WO2022114186A1 - Composition de résine durcissable à l'humidité et adhésif pour appareil électronique - Google Patents

Composition de résine durcissable à l'humidité et adhésif pour appareil électronique Download PDF

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WO2022114186A1
WO2022114186A1 PCT/JP2021/043650 JP2021043650W WO2022114186A1 WO 2022114186 A1 WO2022114186 A1 WO 2022114186A1 JP 2021043650 W JP2021043650 W JP 2021043650W WO 2022114186 A1 WO2022114186 A1 WO 2022114186A1
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moisture
curable resin
meth
resin composition
acrylate
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PCT/JP2021/043650
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English (en)
Japanese (ja)
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康平 萩原
智一 玉川
暁舸 王
彰 結城
拓身 木田
坤 徐
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積水化学工業株式会社
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Priority to CN202180078619.2A priority Critical patent/CN116568760A/zh
Priority to JP2021575274A priority patent/JPWO2022114186A1/ja
Priority to KR1020237017678A priority patent/KR20230113551A/ko
Publication of WO2022114186A1 publication Critical patent/WO2022114186A1/fr

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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • C08G18/08—Processes
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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 moisture-curable resin composition and an adhesive for electronic devices comprising a moisture-curable resin composition.
  • Moisture-curable resin compositions have been studied to impart various performances.
  • Patent Document 1 in order to provide a cured product having excellent flexibility and reliability in a high temperature and high humidity environment, a cured product of a photomoisture curable resin composition containing a radically polymerizable compound and a moisture curable resin is provided. It is shown that the storage elastic modulus at 0 ° C. is 1.0 ⁇ 10 7 Pa or more, and the storage elastic modulus at 50 ° C. is 5.0 ⁇ 10 6 Pa or less.
  • the adhesive used for the portable electronic device has a small adhesive area. Further, in recent years, with the miniaturization of electronic devices, the bonded portion has become thinner and the bonded area has become even smaller.
  • the conventional moisture-curable resin composition does not have sufficient impact resistance, and if the adhesive area is small, there are problems such as the components fixed by the moisture-curable resin composition falling off when dropped. May occur.
  • the cured product of the moisture-curable resin composition has a shear adhesive strength of 4 MPa or more, a breaking elongation of 600% or more, and has no glass transition point in a temperature range of 10 ° C. or more, and is moisture-curable. Resin composition.
  • the moisture-curable resin (A) is a moisture-curable urethane resin, and the moisture-curable urethane resin has at least one of a polyester skeleton, a polyether skeleton, a polyalkylene skeleton, and a polycarbonate skeleton.
  • the moisture-curable resin (A) is a moisture-curable urethane resin
  • the moisture-curable urethane resin is a reaction product of a polyol compound and a polyisocyanate compound.
  • the moisture-curable resin composition according to item 1. [14] The moisture-curable resin composition according to the above [13], wherein the polyol compound contains a polyvalent carboxylic acid and a polyester polyol obtained from the polyol.
  • the content of the radically polymerizable compound (B) is 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B).
  • the photopolymerization initiator (Y) is contained, and the content of the photopolymerization initiator (Y) is 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound.
  • the moisture-curable resin composition according to any one of [17] to [20].
  • the moisture-curable resin composition of the present invention is a composition containing a moisture-curable resin (A).
  • the cured product of the moisture-curable resin composition of the present invention has a shear adhesive strength of 4 MPa or more, a breaking elongation of 600% or more, and does not have a glass transition point in a temperature range of 10 ° C. or more. be.
  • the moisture-curable resin composition of the present invention has high storage elastic modulus and breaking elongation of the cured product as described above, and does not have a glass transition point in the temperature range of 10 ° C. or higher of the cured product.
  • the moisture-curable resin composition of the present invention has at least the moisture-curable resin (A) and has moisture-curable properties.
  • the moisture-curable resin composition has a moisture-curable property, which makes it easy to sufficiently increase the adhesive strength.
