JPWO2019203277A1 - Curable resin composition, cured product, electronic parts and assembly parts - Google Patents

Abstract

The curable resin composition of the present invention is a curable resin composition for adhering electronic parts, which contains a curable resin, and has a width of 10 mm, a length of 45 mm, and a thickness of 0.6 mm. Under the conditions of a chuck distance of 25 mm and a tensile speed of 100 mm / min, the fracture strain was 200% or more, and under the same conditions, the cured product was extended by 5 mm in the length direction and stopped, and after 30 seconds, the cured product was stopped. The tension T is 25 kgf / cm2 or less.

Description

The present invention relates to a curable resin composition, a cured product of the curable resin composition, and an electronic component and an assembly component having a cured product of the curable resin composition.

In recent years, electronic components such as semiconductor chips are required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor chips may be joined via an adhesive layer to form a laminate of semiconductor chips. Further, in the present age when mobile devices with various display elements are widespread, as a method of miniaturizing the display element, a narrow frame is used for the image display unit (hereinafter, also referred to as "narrow frame design"). .. In the narrow frame design, a technique of adhering with an adhesive having a narrow line width using a dispenser or the like is required.

High adhesive strength is generally required for adhesion of these small electronic components and narrow frame design. As such an adhesive, for example, as disclosed in Patent Document 1, a photo-moisture-curable compound containing a radical-polymerizable compound, a thermosetting resin, a photoradical polymerization initiator, and a coupling agent. It is known that resin compositions are used.

International Release 2017/094831

By the way, not only the adhesive strength but also the durability of the adhesive force may be required in the adhesion of small electronic parts and the design of a narrow frame.
Specifically, electronic components such as semiconductor chips and display elements may be exposed to high temperatures of about 80 ° C. during the assembly process and use due to external heating and heat generation of the electronic components themselves during operation. is there. In addition, electronic components may be exposed to a low temperature of 0 ° C. or lower depending on the usage environment. On the other hand, when different materials are bonded to each other with an adhesive, the different materials have different coefficients of thermal expansion. Therefore, when the temperature changes as described above, the adhesive is greatly distorted during the assembly process and use. Sometimes. When such distortion occurs repeatedly, the adhesive is partially broken and the adhesive strength of the adhesive is reduced. Therefore, it may be required to suppress the decrease in the adhesive force and enhance the durability of the adhesive force even after the strain is repeatedly generated.

Therefore, it is an object of the present invention to provide a curable resin composition for adhering electronic components, which has good adhesive strength and good adhesive strength.

As a result of diligent studies, the present inventors have found that the above problems can be solved by keeping the fracture strain and tension T of the cured product within a predetermined range, and have completed the following invention.
The present invention provides the following [1] to [9].
A curable resin composition for adhering electronic components, which comprises a curable resin.
[1] A cured product of the curable resin composition having a width of 10 mm, a length of 45 mm, and a thickness of 0.6 mm has a fracture strain of 200% or more under the conditions of 25 ° C., a chuck distance of 25 mm, and a tensile speed of 100 mm / min. A curable resin composition which is stretched by 5 mm in the length direction and stopped under the same conditions, and the tension T of the cured product after 30 seconds is 25 kgf / cm ^{2 or less.}
[2] The curable resin composition according to the above [1], which has an adhesive force of 10 kgf / cm ^{2 or more in the following adhesiveness test.}
<Adhesion test>
A curable resin composition is applied to 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 the curable resin composition is passed through the curable resin composition. To prepare a sample for adhesion test by stacking glass plates. The adhesiveness test sample is obtained by laminating the aluminum substrate and the glass plate by curing the curable resin composition. After curing the curable resin composition, the prepared sample for adhesion test was left to stand in a 25 ° C. and 50% RH atmosphere for 25 minutes, and then 5 mm in the shearing direction using a tensile tester in a 25 ° C. and 50% RH atmosphere. The adhesive strength is measured by pulling at a speed of / sec and measuring the strength when the aluminum substrate and the glass plate are peeled off.
[3] The curable resin composition according to the above [1] or [2], wherein the curable resin contains at least one selected from the group consisting of a moisture-curable resin, a thermosetting resin, and a photocurable resin. Stuff.
[4] The curable resin contains a moisture-curable resin, and the curable resin contains a moisture-curable resin.
The curing according to any one of [1] to [3] above, wherein the moisture-curable resin contains at least one selected from the group consisting of a moisture-curable urethane resin and a hydrolyzable silyl group-containing resin. Sex resin composition.
[5] The curable resin composition according to any one of [1] to [4] above, wherein the curable resin contains both a moisture-curable resin and a photocurable resin.
[6] A cured product of the curable resin composition according to any one of the above [1] to [5].
[7] An electronic component having the cured product according to the above [6].
[8] It has a first substrate, a second substrate, and a cured product according to the above [6].
An assembly component in which at least a part of the first substrate is joined to at least a part of the second substrate via the cured body.
[9] The assembly component according to the above [8], wherein at least one electronic component is attached to each of the first substrate and the second substrate.

According to the present invention, it is possible to provide a curable resin composition for adhering electronic components, which has good adhesive strength and good adhesive strength durability.

It is the schematic which shows the adhesiveness test method, FIG. 1A is a plan view, and FIG. 1B is a side view.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention is a curable resin composition for adhering electronic components containing a curable resin. The curable resin composition of the present invention has a fracture strain of 200% or more when the cured product is pulled under the conditions of 25 ° C., a chuck distance of 25 mm, and a tensile speed of 100 mm / min. Further, the cured product is pulled under the conditions of 25 ° C., a distance between chucks of 25 mm, and a tensile speed of 100 mm / min, stretched by 5 mm in the length direction, stopped, and the tension T of the cured product is 25 kgf / cm 30 seconds later. It will be ^{2 or less.}

As described above, the curable resin composition of the present invention has good elongation characteristics and excellent stress relaxation characteristics ^{by setting the tension T to 25 kgf / cm 2 or less while increasing the fracture strain.} Therefore, the durability of the adhesive force is improved. Specifically, even if a cured product that adheres between different materials is repeatedly exposed to a low temperature environment and a high temperature environment and strain is repeatedly applied to the cured product, the ability of the cured product to follow the strain is improved. As a result, the adhesive strength is prevented from being lowered.
On the other hand, if the fracture strain is less than 200% or the tension T is ^{larger than 25 kgf / cm 2} , the elongation characteristics are deteriorated and the stress relaxation characteristics are insufficient, so that the durability of the adhesive force is improved. Not sufficiently improved.

