KR102389948B1 - Cationic Curable Adhesive Composition for Camera Module, Cured Product and Adhesive - Google Patents

Abstract

[PROBLEMS] An object of the present invention is to provide a cationically curable adhesive composition having both low-temperature curability and adhesiveness to engineering plastics (especially LCP).
[Solution means] (A) component: a cationic polymerizable resin comprising at least one selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin, (B) component: a thermal cationic polymerization initiator, and (C) a component Cationic curability for camera module, characterized in that it contains at least one of a rubber filler or a styrenic filler comprising at least one selected from the group consisting of diene-based rubber and (meth)acrylic rubber (excluding silicone/acrylic copolymer) adhesive composition.

Description

Cationic Curable Adhesive Composition for Camera Module, Cured Product and Adhesive

This invention relates to the cation-curable adhesive composition for camera modules, and the hardened|cured material of the said composition, and the bonding body formed using the said composition.

Cationic curable compositions containing conventional epoxy resins, etc. are used in various applications such as adhesives, encapsulants, potting agents, coating agents, conductive pastes, etc. in that they are excellent in adhesion, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance. has been In addition, the object is used in various fields, particularly in electronic devices, flat panel displays such as semiconductors, liquid crystal displays, organic electroluminescence and touch panels, hard disk devices, mobile terminal devices, camera modules, and the like.

According to Japanese Patent Application Laid-Open No. 2009-186756, Japanese Patent Application Laid-Open No. 2016-044268, Japanese Patent Application Laid-Open No. 2016-110067, and Japanese Patent Application Laid-Open No. 2016-122055 (corresponding to International Publication No. 2016-103687 pamphlet), Examples of attachment locations for the camera module include between an image sensor such as CMOS or CCD and a substrate, between a cut filter and a substrate, between a substrate and a case, between a case and a cut filter, and between a case and a lens unit. .

International Publication No. 2005/059002 pamphlet discloses a cation-curable epoxy adhesive composition for semiconductor device packages, such as CMOS, containing an epoxy resin component, a photocation initiator, a thermal cation initiator, and a filler.

Engineering plastics, such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), and polycarbonate, are used as a material for the case and lens unit in a camera module. Engineering plastics are plastics excellent in tensile strength even when placed for a long time in an environment of 100°C or higher. The cation-curable epoxy adhesive composition disclosed in International Publication No. 2005/059002 pamphlet was not satisfactory as an adhesive for camera modules in terms of poor adhesion to engineering plastics. Moreover, low-temperature curability (for example, 100 degrees C or less) is calculated|required by the cationically polymerizable adhesive composition for camera modules. This is because, under high temperature curing conditions, damage to the plastic lens used in the camera module is concerned. According to the Example, it is disclosed that the cation-curable epoxy adhesive composition of the international publication 2005/059002 pamphlet is hardened by 120 degreeC heating after ultraviolet irradiation, and it was not satisfied also from a viewpoint of low-temperature curability.

Accordingly, an object of the present invention is to provide a cationically curable adhesive composition having both low-temperature curability and adhesion to engineering plastics (especially LCP).

The present invention overcomes the above-mentioned conventional problems. That is, the present invention is as follows.

[1] component (A): a cationically polymerizable resin comprising at least one selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin, component (B): a thermal cationic polymerization initiator, and (C) component: a diene Cationic curable adhesive for camera modules, characterized in that it contains at least one of a rubber filler or a styrenic filler comprising at least one selected from the group consisting of rubber and (meth)acrylic rubber (excluding silicone/acrylic copolymer) composition.

[2] The camera module according to [1], wherein 0.1 to 30 parts by mass of the component (B) and 0.5 to 20 parts by mass of the component (C) are contained with respect to 100 parts by mass of the component (A). A cationically curable adhesive composition.

[3] The cation curability for camera modules according to [1] or [2], wherein the component (B) is a thermal cationic polymerization initiator containing a salt consisting of a tetrakis (pentafluorophenyl) borate anion and a cation adhesive composition.

[4] The cationically curable adhesive composition for camera modules according to any one of [1] to [3], further comprising a photocationic polymerization initiator as the component (D).

[5] The cationically curable adhesive composition for a camera module according to [4], wherein the component (D) contains at least one of an aromatic iodonium-based photocationic polymerization initiator or an aromatic sulfonium-based photocationic polymerization initiator.

