WO2023153514A1 - 光湿気硬化型樹脂組成物、電子部品用接着剤及び表示素子用接着剤 - Google Patents

光湿気硬化型樹脂組成物、電子部品用接着剤及び表示素子用接着剤 Download PDF

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WO2023153514A1
WO2023153514A1 PCT/JP2023/004815 JP2023004815W WO2023153514A1 WO 2023153514 A1 WO2023153514 A1 WO 2023153514A1 JP 2023004815 W JP2023004815 W JP 2023004815W WO 2023153514 A1 WO2023153514 A1 WO 2023153514A1
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moisture
curable resin
resin composition
meth
light
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PCT/JP2023/004815
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English (en)
French (fr)
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 CN202380021205.5A priority Critical patent/CN118715250A/zh
Priority to KR1020247026719A priority patent/KR20240144936A/ko
Priority to JP2023522422A priority patent/JPWO2023153514A1/ja
Publication of WO2023153514A1 publication Critical patent/WO2023153514A1/ja

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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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

Definitions

  • the present invention relates to a light moisture-curable resin composition, an adhesive for electronic parts, and an adhesive for display elements.
  • Patent Document 1 discloses a light-moisture-curable resin composition having excellent light-shielding properties and adhesiveness. It is proposed to blacken the light and moisture-curable resin composition by using it.
  • the light-moisture-curable adhesive does not exhibit sufficient adhesive strength (initial adhesive strength) immediately after bonding, and has the disadvantage that it takes time to bond members together. . Therefore, conventionally, a light and moisture-curable resin composition capable of exhibiting excellent initial adhesive strength immediately after photocuring has been studied.
  • Patent Document 2 when the composition is linearly applied to a polycarbonate plate and adhered to a glass plate via the composition immediately after photocuring, the ratio of the widths of the bonded portions (inside/outside ratio) of each plate is measured.
  • a light and moisture-curable resin composition is disclosed in which the viscosity is kept within a certain range while keeping the viscosity within a certain range.
  • an object of the present invention is to provide a photo-moisture-curable resin composition having high photo-curability even when it is blackened to impart light-shielding properties.
  • the present inventors have found that the OD value of a 1 mm thick cured product containing a radically polymerizable compound, a moisture-curable resin, a photoradical polymerization initiator, and zirconium nitride after photocuring is 2 or more, the present invention was completed by finding a solution to the above-described problems with a light and moisture-curable resin composition.
  • the present invention provides the following [1] to [19].
  • Photo-moisture curing which contains a radically polymerizable compound, a moisture-curable resin, a photoradical polymerization initiator, and zirconium nitride, and has an OD value of 2 or more in a 1 mm-thick cured product after photocuring. mold resin composition.
  • the content of the zirconium nitride is 0.1 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the total amount of the radically polymerizable compound and the moisture-curable resin.
  • a light and moisture-curable resin composition is 0.1 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the total amount of the radically polymerizable compound and the moisture-curable resin.
  • a light and moisture-curable resin composition [14] The light and moisture-curable resin composition according to any one of [1] to [13], which further contains a filler. [15] An adhesive for electronic parts, comprising the light moisture-curable resin composition according to any one of [1] to [14]. [16] An adhesive for display elements, comprising the light and moisture-curable resin composition according to any one of [1] to [14]. [17] A cured product of the light and moisture-curable resin composition according to any one of [1] to [14]. [18] Use of the light moisture-curable resin composition according to any one of [1] to [14] for electronic parts. [19] Use of the light moisture-curable resin composition according to any one of [1] to [14] for a display element.
  • FIG.2 (a) is a top view
  • FIG.2(b) is a side view
  • FIG.3 (a) is immediately after crimping
  • FIG.3(b) is 1 hour after crimping.
  • the light and moisture-curable resin composition of the present invention contains a radically polymerizable compound, a moisture-curable resin, a photoradical polymerization initiator, and zirconium nitride.
  • the light and moisture-curable resin composition of the present invention contains zirconium nitride.
  • the photo-moisture-curable resin composition contains zirconium nitride, so that even when it is blackened so that the OD value is above a certain level, as described later, it is possible to maintain high photocurability.