From the viewpoint of enhancing the elongation characteristics and increasing the durability of the adhesive force, the fracture strain is preferably 210% or more, more preferably 250% or more. The upper limit of the fracture strain is not particularly limited, but is, for example, 1000%, preferably 700%.
Further, by increasing a balanced stress relaxation properties and mechanical properties, from the viewpoint of a higher durability of the adhesive strength, tension T is preferably 23kgf / cm ² or less, more preferably 20 kgf / cm ² or less, more preferably more Is 15 kgf / cm ² or less. The tension T is not particularly limited, but is substantially ^{preferably 0.5 kgf / cm 2} or more.

Here, the cured product used when measuring the fracture strain and the tension T is a sample having a width of 10 mm, a length of 45 mm, and a thickness of 0.6 mm, which is the same as the curing conditions in which the curable resin composition is used as an adhesive. It may be produced by being cured in the above manner, and may be produced under the following conditions, for example, depending on the curing mechanism.

In the case of a photocurable resin composition, first, the curable resin composition is applied on a release sheet, and another release sheet is attached to the release sheet. At this time, the thickness of the curable resin composition is adjusted to 0.6 mm by using a gap material. Then, the applied photocurable resin composition was photocured by irradiating both sides with a mercury lamp at 3000 mJ / cm ^{2 in} an environment of 25 ° C. and 50 RH%, and the release sheets on both sides were peeled off to obtain a cured product sheet. obtain.
In the case of a moisture-curable resin composition, the moisture-curable resin composition is applied onto a release sheet so that the thickness becomes 0.6 mm, and the composition is left at 25 ° C. and 50 RH% for 7 days. The release sheet is peeled off to obtain a cured product sheet.
In the case of a light-moisture curable resin composition, the curable resin composition is applied on a release sheet, and another release sheet is attached to the release sheet. At this time, the thickness of the curable resin composition is adjusted to 0.6 mm by using a gap material. Then, in an environment of 25 ° C. and 50 RH%, both sides are first photo-cured by irradiating ^{both sides with a mercury lamp at 3000 mJ / cm 2.} Then, one release sheet is peeled off and left at 25 ° C. and 50 RH% for 7 days to be moisture-cured, and after the moisture cure, the other release sheet is peeled off to obtain a cured product sheet.
In the case of a thermosetting resin composition, the curable resin composition is applied on a release sheet, and another release sheet is attached to the release sheet. At this time, the thickness of the curable resin composition is adjusted to 0.6 mm by using a gap material. After bonding, it is cured by heating at 90 ° C. for 2 hours, and after curing, the release sheets on both sides are peeled off to obtain a cured product sheet.
The cured product sheet obtained as described above is cut out so as to have a width of 10 mm and a length of 45 mm to obtain a cured product sample.
The release sheet may be a release sheet that can be peeled from the cured product so that the stress that destroys the cured product is not applied, and for example, a release PET film or the like may be used.

The curable resin composition of the present invention preferably has an adhesive strength of 10 kgf / cm ² or more as measured in an adhesive test described later. When the adhesive strength is 10 kgf / cm ² or more, adherends such as electronic parts and substrates can be adhered to each other with high adhesive strength. ^{The adhesive strength is more preferably 15 kgf / cm 2} or more, still more preferably 20 kgf / cm ² or more, from the viewpoint of increasing the adhesive strength.

(Adhesion test)
In the present invention, the adhesive strength is measured by the following adhesive test.
As shown in FIGS. 1A and 1B, the curable resin composition 10 has a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. Is applied to the aluminum substrate 11 and the glass plates 12 are superposed on the curable resin composition 10 to prepare a sample 13 for an adhesiveness test. The adhesiveness test sample 13 is obtained by bonding the aluminum substrate 11 and the glass plate 12 by curing the curable resin composition 10. The prepared sample 13 for adhesion test was left to stand in a 25 ° C. and 50% RH atmosphere for 25 minutes after curing of the curable resin composition, and then in a shearing direction S using a tensile tester in a 25 ° C. and 50% RH atmosphere. The adhesive strength is measured by pulling at a speed of 5 mm / sec and measuring the strength when the aluminum substrate 11 and the glass plate 12 are peeled off.
Here, the curing conditions of the curable resin composition when preparing the adhesiveness test sample are the same as the curing conditions in which the curable resin composition of the present invention is used as an adhesive, and are described below according to the curing mechanism. It is advisable to prepare a sample under the conditions of.

In the case of the photocurable resin composition, first, a dispensing device is used so that the aluminum substrate has a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm. And stick a glass plate to the aluminum substrate. Then, a sample for adhesion test is prepared by photocuring by irradiating with ^{a mercury lamp at 3000 mJ / cm 2 in} an environment of 25 ° C. and 50 RH%.
In the case of a moisture-curable resin composition, it is applied to an aluminum substrate using a dispensing device 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, a glass plate is attached to an aluminum substrate and left at 25 ° C. and 50 RH% for 7 days to be moisture-cured to obtain a sample for adhesiveness evaluation.

In the case of the photo-moisture-curable resin composition, first, a dispensing device is used to obtain a width of 1.0 ± 0.1 mm, a length of 25 ± 2 mm, and a thickness of 0.4 ± 0.1 mm on the aluminum substrate. It is photocured by irradiating with ^{a mercury lamp at 3000 mJ / cm 2 in} an environment of 25 ° C. and 50 RH%. Then, a glass plate is attached to an aluminum substrate, a weight of 100 g is placed, and the mixture is left to stand at 25 ° C. and 50 RH% for 7 days to be moisture-cured to obtain a sample for adhesiveness evaluation.
In the case of a thermosetting resin composition, it is applied to an aluminum substrate using a dispensing device 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, a glass plate is attached to an aluminum substrate and heated at 90 ° C. for 2 hours to prepare a sample for adhesion test.
In this test, the aluminum alloy "AL-6063" is used for the aluminum substrate. Further, as the glass plate, a glass plate that has been ultrasonically cleaned for 5 minutes is used.

