WO2018092463A1 - Composition adhésive durcissable par voie cationique pour modules de caméra, produit durci et ensemble - Google Patents

Composition adhésive durcissable par voie cationique pour modules de caméra, produit durci et ensemble Download PDF

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Publication number
WO2018092463A1
WO2018092463A1 PCT/JP2017/036518 JP2017036518W WO2018092463A1 WO 2018092463 A1 WO2018092463 A1 WO 2018092463A1 JP 2017036518 W JP2017036518 W JP 2017036518W WO 2018092463 A1 WO2018092463 A1 WO 2018092463A1
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Prior art keywords
component
adhesive composition
curable adhesive
polymerization initiator
cationic
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PCT/JP2017/036518
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English (en)
Japanese (ja)
Inventor
寛人 松岡
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株式会社スリーボンド
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Priority to KR1020197010417A priority Critical patent/KR102389948B1/ko
Priority to JP2018551073A priority patent/JP7007592B2/ja
Priority to CN201780070054.7A priority patent/CN109963920B/zh
Publication of WO2018092463A1 publication Critical patent/WO2018092463A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses

Definitions

  • the present invention relates to a cationic curable adhesive composition for a camera module, a cured product of the composition, and a joined body using the composition.
  • a cationic curable composition containing an epoxy resin or the like has excellent adhesive strength, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance, and therefore adhesives, sealing agents, potting agents, and coatings. It has been used in various applications such as agents and conductive pastes.
  • the object is various, and in electronic devices, it is used for semiconductors, liquid crystal displays, organic electroluminescence, flat panel displays such as touch panels, hard disk devices, mobile terminal devices, camera modules and the like.
  • Adhesion points include between an image sensor such as CMOS and CCD and the substrate, between the cut filter and the substrate, between the substrate and the housing, between the housing and the cut filter, and between the housing and the lens unit. And so on.
  • WO 2005/059002 discloses a cation curable epoxy adhesive composition for semiconductor device packages such as CMOS, which contains an epoxy resin component, a photocationic initiator, a thermal cation initiator, and a filler. ing.
  • Engineering materials such as LCP (Liquid Crystal Polymer), PPS (Polyphenylene Sulfide), and Polycarbonate are used for the housing and lens unit of the camera module.
  • An engineering plastic is a plastic that is excellent in tensile strength even when left in an environment of 100 ° C. or higher for a long time.
  • the cationic curable epoxy adhesive composition disclosed in the pamphlet of International Publication No. 2005/059002 is not satisfactory as an adhesive for camera modules because of poor adhesion to engineering plastics.
  • low-temperature curability (for example, 100 degrees C or less) is calculated
  • the cationic curable epoxy adhesive composition disclosed in WO 2005/059002 is disclosed to be cured by heating at 120 ° C. after UV irradiation, which is also satisfactory from the viewpoint of low-temperature curability. It wasn't.
  • an object of the present invention is to provide a cationic curable adhesive composition having both low-temperature curability and adhesion to engineering plastics (particularly LCP).
  • the present invention overcomes the above-mentioned conventional problems. That is, the present invention is as follows.
  • the component (B) is contained in an amount of 0.1 to 30 parts by mass and the component (C) is contained in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A).
  • the camera module cationic curable adhesive composition (hereinafter also simply referred to as a composition) according to an embodiment of the present invention is selected from the group consisting of component (A): an alicyclic epoxy resin and a hydrogenated epoxy resin. And (C) component: a diene rubber and a (meth) acrylic rubber (excluding a silicone / acrylic copolymer). It contains at least one of a rubber filler or a styrenic filler containing at least one selected from the above.
  • the cationic curable adhesive composition for a camera module having the configuration can have both low-temperature curability (for example, 100 ° C. or less) and adhesiveness to engineering plastics (particularly LCP).
  • X to Y are used to mean that the numerical values (X and Y) described before and after that are included as the lower limit value and the upper limit value. Unless otherwise specified, operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the component (A) of the present invention is a cationically polymerizable resin containing at least one selected from the group consisting of alicyclic epoxy resins and hydrogenated epoxy resins.
  • the cation polymerizable resin is a compound that causes a crosslinking reaction by a cation species generated from a cation polymerization initiator.