  • the moisture-curable resin composition of the present invention preferably contains a radically polymerizable compound (B) and a photopolymerization initiator (Y) in addition to the moisture-curable resin (A).
  • the moisture-curable resin composition is a photomoisture-curable resin composition that is cured by light irradiation and moisture.
  • the light-moisture-curable resin composition has excellent adhesive performance even when cured without heating, the adhesive performance is prevented from damaging the adhesive portion or electronic parts around the adhesive portion due to heating during curing. Can be excellent.
  • the photo-moisture-curable resin composition is first photo-cured to give a relatively low adhesive force (tack property) to a B-stage state, and then further cured by moisture by being left in the air or the like. It is possible to obtain a cured product having a sufficiently high adhesive strength.
  • the shear adhesive strength of the cured product of the moisture-curable resin composition is 4 MPa or more as described above. If the shear adhesive strength is less than 4 MPa, the shock absorption cannot be sufficiently increased, and when an electronic device or the like is dropped, the constituent members fixed by the moisture-curable resin composition of the present invention may fall off. Problems are likely to occur. In addition, problems such as the inability to firmly bond the constituent members of electronic devices are likely to occur.
  • the shear adhesive strength of the cured product of the moisture-curable resin composition is preferably 4.2 MPa or more, more preferably 5 MPa or more, from the viewpoint of shock absorption and adhesiveness.
  • the shear adhesive strength of the cured product of the moisture-curable resin composition is not particularly limited, but is preferably 15 MPa or less from the viewpoint of easily increasing the elongation at break and easily lowering the glass transition point (Tg) to a low temperature. , 12 MPa or less is more preferable, and 10 MPa or less is further preferable.
  • the shear adhesive strength can be appropriately adjusted depending on the type of the moisture-curable resin (A), the type of the radically polymerizable compound (B), the content thereof, and the like.
  • the shear adhesive strength is measured by the following adhesiveness test.
  • the moisture-curable resin composition has a width of 1.0 ⁇ 0.1 mm, a length of 25 ⁇ 2 mm, and a thickness of 0.4 ⁇ 0.1 mm.
  • 10 is applied to an aluminum substrate 11 and glass plates 12 are superposed on the moisture-curable resin composition 10 to prepare a sample 13 for an adhesiveness test.
  • the adhesiveness test sample 13 is obtained by bonding the aluminum substrate 11 and the glass plate 12 by curing the moisture-curable resin composition 10.
  • the prepared adhesiveness test sample 13 was left to stand in a moisture-curable resin composition in a 25 ° C.
  • the curing conditions of the moisture-curable resin composition when preparing the adhesiveness test sample may be such that the moisture-curable resin composition of the present invention is completely cured, and is described below according to the curing mechanism. It is advisable to prepare a sample under the conditions of.
  • a dispenser is used to attach a width of 1.0 ⁇ 0.1 mm, a length of 25 ⁇ 2 mm, and a thickness to an aluminum substrate. The coating was applied so as to have a diameter of 0.4 ⁇ 0.1 mm, a glass plate was attached to an aluminum substrate, and a weight of 100 g was placed for 10 seconds and crimped.
  • the sample After removing the weight, the sample is left at 25 ° C. and 50% RH for 7 days to be moisture-cured to obtain a sample for adhesiveness evaluation.
  • a dispenser is used to obtain a width of 1.0 ⁇ 0.1 mm, a length of 25 ⁇ 2 mm, and a thickness of 0.4 ⁇ 0.1 mm on the aluminum substrate. And it is photo-cured by irradiating with UV-LED (wavelength 365 nm) at 1000 mJ / cm 2 in an environment of 25 ° C. and 50% RH.
  • a glass plate is attached to an aluminum substrate, a 100 g weight is placed for 10 seconds and crimped, and after the weight is removed, the sample is moisture-cured by leaving it at 25 ° C. and 50% RH for 7 days to evaluate the adhesiveness. To get.
  • the cured product of the moisture-curable resin composition has a breaking elongation of 600% or more.