[Curable resin]
The curable resin composition of the present invention may be thermosetting, photocurable, or moisture-curable, but preferably has at least one of photocurability and moisture-curable. When 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 the adhesive portion or the electronic component around the adhesive portion from being damaged by heating.

Further, among the moisture curable property and the photocurable property, the moisture curable property is preferable from the viewpoint of adhesive strength, and the photocurable property is preferable from the viewpoint of the curing rate. Further, it is more preferable that the curable resin composition has both photocurability and moisture curability, that is, photomoisture curability, from the viewpoint of obtaining adhesive strength and curing speed. When the curable resin composition has photomoisture curability, for example, it is sufficiently cured by moisture by first photocuring to impart a relatively low adhesive force and then leaving it in the air or the like. It becomes possible to make a cured product having a strong adhesive force.

The curable resin composition of the present invention contains a curable resin, and the type of curable resin used is selected according to the curing characteristics of the curable resin composition. Specifically, the curable resin may be any of a moisture-curable resin, a thermosetting resin, and a photocurable resin, but at least one selected from the moisture-curable resin and the photocurable resin. Is preferable, and it is more preferable to contain both a moisture-curable resin and a photocurable resin.

The content of the curable resin is preferably 60 parts by mass or more, more preferably 75 parts by mass or more, and further preferably 85 parts by mass or more with respect to 100 parts by mass of the curable resin composition. The content of the curable resin is preferably 98 parts by mass or less, more preferably 95 parts by mass or less, and further preferably 93 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 becomes easy to adjust the fracture strain and the tension T within a predetermined range while increasing the adhesive force.

(Moisture curable resin)
Examples of the moisture-curable resin used in the present invention include a moisture-curable urethane resin, a hydrolyzable silyl group-containing resin, and a moisture-curable cyanoacrylate resin, and examples thereof include a moisture-curable urethane resin and a hydrolyzable silyl group. The contained resin is preferable, and among them, a moisture-curable urethane resin is preferable. The moisture-curable resin may be used alone or in combination of two or more.
The moisture-curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with water in the air or an adherend to cure. The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. Of these, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.

The moisture-curable urethane 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 polyol compound and the polyisocyanate compound is usually performed by the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound [NCO] / [OH] = 2.0 to 2. It is done in the range of .5.

As the polyol compound which is a raw material of the moisture-curable urethane resin, a known polyol compound usually used in the production of polyurethane can be used, and for example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol and the like. Can be mentioned. These polyol compounds may be used alone or in combination of two or more.
Examples of the polyester polyol include a polyester polyol obtained by reacting a polyvalent carboxylic acid with a polyol, a poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone, and the like.
Examples of the polyvalent carboxylic acid used as a raw material for the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid. , Azelaic acid, suberic acid, decamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid and the like.
Examples of the polyol used as a raw material for the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol. Examples thereof include diethylene glycol and cyclohexanediol.

Examples of the polyether polyol include a ring-opening polymer of ethylene glycol, propylene glycol and tetrahydrofuran, a ring-opening polymer of 3-methyl tetrahydrofuran, and a random copolymer or block copolymer of these or derivatives thereof, or a bisphenol type. Polyoxyalkylene modified product of the above, and the like.
Here, the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton. is there. The polyether polyol may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified product preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton.
The bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and bisphenol A type is preferable.

Examples of the polyalkylene polyol include a polybutadiene polyol, a hydrogenated polybutadiene polyol, and a hydrogenated polyisoprene polyol.
Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol and polycyclohexanedimethylene carbonate polyol.

As the polyisocyanate compound which is a raw material of the moisture-curable urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are preferably used.
Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polypeptide MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like.
Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornan diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate. , Bis (isocyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate and the like.
As the polyisocyanate compound, diphenylmethane diisocyanate and its modified product are preferable from the viewpoint that the adhesive force at 25 ° C., the breaking strain, and the tension T can be easily adjusted within a predetermined range.
The polyisocyanate compound may be used alone or in combination of two or more.

The moisture-curable urethane resin is preferably 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), it becomes easy to obtain a curable resin composition having excellent adhesiveness, high breaking strain of the cured product, and low tension T. In addition, it has excellent compatibility with radically polymerizable compounds described later.
Of these, those using a polyether polyol composed of a ring-opening polymerization compound of propylene glycol or a tetrahydrofuran (THF) compound or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable. Further, a ring-opening polymerization compound of a tetrahydrofuran compound is more preferable, and polytetramethylene ether glycol is particularly preferable.

式（１）中、Ｒは、水素原子、メチル基、又は、エチル基を表し、ｌは、０〜５の整数、ｍは、１〜５００の整数、ｎは、１〜１０の整数である。ｌは、０〜４であることが好ましく、ｍは、５０〜２００であることが好ましく、ｎは、１〜５であることが好ましい。なお、ｌが０の場合とは、Ｒと結合した炭素が直接酸素と結合している場合を意味する。
上記した中では、ｎとｌの合計が３以上であることがより好ましく、３〜６がさらに好ましい。また、Ｒは水素原子、メチル基であることがより好ましく、水素原子が特に好ましい。

In the formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group, l is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. .. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5. The 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 3 or more, and further preferably 3 to 6. Further, R is more preferably a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.

In the hydrolyzable silyl group-containing resin used in the present invention, the hydrolyzable silyl group in the molecule reacts with water in the air or the adherend to cure.
The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more hydrolyzable silyl groups. Of these, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule.