  • the light and moisture-curable resin composition contains zirconium nitride, so that the transmittance of visible light is suppressed to a certain level or less, while the transmittance of low wavelengths such as ultraviolet rays is kept above a certain level. Therefore, it is presumed that the light for photocuring can reach the inside of the light and moisture-curable resin composition. In addition, if the photocurability can be increased, the initial adhesive strength tends to be improved.
  • the average primary particle size of the zirconium nitride used in the present invention is not particularly limited, but is preferably 1 nm or more and 700 nm or less, more preferably 5 nm or more and 500 nm or less, and still more preferably 10 nm or more and 100 nm or less.
  • the average primary particle size of zirconium nitride is at least the above lower limit, it becomes easier to adjust the OD value of the light and moisture-curable resin composition to a certain level or more.
  • the particle size of the zirconium nitride is equal to or less than the above upper limit value, the handleability of the light and moisture-curable resin composition is improved.
  • the average primary particle size can be obtained, for example, by measuring 50 or more particles using a scanning electron microscope and calculating the average value.
  • zirconium nitride can be a commercially available product such as "UB-1" (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.).
  • the content of zirconium nitride in the light and moisture-curable resin composition of the present invention is preferably 0.1 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the total amount of the radically polymerizable compound and the moisture-curable resin. , more preferably 0.2 to 1.2 parts by mass, more preferably 0.3 to 1.0 parts by mass.
  • the photo-moisture-curable resin composition of the present invention has an optical density (OD value) of 2 or more as a cured product having a thickness of 1 mm after photocuring. If the OD value is less than 2, the light-shielding property becomes insufficient, and when used in a display element or the like, light leakage may occur, and high contrast may not be obtained.
  • the OD value is preferably 2.5 or more, more preferably 3 or more.
  • the above OD value is preferably as high as possible from the viewpoint of light-shielding properties, but the content of zirconium nitride and other coloring agents is set to a certain level or less, and the viewpoint of improving photocurability and the light and moisture-curable resin composition.
  • the OD value after curing of the light moisture-curable resin composition can be measured using an optical densitometer. For the above OD value, it is preferable to use a sample having a thickness of 1 mm obtained by photocuring the light and moisture-curable resin composition.
  • the light and moisture-curable resin composition of the present invention contains a radically polymerizable compound.
  • the photo-moisture-curable resin composition is imparted with photocurability by containing a radically polymerizable compound. Since the light-moisture-curable resin composition has photocurability, a certain amount of adhesive strength can be imparted only by irradiating with light, making it easier to secure an appropriate initial adhesive strength. In addition, the hardness can be increased to a certain level or higher only by irradiating with light, making it easy to secure handleability.
  • the radically polymerizable compound 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 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 is one or both of a monofunctional radically polymerizable compound having one radically polymerizable functional group in one molecule and a multifunctional radically polymerizable compound having two or more radically polymerizable functional groups in one molecule.
  • it may contain, from the viewpoint of improving the initial adhesive strength of the light moisture-curable resin composition, it is preferable to contain a monofunctional radically polymerizable compound.
  • the radically polymerizable compound more preferably contains at least a monofunctional (meth)acrylic compound, which is a (meth)acrylic compound, as the 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 light and moisture-curable resin composition preferably contains a large amount of a monofunctional radically polymerizable compound as a radically polymerizable compound.
  • a large amount of a monofunctional radically polymerizable compound is contained as the radically polymerizable compound, it is possible to increase the initial adhesive strength because the adhesion area when another adherend is press-bonded after photocuring can be increased.
  • the content of the monofunctional radically polymerizable compound in the light and moisture-curable resin composition is 70 parts by mass or more with respect to 100 parts by mass of the radically polymerizable compound.
  • the upper limit of the content of the monofunctional radically polymerizable compound is not particularly limited, and may be 100 parts by mass or less.
  • the radically polymerizable compound preferably contains a nitrogen-containing compound as a monofunctional radically polymerizable compound.
  • a nitrogen-containing compound tends to improve the adhesive strength of the light and moisture-curable resin composition.
  • 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 contains a nitrogen-containing compound, it is appropriately photocured even in the presence of oxygen, thereby improving the adhesive strength.