  • the elongation at break is less than 600%, the impact resistance becomes insufficient, and when a large impact is applied to an electronic device or the like due to dropping or the like, the constituent members fixed by the moisture-curable resin composition of the present invention are peeled off. A problem occurs.
  • the elongation at break is preferably 700% or more, more preferably 800% or more, still more preferably 900% or more.
  • the elongation at break is not particularly limited, but is preferably 1500% or less, more preferably 1300% or less, still more preferably 1150% or less, from the viewpoint of facilitating the increase in shear adhesive strength.
  • the elongation at break can be appropriately adjusted depending on the type of the moisture-curable resin (A), the type of the radically polymerizable compound (B), the content thereof, and the like.
  • the breaking elongation of the cured product is measured by the following method.
  • the moisture-curable resin composition is poured into a silicone rubber mold having a dumbbell-shaped (No. 6 type specified in "JIS K6251”) hole and cured to form a No. 6 type dumbbell-shaped test piece (cured product). Sample) is obtained.
  • a moisture-curable resin composition in the case of a moisture-curable resin composition (however, it does not have thermosetting and photocuring properties), it is moisture-cured by leaving it at 25 ° C. and 50 RH% for 7 days.
  • a light-moisture-curable resin composition it is photo-cured by irradiating 1000 mJ / cm 2 with a UV-LED (wavelength 365 nm) under an environment of 25 ° C. and 50 RH%, and then photo-curing at 25 ° C. and 50 RH% for 7 days. Moisture cures by leaving in.
  • the obtained test piece is pulled at a tensile speed of 50 mm / min using a tensile tester in an environment of 25 ° C., and the elongation at break is measured.
  • the cured product of the moisture-curable resin composition does not have a glass transition point in the temperature range of 10 ° C. or higher. If the glass transition point is provided in the temperature range of 10 ° C. or higher, the impact resistance cannot be sufficiently increased even if the breaking elongation and the shear adhesive strength are set to the constant values or higher as described above. Therefore, when an impact is applied due to dropping or the like, problems such as peeling of the constituent members fixed by the moisture-curable resin composition of the present invention occur. It is not clear that the impact resistance cannot be sufficiently increased if the glass transition point is provided in the temperature range of 10 ° C. or higher, but it is considered that the impact resistance is deteriorated due to the decrease in the followability to high-speed deformation.
  • the cured product of the moisture-curable resin composition of the present invention preferably has a glass transition point (hereinafter, also referred to as "Tg1") in a temperature range of ⁇ 20 ° C. or higher and lower than 10 ° C.
  • Tg1 glass transition point
  • the glass transition point (Tg1) is more preferably ⁇ 10 ° C. or higher, further preferably ⁇ 5 ° C. or higher, and further preferably 9 ° C. or lower.
  • the cured product of the moisture-curable resin composition may have a glass transition point (hereinafter, also referred to as “Tg2”) in a temperature range of, for example, ⁇ 30 ° C. or lower from the viewpoint of impact resistance.
  • Tg2 glass transition point
  • Tg2 glass transition point
  • the cured product of the moisture-curable resin composition of the present invention has a glass transition point (Tg2) in a temperature range of ⁇ 50 ° C. or lower.
  • the glass transition point (Tg2) is not particularly limited, but may be, for example, ⁇ 80 ° C. or higher, ⁇ 75 ° C. or higher, or ⁇ 70 ° C. or higher.
  • the cured product of the moisture-curable resin composition of the present invention has both of the above glass transition points (Tg1, Tg2).
  • Tg1, Tg2 glass transition points
  • the radically polymerizable compound (B) in addition to the moisture-curable resin (A) and making them incompatible, it becomes easy to have the above-mentioned two glass transition points.
  • the method for incompatible with each other is not particularly limited, and the types of the moisture-curable resin (A) and the radically polymerizable compound (B) may be appropriately selected, but the polyether is used as the moisture-curable resin (A).
