TW202024279A - Curable resin composition and cured product - Google Patents

Abstract

This curable resin composition contains a radical-polymerizable compound. When the curable resin composition is coated using an air dispenser, irradiated with ultraviolet rays having a wavelength of 365 nm using an LED lamp at an irradiation dose of 1000 mJ/cm2 and then left for 16 hours in an environment having a temperature of 25 DEG C and a relative humidity of 50%, the ratio of coating height to line width is 0.6 or more. When a load of 0.03 MPa is applied after irradiation with ultraviolet rays having a wavelength of 365 nm using an LED lamp at an irradiation dose of 1000 mJ/cm2, the degree of change in thickness following the load application is 40% or less.

Description

Curable resin composition and hardened body

The present invention relates to a curable resin composition and a cured body thereof, for example, a curable resin composition used as an adhesive for electronic equipment, and a cured body thereof.

In recent years, electronic components such as semiconductor wafers have been required to have higher integration and miniaturization. For example, there are cases in which a laminate of semiconductor wafers is formed by bonding a plurality of thin semiconductor wafers through an adhesive layer. In addition, the modernization of the popularization of various portable devices with display elements such as mobile phones and portable game consoles requires miniaturization of display elements. As a method of miniaturization of display elements, narrow margins of image display parts are required. (Hereinafter, also referred to as "narrow edge design"). In the multi-layer or narrow-edge design of small semiconductor chips, a bonding technique is required by using an adhesive with a finer line width such as a dispenser.

The laminated body of the semiconductor chip is manufactured by, for example, the following method: after applying an adhesive on a semiconductor chip, it is semi-hardened by light irradiation, another semiconductor chip is laminated through the semi-hardened material, and the semiconductor chip After temporarily bonding, the adhesive is completely cured to bond the wafers. Similarly, for the narrow-edge design, a method to completely harden the applied adhesive after semi-hardening is also studied. As an adhesive for semiconductor chip lamination and narrow-edge design, research the use of light moisture curable resin composition.

As a light moisture curable resin composition used as an adhesive, for example, as disclosed in Patent Document 1, a compound containing a radically polymerizable unsaturated group, a moisture curable urethane prepolymer is known. It is a radical curable urethane resin composition of a thixotropy imparting agent (for example, refer to Patent Document 1). Patent Document 1 shows that by containing a predetermined amount of a thixotropy imparting agent in the resin composition, the adhesion to the substrate becomes better, and the resin collapse is also prevented. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2004-18621

[The problem to be solved by the invention]

However, for example, when a conventional light moisture curable resin composition is used as an adhesive for the casing of a mobile phone or the like, there is a problem of peeling between the adhesive and the casing. In addition, the applied adhesive needs to be in a semi-cured state (ie, B-stage state) after photocuring, and the gap between the adherends must be kept constant when a load is applied.

Therefore, the subject of the present invention is to keep the gap between the adhered bodies fixed during bonding and not easily cause peeling of the adhered body. [Technical means to solve the problem]

The inventors of the present invention have conducted research and found that the casing used in mobile phones and the like sometimes has slight strain and irregularities. Since the adhesive is applied along the irregularities, cavities are generated during bonding. Furthermore, the inventors of the present invention have further studied and found that the thickness change rate after light curing is small, and after coating and curing by a dispenser, the composition is adjusted in such a way that the cured body has a specific shape, thereby The above-mentioned problems are solved, thereby completing the present invention. That is, the present invention provides the following [1] to [8]. [1] A curable resin composition containing a radical polymerizable compound. After the curable resin composition is coated with an air dispenser, it is irradiated with an LED lamp at 1000 mJ/cm ^{2 for} 365 nm ultraviolet rays, after 16 hours at 25°C and 50%RH, the ratio of coating height to line width is above 0.6, and after irradiating 365 nm ultraviolet rays at 1000 mJ/cm ² with LED lamp , A load is applied at 0.03 MPa, and the thickness change rate of the curable resin composition before and after the load is 40% or less. [2] The curable resin composition according to the above [1], wherein the storage elastic modulus of the cured product of the curable resin composition is 500 MPa or less. [3] The curable resin composition as described in [1] or [2], which contains a moisture curable resin. [4] The curable resin composition as described in any one of [1] to [3] above, which has a viscosity of 100 Pa· when measured using a cone-plate viscometer at 25°C and 1 rpm. s above 1000 Pa·s below. [5] The curable resin composition as described in any one of [1] to [4] above, which has a thixotropic index of 1.7 or more and 5.0 or less. [6] The curable resin composition as described in any one of [1] to [5] above, which contains a filler. [7] The curable resin composition as described in any one of [1] to [6] above, which is used as an adhesive for electronic equipment. [8] A cured body which is a cured body of the curable resin composition described in any one of [1] to [7] above. [Effects of Invention]

According to the curable resin composition of the present invention, the gap between the adhered body is kept fixed, and the cavity between the adhesive and the adhered body is reduced, and the peeling of the adhered body is not easily generated.

Hereinafter, the present invention will be described in detail. [Curable resin composition] The curable resin composition of the present invention contains a radical polymerizable compound, and satisfies both the first and second requirements below. The first requirement: After coating the curable resin composition with an air distributor, irradiate 365 nm ultraviolet rays at 1000 mJ/cm ² with an LED lamp, and then pass 16 hours under an environment of 25°C and 50%RH. At this time, the ratio of the coating height to the line width (hereinafter also referred to as the aspect ratio) becomes 0.6 or more. The second requirement: the curable resin composition is irradiated with 365 nm ultraviolet rays at 1000 mJ/cm ² by an LED lamp, and a load is immediately applied at 0.03 MPa. The thickness change rate of the curable resin composition before and after the load is 40% or less . Furthermore, the coating conditions of the air distributor in the first requirement are as follows: gap 1.0 mm, nozzle inner diameter 0.4 mm, ejection pressure 0.38 MPa, coating speed 1.0 mm/sec, and coating length 25 mm. In the measurement of the second requirement, the curable resin composition was coated with a width of 1 mm and a thickness of 0.2 mm, and the thickness change rate was measured in an environment of 25°C.

In the present invention, coating is performed as shown in the first requirement above, and the aspect ratio after curing becomes high. If the aspect ratio after coating and curing becomes higher, even if the bonded body is strained and has minute irregularities, when the curable resin composition follows the irregularities, the cavity between the bonded body will be reduced. Therefore, it is not easy to peel off the adhered body. From the viewpoint of further reducing the cavity, the aspect ratio is preferably 0.60 or more, more preferably 0.70 or more, and still more preferably 0.80 or more. In addition, the aspect ratio is not particularly limited, but from the viewpoint that it is easy to maintain a fixed distance between the gaps between the adherends after bonding, it is preferably 1.0 or less.