  • the nitrogen-containing compound may contain one or both of a linear nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure. It is more preferable to use 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, specifically, amide group-containing compounds such as N-vinyl- ⁇ -caprolactam 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 when using a urethane resin, especially a urethane resin having a polycarbonate skeleton, as a moisture-curable resin, compatibility with the moisture-curable resin is improved and adhesive strength is improved. Easy to improve.
  • urethane (meth)acrylate has a relatively high polarity, so it is easy to increase the adhesive strength especially 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 in the light and moisture-curable resin composition is from the viewpoint of improving the adhesive strength of the light and moisture-curable resin composition. , preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and most preferably 50 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 90 parts by mass, in order to contain an appropriate amount of the radically polymerizable compound other than the nitrogen-containing compound. parts 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 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 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 monofunctional (meth)acrylic compounds are preferred, and (meth)acrylic acid ester compounds are more preferred.
  • 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 is preferably 5 parts by mass with respect to 100 parts by mass of the radically polymerizable compound.
  • the above 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, and most preferably 40 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.
  • aromatic ring-containing (meth)acrylates 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 light-moisture-curable resin composition of the present invention may contain a polyfunctional radically polymerizable compound as a radically polymerizable compound.
  • a polyfunctional radically polymerizable compound By containing a polyfunctional radically polymerizable compound, it becomes easy to make a gel fraction more than a certain level, and to give hardness more than a certain level. Therefore, the shape retention property becomes good after photocuring, and for example, even if the composition is applied to one adherend in a narrow width and photocured, and then the other adherend is crimped, the light and moisture-curable resin composition is crushed. It prevents this and makes it easier to maintain the narrow width.
  • polyfunctional radically polymerizable compounds examples include bifunctional (meth)acrylic acid ester compounds, trifunctional or higher (meth)acrylic acid ester compounds, and bifunctional or higher urethane (meth)acrylates.
  • bifunctional or trifunctional or higher (meth)acrylic acid ester compounds are preferred, and from the viewpoint of increasing the gel fraction, trifunctional or higher (meth)acrylic acid ester compounds are more preferred.
  • the content of the polyfunctional radically-polymerizable compound from the viewpoint of making it easier to improve the shape retention of the light-moisture-curable resin composition, radical polymerization.
  • 0.1 parts by mass or more is preferable, 0.3 parts by mass or more is more preferable, and 0.5 parts by mass or more is even more preferable with respect to 100 parts by mass of the chemical compound.
  • the upper limit of the content of the polyfunctional radically polymerizable compound is not particularly defined, but it imparts appropriate flexibility to the light and moisture-curable resin composition, making it easy to bond the adherends together. 30 parts by mass or less is preferable, and 20 parts by mass or less is more preferable.
  • 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.
  • Difunctional or higher 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.
  • isocyanate compounds used to obtain urethane (meth)acrylates include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Polyisocyanate compounds such as isocyanatophenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate and the like can be mentioned.
  • MDI diisocyanate
  • isocyanate compound a chain-extended polyisocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.
  • 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 resins used in the present invention include moisture-curable urethane resins, hydrolyzable silyl group-containing resins, and moisture-curable cyanoacrylate resins. 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.
  • the isocyanate group is not particularly limited, but is preferably provided at the end of 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.
  • Moisture-curable urethane resins have a polycarbonate skeleton and thus have excellent adhesive strength. Furthermore, it is possible to provide a light and moisture-curable resin composition which is excellent in weather resistance, heat 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 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. By including a chain-like aliphatic saturated hydrocarbon group having 6 or more carbon atoms, it becomes easier to improve stress relaxation and flexibility.
  • the polycarbonate diol is a compound represented by the above formula (1), the ratio of chain aliphatic saturated hydrocarbon groups having 6 or more carbon atoms is 20 mol% or more with respect to R contained in the total polycarbonate diol.
  • the chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms preferably has 6 or more and 12 or less carbon atoms, more preferably 6 or more and 10 or less carbon atoms.
  • R may be linear groups such as tetramethylene group, pentylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group, and for example, 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, more preferably diphenylmethane diisocyanate and a modified product thereof, from the viewpoint of increasing the adhesive strength after full 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 polyols 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. Among these, 1,6-hexanediol or 1,4-butanediol is preferable from the viewpoint of easily increasing adhesive strength at high temperatures.