式（２）中、Ｒ^１は、それぞれ独立に、置換されていてもよい炭素数１以上２０以下のアルキル基、炭素数６以上２０以下アリール基、炭素数７以上２０以下のアラルキル基、又は、−ＯＳｉＲ^２ _３（Ｒ^２は、それぞれ独立に、炭素数１以上２０以下の炭化水素基である）で示されるトリオルガノシロキシ基である。また、式（２）中、Ｘは、それぞれ独立に、ヒドロキシ基又は加水分解性基である。さらに、式（２）中、ａは、１〜３の整数である。The hydrolyzable silyl group is represented by the following formula (2).

In formula (2), R ¹ is 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 an aralkyl group having 7 or more carbon atoms, which may be substituted independently of each other. , -OSiR ² ₃ (R ² is a hydrocarbon group having 1 to 20 carbon atoms independently). Further, in the formula (2), X is independently a hydroxy group or a hydrolyzable group. Further, in the equation (2), a is an integer of 1 to 3.

The hydrolyzable group is not particularly limited, and for example, a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, Examples include a mercapto group. Of these, a halogen atom, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable because of their high activity. Further, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is further preferable, because the hydrolyzability is mild and easy to handle. From the viewpoint of safety, the compounds desorbed by the reaction are ethanol and acetone, respectively, and ethoxy groups and isopropenoxy groups are preferable.

The hydroxy group or the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3. When two or more of the hydroxy groups or the hydrolyzable groups are bonded to one silicon atom, the groups may be the same or different.

From the viewpoint of curability, a in the above formula (2) is preferably 2 or 3, and particularly preferably 3. Further, from the viewpoint of storage stability, a is preferably 2.
As the R ¹ in the formula (2), for example, alkyl groups such as methyl group, ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl, aralkyl groups such as benzyl group, trimethylsiloxy group , Chloromethyl group, methoxymethyl group and the like. Of these, a methyl group is preferable.

Examples of the hydrolyzable silyl group include a methyldimethoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a (chloromethyl) dimethoxysilyl group. Chloromethyl) diethoxysilyl group, (dichloromethyl) dimethoxysilyl group, (1-chloroethyl) dimethoxysilyl group, (1-chloropropyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group Group, (ethoxymethyl) dimethoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, (aminomethyl) dimethoxysilyl group, (N, N-dimethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) dimethoxy Silyl groups, (N, N-diethylaminomethyl) diethoxysilyl groups, (N- (2-aminoethyl) aminomethyl) dimethoxysilyl groups, (acetoxymethyl) dimethoxysilyl groups, (acetoxymethyl) diethoxysilyl groups, etc. Can be mentioned.

Examples of the hydrolyzable silyl group-containing resin include a hydrolyzable silyl group-containing (meth) acrylic resin, an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or the molecular chain terminal site, and a hydrolyzable silyl group-containing resin. Examples include polyurethane resin.
The hydrolyzable silyl group-containing (meth) acrylic resin preferably has a repeating structural unit derived from the hydrolyzable silyl group-containing (meth) acrylic acid ester and the (meth) acrylic acid alkyl ester 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 hydrolyzable silyl group-containing (meth) acrylic acid ester include (meth) acrylic acid 3- (trimethoxysilyl) propyl, (meth) acrylic acid 3- (triethoxysilyl) propyl, and (meth) acrylic acid. 3- (Methyldimethoxysilyl) propyl, 2- (trimethoxysilyl) ethyl (meth) acrylate, 2- (triethoxysilyl) ethyl (meth) acrylate, 2- (methyldimethoxysilyl) ethyl (meth) acrylate , (Meta) acrylate trimethoxysilylmethyl, (meth) acrylate triethoxysilylmethyl, (meth) acrylate (methyldimethoxysilyl) methyl and the like.
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- (meth) acrylate Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) Examples thereof include stearyl acrylate.

As a method for producing a hydrolyzable silyl group-containing (meth) acrylic resin, specifically, for example, the hydrolyzable silicon group-containing (meth) acrylic acid ester-based weight described in International Publication No. 2016/035718. Examples thereof include a method for synthesizing coalescence.
The organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the terminal site of the molecular chain has a hydrolyzable silyl group at at least one of the end of the main chain and the end of the side chain.
The skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers.

Examples of the polyoxyalkylene polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, and a polyoxypropylene-poly. Examples thereof include a polymer having an oxybutylene copolymer structure.
Specific examples of the method for producing an organic polymer having a hydrolyzable silyl group at the terminal of the molecular chain or the terminal site of the molecular chain are described in, for example, International Publication No. 2016/035718, the terminal of the molecular chain or the terminal of the molecular chain. Examples thereof include a method for synthesizing an organic polymer having a crosslinkable silyl group only at the terminal site of the molecular chain. Further, as another method for producing an organic polymer having a hydrolyzable silyl group at the terminal end of the molecular chain or the terminal site of the molecular chain, for example, the reactive silicon group contained in International Publication No. 2012/117902 is described. Examples thereof include a method for synthesizing a polyoxyalkylene polymer.

As a method for producing the above-mentioned hydrolyzable silyl group-containing polyurethane resin, for example, when a polyol compound and a polyisocyanate compound are reacted to produce a polyurethane resin, a silyl group-containing compound such as a silane coupling agent is further added. Examples thereof include a method of reacting. Specific examples thereof include a method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in JP-A-2017-48345.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy-ethoxy) silane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -Γ-Aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-Isocyanoxidepropyltri Examples thereof include methoxysilane and 3-isocyanatepropyltriethoxysilane. Of these, γ-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.

Further, the moisture-curable resin may have a radically polymerizable functional group. As the radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferable, and a (meth) acryloyl group is more preferable from the viewpoint of reactivity. The moisture-curable resin having a radical-polymerizable functional group is not included in the radical-polymerizable compound described later, and is treated as a moisture-curable resin.

