WO2022260053A1 - Composition de résine photodurcissable/durcissable à l'humidité, adhésif pour composants électroniques, corps durci et composant électronique - Google Patents

Composition de résine photodurcissable/durcissable à l'humidité, adhésif pour composants électroniques, corps durci et composant électronique Download PDF

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WO2022260053A1
WO2022260053A1 PCT/JP2022/023015 JP2022023015W WO2022260053A1 WO 2022260053 A1 WO2022260053 A1 WO 2022260053A1 JP 2022023015 W JP2022023015 W JP 2022023015W WO 2022260053 A1 WO2022260053 A1 WO 2022260053A1
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moisture
curable resin
meth
compound
light
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PCT/JP2022/023015
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English (en)
Japanese (ja)
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涼馬 石立
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積水化学工業株式会社
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Priority to CN202280040313.2A priority Critical patent/CN117480194A/zh
Priority to JP2022543049A priority patent/JPWO2022260053A1/ja
Priority to KR1020237041958A priority patent/KR20240018465A/ko
Publication of WO2022260053A1 publication Critical patent/WO2022260053A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/025—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to a light moisture-curable resin composition, an adhesive for electronic parts, a cured product, and an electronic part.
  • narrowing the frame of the image display unit is being performed as a method of miniaturizing the display element (hereinafter also referred to as "narrow frame design").
  • narrow frame design attempts have been made to use light and moisture-curable adhesives in place of double-sided tapes in order to reduce the size and narrow the frame.
  • Patent Document 1 discloses a light moisture adhesive that contains a radically polymerizable compound, a moisture-curable urethane resin, a photoradical polymerization initiator, and a moisture remover.
  • a curable resin composition is disclosed.
  • the moisture remover is blended to improve storage stability and the like, and examples thereof include compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group. It is
  • a light moisture-curable adhesive is generally placed in a B-stage state by photocuring, and the adherends are bonded together by the light-moisture-curable adhesive in the B-stage state, temporarily bonded, and then subjected to moisture Generally, adherends are permanently adhered to each other by curing.
  • the light moisture-curable adhesive may be required to maintain a high adhesive strength (final heat-resistant adhesive strength) even in a high-temperature environment after the main bonding. For example, when it is used for electronic parts, it may be heated to a high temperature by the heat generated by the electronic parts, so it may be necessary to increase the final heat resistant adhesive strength.
  • the final heat-resistant adhesive strength after the main adhesion may not be sufficient.
  • light-moisture-curable adhesives often have insufficient adhesive strength (initial adhesive strength) in the B-stage state immediately after photocuring. It is thought to increase power.
  • the molecular weight of the prepolymer is increased, the bulk strength of the cured product tends to decrease and the final heat resistant adhesive strength tends to decrease.
  • an object of the present invention is to provide a light and moisture-curable resin composition that exhibits good heat-resistant adhesive strength after moisture curing.
  • the present inventors have found that, in addition to the radically polymerizable compound (A), the moisture-curable resin (B) and the photopolymerization initiator (C), in the light and moisture-curable resin composition,
  • the present inventors have found that the above problems can be solved by including a compound (D) having three or more isocyanate groups, and completed the present invention below. That is, the present invention provides the following [1] to [29].
  • [1] Light moisture containing a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having three or more isocyanate groups in the molecule A curable resin composition.
  • the monofunctional (meth)acrylic acid ester compound is at least one selected from the group consisting of alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates.
  • the total content of the alkyl (meth)acrylate, the alicyclic structure-containing (meth)acrylate, and the aromatic ring-containing (meth)acrylate is 5 parts by mass or more based on 100 parts by mass of the radically polymerizable compound (A).
  • the photopolymerization initiator (C) is a benzophenone-based compound, an acetophenone-based compound, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based compound, a titanocene-based compound, an oxime ester-based compound, a benzoin ether-based compound, and thioxanthone, the light and moisture-curable resin composition according to any one of [1] to [20] above.
  • a light and moisture-curable resin composition [24] The light and moisture-curable resin composition according to any one of [1] to [23] above, which has an initial adhesive strength of 0.1 MPa or more. [25] The light and moisture-curable resin composition according to any one of [1] to [24] above, which has a final heat-resistant adhesive strength of 1.0 MPa or more.
  • the content of the compound (D) is 0.1 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B).
  • the light and moisture-curable resin composition according to any one of [1] to [25] above.
  • An adhesive for electronic parts comprising the light moisture-curable resin composition according to any one of [1] to [26] above.
  • An electronic component comprising the cured product according to [28] above.
  • FIG.2 (a) is a top view
  • FIG.2(b) is a side view.
  • the light and moisture-curable resin composition of the present invention comprises a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound having three or more isocyanate groups in the molecule. including (D).
  • the light and moisture-curable resin composition of the present invention contains a radically polymerizable compound (A).
  • the photo-moisture-curable resin composition is imparted with photocurability by containing the radically polymerizable compound (A). Since the light-moisture-curable resin composition has photocurability, a certain amount of adhesive strength can be imparted only by light irradiation, so that a certain amount of initial adhesive strength can be secured.
  • the radically polymerizable compound (A) may have a radically polymerizable functional group in its molecule.
  • a compound having an unsaturated double bond is preferable as the radically polymerizable functional group, and examples thereof include (meth)acryloyl group, vinyl group, styryl group, and allyl group.
  • a (meth)acryloyl group is preferable from the viewpoint of adhesiveness, that is, the radically polymerizable compound (A) preferably contains a compound having a (meth)acryloyl group.
  • the compound which has a (meth)acryloyl group is hereafter also called a "(meth)acrylic compound.”
  • (meth)acryloyl group means acryloyl group or (meth)acryloyl group
  • (meth)acryl means acryl or methacryl, and other similar terms are the same. be.
  • the radically polymerizable compound (A) is a monofunctional radically polymerizable compound having one radically polymerizable functional group in one molecule, or a multifunctional radically polymerizable compound having two or more radically polymerizable functional groups in one molecule. Although one or both of them may be included, it is preferable to include a monofunctional radically polymerizable compound from the viewpoint of improving the initial adhesive strength of the light and moisture-curable resin composition. Moreover, the radically polymerizable compound (A) more preferably contains at least a monofunctional (meth)acrylic compound as a monofunctional radically polymerizable compound.
  • the monofunctional radically polymerizable compound may be a polymerized prepolymer having repeating units, but it is usually preferable to use a monofunctional monomer having no repeating units.
  • the monofunctional radically polymerizable compound may be, for example, 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound (A).
  • the light and moisture-curable resin composition preferably contains a large amount of a monofunctional radically polymerizable compound in order to improve the initial adhesive strength of the light and moisture-curable resin composition.
  • the light and moisture-curable resin composition preferably contains 90 parts by mass or more of a monofunctional radically polymerizable compound, and 95 parts by mass or more, relative to 100 parts by mass of the radically polymerizable compound (A). is preferred, and 100 parts by mass is more preferred.
  • the radically polymerizable compound (A) preferably contains a nitrogen-containing compound as a monofunctional radically polymerizable compound.
  • a nitrogen-containing compound By using a nitrogen-containing compound, the initial adhesive strength of the light and moisture-curable resin composition is improved.
  • the light-moisture-curable resin composition is applied to an adherend and then photocured by irradiating it with an active energy ray such as ultraviolet rays. It is often done. It is presumed that when the radically polymerizable compound (A) contains a nitrogen-containing compound, it is appropriately photocured even in the presence of oxygen, thereby improving the initial adhesive strength.