[6] Hardened|cured material of the cation-curable adhesive composition for camera modules in any one of [1]-[5].

[7] A bonded body formed by bonding two or more adherends using the cationically curable adhesive composition for camera modules according to any one of [1] to [5].

A cationically curable adhesive composition for a camera module according to an embodiment of the present invention (hereinafter, simply referred to as a composition) comprises at least one selected from the group consisting of component (A): an alicyclic epoxy resin and a hydrogenated epoxy resin. Cationic polymerizable resin, (B) component: a thermal cationic polymerization initiator, and (C) component: at least one selected from the group consisting of diene-based rubber and (meth)acrylic rubber (excluding silicone-acrylic copolymer) At least one of a rubber filler and a styrenic filler is included. The cation-curable adhesive composition for camera modules having the above configuration can have both low-temperature curability (eg, 100° C. or less) and adhesiveness to engineering plastics (especially LCP).

In addition, in this specification, "X-Y" is used in the meaning which includes the numerical value (X and Y) described before and after that as a lower limit and an upper limit. In addition, unless otherwise indicated, operation and measurement of physical properties, etc. are made under the conditions of room temperature (20-25 degreeC)/relative humidity 40-50%.

Hereinafter, the present invention will be described in detail.

<(A) component>

Component (A) of the present invention is a cationically polymerizable resin containing at least one selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin. When component (A) is not included, low-temperature curability is inferior (refer to Comparative Example 1 to be described later). Here, cationically polymerizable resin is a compound which raise|generates a crosslinking reaction with the cationic species generate|occur|produced from a cationic polymerization initiator. For example, when an epoxy resin and a thermal cation polymerization initiator are used, the cationic species generated from the thermal cation polymerization initiator are added to the epoxy group by heating, thereby causing ring-opening polymerization of the epoxy group and crosslinking the epoxy resin. A hydrogenated epoxy resin means the compound obtained by nuclear-hydrogenating the aromatic ring of an aromatic epoxy resin. These can be used individually by 1 type or in combination of 2 or more type. Especially, from a viewpoint of further improving the adhesiveness with respect to engineering plastics (especially LCP), it is preferable that (A) component contains a hydrogenated epoxy resin.

Although it does not specifically limit as an alicyclic epoxy resin, For example, 3', 4'- epoxycyclohexyl methyl 3,4-epoxy cyclohexane carboxylate, 3,4-epoxy cyclohexyl methyl (3', 4' -Epoxy) cyclohexanecarboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexyl)adipate, 1, 2-epoxy-4-vinylcyclohexane, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyldivinylcyclohexane, diepoxyvinylcyclohexane, 1,2,4-triepoxyethylcyclohexane, limonene Dioxide, an alicyclic epoxy group containing silicone oligomer, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type. Among them, 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate is particularly preferable from the viewpoint of further improving the effect of the present invention.

Although it does not specifically limit as a commercial item of an alicyclic epoxy resin, For example, Celoxide 2081, Celoxide 2021P, Celoxide 2000, Celoxide 3000, EHPE 3150 (made by Daicel Corporation), TTA21 (made by Jiangsu TetraChem) , Rika Resin DME-100 (manufactured by Shin-Nippon Rica Co., Ltd.), X-40-2670, X-22-169AS, and X-22-169B (manufactured by Shin-Etsu Chemical Industries, Ltd.), but are not limited thereto.

Although it does not specifically limit as a hydrogenated epoxy resin, For example, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, diglycidyl of hydrogenated bisphenol A type alkylene oxide adduct ether, diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol F, hydrogenated phenol novolac epoxy resin, hydrogenated cresol novolac epoxy resin, etc. are mentioned, In particular, from the point of excellent low temperature curability, hydrogenated bisphenol A type An epoxy resin, a hydrogenated bisphenol F-type epoxy resin, and a hydrogenated bisphenol E-type epoxy resin are preferable, and a hydrogenated bisphenol A-type epoxy resin is especially preferable. These can be used individually by 1 type or in combination of 2 or more type.