The weight average molecular weight of the moisture-curable resin is not particularly limited, but the preferable lower limit is 1000 and the preferable upper limit is 10000. When the weight average molecular weight is in this range, the obtained curable resin composition does not have an excessively high crosslink density at the time of curing, and has good fracture strain and tension T. In addition, the curable resin composition has excellent coatability.
The more preferable lower limit of the weight average molecular weight of the moisture-curable resin is 1500, the more preferable upper limit is 7000, the further preferable lower limit is 2000, and the further preferable upper limit is 5000. In this specification, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting it into polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Further, as a solvent used in GPC, tetrahydrofuran can be mentioned.

(Photocurable resin)
Examples of the photocurable resin of the present invention include radically polymerizable compounds. The radically polymerizable compound is preferably used in combination with the above-mentioned moisture-curable resin, and when used in combination, the curable resin composition becomes photo-moisture-curable.

The radically polymerizable compound may be any radically polymerizable compound having photopolymerizability, and is not particularly limited as long as it is a compound having a radically polymerizable functional group in the molecule. Among them, a compound having an unsaturated double bond as a radically polymerizable functional group is preferable, and a compound having a (meth) acryloyl group (hereinafter, also referred to as “(meth) acrylic compound”) is particularly preferable from the viewpoint of reactivity. Suitable.

Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. The urethane (meth) acrylate does not have a residual isocyanate group.

The (meth) acrylic acid ester compound may be monofunctional, bifunctional, or trifunctional or higher.
Among the (meth) acrylic acid ester compounds, monofunctional ones include, for example, phthalimide acrylates such as N-acryloyloxyethyl hexahydrophthalimide, various imide (meth) acrylates, methyl (meth) acrylates, and ethyl (meth) acrylates. , Chrylate (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isononyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) ) Acrylate, ethoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) Acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, Examples thereof include 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, and 2- (meth) acryloyloxyethyl phosphate. ..

Examples of the bifunctional (meth) acrylic acid ester compound include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyldi (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Examples thereof include di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.

Among the (meth) acrylic acid ester compounds, those having trifunctionality or higher include, for example, trimetyl propanetri (meth) acrylate, ethylene oxide-added trimethyl propanetri (meth) acrylate, and propylene oxide-added trimethyl propanthry (meth) acrylate. ) Acrylate, caprolactone-modified trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, tris Examples thereof include (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid. Here, the reaction between the epoxy compound and (meth) acrylic acid may be carried out 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 bifunctional.
Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a 2,2'-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin , Glysidyl ester compound, bisphenol A type episulfide resin and the like.

Among the above epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL370 ), 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, Examples thereof include Denacol Acrylate DA-314 and Denacol Acrylate DA-911 (both manufactured by Nagase ChemteX Corporation).

As the urethane (meth) acrylate, for example, an isocyanate compound reacted with 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, it is preferable to use a tin-based compound in a catalytic amount as a catalyst. The urethane (meth) acrylate may be monofunctional or polyfunctional such as bifunctional, but bifunctional is preferable.
Examples of the isocyanate compound used to obtain urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polypeptide MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Examples thereof include polyisocyanate compounds such as isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecantryisocyanate.
Further, as the isocyanate compound, a chain-extended polyisocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used. Here, examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono (meth) acrylate, mono (meth) acrylate or di (meth) acrylate of trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, and epoxy (meth) acrylate such as bisphenol A type epoxy (meth) acrylate. ) Acrylate and the like can be mentioned.

Commercially available urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Synthetic Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9270, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo 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 new Nakamura Chemical) (Manufactured by Kogyo 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.) and the like.

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

In the present invention, it is preferable to use at least one selected from epoxy (meth) acrylate and urethane (meth) acrylate as the radically polymerizable compound, and it is preferable to use urethane (meth) acrylate. By using these radically polymerizable compounds, it becomes easy to adjust the breaking strain and the tension T within the above range while improving the adhesive force.
Epoxy (meth) acrylate and urethane (meth) acrylate preferably have a relatively high molecular weight. Specifically, the weight average molecular weight is preferably 4000 or more, and more preferably 8000 or more. By setting the weight average molecular weight to these lower limit values or more, it becomes easy to adjust the breaking strain and the tension T within the above ranges. The weight average molecular weight is preferably 50,000 or less, more preferably 30,000 or less.

At least one selected from the epoxy (meth) acrylate and the urethane (meth) acrylate is preferably further used in combination with the (meth) acrylic acid ester compound.
Further, at least one selected from epoxy (meth) acrylate and urethane (meth) acrylate may be monofunctional or may be bifunctional or higher, but polyfunctional is more preferable. It is more preferable that it is bifunctional. On the other hand, the (meth) acrylic acid ester compound is preferably monofunctional. Further, at least one selected from epoxy (meth) acrylate and urethane (meth) acrylate is preferably urethane (meth) acrylate.

(Thermosetting resin)
The thermosetting resin used in the present invention is not particularly limited, but it is preferable to use one that cures by heating to, for example, a temperature of 60 ° C. or higher and lower than 120 ° C., more preferably a temperature of lower than 100 ° C. By setting the curing temperature of the thermosetting resin to less than the above lower limit value, it is possible to prevent the electronic parts in the adhesive portion or the vicinity of the adhesive portion from being damaged by heating.
Specific examples of the thermosetting resin include epoxy resin, phenol resin, urethane resin, unsaturated polyester resin, urea resin, melamine resin and the like. When the curable resin composition contains a thermosetting resin, it may appropriately contain a curing catalyst, a curing accelerator, and the like so that the thermosetting resin can be cured at the above temperature.
Further, the urethane resin or the like is obtained by reacting a polyol compound with a polyisocyanate compound to obtain a urethane resin. Therefore, in the present specification, the components for forming each resin (polyester compound, polyisocyanate compound in the case of urethane resin) are also widely treated as thermosetting resins.

(Photoradical polymerization initiator)
When a radically polymerizable compound is used, the curable resin composition of the present invention preferably contains a photoradical polymerization initiator in order to ensure photocurability.
Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like.
Commercially available photoradical polymerization initiators include, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, and Lucillin TPO. , Benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

The content of the photoradical polymerization initiator in the curable resin composition is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. It is less than a part by mass. When the content of the photoradical polymerization initiator is within this range, the obtained curable resin composition has excellent photocurability and storage stability. Further, when the content is within the above range, the photoradical polymerization compound is appropriately cured, and the adhesive force, fracture strain, and tension T can be easily adjusted within a predetermined range.