The coating conditions shown in the first requirement above are for narrow-edge designs, etc., assuming the standard coating conditions when applying the adhesive, and the curability after coating and curing under the coating conditions of the above first requirement The shape of the resin composition indicates the shape of the standard adhesive after coating and curing. Therefore, by adjusting the composition of the curable resin composition so as to become the above-mentioned first requirement, the cavity between the adhesive and the adherend can be reduced in narrow-edge designs.

Furthermore, in the present invention, as described above, if the aspect ratio is increased, in general, the curable resin composition tends to be compressed between the adherends, and it is difficult to keep the gap between the adhered bodies fixed. In the case of the distance or more, as in the second requirement above, by setting the thickness change rate to 40% or less, the gap can be maintained at a fixed distance or more. From the viewpoint of making the gap retention good, the thickness change rate is preferably 30% or less, and more preferably 20% or less. Also, from the viewpoint of gap retention, the thickness change rate should be as small as possible, and it should be 0% or more. However, from the viewpoint of ensuring the adhesion or adhesion between the adherends, 3% is preferred. Above, more preferably 7% or more. In the present invention, as described below, for example, by adjusting the type and blending amount of the radical polymerizable compound contained in the curable resin composition, and the blending amount of the filler, it can be adjusted to satisfy the first And the second requirement.

Furthermore, as shown in the above-mentioned first requirement, in the measurement of the aspect ratio, the curable resin composition is irradiated with light. Therefore, when measuring the aspect ratio, the curable resin composition is photocured by polymerizing a radically polymerizable compound. In addition, since the curable resin composition is left for a predetermined period of time after light irradiation, when the curable resin composition is moisture curable as described below, it is further cured by moisture. On the other hand, the thickness change rate in the second requirement is measured immediately after light irradiation. Therefore, even in the case of moisture curability described later, the thickness change rate of the curable resin composition in a so-called B-stage state that is cured by light but not cured by moisture is measured.

(Storage elastic modulus) The storage elastic modulus of the cured product of the curable resin composition of the present invention at 25°C is preferably 500 MPa or less. If the storage elastic modulus of the hardened product is 500 MPa or less, it is easy to absorb the impact that acts on the adherend. In addition, the cavity during bonding is easily reduced. From the viewpoint of impact absorption and the viewpoint of reducing the cavity during bonding, the storage elastic modulus is more preferably 100 MPa or less, more preferably 50 MPa or less, and still more preferably 10 MPa or less. In addition, from the viewpoint of imparting a certain mechanical strength to the cured product, the storage elastic modulus is preferably 0.1 MPa or more, more preferably 1 MPa or more. Furthermore, the storage elastic modulus is determined by measuring the cured product. The cured product is obtained by irradiating the curable resin composition with a mercury lamp at 3000 mJ/cm ^{2 and} then placing it in an environment of 23°C and 50RH% Obtained in 3 days. In addition, the detailed measurement method of the storage elastic modulus is as shown in the following Examples.

(Viscosity) The viscosity of the curable resin composition of the present invention is preferably 100 Pa·s or more and 1000 Pa·s or less. If the viscosity is within the above range, when the curable resin composition is applied to the adherend, workability and coating properties are good, and furthermore, it is easy to increase the aspect ratio. In addition, when the dispenser is used for coating, it is easy to coat with a thin line width. From these viewpoints, the viscosity is more preferably 200 Pa·s or more, more preferably 300 Pa·s or more, more preferably 800 Pa·s or less, and still more preferably 600 Pa·s or less. Furthermore, in this specification, the so-called viscosity refers to the viscosity at 1 rpm and 25°C measured with a cone-plate (E-type) viscometer.

(TI value) The curable resin composition of the present invention preferably has a thixotropic index (TI value) of 1.7 or more. If the TI value is 1.7 or more, the fluidity at the time of coating becomes high. On the other hand, the fluidity can be reduced after coating, so the coating properties can be improved and the aspect ratio can be increased. From such a viewpoint, the TI value is more preferably 2.0 or more, still more preferably 2.5 or more, and still more preferably 3.0 or more. Moreover, from the viewpoint of practicality, the TI value is preferably 5.0 or less, more preferably 4.7 or less, and still more preferably 4.5 or less. Furthermore, in this specification, the above-mentioned thixotropy index (TI value) means the viscosity measured using a cone-plate viscometer at 25°C and 1 rpm divided by the viscosity measured with a cone-plate viscometer at 25°C, Value obtained from the viscosity measured at 10 rpm. The above-mentioned storage elastic modulus, viscosity, and TI value are as detailed below, and the types and amounts of the components used in radical polymerizable compounds and moisture curable resins, and the types of additives such as fillers can be appropriately changed. And the amount.

The curable resin composition of the present invention preferably contains a moisture curable resin in addition to the radical polymerizable compound. Here, the curable resin composition becomes a light moisture-curable resin composition that is cured by light irradiation and moisture by containing a moisture-curable resin. Since the curable resin composition contains moisture curable resin in addition to the radical polymerizable compound, it can be cured without heating. Therefore, when the curable resin composition is cured, it is possible to prevent the bonding part or the electronic parts around the bonding part from being damaged by heating. In addition, by having moisture curable resin, it is easy to improve the adhesive force after complete curing. For example, the light moisture curable resin composition is first cured by light to be in a B-stage state to impart relatively low adhesion (viscosity), and then placed in the air to use moisture to make it Harden, and can become a hardened substance with sufficient adhesion. In this way, formal bonding can be performed after temporarily bonding the bonded objects.

＜radical polymerizable compound＞ The radical polymerizable compound contained in the curable resin composition may be a radical polymerizable compound having photopolymerization properties, and it is not particularly limited as long as 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 preferred, and a compound having a (meth)acryloyl group (hereinafter, also referred to as "(meth)acrylic compound") is particularly preferred.

As a (meth)acryl compound, (meth)acrylate compound, epoxy (meth)acrylate, (meth)acrylate amine ester, etc. are mentioned, for example. In addition, the (meth)acrylate amine ester system does not have any residual isocyanate group. In addition, in this specification, "(meth)acryloyl group" means acryloyl group or (meth)acryloyl group, "(meth)acrylate" means acrylate or methacrylate, others are similar The terminology is also the same.