  • the nitrogen-containing compound may contain one or both of a nitrogen-containing compound having a linear structure and a nitrogen-containing compound having a cyclic structure. It preferably contains a nitrogen-containing compound having a structure, and more preferably uses a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure in combination.
  • Nitrogen-containing compounds having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone and N-vinyl- ⁇ -caprolactam, morpholine skeleton-containing compounds such as N-acryloylmorpholine, N-(meth)acryloyloxy cyclic imide compounds such as ethylhexahydrophthalimide; Among these, amide group-containing compounds such as N-vinylcaprolactam are more preferable.
  • a nitrogen-containing compound having a cyclic structure is also referred to as a cyclic nitrogen-containing compound, and a radically polymerizable compound in which a nitrogen atom is contained in the atoms constituting the ring itself is a cyclic nitrogen-containing compound, and other nitrogen-containing compounds.
  • the compound is a chain nitrogen-containing compound.
  • chain nitrogen-containing compounds examples include chain nitrogen-containing compounds such as dimethylamino (meth) acrylate, diethylamino (meth) acrylate, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate.
  • Chain (meth)acrylamides such as amino group-containing (meth)acrylates, diacetoneacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, and methacrylamide compound, N-vinylacetamide, and the like.
  • the chain nitrogen-containing compound may be a monofunctional urethane (meth)acrylate.
  • a monofunctional urethane (meth)acrylate compatibility with the moisture-curable resin (B) is improved when a urethane resin, particularly a urethane resin having a polycarbonate skeleton, is used as the moisture-curable resin (B). becomes good, and it is easy to improve the initial adhesive strength.
  • urethane (meth)acrylate has a relatively high polarity, so it is easy to increase the adhesive strength to glass.
  • a monofunctional urethane (meth)acrylate can be used, for example, obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group.
  • (meth)acrylic acid derivatives having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. and mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin.
  • Isocyanate compounds used to obtain urethane (meth)acrylates include alkane monoisocyanates such as butane isocyanate, hexane isocyanate and decane isocyanate; group monoisocyanates. More specifically, the monofunctional urethane (meth)acrylate is preferably a urethane (meth)acrylate obtained by reacting the monoisocyanate compound described above with a mono(meth)acrylate of a dihydric alcohol.
  • a preferred specific example is 1,2-ethanediol 1-acrylate 2-(N-butylcarbamate).
  • the chain nitrogen-containing compound preferably contains a monofunctional urethane (meth)acrylate, and a monofunctional urethane (meth)acrylate and a monofunctional urethane (meth)acrylate such as a (meth)acrylamide compound. It is also preferable to use compounds other than acrylate together.
  • the content of the nitrogen-containing compound as a monofunctional radically polymerizable compound with respect to 100 parts by mass of the radically polymerizable compound (A) in the light and moisture-curable resin composition improves the initial adhesive strength of the light and moisture-curable resin composition. 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and most preferably 75 parts by mass or more.
  • the content of the nitrogen-containing compound as the monofunctional radically polymerizable compound is preferably 95 parts by mass or less, more preferably 95 parts by mass or less, in order to contain an appropriate amount of the radically polymerizable compound (A) other than the nitrogen-containing compound. is 90 parts by mass or less, more preferably 85 parts by mass or less.
  • the monofunctional radically polymerizable compound has a linear nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure
  • the monofunctional radically polymerizable compound has a nitrogen-containing compound having a cyclic structure relative to the linear nitrogen-containing compound.
  • (cyclic/chain) is preferably 0.1 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less, and still more preferably 0.4 or more and 1.2 or less.
  • the monofunctional radically polymerizable compound contained in the radically polymerizable compound (A) preferably contains a compound other than the nitrogen-containing compound described above (hereinafter also referred to as a nitrogen-free compound).
  • a nitrogen-free compound When the radically polymerizable compound (A) contains a nitrogen-free compound as a monofunctional radically polymerizable compound, it becomes easier to improve adhesive strength and the like.
  • the nitrogen-free compound is not particularly limited as long as it is a compound having a radically polymerizable functional group, but is preferably a monofunctional (meth)acrylic compound, and more preferably a (meth)acrylic acid ester compound.
  • Monofunctional (meth)acrylic acid ester compounds include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates. These may be used alone or in combination of two or more. Among them, one or both of alkyl (meth)acrylates and aromatic ring-containing (meth)acrylates may be used. is preferred.
  • the total content of the alkyl (meth)acrylate, the alicyclic structure-containing (meth)acrylate, and the aromatic ring-containing (meth)acrylate in the radically polymerizable compound (A) is based on 100 parts by mass of the radically polymerizable compound (A). , preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more.
  • the content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, still more preferably 40 parts by mass or less, and most preferably 25 parts by mass or less.
  • alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate ) and alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group, such as acrylates.
  • Alicyclic structure-containing (meth)acrylates include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (Meth)acrylates having an alicyclic structure such as (meth)acrylates can be mentioned.
  • the alicyclic structure is a ring structure in which the ring-constituting elements are carbon atoms.
  • aromatic ring-containing (meth)acrylates examples include phenylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate, and phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate. is mentioned.
  • alkyl (meth) acrylates, alicyclic structure-containing (meth) acrylates, and aromatic ring-containing (meth) acrylates can also be used, for example, cyclic ether group-containing (meth) Acrylates can also be used.
  • Cyclic ether group-containing (meth)acrylates include (meth)acrylates having an epoxy ring, oxetane ring, tetrahydrofuran ring, dioxolane ring, dioxane ring, or the like.
  • Examples of epoxy ring-containing (meth)acrylates include glycidyl (meth)acrylate.
  • Oxetane ring-containing (meth)acrylates include (3-ethyloxetane-3-yl)methyl (meth)acrylate.
  • Tetrahydrofuran ring-containing (meth)acrylates include tetrahydrofurfuryl (meth)acrylate and tetrahydrofurfuryl alcohol (meth)acrylic acid polymeric esters.
  • Dioxolane ring-containing (meth)acrylates include (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2,2-cyclohexyl-1,3-dioxolane-4- yl)methyl (meth)acrylate and the like.
  • Examples of (meth)acrylates having a dioxane ring include cyclic trimethylolpropane formal (meth)acrylates.
  • As the cyclic ether group-containing (meth)acrylate it is preferable to use either an oxetane ring-containing (meth)acrylate or a tetrahydrofuran ring-containing (meth)acrylate, but it is also preferable to use these together.
  • the monofunctional (meth)acrylic acid ester compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • Alkoxyalkyl (meth)acrylates such as hydroxyalkyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate acrylates, alkoxyethylene glycol (meth)acrylates such as ethoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate , ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, and polyoxyethylene-based (meth)acrylate such as ethoxypolyethylene glycol (meth)acrylate may also be used.
  • the monofunctional (meth)acrylic compound a
  • the radically polymerizable compound (A) may contain a polyfunctional radically polymerizable compound as long as the effects of the present invention are exhibited.
  • polyfunctional radically polymerizable compounds include bifunctional (meth)acrylic acid ester compounds, trifunctional or higher (meth)acrylic acid ester compounds, and bifunctional or higher urethane (meth)acrylates.
  • bifunctional (meth)acrylic acid ester compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.
  • tri- or more functional (meth)acrylic acid ester compounds include trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, Caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra (Meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.
  • bifunctional or higher urethane (meth)acrylate for example, one obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group can be used.
  • (meth)acrylic acid derivatives having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
  • isocyanate compounds used to obtain urethane (meth)acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate (MDI ), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, Examples include polyisocyanate compounds such as tetramethylxylylene diisocyanate and 1,6,11-undecane triisocyanate.