  • 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.
  • polypropylene glycol, a ring-opening polymer of tetrahydrofuran, or a ring-opening polymer of 3-methyltetrahydrofuran are preferable from the viewpoint of easily improving the applicability of the light and moisture-curable resin composition.
  • 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.
  • 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 becomes a thing excellent in compatibility with.
  • a polyether polyol composed of a ring-opening polymerization compound of polypropylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group, and polypropylene glycol and tetrahydrofuran.
  • a ring-opening polymerization compound of (THF) compound is more preferred.
  • 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 0-5
  • m is an integer of 1-500
  • n is an integer of 1-10.
  • 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.
  • the moisture-curable urethane resin preferably contains an isocyanate group as described above, but is not limited to one containing an isocyanate group, and may be a urethane resin containing a hydrolyzable silyl group.
  • a hydrolyzable silyl group is represented, for example, 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. are 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 polyurethane resin for example, when producing a polyurethane 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 is not particularly limited, and may be appropriately selected from those listed above and used, but from the viewpoint of reactivity with the isocyanate group, it has an amino group or a mercapto group. It is preferred to use a silane cupping agent. Preferred specific examples are N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane. silane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like.
  • 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 in terms of reactivity.
  • Moisture-curable resins having a radically polymerizable functional group are not included in the radically polymerizable compounds described above and are treated as moisture-curable resins.
  • the moisture-curable resin may be appropriately selected from the various resins described above and used alone, or two or more of them may be used in combination.
  • the weight average molecular weight of the moisture-curable resin is preferably 7500 or more and 30000 or less.
  • the inside/outside ratio a/b and the viscosity at 25° C. of the light and moisture-curable resin composition described later can be set within a predetermined range, and the adhesive strength can be easily increased.
  • the weight average molecular weight of the moisture-curable resin is more preferably 7800 or more, more preferably 10000 or more, still more preferably 11500 or more, more preferably 24000 or less, further preferably 20000 or less, and 16000 or less. Even more preferable.
  • the said weight average molecular weight in this specification is a value which measures by a gel permeation chromatography (GPC), and is calculated
  • 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
  • a moisture-curable urethane resin may be obtained by further reacting a chain extender with a urethane resin.
  • 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. Moreover, 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, 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 when the total amount of the raw material urethane resin and the chain extender is 100 parts by mass. It is 15 mass parts or more and 30 mass parts or less.
  • the mass ratio of the moisture-curable resin to the radical polymerizable compound is preferably 30/70 or more and 90/10 or less, more preferably 40/60 or more and 80/20 or less, and 50/50 or more. 70/30 or less is more preferable.
  • the mass ratio is within these ranges, it is possible to provide the photo-moisture-curable resin composition with well-balanced photocurability and moisture-curability, and to easily adjust the adhesive force within a desired range.
  • the total content of the radical polymerizable compound and the moisture-curable resin in the light moisture-curable resin composition is not particularly limited, but is based on the total amount of the light moisture-curable resin composition, for example 50% by mass or more, preferably 60% by mass. Above, more preferably 70% by mass or more, still more preferably 80% by mass or more. By making the total amount of these not less than the above lower limit, it becomes easier to impart appropriate photocurability and moisture curability to the moisture-curable resin composition.
  • the total content may be less than 100% by mass, but is preferably 99% by mass or less, more preferably 98% by mass or less, in order to contain other components appropriately.
  • the light and moisture-curable resin composition may contain a resin component other than the radically polymerizable compound and the moisture-curable resin as a resin component within a range that does not impair the effects of the present invention. For example, it does not have curability.
  • a resin component such as a thermoplastic resin (for example, an acrylic resin, a urethane resin, etc.), a thermosetting resin, or the like may be contained.
  • the ratio of the resin components other than the radically polymerizable compound and the moisture-curable resin is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, or more, with respect to 100 parts by mass of the total amount of the radically polymerizable compound and the moisture-curable resin. Preferably, it is 10 parts by mass or less.
  • the light-moisture-curable resin composition of the present invention contains a photoradical polymerization initiator.
