Comparative Examples 1 to 3, the adhesive strength at 100 ° C and 120 ° C could not be reduced, so that the reworkability could not be improved.

10‧‧‧curable resin composition

11‧‧‧ aluminum substrate

12‧‧‧ glass plate

13‧‧‧sample

S‧‧‧ shear direction

FIG. 1 is a schematic diagram showing a method of adhesion test, in which FIG. 1 (a) is a plan view and FIG. 1 (b) is a side view.

Claims (11)

A curable resin composition having an adhesive force at 80 ° C. of 6 kgf / cm ² or more and an adhesive force at 120 ° C. of 3.5 kgf / cm ² or less in the following adhesion test, and the curable resin composition The ratio of the volume of 120 ° C to the volume of 25 ° C is 1.2 or less; <Adhesiveness test> The curable resin composition is made to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. It was coated on an aluminum substrate, and then a glass plate was stacked to harden a curable resin composition, and the aluminum substrate and the glass plate were bonded to prepare a sample for adhesion test. The sample was placed at 80 ° C for 10 minutes and heated to 80 ° C. At 80 ° C, a tensile tester was used to stretch at a speed of 5 mm / sec in the shearing direction. The peeling time of the aluminum substrate and the glass plate was measured. The strength was measured at 80 ° C. The adhesion force was measured in the same manner except that the heating temperature was changed to 120 ° C. A curable resin composition having an adhesive force at 80 ° C. of 6 kgf / cm ² or more and an adhesive force of 100 ° C. of 4 kgf / cm ² or less in the following adhesion test, and the curable resin composition The ratio of the volume at 100 ° C to the volume at 25 ° C is 1.2 or less; <Adhesiveness test> The curable resin composition is set to have a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. It was coated on an aluminum substrate, and then a glass plate was stacked to harden a curable resin composition, and the aluminum substrate and the glass plate were bonded to prepare a sample for adhesion test. The sample was placed at 80 ° C for 10 minutes and heated to 80 ° C. At 80 ° C, a tensile tester was used to stretch at a speed of 5 mm / sec in the shearing direction. The peeling time of the aluminum substrate and the glass plate was measured. The strength was measured at 80 ° C. The adhesive force was measured in the same manner except that the heating temperature was changed to 100 ° C. The curable resin composition according to claim 1 or 2, wherein the ratio of the storage modulus at 80 ° C to the storage modulus at 120 ° C is 1.5 or more, and the storage modulus at 25 ° C is 1.0 × 10 ⁵ Pa or more and 1.0 × 10 ⁸ Pa or less. The curable resin composition according to any one of claims 1 to 3, which contains wax particles. The curable resin composition according to claim 4, wherein the ratio of the average particle diameter of the wax particles to the average primary particle diameter is 3 or less. The curable resin composition according to claim 4 or 5, wherein the melting point of the wax particles is 80 ° C or higher and 110 ° C or lower. The curable resin composition according to any one of claims 4 to 6, wherein the average particle diameter of the wax particles is 100 μm or less. A hardened body, which is a hardened body of the curable resin composition according to any one of claims 1 to 7. An electronic component comprising the hardened body according to claim 8. An assembly part comprising a first substrate, a second substrate, and a hardened body according to claim 8; And at least a part of the first substrate is bonded to at least a part of the second substrate via the hardened body. The assembly component according to claim 10, wherein at least one electronic component can be mounted on each of the first substrate and the second substrate.