  • MDI diphenylmethane diisocyanate
  • polystyrene resin a chain-extended polyisocyanate compound (polyol modified product) obtained by reacting a polyol with an excess isocyanate compound
  • polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
  • Polyfunctional urethane (meth)acrylates can be obtained by using these polyisocyanate compounds.
  • moisture-curable resin (B) examples include moisture-curable urethane resins, hydrolyzable silyl group-containing resins, and moisture-curable cyanoacrylate resins. and hydrolyzable silyl group-containing resins are preferred, and moisture-curable urethane resins are more preferred. These may be used individually by 1 type, and may use 2 or more types together.
  • a moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
  • the moisture-curable urethane resin preferably has an isocyanate group in the molecule, and the isocyanate group in the molecule reacts with moisture in the air or in the adherend to cure.
  • the moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. It is preferable to have one or two, more preferably two.
  • the isocyanate group is not particularly limited, but is preferably provided at the ends of the moisture-curable urethane resin, for example, at both ends.
  • the polyol compound that is a raw material for the moisture-curable urethane resin known polyol compounds that are commonly used in the production of polyurethane can be used. is mentioned. These polyol compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the moisture-curable urethane resin is preferably at least one of moisture-curable urethane resins having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, and at least one of moisture-curable urethane resins having a polycarbonate skeleton or a polyether skeleton is preferred.
  • Moisture-curable urethane resins having a polycarbonate skeleton are more preferred.
  • the moisture-curable urethane resin is enhanced in heat resistance, mechanical strength, etc., and tends to be excellent in both initial adhesive strength and final heat-resistant adhesive strength.
  • it is possible to provide a light and moisture-curable resin composition which is excellent in weather resistance, moisture resistance, etc. of the cured product.
  • a moisture-curable urethane resin having a polycarbonate skeleton is obtained by introducing a polycarbonate skeleton into a urethane resin by using a polycarbonate polyol as the polyol compound.
  • a moisture-curable urethane resin having a polycarbonate skeleton is obtained, for example, by reacting a polycarbonate polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
  • Polycarbonate diols are preferred as the polycarbonate polyols, and preferred specific examples of polycarbonate diols include compounds represented by the following formula (1).
  • R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 2 to 500.
  • R is preferably an aliphatic saturated hydrocarbon group.
  • R is an aliphatic saturated hydrocarbon group
  • the heat resistance tends to be good.
  • yellowing or the like due to heat deterioration or the like is less likely to occur, and weather resistance is improved.
  • R composed of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but preferably has a chain structure from the viewpoint of easily improving stress relaxation properties and flexibility.
  • R in the chain structure may be linear or branched.
  • n is preferably 5-200, more preferably 10-150, even more preferably 20-50.
  • R is preferably 5-12.
  • R contained in the polycarbonate polyol constituting the moisture-curable urethane resin may be used singly or in combination of two or more. When two or more of them are used in combination, at least a part thereof is preferably a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms.
  • the chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.
  • R may be linear groups such as a tetramethylene group, pentylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and, for example, a 3-methylpentylene group. It may be branched such as a methylpentylene group such as a methylpentylene group or a methyloctamethylene group. Plural R's in one molecule may be the same or different. Therefore, one molecule may contain two or more types of R, and in that case, one molecule preferably contains two or three types of R.
  • the polycarbonate polyol may be a copolymer containing R having 6 or less carbon atoms and R having 7 or more carbon atoms in one molecule. It is preferable that it is a hydrogen group.
  • R may contain a linear saturated aliphatic hydrocarbon group, or may contain a branched saturated aliphatic hydrocarbon group.
  • branched and linear R may be used in combination, or linear R may be used alone.
  • polycarbonate polyol may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds are preferably used as polyisocyanate compounds that are raw materials for moisture-curable urethane resins.
  • aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
  • aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate. , bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like.
  • the polyisocyanate compound is preferably an aromatic polyisocyanate compound, and more preferably diphenylmethane diisocyanate, from the viewpoint of increasing the adhesive strength after complete curing.
  • Aliphatic polyisocyanate compounds are preferred from the viewpoint of easily imparting stress relaxation properties, flexibility, etc. to the cured product of the light and moisture-curable resin composition.
  • a polyisocyanate compound may be used independently and may be used in combination of 2 or more type.
  • a moisture-curable urethane resin having a polyester skeleton is obtained by introducing a polyester skeleton into a urethane resin by using a polyester polyol as the polyol compound.
  • a moisture-curable urethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. can.
  • polyester polyols examples include polyester polyols obtained by reacting polyvalent carboxylic acids with polyols, poly- ⁇ -caprolactone polyols obtained by ring-opening polymerization of ⁇ -caprolactone, and the like.
  • polyvalent carboxylic acids that are raw materials for polyester polyols include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. , suberic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid, and the like.
  • polyester polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol. , diethylene glycol, cyclohexanediol, and the like.
  • 1,6-hexanediol or 1,4-butanediol is preferable from the viewpoint of easily increasing adhesive strength at high temperatures.
  • the polyisocyanate compound mentioned above can be used as a polyisocyanate compound.
  • polyester polyol may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a moisture-curable urethane resin having a polyether skeleton is obtained by introducing a polyether skeleton into a urethane resin by using a polyether polyol as the polyol compound.
  • a urethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule. .
  • Polyether polyols include, for example, polyethylene glycol, polypropylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, random copolymers or block copolymers of these or their derivatives, bisphenol type polyoxyalkylene modified products of and the like.
  • the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by addition reaction of an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton. be.
  • an alkylene oxide e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.
  • the polyether polyol may be a random copolymer or a block copolymer.
  • one or more alkylene oxides are preferably added to both ends of the bisphenol-type molecular skeleton.
  • the bisphenol type is not particularly limited, and includes A type, F type, S type and the like, preferably bisphenol A type.
  • the polyisocyanate compound mentioned above can be used as a polyisocyanate compound.
  • the moisture-curable urethane resin having a polyether skeleton preferably further includes one obtained using a polyol compound having a structure represented by the following formula (2).
  • a polyol compound having a structure represented by the following formula (2) it is possible to obtain a light and moisture-curable resin composition with excellent adhesiveness and a cured product that is flexible and has good elongation, and a radically polymerizable compound It has excellent compatibility with (A).
  • polypropylene glycol a ring-opening polymer compound of tetrahydrofuran (THF), or a methyl group such as 3-methyltetrahydrofuran
  • THF tetrahydrofuran
  • the ring-opening polymerization compound of tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol.
  • polyether polyol may be used individually by 1 type, and may be used in combination of 2 or more type.
  • 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
  • n is an integer of 1 to 10.
  • l is preferably 0-4, m is preferably 50-200, and n is preferably 1-5.
  • the case where l is 0 means the case where the carbon bonded to R is directly bonded to oxygen.
  • the sum of n and l is more preferably 1 or more, more preferably 1 to 3.
  • R is more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
  • the above-described moisture-curable urethane resin having a polycarbonate, polyester, or polyether skeleton may have two or more skeletons in the molecule, and may have, for example, a polycarbonate skeleton and a polyester skeleton. In that case, it is preferable to use polycarbonate polyol and polyester polyol as the polyol compound as the raw material. Similarly, a moisture-curable urethane resin having a polyester skeleton and a polyether skeleton may also be used. Also, the moisture-curable urethane resin preferably contains an isocyanate group as described above, but is not limited to one containing an isocyanate group. A decomposable silyl group-containing urethane resin may be used.