  • the cationic species generated from the thermal cationic polymerization initiator by heating is added to the epoxy group, thereby causing ring-opening polymerization of the epoxy group and crosslinking the epoxy resin.
  • the hydrogenated epoxy resin means a compound obtained by nuclear hydrogenation of an aromatic ring of an aromatic epoxy resin. These can be used alone or in combination of two or more.
  • (A) component contains a hydrogenated epoxy resin from a viewpoint of further improving the adhesiveness with respect to engineering plastics (especially LCP).
  • the alicyclic epoxy resin is not particularly limited.
  • 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate is particularly preferable from the viewpoint of further improving the effects of the present invention.
  • the hydrogenated epoxy resin is not particularly limited.
  • hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol A type alkylene oxide adduct examples include glycidyl ether, diglycidyl ether of hydrogenated bisphenol F alkylene oxide adduct, hydrogenated phenol novolak epoxy resin, hydrogenated cresol novolac epoxy resin, etc.
  • Resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin are preferable, and hydrogenated bisphenol A type epoxy resin is particularly preferable. These can be used alone or in combination of two or more.
  • Examples of commercially available hydrogenated bisphenol A type epoxy resins include YX-8000, YX-8034 (Mitsubishi Chemical Corporation), EXA-7015 (DIC Corporation), ST-3000 (Nippon Steel & Sumikin Chemical Co., Ltd.). Jamaica Resin HBE-100 (Shin Nihon Rika Co., Ltd.), EX-252 (Nagase ChemteX Corporation), and the like.
  • Examples of commercially available hydrogenated bisphenol F-type epoxy resins include YL-6753 (manufactured by Mitsubishi Chemical Corporation).
  • an alicyclic epoxy resin and a hydrogenated epoxy resin in combination is preferable to use as the component (A), and the mass ratio (alicyclic epoxy resin: hydrogenated epoxy resin) is: 5:95 to 70:30 is preferred, 15:85 to 50:50 is more preferred, and 25:75 to 40:60 is even more preferred.
  • the epoxy equivalent of the component (A) is preferably 50 to 500 g / eq, more preferably 100 to 250 g / eq.
  • (B) component of this invention is a thermal cationic polymerization initiator, and is a compound which generate
  • component (B) even when an engineering plastic having low light transmittance is selected as the adherend, excellent adhesiveness can be exhibited by thermosetting.
  • the thermal cationic polymerization initiator (B1) containing the salt which consists of a hexafluoroantimonate anion and a cation examples include an initiator (B2), a thermal cationic polymerization initiator (B3) containing a salt composed of a tetrakis (pentafluorophenyl) borate anion and a cation.
  • an initiator (B2), a thermal cationic polymerization initiator (B3) containing a salt composed of a tetrakis (pentafluorophenyl) borate anion and a cation examples include an initiator (B2), a thermal cationic polymerization initiator (B3) containing a salt composed of a tetrakis (pentafluorophenyl) borate anion and a cation.
  • tetrakis (pentafluorophenyl) is excellent in low-temperature curability.
  • a thermal cationic polymerization initiator (B3) containing a salt composed of a borate anion and a cation is preferred.
  • 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 alone or in combination of two or more.
  • thermal cationic polymerization initiator (B3) containing a salt composed of a tetrakis (pentafluorophenyl) borate anion and a cation, preferably, tetrakis ( And a thermal cationic polymerization initiator containing a salt comprising a pentafluorophenyl) borate anion and a quaternary ammonium cation.
  • thermal cationic polymerization initiator (B1) containing a salt composed of the hexafluoroantimonate anion and cation examples include SI-60L, SI-80L, SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. It is done.
  • thermal cationic polymerization initiator (B2) containing a salt composed of the hexafluorophosphate anion and cation SI-110L, SI-180L, SI-B2A, SI-B3A (manufactured by Sanshin Chemical Industry Co., Ltd.) are available. Can be mentioned.
  • thermal cationic polymerization initiator (B3) containing a salt composed of the tetrakis (pentafluorophenyl) borate anion and cation examples include CXC-1821 (manufactured by King Industries).
  • the blending amount of the component (B) in the cationic curable adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of the component (A). Is 0.3 to 15 parts by mass, still more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass. If it is 0.1 parts by mass or more, the low-temperature curability is good, and if it is 30 parts by mass or less, the storage stability is good.