  • a compound having a skeleton it tends to be incompatible with the radically polymerizable compound (B), and the cured product tends to have two glass transition points.
  • the glass transition point (Tg1) on the high temperature side can be adjusted within the above-mentioned desired range by appropriately selecting the component of the radically polymerizable compound (B). Further, the glass transition point (Tg2) on the low temperature side can be adjusted within the above-mentioned desired range by appropriately selecting the type of the moisture-curable resin (A) and the like. Therefore, by appropriately adjusting the components of the radically polymerizable compound (B), it is possible to prevent the glass transition point from having a glass transition point in the temperature range of 10 ° C. or higher as described above. Further, the cured product of the moisture-curable resin composition may have three or more glass transition points as long as the temperature is lower than 10 ° C.
  • the glass transition point means the temperature at which the maximum of the loss tangent (tan ⁇ ) obtained by the dynamic viscoelasticity measurement appears due to the micro-brown motion, and is cured from the moisture-curable resin composition. It is advisable to measure the object sample using a dynamic viscoelasticity measuring device. Details of the procedure for preparing the cured product sample are as described later.
  • the cured product of the moisture-curable resin composition preferably has a storage elastic modulus of 7 MPa or more and 50 MPa or less.
  • the storage elastic modulus is preferably 8 MPa or more, more preferably 9 MPa or more, and preferably 40 MPa or less, more preferably 20 MPa or less.
  • the storage elastic modulus can be appropriately adjusted depending on the type of the moisture-curable resin (A), the type of the radically polymerizable compound (B), the content thereof, and the like.
  • the storage elastic modulus of the cured product is measured by the following method.
  • a cured product sample is obtained by pouring the moisture-curable resin composition into a Teflon (registered trademark) mold having a width of 3 mm, a length of 30 mm, and a thickness of 1 mm and curing the mixture.
  • the dynamic viscoelasticity is measured in the range of ⁇ 100 to 150 ° C. by a dynamic viscoelasticity measuring device, and the storage elastic modulus at 25 ° C. is determined.
  • the curing of the moisture-curable resin composition for preparing the glass transition point and the cured product sample for measuring the storage elastic modulus is sufficient as long as the moisture-curable resin composition can be completely cured, but it depends on the curing mechanism. It is recommended to use the following method. For example, in the case of a photo-moisture-curable resin composition, it is photo-cured by irradiating it with ultraviolet rays at 1000 mJ / cm 2 in an environment of 25 ° C. and 50 RH% using a UV-LED (wavelength 365 nm), and then photo-curing. It is carried out by moisture curing by leaving it in an environment of 25 ° C. and 50% RH for 7 days. Further, in the case of a moisture-curable resin composition (however, it does not have thermosetting property and photocuring property), the same procedure as described above is performed except that the photocuring step is omitted.
  • the viscosity of the moisture-curable resin composition of the present invention measured at 80 ° C. and 20 rpm is preferably 50 Pa ⁇ s or less.
  • the viscosity By setting the viscosity to 50 Pa ⁇ s or less, the coatability becomes good, and the moisture-curable resin composition can be coated on the adherend in a fine line shape by various coating devices, especially a jet dispenser. Become. Therefore, it can be suitably used for portable electronic devices and the like.
  • the viscosity is not particularly limited, but is preferably 0.5 Pa ⁇ s or more, preferably 1.0 Pa ⁇ s, for example, from the viewpoint of the performance (shape retention) of maintaining the moisture-curable resin composition after coating in a constant shape. More than s is more preferable, and 2.0 Pa ⁇ s or more is further preferable.
  • the moisture-curable resin composition contains the moisture-curable resin (A).
  • the moisture-curable resin (A) used in the present invention include a moisture-curable urethane resin, a hydrolyzable silyl group-containing resin, and a moisture-curable cyanoacrylate resin.
  • a moisture-curable urethane resin and a hydrolyzable silyl group-containing resin are preferable, and a moisture-curable urethane resin is more preferable.
  • the moisture-curable urethane resin has an isocyanate group in addition to the urethane bond.