  • the hydrolyzable silyl group-containing resin used in the present invention cures when the hydrolyzable silyl group in the molecule reacts with moisture in the air or in the adherend.
  • the hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more hydrolyzable silyl groups. Among them, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule. Note that the hydrolyzable silyl group-containing resin does not include those having an isocyanate group.
  • a hydrolyzable silyl group is represented by the following formula (3).
  • each R 1 is independently an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or , —OSiR 2 3 (each R 2 is independently a hydrocarbon group having 1 to 20 carbon atoms).
  • each X is independently a hydroxy group or a hydrolyzable group.
  • a is an integer of 1-3.
  • the hydrolyzable group is not particularly limited, and examples thereof include halogen atoms, alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and the like. is mentioned. Among them, a halogen atom, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable because of their high activity. Further, alkoxy groups such as methoxy and ethoxy groups are more preferred, and methoxy and ethoxy groups are even more preferred, since they are moderately hydrolyzable and easy to handle. From the viewpoint of safety, an ethoxy group and an isopropenoxy group, which are ethanol and acetone, respectively, are preferred.
  • the hydroxy group or the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3. When two or more hydroxy groups or hydrolyzable groups are bonded to one silicon atom, those groups may be the same or different.
  • a in the above formula (3) is preferably 2 or 3, and particularly preferably 3. From the viewpoint of storage stability, a is preferably 2.
  • R 1 in the above formula (3) include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, aralkyl groups such as a benzyl group, and trimethylsiloxy groups. , chloromethyl group, methoxymethyl group and the like. Among them, a methyl group is preferred.
  • hydrolyzable silyl group examples include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, (chloromethyl)dimethoxysilyl group, ( chloromethyl)diethoxysilyl group, (dichloromethyl)dimethoxysilyl group, (1-chloroethyl)dimethoxysilyl group, (1-chloropropyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (ethoxymethyl)dimethoxysilyl group, (1-methoxyethyl)dimethoxysilyl group, (aminomethyl)dimethoxysilyl group, (N,N-dimethylaminomethyl)dimethoxysilyl group, (N,N-diethyla
  • Hydrolyzable silyl group-containing resins include, for example, hydrolyzable silyl group-containing (meth)acrylic resins, molecular chain terminals or organic polymers having hydrolyzable silyl groups at molecular chain terminal sites, and hydrolyzable silyl group-containing resins.
  • a urethane resin etc. are mentioned.
  • the hydrolyzable silyl group-containing (meth)acrylic resin preferably has repeating structural units derived from a hydrolyzable silyl group-containing (meth)acrylic acid ester and/or (meth)acrylic acid alkyl ester in the main chain.
  • hydrolyzable silyl group-containing (meth)acrylate esters examples include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, and (meth)acrylic acid.
  • Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate.
  • a hydrolyzable silyl group-containing (meth)acrylic resin specifically, for example, a hydrolyzable silicon group-containing (meth)acrylic acid ester polymer described in International Publication No. 2016/035718 Synthetic methods for coalescing and the like can be mentioned.
  • the above-mentioned organic polymer having a hydrolyzable silyl group at the molecular chain terminal or the molecular chain terminal portion has a hydrolyzable silyl group at least one of the terminal of the main chain and the terminal of the side chain.
  • the skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth)acrylic acid ester-based polymers.
  • polyoxyalkylene polymer examples include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, a polyoxypropylene-poly Examples thereof include polymers having an oxybutylene copolymer structure.
  • Specific examples of the method for producing an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or the molecular chain terminal site include, for example, the molecular chain terminal or A method for synthesizing an organic polymer having a crosslinkable silyl group only at the terminal site of the molecular chain can be mentioned.
  • hydrolyzable silyl group-containing urethane resin for example, when producing a urethane resin by reacting a polyol compound and a polyisocyanate compound, a silyl group-containing compound such as a silane coupling agent is further added.
  • a reaction method and the like can be mentioned. Specific examples thereof include a method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in JP-A-2017-48345.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxy-ethoxy)silane, ⁇ -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, ⁇ -glycidoxysilane.
  • ⁇ -mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the moisture-curable urethane resin may have both an isocyanate group and a hydrolyzable silyl group.
  • a moisture-curable urethane resin having both an isocyanate group and a hydrolyzable silyl group is obtained by first obtaining a moisture-curable urethane resin (raw material urethane resin) having an isocyanate group by the method described above, and further adding It is preferable to manufacture by reacting a silane coupling agent.
  • the details of the moisture-curable urethane resin having an isocyanate group are as described above.
  • the silane coupling agent to be reacted with the raw material urethane resin may be appropriately selected from those listed above and used, but from the viewpoint of reactivity with the isocyanate group, a silane coupling agent having an amino group or a mercapto group is used. preferably.
  • Preferred specific examples are N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane.
  • the moisture-curable resin may have a radically polymerizable functional group.
  • a group having an unsaturated double bond is preferable, and a (meth)acryloyl group is particularly preferable from the viewpoint of reactivity.
  • a moisture-curable resin having a radically polymerizable functional group is not included in the radically polymerizable compounds described above, and is treated as a moisture-curable resin (B).
  • the moisture-curable resin (B) may be appropriately selected from the various resins described above and used singly or in combination of two or more.
  • the weight average molecular weight of the moisture-curable resin (B) is preferably 7500 or more and 24000 or less. By setting the weight-average molecular weight within the above range, it becomes easier to increase the initial adhesive strength of the light and moisture-curable resin composition. In addition, by making it equal to or less than the above upper limit, it becomes easy to improve the final heat resistant adhesive strength. From these viewpoints, the weight average molecular weight of the moisture-curable resin (B) is more preferably 7800 or more, more preferably 10000 or more, still more preferably 11500 or more, more preferably 20000 or less, and further preferably 16000 or less. 15000 or less is even more preferable. In addition, the said weight average molecular weight in this specification is a value which measures by a gel permeation chromatography (GPC), and is calculated
  • GPC gel permeation chromatography
  • the moisture-curable resin may be chain-extended to increase the weight-average molecular weight to a certain value or more as described above.
  • a urethane resin having an isocyanate group obtained by reacting a polyol compound with a polyisocyanate compound having two or more isocyanate groups in one molecule (hereinafter referred to as "raw material urethane resin) may be further reacted with a chain extender.
  • the chain extender is preferably used in an appropriate amount so that the isocyanate groups remain in the moisture-curable urethane resin without reacting all of the isocyanate groups in the raw material urethane resin with the chain extender.
  • the raw material urethane resin may be further reacted with the chain extender reacted with the raw material urethane resin.
  • a polyol compound is preferable as the chain extender used in the moisture-curable urethane resin. Details of the polyol compound are as described above.
  • the polyol compound as the chain extender the same kind of polyol compound as the polyol compound used for synthesizing the raw material urethane resin may be used. Therefore, if the polyol compound used to synthesize the starting urethane resin is a polycarbonate polyol, the chain extender may also be a polycarbonate polyol.
  • the amount of the chain extender used is, when the total amount of the raw material urethane resin and the chain extender is 100 parts by mass, For example, 5 parts by mass or more and 40 parts by mass or less, preferably 10 parts by mass or more and 35 parts by mass or less, more preferably 15 parts by mass or more and 30 parts by mass or less.
  • the mass ratio (B/A) of the moisture-curable resin (B) to the radical polymerizable compound (A) is preferably 30/70 or more and 90/10 or less, and 40/60 or more and 80 /20 or less is more preferable, and 50/50 or more and 70/30 or less is even more preferable.