  • the component (C) of the present invention is at least one of a rubber filler or a styrene filler containing at least one selected from the group consisting of diene rubbers and (meth) acrylic rubbers (excluding silicone-acrylic copolymers). is there.
  • Component (C) when combined with the other components of the present invention, does not inhibit the curing of the composition (that is, maintains low-temperature curability) and has a remarkable effect of excellent adhesion to engineering plastics (particularly LCP). Bring.
  • the rubber filler means a rubber-like elastic body at 25 ° C., and examples thereof include a glass transition point (Tg) of less than 25 ° C. Since engineering plastics have relatively high crystallinity, when the adhesive composition disclosed in the pamphlet of International Publication No. 2005/059002 is applied to this, stress is applied to the bonding surface and sufficient adhesiveness cannot be expressed. it is conceivable that. On the other hand, it is considered that the composition according to the present invention contains a rubber filler, so that the stress is relaxed and excellent adhesiveness can be expressed.
  • Tg glass transition point
  • diene rubber examples include polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, polychloroprene rubber, and hydrogenated ones thereof.
  • 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 obtained by polymerizing (meth) acrylic acid ester alone or together with a monomer copolymerizable therewith (excluding silicone / acrylic copolymer), for example, examples thereof include acrylic rubbers such as acrylic ester / 2-chloroethyl vinyl ether copolymer (ACM) and acrylic ester / acrylonitrile copolymer (ANM).
  • ACM acrylic ester / 2-chloroethyl vinyl ether copolymer
  • ACM acrylic ester / acrylonitrile copolymer
  • the silicone / acrylic copolymer is excluded from the definition of the (meth) acrylic rubber is that sufficient adhesiveness to the engineering plastic cannot be obtained (see Comparative Example 5 described later).
  • (meth) acrylic acid esters examples include ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) acrylate, and the like.
  • monomers copolymerizable with (meth) acrylic acid esters include 2-chloroethyl vinyl ether and acrylonitrile.
  • the component (C) preferably contains at least one of polybutadiene rubber or acrylic rubber, and more preferably contains polybutadiene rubber, from the viewpoint of further improving the adhesion to engineering plastics.
  • Styrenic fillers have a glass transition point (Tg) of 50 ° C. obtained by polymerizing at least one styrene derivative (for example, styrene, ⁇ -methylstyrene, divinylbenzene) together with a monomer copolymerizable therewith. Above (upper limit is, for example, 200 ° C. or less) polystyrene filler. Specific examples of the styrenic filler include styrene-glycidyl methacrylate copolymer and styrene-divinylbenzene copolymer, and styrene-divinylbenzene copolymer is preferable. Examples of commercially available products include Marproof G-1005S (manufactured by NOF Corporation) and Fine Pearl PB-3006E (manufactured by Matsuura Corporation). These may be used alone or in admixture of two or more.
  • Tg glass transition point
  • the component (C) of the present invention can be easily dispersed in the composition by previously dispersing it in the component (A) of the present invention.
  • the average particle diameter of the component (C) is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 1 ⁇ m, and particularly preferably 0.1 to 0.6 ⁇ m.
  • the method for measuring the average particle diameter is a laser diffraction / scattering method (50% volume average particle diameter).
  • the amount of component (C) added is preferably 0.1 to 50 parts by weight, more preferably 0.3 to 30 parts by weight, based on 100 parts by weight of component (A).
  • it is more preferably 0.5 to 20 parts by mass, and even more preferably 2 to 12 parts by mass.
  • a lower limit 4 mass parts or more, 5 mass parts or more, or 6 mass parts or more are preferable, and as an upper limit, 10 mass parts or less, 9 mass parts or less, or 8 mass parts or less are preferable.
  • this invention may contain a photocationic polymerization initiator further as (D) component.
  • (D) component By further containing a component, after making it harden
  • the cationic photopolymerization initiator is a compound that generates cationic species upon irradiation with active energy rays.
  • the component (D) is not particularly limited.
  • both photocurability, thermosetting and storage stability are improved.
  • aromatic sulfonium-based photocationic polymerization initiator examples include a photocationic polymerization initiator containing a sulfonium ion in which all three groups bonded to a sulfur atom are aryl groups (for example, a phenyl group).