(Moisture curing accelerator)
When the curable resin composition contains a moisture-curable resin, the curable resin composition may contain a moisture-curing accelerating catalyst that accelerates the moisture-curing reaction of the moisture-curable resin. By using the moisture-curing accelerating catalyst, the curable resin composition becomes more excellent in moisture-curing property and can have higher adhesive strength.
Specific examples of the moisture curing accelerating catalyst include tin compounds such as din-butyltin dilaurate, din-butyltin diacetate, and tin octylate, triethylamine, U-CAT651M (manufactured by San-Apro), and U-CAT660M (manufactured by San-Apro). San-Apro), U-CAT2041 (San-Apro), 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane, etc. Amine compounds, zinc compounds such as zinc octylate and zinc naphthenate, zirconium tetraacetylacetonate, copper naphthenate, cobalt naphthenate and the like can be used.
The content of the moisture curing accelerating catalyst is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the curable resin composition. When the content of the moisture curing accelerating catalyst is within this range, the effect of accelerating the moisture curing reaction is excellent without deteriorating the storage stability of the curable resin composition.

(Coupling agent)
The curable resin composition may contain a coupling agent. By containing a coupling agent, it becomes easy to improve the adhesive strength. Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, a zirconate-based coupling agent, and the like. Of these, a silane coupling agent is preferable because it has an excellent effect of improving adhesiveness. The coupling agent may be used alone or in combination of two or more.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-) Aminoethyl) Aminopropyltriethoxysilane, 3- (2-aminoethyl) Aminopropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3-( Meta) Acryloyloxypropylmethyldimethoxysilane, 3- (meth) Acryloyloxypropylmethyldiethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, 3-Ixionpropyltrimethoxysilane, 3-Ixocyanylpropylmethyldimethoxysilane, 3- Issiapropyltriethoxysilane, 3-Ixionpropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltri Methoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane , Octyltriethoxysilane, tedyltrimethoxysilane, 1,6-bis (trimethoxyryl) hexane and the like.

Examples of the titanate-based coupling agent include titanium diisopropoxybis (acetylacetoneate), titanium tetraacetylacetonate, and titanium diisopropoxybis (ethylacetacetate).
Examples of the zirconate-based coupling agent include zirconium tetranormal propoxide and circonium tetranormal butoxide.

The content of the coupling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 2 parts by mass or less, and 0.5 parts by mass with respect to 100 parts by mass of the curable resin composition. It is more preferably parts by mass or more and 1.5 parts by weight or less. By setting the content of the coupling agent within these ranges, the adhesive strength can be improved without affecting the stress relaxation characteristics, elongation characteristics, and the like.

(filler)
The curable resin composition of the present invention may contain a filler. By containing the filler, the curable resin composition of the present invention has suitable thixophilicity and can sufficiently retain its shape after coating. As the filler, a particulate one may be used.
The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Of these, silica is preferable because the obtained curable resin composition has excellent ultraviolet transmittance. Further, the filler may be subjected to a hydrophobic surface treatment such as a silylation treatment, an alkylation treatment and an epoxidation treatment.
The filler may be used alone or in combination of two or more.
The content of the filler is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the curable resin composition.

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 parts by mass of the curable resin composition is based on the solid content, that is, means the parts by mass excluding the solvent.
In addition to the components described above, the curable resin composition may contain additives such as wax particles, light-shielding agents, colorants, and metal-containing particles.

In the present invention, the curable resin composition adjusts the breaking strain, tension T, and adhesive strength within the above ranges by adjusting the type, content, and the like of each component blended in the curable resin composition. It becomes possible to do.
For example, when a curable resin contains a polymer component having a relatively high molecular weight, the tension T tends to be high, the elongation characteristics are good, and the fracture strain tends to be high. Further, when a polymer component having a relatively low molecular weight is contained, the fracture strain tends to be generally low. Further, the breaking strain and the tension T can be appropriately adjusted depending on the type of the polymer component. Therefore, the breaking strain and the tension T can be adjusted by appropriately adjusting the type, amount, molecular weight, and the like of the polymer component.
For example, by using a polymer component having a relatively low molecular weight and a polymer component having a relatively high molecular weight in combination and reducing the amount of the polymer component having a relatively high molecular weight, the fracture strain and the tension T can be determined. It becomes easy to adjust within the range of, and the adhesive strength also becomes easy to adjust within the desired range.
The polymer component having a relatively high molecular weight is generally a polymer component having a weight average molecular weight of 8,000 or more, preferably 10,000 or more and 20,000 or less. Further, the polymer component having a relatively low molecular weight is a polymer component having a weight average molecular weight of 7,000 or less, preferably 2000 or more and 5000 or less.
Further, from the viewpoint of adjusting the fracture strain and the tension T within a predetermined range while increasing the adhesive force, it is preferable to include a low molecular weight component in the curable resin. The influence of the low molecular weight component on the fracture strain and the tension T differs depending on the type, but when the amount is increased, the tension T tends to be generally lowered. The low molecular weight component is a component having a molecular weight (formula) of less than 1000, and is generally used as a monomer component or a diluent.

The breaking strain and tension T can also be adjusted by changing the cohesive force of the curable resin composition in the cured product. For example, when the cohesive force is improved, the tension T tends to increase, and when the cohesive force is lowered, the tension T tends to decrease. Further, when the cohesive force is set to an appropriate value, the elongation becomes excellent and the fracture strain becomes high.
There are various methods for adjusting the cohesive force, and examples thereof include a method for adjusting the curing density (crosslink density). The crosslink density can be adjusted by, for example, the number of functional groups in the molecule and the molecular weight. For example, when the number of functional groups in each molecule is increased, the crosslink density tends to increase and the cohesive force tends to increase. ..