  • the mass ratio is within these ranges, it is possible to impart photocurability and moisture curability to the light and moisture-curable resin composition in a well-balanced manner, and to adjust both the initial adhesive strength and the final heat-resistant adhesive strength within the desired range. easier to do.
  • the light and moisture-curable resin composition may contain resin components other than the radically polymerizable compound (A) and the moisture-curable resin (B) as resin components within a range that impairs the effects of the present invention,
  • resin component such as a non-curable thermoplastic resin (for example, an acrylic resin, a urethane resin, etc.), a thermosetting resin, or the like.
  • the ratio of resin components other than the radically polymerizable compound (A) and the moisture-curable resin (B) is, for example, 50 parts per 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). It is no more than 30 parts by mass, more preferably no more than 10 parts by mass.
  • the light moisture-curable resin composition of the present invention contains a photopolymerization initiator.
  • the photo-moisture-curable resin composition contains a photopolymerization initiator, so that photocurability is appropriately imparted.
  • photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone. be done.
  • Examples of commercially available photopolymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF), and Inbenzo. ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the like.
  • the content of the photopolymerization initiator in the light moisture-curable resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass, relative to 100 parts by mass of the radically polymerizable compound (A). It is at least 5 parts by mass and no more than 5 parts by mass.
  • the content of the photopolymerization initiator is within these ranges, the resulting photo-moisture-curable resin composition has excellent photocurability and storage stability.
  • the photoradical polymerizable compound is appropriately cured, and the adhesive strength tends to be improved.
  • the light-moisture-curable resin composition of the present invention contains a compound (D) having three or more isocyanate groups in the molecule (hereinafter sometimes simply referred to as compound (D)).
  • compound (D) By including the compound (D), the light and moisture-curable resin composition forms a crosslinked structure in the moisture-cured product, so that the bulk strength increases and the heat-resistant adhesive strength (final heat-resistant adhesive strength) after moisture curing increases. improves. Therefore, as described above, even if the molecular weight of the moisture-curable resin (B) is increased, the bulk strength of the cured product does not decrease, and the final heat-resistant adhesive strength can be improved.
  • the compound (D) is a compound other than the moisture-curable resin (B) described above and may be a compound having three or more isocyanate groups.
  • Compound (D) is preferably a compound having a molecular weight (formula weight) of 1500 or less, for example.
  • Examples of the compound (D) include polyisocyanate-modified products obtained by reacting a polyisocyanate compound with another compound.
  • modified polyisocyanates include buret modified polyisocyanate compounds, isocyanurate modified polyisocyanate compounds, glycerin, trimethylolpropane, or polyols obtained by addition polymerization of alkylene oxides such as propylene oxide and ethylene oxide to these polyols.
  • Polyol-modified products which are adducts obtained by reacting isocyanate compounds, and polymethylene polyphenyl polyisocyanate, which is also called polymeric MDI, can be used.
  • At least part of the isocyanate groups contained in compound (D) may be temporarily protected by a blocking agent, uretdione structure, or the like.
  • the isocyanate group contained in the compound (D) is regenerated by dissociation of the blocking agent, cleavage of the uretdione structure, etc. during use of the light and moisture-curable resin composition.
  • the polyisocyanate compound used as a raw material in the modified product include monomers having no repeating unit.
  • the polyisocyanate compound is preferably a diisocyanate compound.
  • aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, Hydrogenated MDI, norbornane diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, aliphatic isocyanate compounds such as tetramethylxylylene diisocyanate, and the like.
  • aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, iso
  • compounds other than the modified polyisocyanate described above may be used, and polyisocyanates such as triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, and 1,6,11-undecane triisocyanate. It may be a compound.
  • polyisocyanate-modified products are preferred, and isocyanurate-modified products and polymeric MDI are more preferred.
  • the compound (D) preferably has three or more isocyanate groups, and may be a compound having three isocyanate groups. , preferably contains a compound having four or more isocyanate groups, and more preferably contains a compound having five or more isocyanate groups.
  • the upper limit of the number of isocyanate groups in compound (D) is not particularly limited, it is, for example, 10 or less, preferably 8 or less.
  • Examples of the compound having three isocyanate groups include burette modified products, isocyanurate modified products, and polyol modified products, and isocyanurate modified products are preferable.
  • a preferred specific example of the compound having 4 or 5 or more isocyanate groups is polymeric MDI.
  • Compound (D) having three or more isocyanate groups may be a mixture of compounds having different numbers of isocyanate groups, and therefore the number of isocyanate groups in compound (D) may be represented by the average number of isocyanate groups.
  • the average number of isocyanate groups of the compound (D) may be 3 or more, preferably 4 or more, more preferably 5 or more, in order to further improve the heat resistant adhesive strength.
  • the upper limit of the average number of isocyanate groups of the compound (D) is not particularly limited, it is, for example, 10 or less, preferably 8 or less, and more preferably 6.5 or less.
  • the content of the compound (D) in the light moisture-curable resin composition is 0.1 parts by mass or more and 10 parts by mass with respect to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B). It is preferably less than or equal to parts.
  • the compound (D) can form a sufficient crosslinked structure in the cured product after moisture curing, and the final heat resistant adhesive strength can be easily increased.
  • by making it 10 parts by mass or less it is possible to prevent the initial adhesive strength from being lowered due to the influence of the compound (D).
  • the content of the compound (D) is more preferably 0.2 parts by mass or more with respect to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B). It is more preferably 3 parts by mass or more, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.
  • the light and moisture-curable resin composition may contain a diisocyanate compound having two isocyanate groups in addition to the compound (D) having three or more isocyanate groups in the molecule.
  • Specific examples of the diisocyanate compound used here include the diisocyanate compounds listed as raw materials for the modified polyisocyanate.
  • the diisocyanate compound as a raw material may not react in the production process and may remain as an unreacted diisocyanate compound. It may be blended in the light-moisture-curable resin composition.
  • polymethylene polyphenyl polyisocyanate having three or more isocyanate groups may be mixed with MDI, which is a diisocyanate compound, into the light and moisture-curable resin composition.
  • MDI polymethylene polyphenyl polyisocyanate
  • the content of the diisocyanate compound in the light and moisture-curable resin composition is not particularly limited, it is preferably less than the content of the compound (D) on a mass basis, for example.
  • the light and moisture-curable resin composition of the present invention may contain a filler (E).
  • a filler (E) By containing the filler (E), the light and moisture-curable resin composition of the present invention has suitable thixotropy and can sufficiently retain its shape after application.
  • a particulate filler may be used as the filler.
  • the filler (E) is preferably an inorganic filler such as silica, talc, titanium oxide, zinc oxide and calcium carbonate. Among these, silica is preferable because the obtained light and moisture-curable resin composition has excellent ultraviolet transmittance.
  • the filler (E) may be subjected to a hydrophobic surface treatment such as silylation treatment, alkylation treatment or epoxidation treatment.
  • a filler (E) may be used individually by 1 type, and 2 or more types may be used in combination.
  • the content of the filler (E) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 2 parts by mass, with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). It is 3 parts by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less.
  • the light and moisture-curable resin composition may contain a moisture-curing acceleration catalyst that accelerates the moisture-curing reaction of the moisture-curable resin (B).
  • a moisture-curing acceleration catalyst By using a moisture-curing acceleration catalyst, the moisture-curing property of the photo-moisture-curable resin composition becomes more excellent, and the adhesive strength can be easily increased.
  • Specific examples of moisture curing acceleration catalysts include amine-based compounds and metal-based catalysts.