  • aromatic iodonium-based photocationic polymerization initiator examples include a photocationic polymerization initiator containing an iodonium ion in which two groups bonded to an iodine atom are an aryl group (for example, a phenyl group).
  • produces a cationic seed
  • aromatic sulfonium photocationic polymerization initiator examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio].
  • aromatic sulfonium photocationic polymerization initiators include SP-150, SP-170, SP-172 (manufactured by ADEKA Corporation), CPI-100P, CPI-101A, CPI-110B, CPI-200K, CPI -210S (manufactured by San Apro Co., Ltd.), T1608, T1609, T2041, T2042 (manufactured by Tokyo Chemical Industry Co., Ltd.), UVI-6990, UVI-6974 (manufactured by Union Carbide), DTS-200 (manufactured by Midori Chemical Co., Ltd.), etc. Is mentioned.
  • aromatic iodonium-based photocationic polymerization initiator examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, 4- Examples include methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate. Among these, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate is preferable. These may be used alone or in combination.
  • aromatic iodonium-based photocationic polymerization initiators include Irgacure 250 (manufactured by BASF), PI-2074 (manufactured by Rhodia), B2380, B2381, D2238, D2248, D2253, I0591 (Tokyo Chemical Industry Co., Ltd.) WPI-113, WPI-116, WPI-169, WPI-170, WPI-124 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
  • the blending amount of the component (D) in the cationic curable adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.5 to 15 parts by mass, and more preferably 1 to 5 parts by mass. 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
  • the cationic curable adhesive composition of the present invention includes an aromatic epoxy resin, an oxetane compound, a vinyl ether compound, a colorant such as a pigment and a dye, a sensitizer, and a silane coupling as long as the characteristics of the present invention are not impaired.
  • Agent 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 filler with an average particle size of 0.001 to 100 ⁇ m, conductive particles such as silver, flame retardant, plasticizer, organic solvent, phenolic antioxidant, antioxidant such as phosphorus antioxidant, light stability Agent, UV absorber, antifoaming agent, foaming agent, mold release agent, leveling agent, rheology control agent, adhesive Agents, retarders, polyimide resins, polyamide resins, phenoxy resins, cyanate esters, additives such as polyvinyl butyral resin may be appropriate amount.
  • a cationic curable adhesive composition having excellent resin strength, adhesive strength, flame retardancy, thermal conductivity, workability, and the like and a cured product thereof can be obtained.
  • a silane coupling agent is further included from a viewpoint of the further improvement of the adhesiveness with respect to an engineering plastic.
  • aromatic epoxy resin in addition to the (A) component alicyclic epoxy resin and hydrogenated epoxy resin, aromatic epoxy resin, oxetane compound, vinyl ether compound and the like can be used in combination.
  • Aromatic epoxy resins include aromatic bisphenol A type epoxy resin, aromatic bisphenol F type epoxy resin, aromatic bisphenol E type epoxy resin, aromatic bisphenol A type alkylene oxide adduct diglycidyl ether, and aromatic bisphenol F.
  • NBR butadiene rubber
  • 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), EPICLON 830, 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 (stocks) Company Ltd.
  • oxetane compound examples include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-Ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tete
  • Examples of commercially available oxetane compounds include OXT-212, OXT-221, OXT-213, OXT-101 (manufactured by Toa Gosei Co., Ltd.). These can be used alone or in combination of two or more.
  • vinyl ether compound examples 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, 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate, and the like.
  • Sensitizers include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluoreneamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9′-spirobi [9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, 1-hydride
  • silane coupling agent examples include vinyl group-containing silane coupling agents such as vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane, and (meth) such as ⁇ -methacryloxypropyltrimethoxysilane.
  • Amino group-containing silanes such as acrylic group-containing silane coupling agents, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane
  • the coupling agent include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -chloropropyltrimethoxysilane.
  • a glycidyl group-containing silane coupling agent is preferably used, and among the glycidyl group-containing silane coupling agents, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable. These may be used independently and 2 or more types may be used together.
  • polyol compound it may be added in order to adjust the curing speed and increase the adhesive strength.