  • the isocyanate group in the molecule reacts with the moisture in the air or 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. Above all, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.
  • the moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
  • the moisture-curable urethane resin may have a polyester skeleton, a polyether skeleton, a polyalkylene skeleton, a polycarbonate skeleton, etc.
  • the polyester skeleton and the polyester skeleton from the viewpoint of increasing the elongation at break and improving the impact resistance. It preferably has at least one of the polyether skeletons and may have both.
  • the moisture-curable urethane resin When the moisture-curable urethane resin has both a polyester skeleton and a polyether skeleton, it may have both a polyester skeleton and a polyether skeleton in one molecule, but a moisture-curable urethane resin having a polyester skeleton and It is preferable to use a moisture-curable urethane resin having a polyether skeleton in combination.
  • the moisture-curable urethane resin is a moisture-curable urethane resin having a polyether skeleton from the viewpoint of improving impact resistance, making the composition easy to reduce the viscosity, and making it easy to have two or more glass transition points. Is more preferable.
  • the polyol compound which is a raw material of the moisture-curable urethane resin examples include polyester polyols, polyether polyols, polyalkylene polyols, polycarbonate polyols and the like. By using each of these, the moisture-curable urethane resin can have a polyester skeleton, a polyether skeleton, a polyalkylene skeleton, and a polycarbonate skeleton, respectively. Therefore, as the polyol compound, at least one selected from polyester polyols and polyether polyols is preferable, and among them, polyether polyols are more preferable. These polyol compounds may be used alone or in combination of two or more.
  • polyester polyol examples include a polyester polyol obtained by reacting a polyvalent carboxylic acid with a polyol, a poly- ⁇ -caprolactone polyol obtained by ring-opening polymerization of ⁇ -caprolactone, and the like.
  • polyvalent carboxylic acid used as a raw material for the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and sveric acid. , Azelaic acid, sebacic acid, decamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid and the like.
  • polyol that is a raw material of the polyester polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol.
  • examples thereof include diethylene glycol and cyclohexanediol.
  • polyether polyol examples include a ring-opening polymer of ethylene glycol, propylene glycol and tetrahydrofuran, a ring-opening polymer of 3-methyltetrachloride, and a random copolymer or block copolymer of these or derivatives thereof, or a bisphenol type.
  • the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen moiety of the bisphenol-type molecular skeleton. be.
  • the polyether polyol may be a random copolymer or a block copolymer.
  • the bisphenol-type polyoxyalkylene modified product preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton.
  • the bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and bisphenol A type is preferable.
  • polyalkylene polyol examples include a polybutadiene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol and the like.
  • polycarbonate polyol examples include polyhexamethylene carbonate polyol and polycyclohexanedimethylene carbonate polyol.
  • the polyol used as a raw material for the moisture-curable urethane resin preferably has an average molecular weight of 500 or more, more preferably 1500 or more, further preferably 2500 or more, and preferably 15000 or less. , 8000 or less, more preferably 4000 or less.
  • the moisture-curable urethane resin is preferably obtained by using a polyol compound having a structure represented by the following formula (1).
  • a polyol compound having a structure represented by the following formula (1) it becomes easy to increase the elongation at break while maintaining good shear adhesive strength.
  • the storage elastic modulus can be easily adjusted within the above-mentioned desired range.
  • those using a polyether polyol composed of a ring-opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable.
  • the moisture-curable urethane resin may contain a moisture-curable urethane resin obtained from polytetramethylene ether glycol and a moisture-curable urethane resin obtained from propylene glycol.
  • 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 to 4.
  • the case where l is 0 means the case where the carbon bonded to R is directly bonded to oxygen.
  • m is preferably 20 to 300, and more preferably 30 to 100.
  • the total of n and l is more preferably 1 or more, preferably 2 or more, further preferably 3 to 6, and most preferably 3.
  • R is more preferably a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable. Therefore, the structural unit represented by the formula (1) is preferably linear. Since the structural unit represented by the formula (1) is linear, the shear adhesive strength can be increased.