The breaking strain and tension T can also be adjusted by the molecular structure of the curable resin. For example, the molecular chain structure is made into a linear structure and the hydrocarbon chain is made long so that the molecular movement is easy. Then, it becomes easy to adjust the breaking strain and the tension T within the above range. Further, by increasing the content ratio of the curable resin in the curable resin composition, it becomes easy to increase the breaking strain and the tension T while increasing the adhesive force.

From the above viewpoint, for example, when the curable resin composition is light-moisture-curable, the types, blending amounts, molecular weights, etc. of the moisture-curable resin and the radically polymerizable compound may be appropriately adjusted.
Here, the radically polymerizable compound may contain, for example, at least one selected from epoxy (meth) acrylate and urethane (meth) acrylate (hereinafter, also simply referred to as “component A”) as described above. .. In that case, the mass ratio (A / B) of the content of the component A to the content of the moisture-curable resin (referred to as "component B") is preferably 0.01 or more and 0.30 or less, preferably 0.04 or more. It is more preferably 0.25 or less, and further preferably 0.06 or more and 0.18 or less.
Further, the component A is preferably urethane (meth) acrylate as described above, and the weight average molecular weight of the component A is preferably a relatively high molecular weight as described above. On the other hand, the moisture-curable resin is preferably a moisture-curable urethane resin, and the weight average molecular weight of the moisture-curable resin is preferably relatively low as described above.

Further, when the curable resin composition contains the component A and the moisture-curable resin, it is preferable that the curable resin composition further contains a (meth) acrylic acid ester compound as a low molecular weight component.
The content (C) of the (meth) acrylic acid ester compound in the curable resin composition is a mass ratio [C / (A + B)] with respect to the total content (A + B) of the component A and the moisture-curable resin. It is preferably 0.35 or more and 1.3 or less, and more preferably 0.50 or more and 1.1 or less.
As the (meth) acrylic acid ester compound, the above-mentioned compounds can be used, but monofunctional ones are preferable from the viewpoint of keeping the adhesive force, fracture strain and tension T within the above-mentioned predetermined ranges.

In the above, the method for adjusting the breaking strain, the tension T, and the adhesive force when the curable resin composition is a photomoisture curable resin composition has been described in detail. However, as described above, the thermosetting resin composition, the photocurable resin composition, and the moisture-curable resin composition can also be subjected to breaking strain by appropriately adjusting the type, blending amount, molecular weight, etc. of the curable resin. The tension and adhesive strength can be adjusted.

Further, in the curable resin composition, the breaking strain and the tension T can be adjusted by changing the type and amount of the catalyst for accelerating the curing and reaction of the curable resin. For example, when the amount of the photoradical polymerization initiator is increased, the crosslink density generally tends to increase and the cohesive force tends to increase, so that the tension T tends to increase. On the other hand, when the amount of the photoradical polymerization initiator is reduced, the cohesive force tends to be low, so that the tension T also tends to be low. It is also possible to increase the fracture strain by adjusting the amount of the photoradical polymerization initiator to an appropriate amount.

The viscosity of the curable resin composition is preferably 50 Pa · s or more and 1000 Pa · s or less. The viscosity is a viscosity measured under the conditions of 25 ° C. and 1 rpm using a cone plate type viscometer. When the viscosity is in this range, the workability when the curable resin composition is applied to an adherend such as a substrate becomes excellent. The viscosity is more preferably 80 Pa · s or more, more preferably 500 Pa · s or less, still more preferably 400 Pa · s or less. If the viscosity of the curable resin composition is too high, the coatability can be improved by heating at the time of coating.

As a method for producing the curable resin composition of the present invention, a curable resin, a photoradical polymerization initiator, a moisture curing accelerator, a silane coupling agent, and a filling, which are blended as needed, are used in a mixer. Examples thereof include a method of mixing with other additives such as an agent. Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer (planetary stirrer), a kneader, and three rolls.

The cured product of the present invention is obtained by curing the above-mentioned curable resin composition.
In the cured product of the present invention, a predetermined adhesive force is exhibited by curing the curable resin composition, and the adherends are adhered to each other. Further, in the cured product of the present invention, the durability of the adhesive force is improved when the fracture strain and the tension T are within the above-mentioned predetermined ranges. Therefore, for example, when a cured product adheres between different materials, high adhesive strength is maintained even if the cured product is repeatedly exposed to a low temperature environment and a high temperature environment and the cured product is repeatedly strained.
The curable resin composition may be appropriately cured according to the type of the curable resin. For example, if it is photocurable, it may be cured by irradiating it with various types of light such as ultraviolet rays, and if it is moisture-curable, it may be cured by leaving it in the atmosphere.

When the curable resin composition of the present invention has photomoisture curability, it first cures the photocurable resin by irradiating it with light such as ultraviolet rays to impart a relatively low adhesive force. At this time, the photocurable curable resin composition may have adhesiveness. Then, by further leaving it in the air or the like, it may be cured by moisture to obtain a cured product having sufficient adhesive strength.
More specifically, for example, in the case of joining two adherends, the curable resin composition of the present invention is first applied to one of the adherends, and then the curable resin is irradiated with light. The photocurable resin in the composition is cured, and the curable resin composition is adhered to one of the adherends with a relatively low adhesive force. Next, the other adherend is attached to one adherend via a photocurable curable resin composition, and then left in the air or the like, whereby the curable resin composition is cured by moisture. Is cured and the two adherends are joined with sufficient adhesive force.

The curable resin composition of the present invention is used for adhering electronic components. Specifically, the curable resin composition of the present invention is used for adhering various members (adhesive bodies) constituting electronic components used in electronic devices and the like. 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 shape, a box shape, and a housing shape.

For example, the curable resin composition of the present invention is used to bond members constituting electronic components to each other. As a result, the electronic component has the cured product of the present invention.
Further, the curable resin composition of the present invention is used inside an electronic device or the like to obtain an assembled part by, for example, adhering a substrate to a substrate. The assembly component thus obtained has a first substrate, a second substrate, and a cured product of the present invention, and at least a part of the first substrate is at least a part of the second substrate. Is joined via a cured product. It should be noted that preferably, at least one electronic component is attached to each of the first substrate and the second substrate.