  • Examples of amine compounds include compounds having a morpholine skeleton such as di(methylmorpholino) diethyl ether, 4-morpholinopropyl morpholine, 2,2′-dimorpholino diethyl ether, bis(2-dimethylaminoethyl) ether, 1,2 -Dimethylamino group-containing amine compounds having two dimethylamino groups such as bis(dimethylamino)ethane, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4 -diazabicyclo[2.2.2]octane and the like.
  • a morpholine skeleton such as di(methylmorpholino) diethyl ether, 4-morpholinopropyl morpholine, 2,2′-dimorpholino diethyl ether, bis(2-dimethylaminoethyl) ether, 1,2 -Dimethylamin
  • metal-based catalysts examples include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate and tin octylate; zinc compounds such as zinc octoate and zinc naphthenate; zirconium tetraacetylacetonate; copper naphthenate; Other metal compounds such as cobalt naphthenate are included.
  • the content of the moisture curing acceleration catalyst is preferably 0.01 to 8 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the moisture-curable resin (B).
  • the content of the moisture-curing accelerating catalyst is within the above range, the effect of accelerating the moisture-curing reaction is excellent without deteriorating the storage stability and the like of the light moisture-curable resin composition.
  • the light and moisture-curable resin composition of the present invention may contain a colorant.
  • coloring agents include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black.
  • the light-moisture-curable resin composition has good light-shielding properties.
  • titanium black is preferred. Titanium black has the property of sufficiently shielding light with a wavelength in the visible light region and transmitting light with a wavelength near the ultraviolet region, so it prevents the photocurability of the light moisture-curable resin composition from deteriorating. can.
  • the content of the colorant in the light and moisture-curable resin composition is preferably 0.05 parts by mass or more and 8 parts by mass with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). part or less, more preferably 0.1 to 2 parts by mass.
  • the light and moisture-curable resin composition may contain other additives such as coupling agents, wax particles, ionic liquids, expanded particles, expanded particles, and reactive diluents. good.
  • the coupling agent include silane coupling agents, titanate-based coupling agents, zirconate-based coupling agents, etc. Among these, silane coupling agents are preferred.
  • the light-moisture-curable resin composition generally does not contain a solvent, but may contain a solvent, if necessary, to the extent that the effects of the present invention are not impaired.
  • the light and moisture-curable resin composition of the present invention has a viscosity measured at 25° C. and 5.0 rpm using a cone-plate viscometer (hereinafter also referred to as “25° C. viscosity”) of 40 Pa s to 600 Pa s. s or less.
  • the 25° C. viscosity of the moisture-curable resin composition described above is measured under a high shear of 5.0 rpm, and is a viscosity that is not easily affected by fillers. Therefore, if the viscosity at 25° C.
  • the low-molecular-weight components contained in the moisture-curable resin (B) tend to decrease, and the moisture-curable resin (B) etc. permeates the interface after light irradiation. It becomes difficult to take out, and it becomes easy to improve the initial adhesive strength. That is, when the low-molecular-weight moisture-curable resin (B) or the like hardly seeps out to the interface after light irradiation, it becomes difficult for slippage to occur between the adherend and the adhesive force, and the initial adhesive force is improved as a result. make it easier to In the present invention, by increasing the 25° C.
  • the moisture-curable resin composition contains a large amount of high-molecular-weight components, and the content of moisture-curable functional groups tends to decrease.
  • the bulk strength after moisture curing may be lowered, but by including the compound (D) described above, the bulk strength after moisture curing is increased and the final heat resistant adhesive strength is improved.
  • the viscosity at 25 ° C. is 600 Pa s or less
  • the inherent tackiness of the moisture-curable resin (B) is likely to be expressed, thereby easily improving the initial adhesive strength and final heat-resistant adhesive strength.
  • problems such as dripping and inability to apply at room temperature are less likely to occur, thereby improving workability.
  • the 25 ° C. viscosity of the light and moisture-curable resin composition is more preferably 45 Pa s or more, more preferably 90 Pa s or more, even more preferably 110 Pa s or more, and more preferably 500 Pa s or less, and 350 Pa s. s or less is more preferable, and 230 Pa ⁇ s or less is even more preferable.
  • the 25° C. viscosity is within the above range, it becomes easier to improve workability and initial adhesive strength.
  • it is equal to or less than the above upper limit it is possible to prevent the molecular weight of the moisture-curable resin (A) from becoming excessively high, so that the initial adhesive strength is likely to be improved, and furthermore, the adhesive strength is sufficiently high due to moisture curing. It becomes easier to improve the final heat-resistant adhesive strength.
  • the light moisture-curable resin composition of the present invention is applied linearly to an aluminum substrate under the predetermined conditions described later, and when the glass plate is further pressed after being photocured with UV, the adhesive portion on the glass plate side a/b (also referred to as "inner/outer ratio a/b") is, for example, 0.5 or more and 0.99 or less, where a is the average width of the aluminum substrate side and b is the average width of the bonded portion on the aluminum substrate side.
  • the inside-outside ratio a/b is 0.5 or more, the light-moisture-curable resin composition of the present invention has a large inside-outside ratio a/b, and is easily crushed immediately after photocuring.
  • Adhesion increases, and the initial adhesive strength to the adherend tends to increase.
  • the inside/outside ratio a/b is more preferably 0.58 or more, more preferably 0.63 or more, still more preferably 0.7 or more, more preferably 0.95 or less, and still more preferably 0.93 or less.
  • the inside/outside ratio a/b is within these ranges, the initial adhesive strength can be easily improved.
  • the inside/outside ratio a/b is measured as follows. First, as shown in FIG. 1A, a moisture-curable resin composition 10 is applied to an aluminum substrate 11 with a line width of 1.0 mm. Here, the line width of 1.0 mm does not need to be exactly 1.0 mm, and may have an error of 1.0 ⁇ 0.1 mm. Next, as shown in FIG. 1B, the moisture-curable resin composition 10 is irradiated with ultraviolet rays of 1000 mJ/cm 2 to cure the moisture-curable resin composition 10 . Immediately thereafter (within 10 seconds), as shown in FIG. The area is pressed at 0.08 MPa for 120 seconds.
  • the width a1 of the bonded portion of the moisture-curable resin composition 10 to the glass plate 12 is measured.
  • the width a1 is measured at five points, and the average value thereof is taken as the average width a.
  • the width b1 of the adhesion portion of the moisture-curable resin composition 10 to the aluminum substrate 11 is measured.
  • the width b1 is measured at five points, the average value thereof is taken as the average width b, and the inside/outside ratio a/b is calculated from the average widths a and b. It should be noted that the crimping should be performed using a weight, and the widths a1 and b1 should be measured 5 minutes after removing the weight.
  • the inside/outside ratio a/b can be adjusted within the above range by adjusting the type of the radically polymerizable compound. For example, when the light and moisture-curable resin composition contains a large amount of a monofunctional radically polymerizable compound as the radically polymerizable compound, the ratio of the crosslinked structure formed after photocuring is reduced, so the inside/outside ratio a/b should be increased. can be done. Further, for example, even if the optical moisture-curable resin composition contains a large amount of a radically polymerizable compound having a low homopolymer glass transition point as a radically polymerizable compound, the cured product after photocuring becomes flexible, so that the internal/external ratio a /b can be increased. Furthermore, it can also be adjusted by the weight average molecular weight of the moisture-curable resin (B).
  • the light moisture-curable resin composition of the present invention may have an initial adhesive strength of, for example, 0.05 MPa or more, and preferably 0.1 MPa or more. Further, the light moisture-curable resin composition of the present invention preferably has a final heat-resistant adhesive strength of 1.0 MPa or more.