Examples of commercially available hydrogenated bisphenol A epoxy resins include YX-8000, YX-8034 (manufactured by Mitsubishi Chemical Corporation), EXA-7015 (manufactured by DIC Corporation), ST-3000 (manufactured by Nippon Steel Co., Ltd.), Rika Resin HBE-100 (Shin Nippon Rica Co., Ltd.), EX-252 (Nagase Chemtex Co., Ltd.), etc. are mentioned. Moreover, as a commercial item of hydrogenated bisphenol F-type epoxy resin, YL-6753 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

From the viewpoint of further improving the effect of the present invention, it is preferable to use an alicyclic epoxy resin and a hydrogenated epoxy resin together as component (A), and the mass ratio (alicyclic epoxy resin: hydrogenated epoxy resin) is 5:95 to 70 :30 is preferable, 15:85-50:50 is more preferable, and 25:75-40:60 is still more preferable.

From a viewpoint of further improving the effect of this invention, the epoxy equivalent of (A) component becomes like this. Preferably it is 50-500 g/eq, More preferably, it is 100-250 g/eq.

<(B) component>

Component (B) of the present invention is a thermal cationic polymerization initiator, and is a compound that generates cationic species by heating. By containing the component (B), even when an engineering plastic having low light transmittance is selected as an adherend, excellent adhesiveness can be exhibited by thermosetting.

The component (B) is not particularly limited, but includes, for example, a thermal cationic polymerization initiator (B1) containing a salt composed of a hexafluoroantimonate anion and a cation, a salt composed of a hexafluorophosphate anion and a cation and a thermal cationic polymerization initiator (B2), a thermal cationic polymerization initiator (B3) containing a salt consisting of a tetrakis (pentafluorophenyl) borate anion and a cation, and the like. A thermocationic polymerization initiator (B3) containing a salt comprising a tetrakis(pentafluorophenyl)borate anion and a cation is preferable. Examples of the cation include a quaternary ammonium cation and a sulfonium ion in which at least one of the three groups bonded to the sulfur atom is an alkyl group having 1 to 8 carbon atoms. These may be used individually by 1 type, and 2 or more types may be used together.

As the thermal cationic polymerization initiator (B3) containing a salt consisting of a tetrakis (pentafluorophenyl) borate anion and a cation, it is preferable that tetrakis The thermal cation polymerization initiator containing the salt which consists of a (pentafluorophenyl) borate anion and a quaternary ammonium cation, etc. are mentioned.

Examples of commercially available products of the thermal cationic polymerization initiator (B1) containing a salt comprising a hexafluoroantimonate anion and a cation include SI-60L, SI-80L, and SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.). . Alternatively, examples of the thermal cationic polymerization initiator (B2) containing a salt comprising a hexafluorophosphate anion and a cation include SI-110L, SI-180L, SI-B2A, and SI-B3A (manufactured by Sanshin Chemical Industry Co., Ltd.). Moreover, as a commercial item of the said thermocationic polymerization initiator (B3) containing the salt which consists of the said tetrakis (pentafluorophenyl) borate anion and a cation, CXC-1821 (made by King Industries) etc. are mentioned, for example. .

Although the compounding quantity in particular of (B) component in the cation-curable adhesive composition of this invention is not restrict|limited, Preferably it is 0.1-30 mass parts with respect to 100 mass parts of said (A) component, More preferably, 0.3-15 mass parts It is a mass part, More preferably, it is 0.5-5 mass parts, Especially preferably, it is 1-3 mass parts. If it is 0.1 mass part or more, low temperature sclerosis|hardenability will become favorable, and if it is 30 mass parts or less, storage stability will become favorable.

<(C) component>

Component (C) of the present invention is at least one of a rubber filler or a styrenic filler containing at least one selected from the group consisting of diene rubbers and (meth)acrylic rubbers (excluding silicone/acrylic copolymers). (C) component, by combining with other components of the present invention, does not inhibit curing of the composition (that is, maintain low-temperature curability), and has a remarkable effect of excellent adhesion to engineering plastics (especially LCP). cause

Here, the rubber filler means a rubbery elastic body at 25°C, and examples thereof include those having a glass transition point (Tg) of less than 25°C. Since engineering plastics have relatively high crystallinity, it is considered that, when the adhesive composition disclosed in International Publication No. 2005/059002 pamphlet is applied to this, stress acts on the adhesive surface and sufficient adhesiveness cannot be expressed. On the other hand, it is thought that the stress is relieved and the composition which concerns on this invention can express the outstanding adhesiveness by containing a rubber filler.

Examples of the diene-based rubber include polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene rubber, and hydrogenated ones thereof. , Among them, polybutadiene rubber, styrene butadiene rubber, and acrylonitrile butadiene rubber are preferable, polybutadiene rubber or acrylonitrile butadiene rubber is more preferable, and polybutadiene rubber is particularly preferable. These may be used individually by 1 type, and may use 2 or more types together.