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

In this example, various physical properties were evaluated as follows.
(Fracture strain and tension T)
According to the method described in the specification, the tensile tester "Autograph AG-X" (manufactured by Shimadzu Corporation) was used to determine the fracture strain and tension T of the curable resin composition obtained in each Example and Comparative Example. I asked.
(Adhesion test)
According to the method described in the specification, the adhesive strength of the curable resin composition obtained in each Example and Comparative Example was measured at 25 ° C.

(Change in adhesive strength after cooling cycle)
First, a sample for the adhesiveness test was prepared in the same manner as the adhesiveness test. The adhesiveness test sample was subjected to 1000 cycles of a thermal cycle test in which 40 ° C. for 30 minutes and 80 ° C. for 30 minutes were repeated. The adhesive strength of the sample for the adhesiveness test after the cold test was measured by the same method as the above-mentioned adhesiveness test. The adhesive strength before the cold cycle test and the adhesive strength after the cold cycle test were evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: (Adhesive force after cold cycle) / (Adhesive force before cold cycle) ≧ 0.8
B: 0.8> (Adhesive force after cold cycle) / (Adhesive force before cold cycle) ≧ 0.6
C: 0.6> (Adhesive force after cold cycle) / (Adhesive force before cold cycle) ≧ 0.4
D: 0.4> (Adhesive force after cold cycle) / (Adhesive force before cold cycle)

The moisture-curable urethane resin used in each Example and Comparative Example was prepared according to the following Synthesis Example 1.
[Synthesis Example 1]
100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-2000") and 0.01 parts by mass of dibutyltin dilaurate as a polyol compound are placed in a separable flask having a capacity of 500 mL and placed under vacuum. (20 mmHg or less), stirred at 100 ° C. for 30 minutes and mixed. After that, the pressure was adjusted to normal pressure, 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred at 80 ° C. for 3 hours to react, and a moisture-curable urethane resin (a moisture-curable urethane resin) ( Weight average molecular weight 2700) was obtained.

The components other than the moisture-curable urethane resin used in each Example and Comparative Example were as follows.
(Radical polymerizable compound)
Urethane acrylate (80%): manufactured by Daicel Ornex, trade name "EBECRYL8411", bifunctional, weight average molecular weight 12000, diluted with 20% by mass isobonyl acrylate (IBOA), urethane acrylate content 80% by mass
1,6-Hexanediol diacrylate: Daicel Ornex, "HDDA", Bifunctional isobornyl acrylate: Daicel Ornex, "IBOA-B", Monofunctional phenoxyethyl acrylate: Kyoeisha Chemical Co., Ltd., "Light acrylate PO-A", monofunctional lauryl acrylate: manufactured by Kyoeisha Chemical Co., Ltd., "light acrylate LA", monofunctional ethoxydiethylene glycol acrylate: manufactured by Kyoeisha Chemical Co., Ltd., "light acrylate EC-A", monofunctional silane Coupling agent: 3-Isocyanoxide triethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE-9007"
Photoradical polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, manufactured by BASF, "IRGACURE 369"
Moisture curing accelerator: "U-CAT 651M" manufactured by Sun Appro
Filler: Siliconized silica, manufactured by Nippon Aerosil Co., Ltd., "RY300", primary particle diameter 7 nm

[Examples 1 to 4, Comparative Examples 1 to 3]
According to the compounding ratios shown in Table 1, each material is stirred at a temperature of 50 ° C. with a planetary stirrer (Sinky Co., Ltd., “Awatori Rentaro”), and then at a temperature of 50 ° C. with three ceramic rolls. The curable resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained by uniformly mixing.

As shown in Table 1, in each example, the breaking strain was 200% or more and the tension T was 25 kgf / cm ² or less, so that the elongation characteristics and the stress relaxation characteristics were excellent. Therefore, the durability of the adhesive force is excellent, and good adhesive performance is maintained even after the cooling / heating cycle.

Claims (9)

A curable resin composition for adhering electronic components, which comprises a curable resin.
A cured product of the curable resin composition having a width of 10 mm, a length of 45 mm, and a thickness of 0.6 mm has a fracture strain of 200% or more under the conditions of 25 ° C., a chuck distance of 25 mm, and a tensile speed of 100 mm / min. A curable resin composition which is stretched by 5 mm in the length direction and stopped under the same conditions, and the tension T of the cured product after 30 seconds is 25 kgf / cm ^{2 or less.} The curable resin composition according to claim 1, wherein the adhesive strength is 10 kgf / cm ^{2 or more in the following adhesiveness test.}
<Adhesion test>
A curable resin composition is applied to 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 the curable resin composition is passed through the curable resin composition. To prepare a sample for adhesion test by stacking glass plates. The adhesiveness test sample is obtained by laminating the aluminum substrate and the glass plate by curing the curable resin composition. After curing the curable resin composition, the prepared sample for adhesion test was left to stand in a 25 ° C. and 50% RH atmosphere for 25 minutes, and then 5 mm in the shearing direction using a tensile tester in a 25 ° C. and 50% RH atmosphere. The adhesive strength is measured by pulling at a speed of / sec and measuring the strength when the aluminum substrate and the glass plate are peeled off. The curable resin composition according to claim 1 or 2, wherein the curable resin contains at least one selected from the group consisting of a moisture-curable resin, a thermosetting resin, and a photocurable resin. The curable resin contains a moisture curable resin and contains
The curable resin composition according to any one of claims 1 to 3, wherein the moisture-curable resin contains at least one selected from the group consisting of a moisture-curable urethane resin and a hydrolyzable silyl group-containing resin. Stuff. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains both a moisture-curable resin and a photocurable resin. A cured product of the curable resin composition according to any one of claims 1 to 5. The electronic component having the cured product according to claim 6. It has a first substrate, a second substrate, and a cured product according to claim 6.
An assembly component in which at least a part of the first substrate is joined to at least a part of the second substrate via the cured body. The assembly component according to claim 8, wherein at least one electronic component is attached to each of the first substrate and the second substrate.

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