  • the photo-moisture-curable resin composition contains a photoradical polymerization initiator, so that the photo-curing property is appropriately imparted.
  • photoradical polymerization initiators include benzophenone-based compounds, acetophenone-based compounds, alkylphenone-based photoradical polymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, thioxanthone, and the like. is mentioned.
  • photoradical polymerization initiators examples include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all BASF), benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), Omnirad 819, and Omnirad TPO H (all manufactured by IGM Resins B.V.).
  • an acylphosphine oxide compound is preferable.
  • Acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 ,4,4-trimethyl-pentylphosphine oxide and the like. Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is more preferable.
  • the content of the photo-radical polymerization 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 with respect to 100 parts by mass of the radically polymerizable compound. It is more than 5 parts by mass or less.
  • the content of the radical photopolymerization initiator is within these ranges, the resulting photomoisture-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 and moisture-curable resin composition of the present invention preferably contains a filler.
  • a filler By containing a filler, 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.
  • Preferred fillers include inorganic fillers 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 may be subjected to hydrophobic surface treatment such as silylation treatment, alkylation treatment, and epoxidation treatment.
  • a filler may be used individually by 1 type, and 2 or more types may be used in combination.
  • the content of the filler is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture-curable resin It is preferably 3 parts by mass or more and 15 parts by mass or less.
  • the light and moisture-curable resin composition of the present invention contains a coloring agent other than zirconium nitride, a moisture curing acceleration catalyst, a coupling agent, and a wax as long as the effects of the present invention are not impaired.
  • a coloring agent other than zirconium nitride a moisture curing acceleration catalyst, a coupling agent, and a wax as long as the effects of the present invention are not impaired.
  • Other additives such as particles, ionic liquids, foamed particles, expanded particles, reactive diluents, etc. may be included.
  • Colorants other than zirconium nitride include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black.
  • Examples of coupling agents include silane coupling agents, titanate coupling agents, zirconate coupling agents, and the like.
  • the light and moisture-curable resin composition may be diluted with a solvent, if necessary.
  • the amount of the light and moisture-curable resin composition described above is based on the solid content, that is, the mass excluding the solvent.
  • a mixer is used to prepare a radically polymerizable compound, a moisture-curable resin, a photoradical polymerization initiator, and zirconium nitride, and if necessary, and a method of mixing other additives such as fillers, moisture curing acceleration catalysts, and colorants.
  • mixers include homodispers, homomixers, universal mixers, planetary mixers (planetary stirring devices), kneaders, and three rolls.
  • the moisture-curable urethane resin may be increased in molecular weight with 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 urethane resin, and then mixed with other raw materials such as a radically polymerizable compound as described above. Good.
  • the raw material resin, chain extender, and radically polymerizable compound are mixed, and the mixture is heated as necessary to react the chain extender with the raw material resin, thereby synthesizing a moisture-curable resin. You may In this case, a mixture of a moisture-curable resin and a radically polymerizable compound is obtained.
  • a resin composition may be obtained.
  • the moisture-curable resin composition of the present invention preferably has an inside/outside ratio a/b of 0.5 or more and 0.95 or less.
  • the inside/outside ratio a/b is 0.5 or more, it becomes difficult to collapse immediately after photocuring, and even when the moisture-curable resin composition is blackened, the initial adhesive strength tends to be improved.
  • the inside/outside ratio a/b is 0.95 or less, it is not too crushed immediately after photocuring, and peeling from the adherend is less likely to occur, and even when the moisture-curable resin composition is blackened, the adhesive strength is low. A decrease can be prevented.
  • the inside/outside ratio a/b is preferably 0.54 or more, more preferably 0.58 or more, still more preferably 0.60 or more, preferably 0.92 or less, more preferably 0.89 or less, and 0.54 or more. 87 or less is more preferable.
  • the inside/outside ratio a/b is within the above range, it becomes easy to improve the initial adhesive strength.
  • 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. 1(b), the moisture-curable resin composition 10 is irradiated with ultraviolet rays of 1500 mJ/cm 2 to cure the moisture-curable resin composition 10 . Immediately thereafter (within 10 seconds), as shown in FIG. Crimping is performed 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.
  • 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 photo-moisture-curable resin composition contains a large amount of a monofunctional radically polymerizable compound as a 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 urethane resin.