The (meth)acrylate compound may be monofunctional, bifunctional, or trifunctional or more. Examples of monofunctional (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and 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, isodecyl (meth)acrylate, lauryl (meth)acrylate, isotetradecyl (meth)acrylate, stearyl (meth)acrylate, etc. (meth) ) Alkyl acrylate; cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid esters with alicyclic structure such as isobornyl acrylate and dicyclopentenyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-hydroxy (meth)acrylate Propyl ester, (meth)acryloyl ethylene-butyl amide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; Alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, etc.; Alkoxyglycol (meth)acrylates such as methoxyglycol (meth)acrylate and ethoxyglycol (meth)acrylate; methoxydiethyleneglycol (meth) Acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, ethoxy diethylene glycol Polyoxyethylene-based (meth)acrylates such as (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate.

In addition, the (meth)acrylate compound may have an aromatic ring, and examples thereof include phenyl alkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; (Meth)acrylic acid phenoxyalkyl esters such as phenoxyethyl meth)acrylate and the like. Furthermore, it may be a (meth)acrylate having plural benzene rings such as a stilbene skeleton and a biphenyl skeleton, and specific examples thereof include stilbene type (meth)acrylate, ethoxylated o-phenylphenol acrylate, and the like. In addition, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxydiethylene glycol (meth)acrylate, Phenoxy polyoxyethylene-based (meth)acrylates such as nonylphenoxy polyethylene glycol (meth)acrylate. Furthermore, as a (meth)acrylate compound which has an aromatic ring, phthalimide acrylates, such as N-acryloyloxy ethyl phthalimide, are mentioned.

Furthermore, as a monofunctional (meth)acrylate compound, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropane Formaldehyde (meth)acrylate, (3-ethyl-3-oxetanyl) methyl (meth)acrylate and other (meth)acrylates with heterocyclic structure; various imines (methyl) ) Acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-(meth)acrylate Fluoropentyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)propylene Acetyloxyethylhexahydrophthalic acid, N-propenyloxyethylhexahydrophthalimide, phthalic acid 2-(meth)acryloxyethyl-2-hydroxy Propyl ester, glycidyl (meth)acrylate, 2-(meth)acryloxyethyl phosphate, etc. In addition, as the above-mentioned various amide (meth)acrylates, hexahydrophthalimides such as the above-mentioned phthalimide acrylates, N-acryloxyethyl hexahydrophthalimide, etc. In addition to dimethylimines, examples thereof include succinimide acrylates such as (meth)acryloxy succinimide; and maleimides such as maleimide (meth)acrylate. Imine acrylates; in addition, various acrylimines having iminium groups and (meth)acrylic acid groups.

Examples of the bifunctional (meth)acrylate compound include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, 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 bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, di(meth)acrylic acid Dimethylol dicyclopentadiene ester, neopentyl glycol di(meth)acrylate, ethylene oxide modified trimeric isocyanate di(meth)acrylate, (meth)acrylic acid (2- Hydroxy-3-(meth)acryloyloxy)propyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylic acid Ester, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the tri- or more-functional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, and ethylene oxide addition trimethylolpropane tri(methyl) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modification trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate , Ethylene oxide addition trimeric isocyanate tris (meth)acrylate, tri (meth) glyceryl acrylate, propylene oxide addition tri (meth) glyceryl acrylate, tri (meth) propylene phosphate Glyoxyethyl, di-trimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentyl erythritol penta (meth) acrylate, dineopentaerythritol Alcohol six (meth)acrylate and so on.

The (meth)acrylate compound is preferably a monofunctional (meth)acrylate compound. Among them, as described below, those having an alicyclic structure and an aromatic ring are preferred. Preferred examples of (meth)acrylates having an alicyclic structure include: 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethyl (meth)acrylate Hexahydrophthalimide, such as cyclohexyl ester, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, etc. Amines, etc. Moreover, as a preferable example of the (meth)acrylate compound which has an aromatic ring, phenoxyalkyl (meth)acrylate, a phthalimide acrylate, etc. are mentioned. Moreover, it is also preferable that the monofunctional (meth)acrylate compound contains the (meth)acrylate which has an imino group. As the (meth)acrylate having an imino group, as described above, in addition to hexahydrophthalimide acrylates and phthalimide acrylates, butadiene Amino acrylates, maleimide acrylates, acrylimines, etc.

As said epoxy (meth)acrylate, the thing obtained by reacting an epoxy compound and (meth)acrylic acid etc. is mentioned, for example. Here, the reaction of the epoxy compound and (meth)acrylic acid may be carried out in the presence of a basic catalyst according to a conventional method. The epoxy (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, but is preferably polyfunctional. As the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2,-Diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type ring Oxygen resin, dicyclopentadiene novolak type epoxy resin, biphenol novolak type epoxy resin, naphthol novolak type epoxy resin, glycidamine type epoxy resin, alkyl polyol type epoxy resin, Rubber modified epoxy resin, glycidyl ester compound, bisphenol A episulfide resin, etc.

Examples of commercially available epoxy (meth)acrylates include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYDa Manufacturing); EA-1010, EA-1020, EA-5323, EA-5520, EACHD, EMA-1020 (all manufactured by Shinnakamura 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 (all manufactured by Nagase Kasei), etc.

The amine (meth)acrylate can be obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, for example. Here, the reaction of the isocyanate compound and the (meth)acrylic acid derivative may use a catalytic amount of tin-based compound or the like as a catalyst. The amine (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, but is preferably bifunctional. As the isocyanate compound used to obtain (meth)acrylate amine ester, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, tri Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate , XDI, hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, tetramethyl stubborn diisocyanate, 1 , 6,11-Undecane triisocyanate and other polyisocyanate compounds. Furthermore, as the isocyanate compound, a polyisocyanate compound with an extended chain obtained by the reaction of a polyol and an excess isocyanate compound can also be used. Here, as the polyol, for example, ethylene glycol, 1,2-propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone Esterdiol etc.

As the (meth)acrylic acid derivative having a hydroxyl group, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, poly Mono(meth)acrylate of diols such as ethylene glycol; or mono(meth)acrylate or di(meth)acrylic acid of triols such as trimethylolethane, trimethylolpropane, glycerin Esters; or epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate.

Examples of commercially available amine (meth)acrylates include: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411 , EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9270, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel Allnex); Artresin UN-9000, Artresin UN-9000, Artresin UN-9000, Artresin UN-9000 , Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Nejo Industrial Co.); U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U -6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA , UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all manufactured by Shinnakamura Chemical Industry Co., Ltd.); AI-600 , AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.); CN-902, CN-973, CN -9021, CN-9782, CN-9833 (all manufactured by Arkema), etc.