  • the initial adhesive strength means the adhesive strength at 25 ° C. immediately after photocuring the light and moisture-curable resin composition
  • the final heat resistant adhesive strength refers to the photocuring of the light and moisture-curable resin composition
  • it means the adhesive force measured in a 70° C. environment after being left at 25° C. and 50 RH% for 24 hours. The details of the method for measuring the initial adhesive strength and the final heat-resistant adhesive strength are as described in Examples below.
  • the light-moisture-curable resin composition can temporarily bond the adherends to each other immediately after photocuring with an adhesive strength of a certain level or more, and at the time of temporary bonding. Workability is improved. Further, when the final heat-resistant adhesive strength is 1.0 MPa or more, the adherends can be strongly bonded together by the final adhesion by moisture curing after temporary adhesion even in a high-temperature environment.
  • the light and moisture-curable resin composition preferably has an initial adhesive strength of 0.2 MPa or more in order to further increase the adhesive stability during temporary adhesion.
  • the initial adhesive strength is not particularly limited, but is preferably less than 1.5 MPa, for example, in order to facilitate re-sticking at the time of temporary adhesion.
  • the final heat-resistant adhesive strength of the light and moisture-curable resin composition is more preferably 2.0 MPa or more in order to more firmly bond the adherends after the main adhesion.
  • the final heat-resistant adhesive strength is not particularly limited as the higher the better, but it is, for example, 20 MPa or less, and may be 10 MPa or less.
  • a mixer is used to prepare a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound ( D), Furthermore, a method of mixing other additives such as a filler, a moisture curing acceleration catalyst, a colorant, etc., which are blended as necessary, may be used.
  • mixers include homodispers, homomixers, universal mixers, planetary mixers, planetary mixers, kneaders, and three rolls.
  • the molecular weight of a moisture-curable resin such as a moisture-curable urethane resin may be increased by using a chain extender.
  • a raw material resin such as a raw material urethane resin is reacted in advance with a chain extender to obtain a moisture-curable resin (B), and then, as described above, the radically polymerizable compound (A), photopolymerization, It may be mixed with other raw materials such as initiator (C) and compound (D).
  • the raw material resin, the chain extender, and the radically polymerizable compound (A) are mixed, and the mixture is heated, if necessary, to react the chain extender with the raw material resin, resulting in a moisture-curing property.
  • Resin (B) may be synthesized. In this case, a mixture of the moisture-curable resin (B) and the radical polymerizable compound (A) is obtained.
  • Other additives may be added to obtain a light and moisture-curable resin composition.
  • the light and moisture-curable resin composition of the present invention is cured and used as a cured product.
  • the photo-moisture-curable resin composition of the present invention is first photo-cured by light irradiation to, for example, a B-stage state (semi-cured state), and then fully cured by curing with moisture. good.
  • the optical moisture-curable resin composition when placed between adherends and the adherends are to be joined together, it is applied to one of the adherends, and then photocured by light irradiation, For example, when the B-stage state is set, the other adherend is superimposed on the light moisture-curable resin composition in the photocured state, and the adherend is temporarily adhered with an appropriate adhesive strength (initial adhesive strength). good. After that, the optical moisture-curable resin composition in the B-stage state is completely cured by curing the moisture-curable resin with moisture, and the adherends superimposed via the optical moisture-curable resin composition are separated from each other. Glued and joined with sufficient adhesive strength.
  • the application of the light and moisture-curable resin composition to the adherend is preferably performed by, for example, a dispenser, but is not particularly limited.
  • the light for photocuring is not particularly limited as long as it cures the radically polymerizable compound, but ultraviolet light is preferred.
  • the photo-moisture-curable resin composition is to be completely cured by moisture after being photocured, it may be left in the air for a predetermined period of time.
  • the application of the light moisture-curable resin composition to the adherend is not particularly limited, it is preferably carried out at around room temperature, specifically at a temperature of about 10 to 35°C.
  • the light-moisture-curable resin composition of the present invention has a 25° C.
  • the photo-moisture-curable resin composition of the present invention exhibits an initial adhesive strength of a certain value or more immediately after light irradiation, temporary adhesion can be performed immediately after light curing, resulting in good workability.
  • the light and moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic parts. That is, the present invention also provides an adhesive for electronic parts comprising the above-mentioned light moisture-curable resin composition. Therefore, the adherends described above are preferably various electronic components constituting electronic devices. Examples of various electronic components that make up an electronic device include, for example, various electronic components that are provided in a display element and that make up an electronic circuit, substrates on which the electronic components are attached, housings that make up the electronic device, semiconductor chips, and the like. be done.
  • the material of the adherend may be metal, glass, plastic, or the like.
  • the shape of the adherend is not particularly limited, and examples thereof include film-like, sheet-like, plate-like, panel-like, tray-like, rod-like, box-like, and housing-like shapes. .
  • the light and moisture-curable resin composition of the present invention is preferably used for bonding electronic parts constituting electronic equipment. Moreover, the light and moisture-curable resin composition of the present invention is preferably used for bonding electronic parts to other parts. With these configurations, the electronic component has the cured body of the present invention. Moreover, the optical moisture-curable resin composition of the present invention is used in the inside of an electronic device, for example, to obtain an assembly part by bonding substrates together. The assembly part thus obtained has a first substrate, a second substrate, and the cured product of the present invention, wherein at least a portion of the first substrate is at least a portion of the second substrate. is joined through a hardened body. Note that the first substrate and the second substrate are preferably attached with electronic components that form at least one electronic circuit, respectively.
  • the light and moisture-curable resin composition of the present invention is preferably used for narrow frame applications.
  • an adhesive is applied on a narrow rectangular frame-shaped (that is, a narrow frame) base, and display is performed through the adhesive. Panels, touch panels, etc. are assembled, and the light and moisture-curable resin composition of the present invention is preferably used as an adhesive therefor.
  • the light-moisture-curable resin composition of the present invention is used for semiconductor chips, for example, to bond semiconductor chips together.
  • the weight-average molecular weight of the moisture-curable resin (B) in each example and comparative example was measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion.
  • GPC measurement used Shodex KF-806L (manufactured by Showa Denko KK) as a column. Tetrahydrofuran (THF) was used as the solvent and mobile phase.
  • GPC measurement conditions were a flow rate of 1.0 ml/min and a measurement temperature of 40°C.
  • the weight average molecular weight was measured using a mixture of the radically polymerizable compound (A) and the moisture-curable resin (B) as a sample.
  • the peak of the radical polymerizable compound (A) appears on the low molecular weight side
  • the peak of the moisture-curable resin (B) appears on the high molecular weight side.
  • Average molecular weight can be determined.
  • the inside/outside ratio a/b was measured by the method described in the specification.
  • an aluminum alloy "A6063S” having a size of 2 mm ⁇ 25 mm ⁇ 60 mm, and a glass plate having a smooth surface after ultrasonic cleaning for 5 minutes were used.
  • Application of the moisture-curable resin composition is performed at room temperature (25 ° C.) using a dispensing device “SHOTMASTER 300SX” manufactured by Musashi Engineering Co., Ltd., with a width of 1.0 ⁇ 0.1 mm, a length of 25 mm, and a thickness of It was applied linearly to the aluminum substrate so as to be 0.4 ⁇ 0.1 mm.
  • the applied light-moisture-curable resin composition was irradiated with ultraviolet rays having a wavelength of 405 nm at 1000 mW and 1000 mJ/cm 2 from a line type LED irradiator (manufactured by HOYA Corporation).
  • the pressure bonding of the glass plate to the aluminum substrate was performed using a weight as a weight, and the widths a1 and b1 were measured 5 minutes after removing the weight.