  • 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. If the viscosity at 25° C. is 40 Pa s or more, the amount of low-molecular-weight components contained in the moisture-curable resin, etc., is reduced, so that the moisture-curable resin, etc. is prevented from exuding to the interface after light irradiation, and the light-moisture-curable type Even when the resin composition is blackened, it becomes easier to improve the initial adhesive strength.
  • 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 preferably 500 Pa s or less, and 350 Pa s. The following is more preferable, and 230 Pa ⁇ s or less is even more preferable.
  • the final adhesive strength means the adhesive strength of the photo-moisture-curable resin composition after photo-curing and moisture-curing.
  • the light and moisture-curable resin composition of the present invention preferably has both the inside/outside ratio a/b and the viscosity at 25°C within the above numerical ranges.
  • the light and moisture-curable resin composition of the present invention preferably has an initial shearing force of 0.2 MPa or more, more preferably 0.25 MPa or more, and even more preferably 0.3 MPa or more.
  • the initial shearing force is at least the above lower limit, excellent adhesive strength can be imparted even when the light and moisture-curable resin composition of the present invention is blackened.
  • the adherends can be temporarily adhered to each other with a relatively high adhesive strength, improving workability during temporary adhesion.
  • the upper limit of the initial shear force is not particularly limited, but from a practical viewpoint, it is, for example, 10.0 MPa or less.
  • the initial shear force means the shear force at 25° C. immediately after the photo-moisture-curable resin composition is photocured. The details of the method for measuring the initial shear force are as described in Examples below.
  • the initial creep force is obtained by applying the light moisture-curable resin composition to the polycarbonate substrate and photocuring it, and then applying the light moisture-curable resin composition to the glass plate. It can be expressed by the distance h by which the glass plate deviates from the polycarbonate substrate in one hour when the evaluation sample obtained by bonding is vertically set. The shorter the distance h, the higher the initial creep force. Specifically, the distance h is preferably 0.15 mm or less, more preferably 0.10 mm or less. By setting the initial creep force to the above upper limit or less, the initial adhesive strength increases.
  • the distance h is preferably as short as possible, and should be 0 mm or more.
  • the initial creep force means the creep force at 25° C. immediately after the photo-moisture-curable resin composition is photocured, and the details of the method for measuring the distance h are as described later in Examples.
  • the photo-moisture-curable resin composition of the present invention preferably has a gel fraction after photocuring of 10% or more, more preferably 12% or more. It is more preferably 15% or more.
  • the gel fraction is at least the above lower limit value, a certain degree of hardness is imparted to the light and moisture-curable resin composition. Therefore, the shape retainability after photocuring becomes good, and for example, even if the other adherend is crimped after being applied to one adherend in a narrow width and photocured, the light moisture-curable resin composition can be It is prevented from collapsing and maintained in a narrow state.
  • the upper limit of the gel fraction after photocuring is not particularly limited from the viewpoint of improving shape retention, it is preferably 60% or less, more preferably 50% or less, and 40% or less. is more preferable.
  • the gel fraction is equal to or less than the above upper limit, the light and moisture-curable resin composition is imparted with appropriate flexibility, and adherends are easily adhered to each other.
  • the photo-moisture-curable resin composition of the present invention preferably has a gel fraction after photocuring of less than 10%, more preferably 5% or less, from the viewpoint of increasing the initial adhesive strength. , 1% or less.
  • the adhesive area can be increased when another adherend is pressure-bonded after photocuring, so the initial adhesive strength can be increased.
  • the lower limit of the gel fraction after photocuring is not particularly limited, and may be 0% or more.
  • the gel fraction after photocuring can be calculated
  • About 1.0 g of the light and moisture-curable resin composition is sampled and weighed to obtain the sample weight (W1).
  • a sample for analysis is prepared by coating it on a glass plate to a thickness of 1.0 mm and irradiating it with ultraviolet rays of 1500 mJ/cm 2 for photocuring.
  • the analysis sample prepared above is immersed in THF at 25° C. for 48 hours.