As the radically polymerizable compound, other radically polymerizable compounds other than the above can also be suitably used. As other radical polymerizable compounds, for example, N,N-dimethyl (meth)acrylamide, N-(meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide Amine, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, etc. (former Base) acrylamide compounds; vinyl compounds such as styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, etc.

In the present invention, as the radically polymerizable compound, it is preferable to use the above-mentioned medium viscosity relatively low, for example, it is preferable to use a monofunctional (meth)acrylate compound. If a low-viscosity one is used, as described below, even if the content of the filler is relatively large, the viscosity of the curable resin composition can be made low and the coating properties are good. From the above viewpoints, as described above, as the monofunctional (meth)acrylate compound, it is preferable to have at least any one of an aromatic ring and an alicyclic structure, and it is also preferable to use a combination with an aromatic ring. (Meth)acrylate compounds and (meth)acrylate compounds having an alicyclic structure. The content of the monofunctional (meth)acrylate compound having at least any one of an aromatic ring and an alicyclic structure is based on the total amount of radically polymerizable compounds, preferably 30% by mass or more, more preferably More than 50% by mass. There is no particular limitation, but the upper limit is preferably 100% by mass. In addition, as described above, when the radically polymerizable compound contains (meth)acrylate having an amide group, the content of the (meth)acrylate having an amide group is the total amount of the radically polymerizable compound The amount is based on a reference, and is preferably 5 mass% or more, more preferably 12 mass% or more, and still more preferably 24 mass% or more. In addition, the content of the (meth)acrylate having an imino group is based on the total amount of the radical polymerizable compound, and is preferably 50% by mass or less, and more preferably 40% by mass or less. Furthermore, the (meth)acrylate having an imino group may have an aromatic ring, may have an alicyclic structure, or may not have both, but is preferably monofunctional.

＜Moisture hardening resin＞ As the moisture-curable resin used in the present invention, for example, moisture-curable urethane resin, hydrolyzable silicon group-containing resin, moisture-curable cyanoacrylate resin, etc., are preferably moisture-curable amine Ester resins and resins containing hydrolyzable silicon groups, among them, moisture curable urethane resins are more preferred. The moisture-curable urethane resin has an isocyanate group. The isocyanate group in the moisture curable urethane resin molecule reacts with moisture in the air or in the bonded body to harden. The moisture curable urethane resin may have only one isocyanate group in one molecule, or may have two or more. Among them, 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 and a polyisocyanate compound having two or more isocyanate groups in one molecule. The reaction between the polyol compound and the polyisocyanate compound is usually based on the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound [NCO]/[OH]=2.0～ Within 2.5.

As the polyol compound as the raw material of the moisture-curable urethane resin, known polyol compounds commonly used in the production of polyurethane can be used, for example, polyester polyols, polyether polyols, polyalkylene polyols, Polycarbonate polyol, etc. These polyol compounds may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the polyester polyol include: polyester polyol obtained by the reaction of polycarboxylic acid and polyol, poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone Wait. Examples of the above-mentioned polycarboxylic acids used as raw materials for polyester polyols include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecane dicarboxylic acid, etc. Examples of polyols used as raw materials for polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentane Glycol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc.

Examples of polyether polyols include: ethylene glycol, 1,2-propylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers of these or their derivatives Or block copolymer, bisphenol type polyoxyalkylene modified body, etc. Here, the bisphenol-type polyoxyalkylene modification system makes the alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and the bisphenol-type molecular skeleton active A polyether polyol obtained by the addition reaction of the hydrogen part. The polyether polyol may be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modification body preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. It does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, A bisphenol A type is preferable.

Examples of polyalkylene polyols include polybutadiene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols. As a polycarbonate polyol, polyhexamethylene carbonate polyol, polycyclohexane dimethylene carbonate polyol, etc. are mentioned, for example.

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

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), a curable resin composition with excellent adhesiveness, a soft cured product with good elongation, and compatibility with radical polymerizable compounds can be obtained Excellent. In addition, it is easy to adjust the storage elastic modulus to the aforementioned required range. Among them, it is preferable to use a polyether polyol composed of a ring-opening polymer compound of 1,2-propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymer compound of a tetrahydrofuran compound having a substituent such as a methyl group. Moreover, it is more preferably a ring-opening polymer compound of a tetrahydrofuran compound, and particularly preferably is polytetramethylene ether glycol.

式（1）中，R表示氫原子、甲基、或乙基，l為0～5之整數，m為1～500之整數，n為1～10之整數。l較佳為0～4，m較佳為50～200，n較佳為1～5。再者，所謂l為0之情形意指與R鍵結之碳直接與氧鍵結之情形。 上述中，n與l之合計更佳為1以上，進而較佳為3～6。又，R更佳為氫原子、甲基，特佳為氫原子。

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 0-4, m is preferably 50-200, and n is preferably 1-5. Furthermore, the so-called case where l is 0 means the case where the carbon bonded to R is directly bonded to oxygen. Among the above, the total of n and l is more preferably 1 or more, and still more preferably 3-6. Furthermore, R is more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

The hydrolyzable silicon group-containing resin used in the present invention reacts with water in the air or in the adherend to harden the hydrolyzable silicon group in the molecule. The resin containing hydrolyzable silicon groups may have only one hydrolyzable silicon group in one molecule, or may have more than two. Among them, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule. In addition, the above-mentioned hydrolyzable silicon group-containing resin does not include those having isocyanate groups.

式（2）中，R¹ 分別獨立地為可經取代之碳數1以上20以下之烷基、碳數6以上20以下之芳基、碳數7以上20以下之芳烷基、或-OSiR² ₃ （R² 分別獨立地為碳數1以上20以下之烴基）所表示之三有機矽烷氧基。又，式（2）中，X分別獨立地為羥基或水解性基。進而，式（2）中，a為1～3之整數。The hydrolyzable silyl group is represented by the following formula (2).

In formula (2), R ^{1 is} each independently a substituted alkyl group with 1 to 20 carbons, an aryl group with 6 to 20 carbons, an aralkyl group with 7 to 20 carbons, or -OSiR ² ₃ (R ^{2 is} each independently a hydrocarbon group with a carbon number of 1 or more and 20 or less) a triorganosilalkoxy group represented by 2 3 Moreover, 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 above-mentioned hydrolyzable group is not particularly limited, and examples thereof include halogen atoms, alkoxy groups, alkenoxy groups, aryloxy groups, acetoxy groups, ketoximate groups, amino groups, amide groups, and acid groups. Amine group, aminooxy group, mercapto group, etc. Among them, in terms of high activity, a halogen atom, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable. In addition, in terms of stable hydrolysis and easy handling, alkoxy groups such as methoxy and ethoxy are more preferred, and methoxy and ethoxy are still more preferred. Furthermore, from the viewpoint of safety, it is preferable that the compounds to be released by the reaction are the ethoxy group and isopropenoxy group of ethanol and acetone, respectively.