(meth)acrylic rubber refers to a polymer (except silicone/acrylic copolymer) obtained by polymerizing (meth)acrylic acid ester alone or with a monomer copolymerizable therewith, for example, acrylic acid ester-2-chloroethyl vinyl ether Acrylic rubber, such as a copolymer (ACM) and an acrylic acid ester/acrylonitrile copolymer (ANM), etc. are mentioned. Here, the reason that silicone/acrylic copolymer is excluded from the definition of (meth)acrylic rubber is because sufficient adhesion to engineering plastics cannot be obtained (refer to Comparative Example 5 to be described later).

As (meth)acrylic acid ester, (meth)acrylate, butyl (meth)acrylate, methoxyethyl (meth)acrylate, etc. are mentioned, for example. As a monomer copolymerizable with (meth)acrylic acid ester, 2-chloroethyl vinyl ether, acrylonitrile, etc. are mentioned, for example.

From the viewpoint of further improving the adhesiveness to engineering plastics, the component (C) preferably contains at least one of polybutadiene rubber or acrylic rubber, more preferably polybutadiene rubber.

A styrenic filler refers to a glass transition point (Tg) obtained by polymerization of at least one styrene derivative (eg, styrene, α-methylstyrene, divinylbenzene) with a monomer copolymerizable therewith of 50° C. or higher (upper limit). is, for example, 200° C. or less) of a polystyrene-based filler. Specific examples of the styrene-based filler include a styrene-glycidyl methacrylate copolymer and a styrene-divinylbenzene copolymer, and a styrene-divinylbenzene copolymer is preferable. As a commercial item, Maproof G-1005S (made by Nichiyu Corporation), Pinepearl PB-3006E (made by Matsuura Corporation), etc. are mentioned. These may be used independently, respectively, and may also mix and use 2 or more types.

On the other hand, it is also possible to facilitate dispersion in the composition by dispersing the component (C) of the present invention in advance in the component (A) of the present invention.

The average particle diameter of the component (C) is preferably 0.01 to 5 µm, more preferably 0.05 to 1 µm, and particularly preferably 0.1 to 0.6 µm. If it is 0.01 μm or more, the viscosity of the adhesive composition does not increase and workability is good, and if it is 5 μm or less, it is preferable from the viewpoint of excellent adhesion to engineering plastics. The measuring method of the said average particle diameter is a laser refraction/scattering method (50% volume average particle diameter).

Further, the amount of component (C) added is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 30 parts by mass, with respect to 100 parts by mass of component (A), and the adhesiveness to engineering plastics (especially LCP) is From a viewpoint of further height, More preferably, it is 0.5-20 mass parts, More preferably, it is 2-12 mass parts. Especially, 4 mass parts or more, 5 mass parts or more, or 6 mass parts or more are preferable as a lower limit, and 10 mass parts or less, 9 mass parts or less, or 8 mass parts or less are preferable as an upper limit.

<(D) component>

This invention can also contain a photocationic polymerization initiator as (D)component further in the range which does not impair the characteristic of this invention. (D) By further containing the component, the core can be cured with heat after temporary curing with light. Therefore, the hardened|cured material crosslinked to the deep part is obtained, and adhesiveness can be expressed more stably. A photocationic polymerization initiator is a compound which generate|occur|produces cationic species by irradiation of an active energy ray. The component (D) is not particularly limited, but, for example, when a salt containing a tetrakis(pentafluorophenyl)borate anion is selected as component (B), photocurability, thermosetting property and storage stability are all improved. In, it is preferable to include at least one of an aromatic iodonium-based photocationic polymerization initiator or an aromatic sulfonium-based photocationic polymerization initiator. These may be used independently and 2 or more types may be used together. Especially, it is preferable that an aromatic iodonium-type photocationic polymerization initiator is included.

Examples of the aromatic sulfonium-based photocationic polymerization initiator include a photocationic polymerization initiator containing a sulfonium ion in which all three groups bonded to the sulfur atom are aryl groups (eg, phenyl groups). Moreover, the photocationic polymerization initiator etc. containing the iodonium ion whose two groups couple|bonded with the iodine atom are an aryl group (for example, a phenyl group) are mentioned with an aromatic iodonium-type photocationic polymerization initiator. In addition, the initiator which generate|occur|produces cationic species also with either a heat|fever and an active energy ray shall be classified as (B) component in this invention.