  • the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonanediol, neopentyl glycol, tricyclodecane dimethylol, cyclohexane dimethylol, tri Aliphatic polyols such as methylolpropane, glycerin, hydrogenated polybutadiene polyol, hydrogenated dimer diol, diethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane polyethoxytriol, glycerin polypropoxytriol, bisphenol Ether bonds such as A polyethoxydiol, bisphenol F polyethoxydiol, and ditrimethylolpropane One or more,
  • the present invention also provides a cured product of the above cationic curable adhesive composition for camera modules.
  • the heating temperature is not particularly limited. For example, it is preferably a temperature of 45 ° C. or more and less than 100 ° C., more preferably 50 ° C. It is more than 95 degreeC above.
  • the heating time is not particularly limited, but for example, preferably 5 to 120 minutes, more preferably 10 to 60 minutes.
  • the composition which concerns on this invention can be hardened by active energy ray irradiation by containing (D) component.
  • the active energy ray in this case include ultraviolet rays, electron beams, and visible rays, but are not particularly limited.
  • the integrated light amount of the active energy ray is preferably 300 to 100,000 mJ / cm 2 , and the wavelength of the active energy ray is preferably 150 to 830 nm, more preferably 200 to 400 nm.
  • active energy ray irradiation and heating may be used in combination.
  • the application of the cationic curable adhesive composition of the present invention is a camera module.
  • the adhesion points of the camera module are between an image sensor such as CMOS and CCD and the substrate, between the cut filter and the substrate, between the substrate and the case, between the case and the cut filter, and between the case and the lens.
  • the material of the housing and the lens unit is not particularly limited, and examples thereof include engineering plastics such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), and polycarbonate because of excellent moldability.
  • the cured product of the cationic curable adhesive composition of the present invention has excellent adhesion to these engineering plastics (particularly LCP). That is, other embodiment of this invention is a camera module containing the hardened
  • the present invention also provides a joined body obtained by adhering two or more adherends using the above cationic curable adhesive composition for a camera module.
  • a joined body obtained by adhering two or more adherends using the above cationic curable adhesive composition for a camera module.
  • engineering plastics such as LCP, PPS, a polycarbonate, etc. are mentioned, Among these, LCP is preferable.
  • a preferred embodiment of the present invention is a joined body obtained by adhering two or more LCPs using the above-described cationic curable adhesive composition for camera modules.
  • ⁇ (A) component> a1 Hydrogenated bisphenol A type epoxy resin (YX8000, epoxy equivalent 205 g / eq, manufactured by Mitsubishi Chemical Corporation) a2: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P, epoxy equivalent 137 g / eq, manufactured by Daicel Corporation) ⁇ Comparison component of component (A)> a′1: Aromatic bisphenol A type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation) ⁇ (B) component> b1: Thermal cationic polymerization initiator containing a salt composed 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 size of 0.2 ⁇ m (Tg
  • c′2 Hydroxyl group polybutadiene liquid at 25 ° C.
  • Poly bd registered trademark
  • c′3 Rubber filler of silicone / acrylic copolymer having an average particle diameter of 0.4 ⁇ m
  • c′4 Urethane rubber filler having an average particle diameter of 0.3 ⁇ m
  • c′5 Flakes-shaped acrylic resin having no rubber elasticity at 25 ° C.
  • test methods used in the examples and comparative examples are as follows.
  • Preferred chip strength in the present invention is 6.0 N / m 2 or more, more preferably 7.0 N / mm 2 or more, even more preferably 8.0 N / mm 2 or more, particularly preferably 10 N / it is mm 2 or more (the upper limit is, for example, 20 N / mm 2 or less).
  • “impossible to measure” means that the test could not be performed because the cationic curable adhesive composition did not cure even when heated at 80 ° C. for 1 hour. To do.
  • Examples 1 to 11 show that the cationic curable adhesive composition of the present invention has both low-temperature curability (100 ° C. or lower) and adhesion to engineering plastics (LCP).
  • LCP adhesion to engineering plastics
  • Comparative Example 1 is a composition that does not contain any of the alicyclic epoxy resin or hydrogenated epoxy resin, which is an essential component of the component (A) of the present invention, and contains only the aromatic bisphenol A type epoxy resin, but is low temperature cured. It turns out that the property is remarkably inferior. Moreover, although the comparative example 2 is a composition which does not contain the (C) component of this invention, it turns out that the adhesiveness with respect to an engineering plastic (LCP) is inferior.