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

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

Examples of the hydrolyzable silyl group include: methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, tris(2-propenoxy)silyl, and triethoxysilyl Group, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethoxy Silyl, (1-chloropropyl) dimethoxysilyl, (methoxymethyl) dimethoxysilyl, (methoxymethyl) diethoxysilyl, (ethoxymethyl) Group) dimethoxysilyl, (1-methoxyethyl) dimethoxysilyl, (aminomethyl) dimethoxysilyl, (N,N-dimethylaminomethyl) )Dimethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl, (N -(2-Aminoethyl)aminomethyl)dimethoxysilyl, (acetoxymethyl)dimethoxysilyl, (acetoxymethyl)diethoxysilyl Wait.

Examples of resins containing hydrolyzable silicon groups include: (meth)acrylic resins containing hydrolyzable silicon groups, organic polymers having hydrolyzable silicon groups at the end of the molecular chain or at the end of the molecular chain, and hydrolyzable silicon groups. The polyurethane resin and so on. The hydrolyzable silicon group-containing (meth)acrylic resin preferably has repeating structural units derived from the hydrolyzable silicon group-containing (meth)acrylate and/or alkyl (meth)acrylate in the main chain.

Examples of (meth)acrylates containing hydrolyzable silicon groups 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 (Methoxysilyl) ethyl, 2-(methyldimethoxysilyl) ethyl (meth)acrylate, trimethoxysilyl methyl (meth)acrylate, triethoxy (meth)acrylate Methyl silyl, (meth)acrylic acid (methyldimethoxysilyl) methyl ester, etc. Examples of the above-mentioned alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid 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, etc.

As a method of producing a (meth)acrylic resin containing a hydrolyzable silicon group, specifically, for example, the hydrolyzable silicon group-containing (meth)acrylate polymer described in International Publication No. 2016/035718 Synthesis method, etc. The above-mentioned organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the end of the molecular chain has a hydrolyzable silyl group at 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)acrylate-based polymers.

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

As a method of producing the above-mentioned hydrolyzable silicon group-containing polyurethane resin, for example, a method of reacting a polyol compound and a polyisocyanate compound to produce a polyurethane resin and further reacting a silicon group-containing compound such as a silane coupling agent. Specifically, for example, a method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in JP 2017-48345 A, etc. can be cited.

Examples of the silane coupling agent include: vinyl trichlorosilane, vinyl triethoxy silane, vinyl tris (β-methoxy-ethoxy) silane, β-(3,4-epoxy ring) Hexyl)-ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane, γ-methacryloxypropyl Trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethyl Oxyoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane , 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. Among them, 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.

In addition, the moisture curable urethane resin may have both an isocyanate group and a hydrolyzable silicon group. The moisture-curable urethane resin having both an isocyanate group and a hydrolyzable silicon group is preferably produced by the following method: First, a moisture-curable urethane resin having an isocyanate group is obtained by the above method , And further react the silane coupling agent with the moisture curable urethane resin. Furthermore, the details of the moisture curable urethane resin having an isocyanate group are as described above. Furthermore, as the silane coupling agent that reacts with the moisture-curable urethane resin, it may be suitably selected from those listed above, but from the viewpoint of reactivity with isocyanate groups, it is preferable to use Amine or mercapto silane coupling agent. As preferred specific examples, include: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyl Dimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanate Propyl trimethoxysilane and so on.

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

The moisture curable resin can be appropriately selected from the various resins described above, and one type may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, for example, it is preferable to use two or more kinds of urethane resins in combination, and it is more preferable to use a moisture-curable urethane resin containing hydrolyzable silicon groups in combination with the above-mentioned urethane bond and isocyanate. Moisture-curing urethane resin based.

The weight average molecular weight of the moisture curable resin is not particularly limited, and the preferred lower limit is 800, and the preferred upper limit is 30,000. If the weight average molecular weight is within this range, it is easy to adjust the storage elastic modulus, viscosity, etc. of the curable composition within the above range. The lower limit of the weight average molecular weight of the moisture curable resin is more preferably 2,000, the upper limit is more preferably 25,000, the lower limit is still more preferably 2,500, and the upper limit is more preferably 20,000. In addition, in this specification, the said weight average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC). Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) is used as a column for measuring the weight average molecular weight in terms of polystyrene by GPC. Moreover, as a solvent used for GPC, tetrahydrofuran is mentioned.

In the curable resin composition, the total content of the radical polymerizable compound and the moisture curable resin relative to 100 parts by mass of the curable resin composition is preferably 60 parts by mass or more, more preferably 75 parts by mass or more, and Preferably it is 80 parts by mass or more. Furthermore, the total content may be 100 parts by mass or less with respect to the total amount of the curable resin composition, but is preferably 98 parts by mass or less, and more preferably 95 parts by mass or less. If the total content of the radical polymerizable compound and the moisture curable resin is within the predetermined range, it is easy to adjust the aspect ratio, the thickness change rate, etc., to fall within the above range. Furthermore, in the present invention, the curable resin composition may also contain no moisture curable resin. In this case, the above total content means the content of the radically polymerizable compound alone.

When the curable resin composition contains moisture curable resin, the mass ratio of the moisture curable resin relative to the radical polymerizable compound is preferably 0.3 or more and 6 or less, more preferably 0.5 or more and 4 or less, and more preferably 0.75 or more and 3 or less. In the present invention, by setting the blending amount of the radical polymerizable compound and the moisture curable resin within the above range, a certain hardness is imparted in the B-stage state, and it is easy to adjust the thickness change rate within the above range . In addition, it is easy to improve the adhesive force when fully cured by moisture hardening, and it is also easy to adjust the storage elastic modulus to a desired range.

Furthermore, in the present invention, as described above, in order to reduce the storage elastic modulus of the cured product, the cured product may contain a component whose elastic modulus decreases. As specific examples of such components, radical polymerizable compounds include phenoxyalkyl (meth)acrylate, alkyl (meth)acrylate, furfuryl (meth)acrylate, and polyether acrylic acid. Ester acrylate and so on. Moreover, as a moisture curable resin, the moisture curable urethane resin derived from polyether polyol can be mentioned. In the present invention, either the radical polymerizable compound or the moisture curable resin may contain the component whose elastic modulus is lowered, but both may contain the component whose elastic modulus is lowered.