Examples of the aromatic sulfonium-based photocationic polymerization initiator include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4 '-Bis[diphenylsulfonio]diphenylsulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide-bishexafluoro Rho antimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide-bishexafluorophosphate, 7-[di(p-toluyl)sulfonio ]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, etc. can It is not limited to these. These aromatic sulfonium-type photocationic polymerization initiators may be used individually or in mixture.

Commercially available aromatic sulfonium-based photocationic polymerization initiators include SP-150, SP-170, SP-172 (manufactured by ADEKA Corporation), CPI-100P, CPI-101A, CPI-110B, CPI-200K, and CPI-210S ( Pro Co., Ltd.), T1608, T1609, T2041, T2042 (manufactured by Tokyo Chemical Industries, Ltd.), UVI-6990, UVI-6974 (manufactured by Union Carbide Corporation), DTS-200 (manufactured by Midori Chemical Corporation), and the like.

Examples of the aromatic iodonium-based photocationic polymerization initiator include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4- Nonylphenyl)iodonium hexafluorophosphate 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate etc. are mentioned. Among them, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate is preferred. These can also be used individually or in mixture.

Commercially available aromatic iodonium-based photocationic polymerization initiators include Igacure 250 (manufactured by BASF), PI-2074 (manufactured by Rhodia Corporation), B2380, B2381, D2238, D2248, D2253, I0591 (manufactured by Tokyo Kyungsung Industrial Co., Ltd.), WPI- 113, WPI-116, WPI-169, WPI-170, WPI-124 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Although the compounding quantity in particular of (D)component in the cation curable adhesive composition of this invention is not restrict|limited, Preferably it is 0.1-30 mass parts with respect to 100 mass parts of said (A) component, More preferably, it is 0.5-15 It is a mass part, More preferably, it is 1-5 mass parts. If it is 0.1 mass part or more, photocurability will become favorable, and if it is 30 mass parts or less, it will become easy to melt|dissolve in the said (A) component.

<Optional ingredients>

In addition, the cationically curable adhesive composition of the present invention contains an aromatic epoxy resin, an oxetane compound, a vinyl ether compound, a pigment, a colorant such as a dye, a sensitizer, a silane coupling agent, a polyol compound, Peroxide, thiol compound, storage stabilizer, calcium carbonate, magnesium carbonate, titanium oxide, magnesium hydroxide, talc, silica, alumina, glass, aluminum hydroxide, boron nitride, aluminum nitride, magnesium oxide, etc. inorganic particles with an average particle diameter of 0.001 to 100 μm Fillers, conductive particles such as silver, flame retardants, plasticizers, organic solvents, phenolic antioxidants, antioxidants such as phosphorus antioxidants, light stabilizers, ultraviolet absorbers, defoamers, foaming agents, mold release agents, leveling agents, rheology regulators, tackifiers , a curing retarder, a polyimide resin, a polyamide resin, a phenoxy resin, a cyanate ester, a polyvinyl butyral resin may be blended in an appropriate amount. By these additions, the cationically curable adhesive composition and its hardened|cured material which are more excellent in resin strength, adhesive strength, flame retardance, thermal conductivity, workability, etc. can be obtained. Especially, it is preferable to further contain a silane coupling agent from a viewpoint of further improving the adhesiveness to engineering plastics.

In this invention, an aromatic epoxy resin, an oxetane compound, a vinyl ether compound, etc. can be used together other than the alicyclic epoxy resin and hydrogenated epoxy resin of (A) component.

Examples of the aromatic epoxy resin include an aromatic bisphenol A-type epoxy resin, an aromatic bisphenol F-type epoxy resin, an aromatic bisphenol E-type epoxy resin, a diglycidyl ether of an aromatic bisphenol A-type alkylene oxide adduct, and an aromatic bisphenol F-type alkyl Diglycidyl ether of renoxide adduct, diglycidyl ether of alkylene oxide adduct of aromatic bisphenol E type, aromatic novolak type epoxy resin, urethane-modified aromatic epoxy resin, nitrogen-containing aromatic epoxy resin, polybutadiene or and rubber-modified aromatic epoxy resins containing nitrile butadiene rubber (NBR) and the like. These can be used individually by 1 type or in combination of 2 or more type.