  • the light and moisture-curable resin composition in a photocured state was taken out onto a 200-mesh wire mesh, washed with fresh THF five times, and then the swollen gel remaining on the wire mesh was removed at 100°C. for 2 hours to volatilize THF, the weight of the dried gel (W2) is weighed, and the gel fraction is measured by the following formula.
  • Gel fraction (%) W2/W1 x 100
  • 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 the optical moisture-curable resin composition is 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 urethane resin with moisture, and the adherends superimposed via the optical moisture-curable resin composition are separated from each other. They are permanently adhered and joined with sufficient adhesive strength (final adhesive strength).
  • the application of the light moisture-curable resin composition to the adherend is preferably carried out, for example, with 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 light and moisture-curable resin composition of the present invention has a high OD value and high light-shielding properties, but has a relatively high transmittance to ultraviolet rays, so that it can be cured with high curability by using ultraviolet rays.
  • the photo-moisture-curable resin composition when 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 25° C. viscosity of the light and moisture-curable resin composition of the present invention is within the above-described predetermined range, it can be applied more easily even when it is applied at around room temperature, and dripping occurs. neither does it.
  • 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 constituting electronic devices include various electronic components provided in display elements, substrates to which electronic components are attached, semiconductor chips, and the like.
  • 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. At least one electronic component is preferably attached to each of the first substrate and the second substrate.
  • the light-moisture-curable resin composition of the present invention is used for display devices. That is, the present invention also provides an adhesive for display elements comprising the above-described light and moisture-curable resin composition. Since the light-moisture-curable resin composition of the present invention has high light-shielding properties and can prevent light leakage, high contrast can be obtained by using the composition for display devices.
  • an adhesive is applied on a narrow rectangular frame-shaped (that is, narrow frame) base.
  • a display panel, a touch panel, or the like is assembled through the adhesive, and the photo-moisture-curable resin composition of the present invention is preferably used as the adhesive. Furthermore, the light moisture-curable resin composition of the present invention may be used for semiconductor chips. 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 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 a radically polymerizable compound and a moisture-curable resin as a sample.
  • the peak of the radical polymerizable compound appears on the low molecular weight side
  • the peak of the moisture-curable resin appears on the high molecular weight side, so the weight average molecular weight of the moisture-curable resin can be determined from the peak on the high molecular weight side.
  • Each light-moisture-curable resin composition obtained in Examples and Comparative Examples was uniformly applied to a slide glass ("S1214", manufactured by Matsunami Glass Industry Co., Ltd.) so as to have a thickness of 1 mm, and a UV-LED irradiation device was applied. (manufactured by CCS Co., Ltd.), the photo-moisture-curable resin composition was photo-cured by irradiating 1500 mJ/cm 2 of ultraviolet rays having a wavelength of 365 nm to obtain a sample for light shielding evaluation. The OD value of the resulting light-shielding evaluation sample was measured using an optical densitometer (manufactured by X-rite, "Spectrometer").
  • the illuminance during photocuring was adjusted in the range of 500 to 3000 mW/cm 2 .
  • ⁇ Gel fraction> The gel fraction was measured by the method described in the specification.
  • the applied light moisture-curable resin composition was irradiated with 1500 mJ/cm 2 of ultraviolet rays having a wavelength of 365 nm using a UV-LED irradiator (manufactured by CCS Co., Ltd.). Immersion in THF was carried out using 100 ml of THF in a glass bottle with gentle stirring.
  • 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 1500 mJ/cm 2 of ultraviolet rays having a wavelength of 365 nm with a line-type LED irradiator (manufactured by HOYA).
  • a glass plate 22 is attached to an aluminum substrate 21 via a light-cured light-moisture-curable resin composition 20, and a weight is used to apply pressure to the coating area at 0.08 MPa for 120 seconds, followed by initial shearing.
  • a sample 23 for force evaluation was obtained.
  • a tension tester (“Tensile/compression tester SVZ-50NB” manufactured by Imada Seisakusho Co., Ltd.) was used to pull in the shearing direction S at a rate of 10 mm/min.
  • the initial shear force was determined by measuring the maximum stress when the film was peeled off.
  • the time from the end of photocuring to the start of the tensile test was within 150 seconds.
  • the initial shear force was evaluated according to the following evaluation criteria.