  • the widths a1 and b1 after pressure bonding were measured by observing the pressure bonding surface from the glass plate side using a microscope.
  • the aluminum substrate 21 was coated with a width of 1.0 ⁇ 0.1 mm, a length of 25 mm, and a thickness of 0.4 ⁇ 0.1 mm using the dispensing apparatus described above.
  • the light moisture-curable resin composition 20 was applied at room temperature (25° C.) such that Then, it was photo-cured by irradiating 1000 mJ/cm 2 of ultraviolet rays having a wavelength of 405 nm at 1000 mW with a line-type LED irradiator (manufactured by HOYA Corporation).
  • a glass plate 22 is attached to an aluminum substrate 21 via a light-cured light-moisture-curable resin composition 20, and pressed at 0.08 MPa for 120 seconds using a weight to obtain an adhesion evaluation sample 23. Obtained.
  • the aluminum substrate 21 and the glass plate 22 were pulled in the shearing direction S at a speed of 10 mm/min using a tensile tester (“Tension/compression tester SVZ-50NB” manufactured by Imada Seisakusho) in an atmosphere of 25°C.
  • the maximum stress at the time of peeling was measured and defined as the initial adhesive strength.
  • the time from the end of photocuring to the start of the tensile test was within 150 seconds.
  • the initial adhesive strength was evaluated according to the following evaluation criteria. A: 0.2 MPa or more B: 0.1 MPa or more and less than 0.2 MPa C: less than 0.1 MPa
  • the urethane resin raw material used in each example and comparative example was produced by the following method.
  • Synthesis Example 1 PC urethane resin raw material
  • 100 parts by mass of polycarbonate diol compound represented by formula (1), 90 mol% of R is 3-methylpentylene group, 10 mol% is hexamethylene group, manufactured by Kuraray Co., Ltd., trade name "Kuraraypolyol C -1090" and 0.01 part by mass of dibutyltin dilaurate were placed in a 500 mL separable flask. The inside of the flask was stirred and mixed at 100° C. for 30 minutes under vacuum (20 mmHg or less).
  • the pressure is adjusted to normal pressure, and 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name “Pure MDI”) is added as a polyisocyanate compound, stirred at 80 ° C. for 3 hours to react, and has a polycarbonate skeleton and both ends.
  • a moisture-curable urethane resin (raw material for PC urethane resin) having an isocyanate group was obtained.
  • the weight average molecular weight of the obtained urethane resin raw material was 6,700.
  • Example 1 To 40 parts by mass of acrylic B as shown in Table 5, 60 parts by mass of each raw material constituting the moisture-curable resin (PC-L25) was added. Acrylic B was obtained by mixing each compound at the compounding ratio shown in Table 2. As a moisture-curable resin (PC-L25), a PC urethane resin raw material and a PC polyol were added in order to Acrylic B at the mass ratio shown in Table 3 to obtain a mixture. As the PC polyol, the polycarbonate diol used in Synthesis Example 1 was used.
  • Examples 2, 3, 5 instead of polyfunctional isocyanate a, polyfunctional isocyanate b was used, and the procedure was carried out in the same manner as in Example 1, except that the blending amount was changed as shown in Table 5.
  • Example 4 Polyfunctional isocyanate b, a photopolymerization initiator, a filler, and a colorant were added to the resulting mixture of acrylic B and moisture-curable urethane resin according to the formulation shown in Table 5 and mixed to obtain a light-moisture-curable resin composition. It was carried out in the same manner as in Example 3, except that a product was obtained.
  • Example 6 As the moisture-curable resin, instead of the moisture-curable resin (PC-L25), as described in Tables 4 and 5, the same as in Example 3 except that the moisture-curable resin (ET-L25) was used. was carried out on That is, except that the mixing ratio and type of urethane resin raw materials and polyols added to acrylic B were changed as shown in Table 4 to obtain a mixture of acrylic B and moisture-curable urethane resin, It was carried out in the same manner as in 3. As the ET polyol in Table 4, the polytetramethylene ether glycol used in Synthesis Example 2 was used.
  • Example 3 was repeated except that acrylics C, D and A were used instead of acrylic B. Each of the acrylics C, D, and A was obtained by mixing each compound at the compounding ratio shown in Table 2.
  • Comparative Examples 1 to 5 were carried out in the same manner as Examples 1 and 6 to 9, respectively, except that no polyfunctional isocyanate was blended.
  • Example 7 It was carried out in the same manner as in Example 6, except that difunctional isocyanate (MDI) was used instead of polyfunctional isocyanate.
  • MDI difunctional isocyanate
  • polyfunctional isocyanate a is an isocyanurate modified product, which is a compound having three isocyanate groups in the molecule.
  • Polyfunctional isocyanate b is a mixture of MDI (difunctional isocyanate) and polymeric MDI (polymethylene polyphenyl polyisocyanate: compound (D)) having three or more isocyanate groups, and the proportion of MDI is 40% by mass.
  • the proportion of polymeric MDI is 60% by weight.
  • the average number of isocyanate groups in polymeric MDI is 5-6.
  • Acrylics A to D used in Examples and Comparative Examples were as follows.
  • the moisture-curable resins (B) used in Examples and Comparative Examples were as shown in Tables 3 and 4 below. As described above, the reaction product of the following urethane resin raw material and polyol was used as the moisture-curable resin (B).
  • the photo-moisture-curable resin compositions of Examples 1 to 9 have 3 isocyanate groups in the molecule. Since the compound (D) having two or more compounds was contained, the final heat-resistant adhesive strength after moisture curing was increased, and high adhesive strength could be maintained even in a high-temperature environment. On the other hand, the light and moisture-curable resin compositions of Comparative Examples 1 to 5 do not contain the compound (D) having 3 or more isocyanate groups in the molecule, so the final heat-resistant adhesive strength after moisture curing is low, High adhesive strength could not be secured in a high-temperature environment. This tendency was the same in Comparative Examples 6 and 7 in which a diisocyanate compound was used instead of the compound (D) having 3 or more isocyanate groups.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Cette composition de résine photodurcissable/durcissable à l'humidité comprend un composé polymérisable par voie radicalaire (A), une résine durcissable à l'humidité (B), un initiateur de photopolymérisation (C), et un composé (D) ayant au moins trois groupes isocyanate dans sa molécule.
PCT/JP2022/023015 2021-06-08 2022-06-07 Composition de résine photodurcissable/durcissable à l'humidité, adhésif pour composants électroniques, corps durci et composant électronique WO2022260053A1 (fr)

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JP2022543049A JPWO2022260053A1 (fr) 2021-06-08 2022-06-07
KR1020237041958A KR20240018465A (ko) 2021-06-08 2022-06-07 광 습기 경화형 수지 조성물, 전자 부품용 접착제, 경화체, 및 전자 부품

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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2016074782A (ja) * 2014-10-03 2016-05-12 積水化学工業株式会社 湿気硬化型樹脂組成物
JP2019203064A (ja) * 2018-05-23 2019-11-28 サンユレック株式会社 光湿気硬化型樹脂組成物
JP2020147687A (ja) * 2019-03-14 2020-09-17 Dic株式会社 ウレタン樹脂組成物、接着剤、及び、床構造体

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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016074782A (ja) * 2014-10-03 2016-05-12 積水化学工業株式会社 湿気硬化型樹脂組成物
JP2019203064A (ja) * 2018-05-23 2019-11-28 サンユレック株式会社 光湿気硬化型樹脂組成物
JP2020147687A (ja) * 2019-03-14 2020-09-17 Dic株式会社 ウレタン樹脂組成物、接着剤、及び、床構造体

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