Examples of commercially available aromatic epoxy resins include jER825, 827, 828, 828EL, 828US, 828XA, 834, 806, 806H, 807, 604, 630 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EXA-830LVP, EXA-850CRP , 835LV, HP4032D, 703, 720, 726, HP820, N-660, N-680, N-695, N-655-EXP-S, N-665-EXP-S, N-685-EXP-S, N -740, N-775, N-865 (manufactured by DIC Corporation), EP4100, EP4000, EP4080, EP4085, EP4088, EP4100HF, EP4901HF, EP4000S, EP4000L, EP4003S, EP4010S, EP4010L (manufactured by ADEKA Corporation), Denacol EX614B, EX411 , EX314, EX201, EX212, EX252 (manufactured by Nagase Chemtex Co., Ltd.), and the like, but are not limited thereto. These may be used individually, respectively, and may mix and use 2 or more types.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanylmethoxy)methylbenzene. , 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenylether, isobutoxymethyl (3 -Ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, tetrahydro Furfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-ox Cetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, ethylene glycol bis (3-ethyl-3) -Oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, trimethylol propane tris (3) -Ethyl-3-oxetanylmethyl)ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl)ether, di pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl)ether, etc. are mentioned. As a commercial item of the said oxetane compound, OXT-212, OXT-221, OXT-213, OXT-101 (made by Toa Synthesis Co., Ltd.) etc. are mentioned, for example. These can be used individually by 1 type or in combination of 2 or more type.

Examples of the vinyl ether compound include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal Butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, acrylic acid 2-(2- Vinyloxyethoxy)ethyl, 2-(2-vinyloxyethoxy)ethyl methacrylate, etc. are mentioned. Commercial products of the vinyl ether compound include NPVE, IPVE, NBVE, IBVE, EHVECHVE (manufactured by Nippon Carbide Industries, Ltd.), HEVE, DEGV, HBVE (manufactured by Maruzen Petrochemical Co., Ltd.), VEEA, VEEM (manufactured by Nippon Shokubai Co., Ltd.), etc. can be heard These can be used individually by 1 type or in combination of 2 or more type.

The sensitizer includes 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2- Iodofluorene, 2-fluorenamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9'-spirobi [ 9H-fluorene], 2-fluorenecarboxyaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- On, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morphol No(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-( 1-methylvinyl)phenyl]propanone oligomer, a nitro compound, a dye, etc. are mentioned. The amount of addition is not particularly limited, but it is necessary to refer to the absorption wavelength and the molar extinction coefficient.

Examples of the silane coupling agent include a silane coupling agent containing a vinyl group such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane, γ-methacryloxypropyl trimethoxy (meth)acryl group-containing silane coupling agent such as silane, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, N-phenyl-γ-aminopropyl trime Amino group-containing silane coupling agents, such as oxysilane, other (gamma)-mercaptopropyl trimethoxysilane, (gamma)-chloropropyl trimethoxysilane, etc. are mentioned. Among these, a glycidyl group-containing silane coupling agent is preferably used, and among the glycidyl group-containing silane coupling agents, 3-glycidoxypropyl trimethoxysilane and 3-glycidoxypropyl triethoxysilane are preferable. These may be used independently and 2 or more types may be used together.

A polyol compound can also be added in order to improve the adjustment of a cure rate or adhesive force more. Examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonanediol, neopentyl glycol, tricyclodecanedimethylol, cyclohexanedimethylol, trimethyl Aliphatic polyols such as allpropane, glycerin, hydrogenated polybutadiene polyol, and hydrogenated dimerdiol, diethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane polyethoxytriol, glycerin polypro (poly)ether polyols, polyester polyol compounds, polycaprolactone polyol compounds having one or more ether bonds, such as poxytriol, bisphenol A polyethoxydiol, bisphenol F polyethoxydiol, and ditrimethylolpropane , a polyol compound having a phenolic hydroxyl group, and polycarbonate polyols such as polycarbonetdiol.

<Curing method and cured product>

The present invention also provides a cured product of the cationically curable adhesive composition for camera modules. In the case of heat curing the cationically curable adhesive composition of the present invention to obtain a cured product, the heating temperature is not particularly limited, but for example, is preferably a temperature of 45° C. or higher and less than 100° C., more preferably 50° C. or higher. less than 95°C. In addition, the heating time is not particularly limited either, but for example, preferably 5 to 120 minutes, more preferably 10 to 60 minutes. In addition, the composition according to the present invention can be cured by irradiation with active energy rays by including the component (D). Although ultraviolet rays, electron beams, visible rays, etc. are mentioned as an active energy ray in this case, it does not restrict|limit in particular. As for the amount of accumulated light of an active energy ray, 300-100000 mJ/cm<2> is preferable, 150-830 nm of the wavelength of an active energy ray is preferable, More preferably, it is 200-400 nm. On the other hand, as a curing method of the cationically curable adhesive composition of the present invention, active energy ray irradiation and heating may be used in combination.