(Filler) The curable resin composition of the present invention preferably contains a filler. By containing the filler, it is easy to adjust the TI value and viscosity of the curable resin composition of the present invention within the above-mentioned range. In addition, the shape retention after coating is good, and the aspect ratio can be increased. As the filler, particles in the form of particles may be used. The primary particle size of the filler is preferably 1 nm or more and 100 nm or less. By setting the primary particle size of the filler within this range, the coating property of the curable resin composition obtained is good. In addition, it has excellent shape retention after coating, and it is easy to increase the aspect ratio. The primary particle size of the filler is more preferably 3 nm or more and 80 nm or less, and still more preferably 5 nm or more and 50 nm or less. In addition, the primary particle size of the filler can be measured by dispersing the filler in a solvent (water, organic solvent, etc.) using a particle size distribution measuring device such as NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, alumina, calcium carbonate, and the like. Among them, since the obtained light moisture curable resin composition has excellent ultraviolet transmittance, silicon oxide is preferred.

The filler is preferably subjected to hydrophobic surface treatment. By the hydrophobic surface treatment, the cured resin composition obtained has good shape retention after coating, and it is easy to increase the aspect ratio. Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Among them, from the viewpoint of increasing the aspect ratio, the silylation treatment is preferred, and the trimethylsilylation treatment is more preferred.

As a method of performing hydrophobic surface treatment on the filler, for example, a method of using a surface treatment agent such as a silane coupling agent to treat the surface of the filler, and the like. For example, the above-mentioned trimethylsilylation-treated silica can be produced by, for example, the following methods: synthesizing silica by a sol-gel method, etc., spraying hexamethyldisilazane in a mist state while the silica is flowing Alkane; Silica is added to organic solvents such as alcohol and toluene, and hexamethyldisilazane and water are added, and then the water and organic solvent are evaporated to dryness using an evaporator.

The content of the filler relative to 100 parts by mass of the curable resin composition is, for example, 5 parts by mass or more, and preferably 8 parts by mass or more. By setting it to 8 parts by mass or more, from the viewpoints of workability and coating properties, the above-mentioned low-viscosity compound is used as a radical polymerizable compound or moisture-curable resin, and the shape stability after coating is also good. The above aspect ratio tends to become larger. From these viewpoints, the content of the filler is preferably 9 parts by mass or more, more preferably 10 parts by mass or more. In addition, from the viewpoints of coatability, adhesiveness, etc., the content of the filler relative to 100 parts by mass of the curable resin composition is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 16 parts by mass. Parts by mass or less. A filler may be used individually by 1 type, and may be used in combination of 2 or more types.

等。該等中，就容易將黏性值、及儲存彈性模數調整至規定範圍內之觀點而言，較佳為苯乙酮系化合物，更佳為α-胺烷基苯酮。 作為上述光自由基聚合起始劑中之市售者，例如可列舉：IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE379EG、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、Lucirin TPO（均為BASF公司製造）；安息香甲醚、安息香乙醚、安息香異丙醚（均為東京化成工業公司製造）等。(Photo-radical polymerization initiator) In order to ensure photocurability, the curable resin composition of the present invention preferably contains a photo-radical polymerization initiator. As the photoradical polymerization initiator, for example, acetophenone-based compounds such as benzophenone-based compounds, α-aminoalkylphenone, and α-hydroxyalkylphenone; phosphine oxide-based compounds; Titanocene compounds; oxime ester compounds; benzoin ether compounds; 9-oxysulfur 𠮿

Wait. Among them, from the viewpoint of easy adjustment of the viscosity value and storage elastic modulus within a predetermined range, an acetophenone-based compound is preferable, and α-aminoalkylphenone is more preferable. Examples of commercially available photo radical polymerization initiators include: IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF); Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photo-radical polymerization initiator in the curable resin composition relative to 100 parts by mass of the radical polymerizable compound is preferably from 0.01 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass . When the content of the photoradical polymerization initiator is within this range, the curable resin composition obtained has excellent photocurability and storage stability. In addition, by setting it within the above range, the photoradical polymerizable compound is moderately cured, and it is easy to adjust the storage elastic modulus, aspect ratio, and thickness change rate within the predetermined range.

(Moisture hardening promotion catalyst) The curable resin composition may contain a moisture hardening accelerating catalyst that promotes the moisture hardening reaction of the moisture hardening resin. By using the moisture hardening accelerating catalyst, the curable resin composition has better moisture hardening properties, and the adhesive force can be further improved. As the moisture hardening accelerating catalyst, specifically, for example, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and stannous octoate; triethylamine, U-CAT651M (manufactured by San-Apro Ltd) can be used. , U-CAT660M (manufactured by San-Apro Ltd), U-CAT2041 (manufactured by San-Apro Ltd), 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane ), 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane and other amine compounds; zinc octoate, zinc naphthenate and other zinc compounds; zirconium tetraacetylpyruvate, cyclo Copper alkanoate, cobalt naphthenate, etc. The content of the moisture hardening accelerating catalyst relative to 100 parts by mass of the curable resin composition is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 7 parts by mass or less. By making the content of the moisture hardening accelerating catalyst within this range, the effect of promoting the moisture hardening 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 the coupling agent, it is easy to improve the adhesion. As a coupling agent, a silane coupling agent, a titanate type coupling agent, a zirconate type coupling agent, etc. are mentioned, for example. Among them, the silane coupling agent is preferred in terms of its excellent effect of improving adhesiveness. The above-mentioned coupling agents may be used alone or in combination of two or more kinds. The content of the coupling agent relative to 100 parts by mass of the curable resin composition is preferably from 0.05 parts by mass to 5 parts by mass, and more preferably from 0.2 parts by mass to 3 parts by mass. By keeping the content of the coupling agent within these ranges, various physical properties are not affected and the adhesive force is improved. In addition, the curable resin composition may contain other additives such as wax particles, ionic liquids, colorants, expanded particles, expanded particles, and reactive diluents in addition to the components described above.

The curable resin composition of the present invention can 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 are based on the solid content, which means parts by mass excluding the solvent.

As a method of producing the curable resin composition of the present invention, examples include: using a mixer to blend a radical polymerizable compound, a moisture curable resin, and optionally a photoradical polymerization initiator, filler, etc. Methods of mixing other additives, etc. As the mixer, for example, a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer (planetary mixer), a kneader, a three-roll mill, etc. can be cited.

[How to use curable resin composition] The curable resin composition of the present invention is cured to be used as a cured body. The curable resin composition of the present invention is at least light-cured by light irradiation. The curable resin composition of the present invention can be cured to join the adherends in a state of being arranged between the adherends, for example. At this time, it is only necessary to apply to one adherend, and thereafter, overlap another adherend on one adherend via the applied curable resin composition.