  • B 0.2 MPa or more and less than 0.3 MPa C: less than 0.2 MPa
  • a light moisture-curable resin composition 31 is applied to a polycarbonate substrate 30, and the four sides of the light moisture-curable resin composition 31 have dimensions of 9.5 cm ⁇ 9.5 cm, and It was applied at room temperature (25° C.) to a thickness of 0.4 ⁇ 0.1 mm. Then, it was photo-cured by irradiating 1500 mJ/cm 2 of ultraviolet rays having a wavelength of 365 nm with a line-type LED irradiator (manufactured by HOYA).
  • a 10 cm ⁇ 10 cm glass plate 32 (manufactured by Nippon Test Panel Co., Ltd.) with a thickness of 12 mm is attached to the polycarbonate substrate 30 via a photo-cured light moisture-curable resin composition 31, and a weight is used to determine the coating area. was pressed against for 120 seconds at 0.08 MPa to obtain a sample 33 for initial creep force evaluation. After that, the initial creep force evaluation sample 33 was set upright and left for 1 hour in an environment with a temperature of 25° C. and a humidity of 50% RH. The time from the end of photocuring to the start of the initial creep force test was within 300 seconds. Based on the distance h, the initial creep force was evaluated according to the following evaluation criteria. A shorter distance h means a higher initial creep force. A: Distance h is less than 0.10 mm B: Distance h is 0.10 mm or more and 0.15 mm or less C: Distance h is more than 0.15 mm
  • 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 as the aluminum substrate and the glass plate.
  • 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 1500 mJ/cm 2 of ultraviolet light having a wavelength of 365 nm using 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 urethane resin raw material used in each example and comparative example was produced by the following method.
  • Synthesis Example 1 ⁇ raw material for PC urethane resin>
  • 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”
  • 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).
  • diphenylmethane diisocyanate manufactured by Nisso Shoji Co., Ltd., trade name “Pure MDI”
  • Pure MDI diphenylmethane diisocyanate
  • 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 As shown in Table 4, to 40 parts by mass of acrylic B, 60 parts by mass of each raw material constituting moisture-curable resin a was added. Acrylic B was obtained by mixing each compound at the compounding ratio shown in Table 2. As a moisture-curable resin a, a PC urethane resin raw material and a PC polyol were sequentially added to the 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 5-8, Comparative Examples 4-6 As shown in Table 5, light and moisture-curable resin compositions were obtained in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 3, except that acrylic A was used instead of acrylic B. Weight average molecular weight, OD value, viscosity, internal/external ratio, initial shear force, and initial creep force were measured for the obtained light-moisture-curable resin composition, and the initial shear force and initial creep force were evaluated.
  • Acrylics A and B used in each example and comparative example are shown in Table 2.
  • the moisture-curable resin a used in each example and comparative example is as shown in Table 3 below.
  • the photo-moisture-curable resin compositions in Examples 1 to 4 used zirconium nitride even when the OD value was set to 2 or more and turned black, so the gel fraction after photocuring increased. , good photocurability could be expressed.
  • Comparative Examples 1 to 3 due to the use of titanium black instead of zirconium nitride, the gel fraction after photocuring was lowered, and good photocurability could not be exhibited.
  • the photo-moisture-curable resin composition in each example had excellent photocurability due to the use of zirconium nitride, even when the OD value was set to 2 or more and turned black. . Therefore, the initial shear force and the initial creep force were improved, and excellent initial adhesive strength could be exhibited. On the other hand, in Comparative Examples in which titanium black was used instead of zirconium nitride as a coloring agent, the photocurability was insufficient and the initial adhesive strength was not excellent.

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WO2015111570A1 (ja) * 2014-01-21 2015-07-30 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤
JP2020076794A (ja) * 2018-11-05 2020-05-21 協立化学産業株式会社 液晶表示素子用シール剤組成物
WO2021230372A1 (ja) * 2020-05-15 2021-11-18 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、硬化体、及び電子部品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015111570A1 (ja) * 2014-01-21 2015-07-30 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤
JP2020076794A (ja) * 2018-11-05 2020-05-21 協立化学産業株式会社 液晶表示素子用シール剤組成物
WO2021230372A1 (ja) * 2020-05-15 2021-11-18 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、硬化体、及び電子部品

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