<Use>

The use of the cationically curable adhesive composition of the present invention is a camera module. The adhesion part of the camera module is between an image sensor such as CMOS or CCD and a substrate, between a cut filter and a substrate, between a substrate and a case, between a case and a cut filter, between a case and a lens unit, etc. . The material of the case or lens unit is not particularly limited, and for example, engineering plastics such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), and polycarbonate are exemplified in view of excellent moldability. . The cured product of the cationically curable adhesive composition of the present invention has excellent adhesion to these engineering plastics (especially LCP). That is, another embodiment of this invention is a camera module containing the hardened|cured material of the said cation-curable adhesive composition.

<Conjugate>

This invention also provides the bonding body formed by bonding two or more to-be-adhered bodies using said cation-curable adhesive composition for camera modules. Although it does not specifically limit as a to-be-adhered body, For example, Engineering plastics, such as LCP, PPS, and polycarbonate, etc. are mentioned, Especially, LCP is preferable especially. Therefore, one preferred embodiment of the present invention is a bonding body formed by bonding two or more LCPs using the cation-curable adhesive composition for camera modules described above.

Example

The present invention will be specifically described below by way of Examples, but the present invention is not limited by the Examples below.

<Preparation of cation-curable adhesive composition>

Each component was collected in parts by mass shown in Table 1, mixed with a planetary mixer for 60 minutes at room temperature under light blocking to prepare a cation-curable adhesive composition, and various physical properties were measured as follows.

<(A) component>

a1: hydrogenated bisphenol A type epoxy resin (YX8000, epoxy equivalent 205 g/eq, manufactured by Mitsubishi Chemical Corporation)

a2: 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate (Celoxide 2021P, epoxy equivalent 137g/eq, manufactured by Daicel Co., Ltd.)

<Comparative component of component (A)>

a' 1: Aromatic bisphenol A epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation)

<(B) component>

b1: Thermal cationic polymerization initiator containing a salt consisting of a tetrakis (pentafluorophenyl) borate anion and a quaternary ammonium cation (CXC-1821, manufactured by King Industries)

<(C) component>

c1: polybutadiene rubber filler having an average particle diameter of 0.2 µm (Tg less than 25°C)

c2: Styrene-butadiene rubber filler with an average particle diameter of 0.1 µm (Tg less than 25°C)

c3: average particle diameter 0.3㎛ acrylic rubber filler (Tg less than 25℃)

c4: Acrylonitrile-butadiene rubber filler with an average particle diameter of 0.3 µm (Tg less than 25°C)

c5: styrene-based filler of styrene-divinylbenzene copolymer having an average particle diameter of 0.6 μm (Tg 100° C.)

<Comparative component of component (C)>

c’1: Hydroxyl-terminated polyisoprene that is liquid at 25°C (Poly ip (registered trademark), manufactured by Idemitsu Kosan Co., Ltd.)

c'2: Hydroxyl group polybutadiene liquid at 25°C (Poly bd (registered trademark), manufactured by Idemitsu Kosan Co., Ltd.)

c'3: Rubber filler of silicone/acrylic copolymer with an average particle diameter of 0.4 μm

c'4: Urethane rubber filler with an average particle diameter of 0.3㎛

c'5: Flake-shaped acrylic resin that does not have rubber elasticity at 25°C (ARUFON (registered trademark) UG-4035, manufactured by Doah Synthetic Co., Ltd.)

<(D) component>

d1: photocationic polymerization initiator containing aromatic iodonium salt (PI-2074, manufactured by Rhodia)

<Other ingredients>

Silane coupling agent: 3-glycidoxypropyl trimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

Test methods used in Examples and Comparative Examples are as follows.

<Low-Temperature Hardening Test>

0.1 g of each cation-curable adhesive composition was dropped onto a hot plate set at 80° C., and after 30 minutes, it was contacted with a pointed glass rod to visually evaluate the curability of the composition based on the following criteria. If it is ○ in the following reference|standard, it can be said that low-temperature hardenability is favorable. A result is shown in Table 1.