  • the moisture-curable urethane resin obtained from the above-mentioned linear polyether polyol, such as the moisture-curable urethane resin obtained from polytetramethylene ether glycol, is 50% by mass based on the total amount of the moisture-curable resin (A). It is preferably 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less.
  • an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are preferably used.
  • the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polypeptide MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like.
  • Examples of the aliphatic polyisocyanate compound 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 (isocyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate and the like.
  • polyisocyanate compound diphenylmethane diisocyanate and its modified product are particularly preferable from the viewpoint of being able to increase the adhesive strength after total curing.
  • the polyisocyanate compound may be used alone or in combination of two or more.
  • the moisture-curable urethane resin further preferably contains a compound having a urethane bond, an isocyanate group, and a reactive double bond at the terminal (hereinafter, also referred to as "reactive double bond-containing urethane resin"). ..
  • a reactive double bond-containing urethane resin By containing the above-mentioned reactive double bond-containing urethane resin as the moisture-curable urethane resin, the cured product tends to have a glass transition point in the temperature range of -20 ° C or higher and lower than 10 ° C, and the impact resistance of the cured product Is improved.
  • the said "end” means the end of the main chain.
  • the reactive double bond is a radically polymerizable group
  • the reactive double bond-containing urethane resin is treated as a moisture-curable urethane resin instead of a radically polymerizable compound.
  • the reactive double bond-containing urethane resin preferably has an isocyanate group ratio of 0.8% by mass or less in the structure.
  • the reactive double bond-containing urethane resin preferably has an isocyanate group ratio of 0.5% by mass or less in the structure.
  • the reactive double bond-containing urethane resin preferably has an isocyanate group ratio of 0.1% by mass or more in the structure.
  • the content of the reactive double bond-containing urethane resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the moisture-curable urethane resin. It is 20 parts by mass or less.
  • the content of the urethane resin containing a reactive double bond is within the above range, both impact resistance and moisture curability are excellent.
  • the hydrolyzable silyl group in the molecule reacts with moisture in the air or the adherend to be cured.
  • 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. Above all, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule.
  • the hydrolyzable silyl group-containing resin does not include those having an isocyanate group.
  • the hydrolyzable silyl group is represented by the following formula (2).
  • R 1 is an alkyl group having 1 or more and 20 or less carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, which may be substituted independently, respectively.
  • -OSiR 2 3 R 2 is a hydrocarbon group having 1 or more and 20 or less carbon atoms independently).
  • X is independently a hydroxy group or a hydrolyzable group.
  • a is an integer of 1 to 3.
  • the hydrolyzable group is not particularly limited, and for example, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and the like. Can be mentioned. Of these, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferable because of their high activity. Further, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is further preferable, because the hydrolysis property is mild and easy to handle. From the viewpoint of safety, the compounds desorbed by the reaction are ethanol and acetone, respectively, preferably an ethoxy group and an isopropenoxy group.
  • the hydroxy group or the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3.
  • the groups may be the same or different.
  • a in the above formula (2) is preferably 2 or 3, and particularly preferably 3. Further, from the viewpoint of storage stability, a is preferably 2.
  • the R1 in the above formula (2) is, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or a trimethylsiloxy group. , Chloromethyl group, methoxymethyl group and the like. Of these, a methyl group is preferable.
  • hydrolyzable silyl group examples include a methyldimethoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a (chloromethyl) dimethoxysilyl group.
  • Chloromethyl) diethoxysilyl group (dichloromethyl) dimethoxysilyl group, (1-chloroethyl) dimethoxysilyl group, (1-chloropropyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group Group, (ethoxymethyl) dimethoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, (aminomethyl) dimethoxysilyl group, (N, N-dimethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) dimethoxy Cyril group, (N, N-diethylaminomethyl) diethoxysilyl group, (N- (2-aminoethyl) aminomethyl) dimethoxysilyl group, (acetoxymethyl) dimethoxysilyl group, (acetoxymethyl
  • hydrolyzable silyl group-containing resin examples include a hydrolyzable silyl group-containing (meth) acrylic resin, an organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the end of the molecular chain, and a hydrolyzable silyl group.