  • LCP engineering plastic
  • Comparative Examples 3 to 5 in place of the component (C) of the present invention, a hydroxyl group-terminated polyisoprene that is liquid at 25 ° C., a hydroxyl group polybutadiene that is liquid at 25 ° C., or a silicone / acrylic copolymer having an average particle size of 0.4 ⁇ m. Although it is a composition using coalescence, it can be seen that the adhesion to engineering plastics is poor. Moreover, although the comparative example 6 is a composition which used the urethane rubber instead of (C) component of this invention, the low-temperature curability was remarkably inferior. Moreover, although the comparative example 7 is a composition using the flaky acrylic resin which is not a rubber elastic body at 25 degreeC instead of (C) component of this invention, low-temperature curability was remarkably inferior.
  • the present invention is a cationic curable adhesive composition having both low temperature curability and adhesion to engineering plastics (particularly LCP), and is industrially useful because it can be applied to an adhesive for camera modules.

Abstract

Le problème décrit par la présente invention est de fournir une composition adhésive durcissable par voie cationique qui combine une aptitude au durcissement à basse température avec une adhésivité à des plastiques techniques (en particulier, des LCP). La solution selon l'invention porte sur une composition adhésive durcissable par voie cationique pour modules de caméra, caractérisée en ce qu'elle comprend : un constituant (A) qui est une résine polymérisable par voie cationique comprenant au moins un constituant choisi dans le groupe constitué par les résines époxydes alicycliques et les résines époxydes hydrogénées ; un constituant (B) qui est un initiateur de polymérisation cationique thermique ; et un constituant (C) qui est une charge de caoutchouc et/ou une charge de styrène, ladite charge de caoutchouc comprenant au moins un caoutchouc choisi dans le groupe constitué par les caoutchoucs diéniques et les caoutchoucs (méth)acryliques (à l'exclusion des copolymères siliconés/acryliques).
PCT/JP2017/036518 2016-11-18 2017-10-06 Composition adhésive durcissable par voie cationique pour modules de caméra, produit durci et ensemble WO2018092463A1 (fr)

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JP2018551073A JP7007592B2 (ja) 2016-11-18 2017-10-06 カメラモジュール用カチオン硬化性接着剤組成物、硬化物および接合体
CN201780070054.7A CN109963920B (zh) 2016-11-18 2017-10-06 相机模组用阳离子固化性胶粘剂组合物、固化物以及接合体

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WO2020261501A1 (fr) * 2019-06-27 2020-12-30 昭和電工マテリアルズ株式会社 Composition adhésive et procédé de sélection associé, film adhésif et procédé de production associé, et corps adhésif et procédé de production associé
WO2021193576A1 (fr) * 2020-03-23 2021-09-30 Henkel Ag & Co. Kgaa Composition adhésive à double durcissement
CN115368856A (zh) * 2022-07-14 2022-11-22 深圳市撒比斯科技有限公司 一种具有光开关光热响应型胶黏剂及其制备方法
WO2023032722A1 (fr) * 2021-08-30 2023-03-09 デクセリアルズ株式会社 Procédé de fabrication d'un module de lentille et adhésif thermodurcissable

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WO2020261501A1 (fr) * 2019-06-27 2020-12-30 昭和電工マテリアルズ株式会社 Composition adhésive et procédé de sélection associé, film adhésif et procédé de production associé, et corps adhésif et procédé de production associé
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WO2021193576A1 (fr) * 2020-03-23 2021-09-30 Henkel Ag & Co. Kgaa Composition adhésive à double durcissement
EP4127092A4 (fr) * 2020-03-23 2024-04-03 Henkel Ag & Co Kgaa Composition adhésive à double durcissement
WO2023032722A1 (fr) * 2021-08-30 2023-03-09 デクセリアルズ株式会社 Procédé de fabrication d'un module de lentille et adhésif thermodurcissable
CN115368856A (zh) * 2022-07-14 2022-11-22 深圳市撒比斯科技有限公司 一种具有光开关光热响应型胶黏剂及其制备方法
CN115368856B (zh) * 2022-07-14 2024-03-26 深圳市撒比斯科技有限公司 一种具有光开关光热响应型胶黏剂及其制备方法

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KR20190084947A (ko) 2019-07-17
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