In the case of the light moisture curing type, it is photocured by light irradiation to achieve, for example, a B-stage state (semi-cured state), and thereafter, it can be cured completely by moisture. . Here, when the light moisture curing type curable resin composition is arranged between the adherends to join the adherends, it is applied to an adherend, and then irradiated with light. Light-curing, for example, is in a B-stage state, and another adherend is superimposed on the light-cured curable resin composition, and the adherend can be temporarily adhered with a moderate adhesive force (initial adhesive force). Thereafter, the curable resin composition in the B-stage state is completely cured by curing the moisture-curable resin with moisture, and the adherends overlapped by the curable resin composition are joined with sufficient adhesive force.

The application of the curable resin composition to the adherend is preferably performed using a dispenser. Examples of dispensers include air dispensers, jet dispensers, Mono pump dispensers, screw dispensers, handgun dispensers, etc., but none Specially limited. In addition, the light irradiated during photocuring may be light for curing the radical polymerizable compound, and is not particularly limited, but is preferably ultraviolet light. In addition, when the curable resin composition is completely cured by moisture, it may be left in the atmosphere for a predetermined time.

The curable resin composition of the present invention is preferably used in an adhesive for electronic equipment. Therefore, the adherend is not particularly limited, but it is preferably various parts constituting an electronic device. The various components constituting the electronic equipment are electronic components, or substrates on which electronic components are mounted. More specifically, various electronic components provided on display elements, substrates on which electronic components are mounted, semiconductor wafers, etc. can be cited. As the material of the bonded body, it can be any of metal, glass, plastic, etc. In addition, the shape of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a panel shape, a disk shape, a rod (rod) shape, a box shape, and a shell shape.

For example, the curable resin composition of the present invention is used in the interior of electronic equipment, for example, to bond a substrate and a substrate to obtain assembled parts. The assembled parts obtained in this way have a first substrate, a second substrate, and the hardened body of the present invention, and at least a part of the first substrate is joined to at least a part of the second substrate through the hardened body. Furthermore, it is preferable that the first substrate and the second substrate each have at least one electronic component mounted thereon.

Furthermore, the curable resin composition of the present invention is preferably used for narrow-edge applications. For example, in various portable machines with display elements, such as smartphones and other mobile phones, portable game consoles, etc., an adhesive is coated on a narrow square frame (ie, narrow edge) substrate, and The adhesive assembles a display panel, a touch panel, etc., and in the present invention, a curable resin composition is used as the adhesive. Furthermore, the curable resin composition of the present invention is preferably used for semiconductor wafer applications. The curable resin composition of the present invention is used for semiconductor wafer applications, for example, to bond semiconductor wafers to each other.

For semiconductor wafers or narrow edge applications, it is necessary to apply the adhesive to a narrow width of, for example, 0.2-2 mm, preferably 0.3-1.0 mm. The curable resin composition of the present invention has various characteristics (TI value). , Viscosity, etc.), so it can be coated in such a narrow width. In addition, even if the coating is narrow, by satisfying the first requirement, there are fewer cavities between the curable resin composition and the adherend, so that peeling of the adherend is less likely to occur. Furthermore, by satisfying the second requirement, even if a load is applied to the curable resin composition, the thickness of the curable resin composition does not change significantly, so the gap between the adherends can be maintained constant. Example

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

In this example, the measurement and evaluation of various physical properties were performed as follows. ＜Viscosity, and TI value＞ The viscosity was measured using a cone-plate viscometer (trade name TVE-35, manufactured by Toki Sangyo Co., Ltd.) at 1 rpm and 25°C. In addition, the TI value is the value obtained by dividing the viscosity measured under the conditions of 25°C and 1 rpm with the same cone-plate type viscometer by the viscosity measured under the conditions of 25°C and 10 rpm.

<Storage elastic modulus> The curable resin composition is poured into a Teflon (registered trademark) mold with a width of 3 mm, a length of 30 mm, and a thickness of 1 mm, and it is cured to obtain a cured body. The curing of the curable resin composition is carried out by light curing by irradiating with a mercury lamp at 3000 mJ/cm ² , and then placing it in an environment of 23° C. and 50 RH% for 3 days to perform wet Gas hardening. Using the obtained hardened body, the dynamic viscoelasticity was measured with a dynamic viscoelasticity measuring device (manufactured by IT Meter. and Control, Inc., trade name "DVA-200") in the range of -100°C to 150°C to obtain The storage elastic modulus at room temperature (25℃). The measurement conditions are that the deformation mode is tensile, the set strain is 1%, the measurement frequency is 1 Hz, and the temperature rise rate is 5°C/min.

<Aspect Ratio> Use an air distributor ("SHOTMASTER200DS", manufactured by Musashi High-Tech Co., Ltd.) to coat a polycarbonate substrate (trade name "Iupilon GSH2010LR-Y082 GF10%", manufactured by Mitsubishi Engineering-Plastics) to Resin at 50°C. The coating conditions were performed with a gap of 1.0 mm, a nozzle inner diameter of 0.4 mm, a discharge pressure of 0.38 MPa, a speed of 1.0 mm/sec, and a coating length of 25 mm. Using an LED lamp (trade name "EXECURE H-1VC2", manufactured by HOYA CANDEO OPTRONICS, using "H-1VH-01" for the head unit), the curable resin composition after 5 seconds after the coating is applied at 1000 mJ/cm ² Irradiate 365 nm ultraviolet rays. Next, after leaving for 16 hours in an environment of 25°C and 50%RH, the width (maximum width) and height of the cured resin are measured with a laser microscope (trade name "VK-X200", manufactured by Keyence Corporation) (Maximum height), calculate the ratio of the height of the hardened object to the width as the aspect ratio.

<Thickness change rate> An aluminum substrate (length 72 mm, width 52 mm, thickness 2 mm) was prepared, and the curable resin composition was applied to one surface of the substrate along the outer edge of the substrate over the entire circumference. The coating of the curable resin composition is performed so that the line width becomes 1 mm and the thickness becomes 0.2 mm. Next, the coated curable resin composition was irradiated with ultraviolet rays of 365 nm at 1000 mJ/cm ² using an LED lamp to make it photocured. Thereafter, a glass substrate of the same size as the aluminum substrate was superimposed on the light-cured curable resin composition in an environment of 25°C, and a weight of 280 g was applied, thereby applying a load of 0.03 MPa to measure the thickness change rate. If the thickness of the curable resin composition before the overlap of the glass substrates is set to A, and the thickness of the curable resin composition after the overlap of the glass substrates and the weight of 280 g is applied for 10 seconds is set to B, then by (AB) /A×100 Determine the thickness change rate. In addition, as an evaluation of the gap formation property, when the thickness change rate is 30% or less, it is evaluated as AA, when it exceeds 30% and 40% or less, it is evaluated as A, and when it exceeds 40%, it is evaluated as B. In addition, the thickness of the curable resin composition was measured by observation with a digital microscope (trade name "KH-7800", manufactured by HIROX Corporation).