[Evaluation standard]

○: There is no attachment to the rod

x: There is an adhering to a rod.

<Adhesiveness to engineering plastics>

A polytetrafluoroethylene tape is pasted on the back of the SUS washer having a hole of 0.5 mm in thickness and 6.1 mm in diameter, and an LCP test piece measuring 250 mm in width × 10 mm in length × 3 mm in thickness (VECTRA E130i manufactured by Polyplastics Co., Ltd.) ) was installed above. Next, each cation-curable adhesive composition was apply|coated to the inside of a washer, and it heated and hardened|cured 80 degreeC x 1 hour. Thereby, the test piece to which the test piece made from LCP and the hardened|cured material of the cation-curable adhesive composition adhere|attached was obtained. Then, the chip strength [N/mm 2 ] was measured with a push-pull gauge using the test piece. A result is shown in Table 1.

In the present invention, the preferred chip strength is 6.0 N/m 2 or more, more preferably 7.0 N/mm 2 or more, still more preferably 8.0 N/mm 2 or more, and particularly preferably 10 N/mm 2 or more (the upper limit is For example, it is 20 N/mm2 or less). On the other hand, "measurable" in Table 1 means that even when heated at 80°C for 1 hour, the cationically curable adhesive composition did not cure and it was impossible to perform the main test.

[Table 1]

Examples 1 to 11 show that the cationically curable adhesive composition of the present invention has both low-temperature curability (100°C or less) and adhesiveness to engineering plastics (LCP).

Comparative Example 1 is a composition containing only an aromatic bisphenol A type epoxy resin without any of the alicyclic epoxy resin or hydrogenated epoxy resin, which are essential components of component (A) of the present invention, but low-temperature curability is remarkably poor. Able to know. In addition, it can be seen that Comparative Example 2 is a composition that does not contain component (C) of the present invention, but has poor adhesion to engineering plastics (LCP). In Comparative Examples 3 to 5, instead of the component (C) of the present invention, a polyisoprene with hydroxyl group which is liquid at 25°C, polybutadiene with hydroxyl group which is liquid at 25°C, or a silicone/acrylic copolymer having an average particle diameter of 0.4 μm is used. , it can be seen that the adhesion to engineering plastics is poor. In Comparative Example 6, a composition using a urethane rubber instead of the component (C) of the present invention, but the low-temperature curability was remarkably poor. In Comparative Example 7, a composition using a flake-shaped acrylic resin instead of a rubber elastomer at 25° C. instead of the component (C) of the present invention, but remarkably inferior in low-temperature curability.

Industrial Applicability

The present invention is a cation-curable adhesive composition having both low-temperature curability and adhesion to engineering plastics (especially LCP), and is useful industrially in that it can be applied to adhesives for camera modules.

In addition, application of this invention is not limited to the above-mentioned embodiment, It can change suitably in the range which does not deviate from the meaning of this invention.

This application is based on Japanese Patent Application No. 2016-225225 filed on November 18, 2016, the disclosure of which is incorporated by reference in its entirety.

Claims (7)

(A) component: a cationic polymerizable resin containing at least one selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin;
(B) component: a thermocationic polymerization initiator, and
(C) component: at least one of a rubber filler or a styrenic filler comprising at least one selected from the group consisting of diene-based rubber and (meth)acrylic rubber (excluding silicone/acrylic copolymer) ,
0.1-30 mass parts of said (B) component and 0.5-20 mass parts of said (C)components are contained with respect to 100 mass parts of said (A) component, Cationic curable adhesive composition for camera modules characterized by the above-mentioned. delete The method of claim 1,
The cation-curable adhesive composition for a camera module, characterized in that the component (B) is a thermal cationic polymerization initiator comprising a salt consisting of a tetrakis (pentafluorophenyl) borate anion and a cation. The method of claim 1,
(D) The cation-curable adhesive composition for camera modules further containing a photocationic polymerization initiator as a component. 5. The method of claim 4,
The component (D) comprises at least one of an aromatic iodonium-based photocationic polymerization initiator or an aromatic sulfonium-based photocationic polymerization initiator. Cationic curable adhesive composition for a camera module. Hardened|cured material of the cation-curable adhesive composition for camera modules of Claim 1. A bonding body formed by bonding two or more adherends using the cationically curable adhesive composition for camera modules according to claim 1 .