<The cavity during bonding> Prepare an aluminum substrate (length 72 mm, width 52 mm, thickness 2 mm), and apply a curable resin composition on the substrate so that the outer circumference becomes 70 mm × 48 mm. The coating of the curable resin composition is performed so that the line width becomes 0.4 mm. Next, the coated curable resin composition was irradiated with ultraviolet rays of 365 nm at 1000 mJ/cm ² using an LED lamp to light-harden it. Thereafter, a glass substrate of the same size as the aluminum substrate was superimposed on the curable resin composition cured by light and a weight of 200 g was applied for 10 seconds. Observing the test piece with a digital microscope (trade name "KH-7800", manufactured by HIROX), even one cavity was evaluated as B, and if there was no cavity, it was evaluated as A.

The moisture-curable urethane resin A was produced according to Synthesis Example 1 below. [Synthesis Example 1] 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-2000") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate were charged to a 500 mL capacity In a separable flask, stir for 30 minutes at 100°C under vacuum (below 20 mmHg) for mixing. After that, it was set to normal pressure, and 26.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the mixture was stirred at 80°C for 3 hours to react , To obtain moisture-curing urethane resin (weight average molecular weight of 2700).

The moisture-curable urethane resin B was produced according to Synthesis Example 2 below. [Synthesis Example 2] 100 parts by mass of polycaprolactone (manufactured by Daicel, trade name "PLACCEL H1P") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate were charged into a 500 mL capacity separable flask, Stir at 100°C for 30 minutes under vacuum (below 20 mmHg) to mix. Thereafter, the pressure was set to normal pressure, and 5.3 parts by mass of diphenylmethane diisocyanate (manufactured by Nissho Corporation, trade name "Pure MDI") as a polyisocyanate compound was added, and the mixture was stirred at 80°C for 3 hours to make it react , To obtain moisture-curing urethane resin (weight average molecular weight of 12000).

The components other than the moisture curable urethane resin used in each example and comparative example are as follows. Monofunctional acrylate 1: Phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., "Light acrylate PO-A") Monofunctional acrylate 2: Isobornyl acrylate (manufactured by Daicel Allnex, "IBOAB") Monofunctional acrylate 3: N-acryloyloxyethyl hexahydrophthalimide (manufactured by Toagosei Co., Ltd., "ARONIX M-140") Light radical polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (manufactured by BASF Corporation, "IRGACURE369") Moisture hardening accelerator: U-CAT660M (manufactured by San-Apro Ltd) Filler: Trimethylsilylized silica (manufactured by Japan Aerosil Corporation, "R812", primary particle size 7 nm)

[Examples 1 to 6, Comparative Examples 1 to 3] According to the blending ratio described in Table 1, the materials were stirred at a temperature of 50°C using a planetary stirring device (manufactured by Thinky, "Defoaming Stirring Taro"), and then mixed uniformly at a temperature of 50°C using a ceramic three-roll mill , And the curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were obtained.

[Table 1] Example Comparative example 1 2 3 4 5 6 1 2 3 Composition (parts by mass) Moisture hardening resin Moisture hardening urethane resin A 44 60 44 62 48 67 Moisture hardening urethane resin B 44 44 44 Radical polymerizable compound Monofunctional acrylate 1 29 15 29 twenty four 32 twenty four Monofunctional acrylate 2 29 29 36 Monofunctional acrylate 3 15 9 15 15 15 5 15 15 Light radical polymerization initiator 1 1 1 1 1 1 1 1 1 Moisture hardening promotion catalyst 1 1 1 1 1 1 1 1 1 Filler 10 14 10 10 10 7 3 3 7 total 100 100 100 100 100 100 100 100 100 Physical properties Viscosity (Pa·s (1 rpm)) 342 525 381 490 518 350 62 98 362 Thixotropic Index 2.8 3.9 2.9 3.2 3.2 2.7 1.6 1.3 2.6 Thickness change rate before and after load (%) 18 26 6 15 3 38 4 10 42 aspect ratio 0.71 0.92 0.72 0.76 0.85 0.62 0.34 0.3 0.61 Storage elastic modulus at 25℃ (MPa) 8 10 86 98 250 15 210 6 16 Gap formation AA AA AA AA AA A AA AA B The cavity when fitting A A A A A A B B A

As shown in the above Examples 1 to 6, the curable resin composition has an aspect ratio of 0.6 or more after coating and curing, so that the cavity during bonding can be reduced, so peeling and the like are less likely to occur. In addition, even if a load is applied, the thickness change rate is small, so although the aspect ratio is large, it is easy to form a fixed gap between the adherends. In contrast, in Comparative Examples 1 to 3, since the curable resin composition has a small aspect ratio after application and curing, the cavity at the time of bonding cannot be reduced, and peeling easily occurs.

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Claims (8)

A curable resin composition containing a radically polymerizable compound. After coating the curable resin composition with an air dispenser, the LED lamp is used to irradiate 365 nm ultraviolet rays at 1000 mJ/cm ² After 16 hours in an environment of 25°C and 50%RH, the ratio of the coating height to the line width is above 0.6, and after irradiating 365 nm ultraviolet rays at 1000 mJ/cm ² with an LED lamp, the ratio is 0.03 When a load is applied in MPa, the thickness change rate of the curable resin composition before and after the load is 40% or less. The curable resin composition according to claim 1, wherein the storage elastic modulus of the cured product of the curable resin composition is 500 MPa or less. The curable resin composition according to claim 1 or 2, which contains a moisture curable resin. The curable resin composition according to any one of claims 1 to 3, which has a viscosity of 100 Pa·s or more and 1000 Pa·s as measured by a cone-plate viscometer at 25°C and 1 rpm the following. The curable resin composition according to any one of claims 1 to 4 has a thixotropic index of 1.7 or more and 5.0 or less. The curable resin composition according to any one of claims 1 to 5, which contains a filler. The curable resin composition according to any one of claims 1 to 6, which is used in an adhesive for electronic equipment. A hardened body which is a hardened body of the curable resin composition according to any one of claims 1 to 7.