  • examples include polyurethane resin.
  • the hydrolyzable silyl group-containing (meth) acrylic resin preferably has a repeating constituent unit derived from the hydrolyzable silyl group-containing (meth) acrylic acid ester and / or (meth) acrylic acid alkyl ester in the main chain.
  • hydrolyzable silyl group-containing (meth) acrylic acid ester examples include (meth) acrylic acid 3- (trimethoxysilyl) propyl, (meth) acrylic acid 3- (triethoxysilyl) propyl, and (meth) acrylic acid.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid.
  • examples thereof include stearyl acrylate.
  • As a method for producing a hydrolyzable silyl group-containing (meth) acrylic resin specifically, for example, the hydrolyzable silicon group-containing (meth) acrylic acid ester-based weight described in International Publication No. 2016/035718. Examples thereof include a method for synthesizing coalescence.
  • the organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the terminal portion of the molecular chain has a hydrolyzable silyl group at at least one of the end of the main chain and the end of the side chain.
  • the skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers.
  • polyoxyalkylene-based polymer examples include polyoxyethylene structure, polyoxypropylene structure, polyoxybutylene structure, polyoxytetramethylene structure, polyoxyethylene-polyoxypropylene copolymer structure, and polyoxypropylene-poly.
  • examples thereof include a polymer having an oxybutylene copolymer structure.
  • Specific examples of the method for producing an organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the end of the molecular chain are described in, for example, International Publication No. 2016/035718. Examples thereof include a method for synthesizing an organic polymer having a crosslinkable silyl group only at the terminal site of the molecular chain.
  • an organic polymer having a hydrolyzable silyl group at the end of the molecular chain or the end of the molecular chain for example, the reactive silicon group contained in International Publication No. 2012/11792 is described. Examples thereof include a method for synthesizing a polyoxyalkylene polymer.
  • a silyl group-containing compound such as a silane coupling agent
  • examples thereof include a method of reacting. Specific examples thereof include the 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, and ⁇ -glycidoxy.
  • 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 an isocyanate group is obtained by the above-mentioned method, and further, silane coupling is performed on the moisture-curable urethane resin. It is preferably produced by reacting the agent.
  • the details of the moisture-curable urethane resin having an isocyanate group are as described above.
  • the silane coupling agent that reacts with moisture curability 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. It is preferable to use. Preferred specifics are N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxy. Examples thereof include silane, 3-mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and 3-isocyanuppropyltrimethoxysilane.
  • the moisture-curable resin (A) may have a radically polymerizable functional group other than the moisture-curable urethane resin.
  • a radically polymerizable functional group a group having a reactive double bond is preferable, and a (meth) acryloyl group is more preferable from the viewpoint of reactivity.
  • a moisture-curable resin having a radical-polymerizable functional group other than the moisture-curable urethane resin is not included in the radical-polymerizable compound (B) described later, and is treated as a moisture-curable resin.
  • the moisture-curable resin (A) may be appropriately selected from the above-mentioned various resins and used alone or in combination of two or more.
  • the weight average molecular weight of the moisture-curable resin (A) is not particularly limited, but is preferably 1000 or more and 100,000 or less, more preferably 2000 or more and 70,000 or less, and further preferably 3000 or more and 50,000 or less.
  • the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting into polystyrene.
  • GPC gel permeation chromatography
  • Shodex LF-804 manufactured by Showa Denko KK
  • examples of the solvent used in GPC include tetrahydrofuran.
  • the moisture-curable resin composition preferably further contains the radically polymerizable compound (B).
  • the radically polymerizable compound (B) is not particularly limited as long as it is a radically polymerizable compound having a radically polymerizable functional group in the molecule.
  • the radically polymerizable compound (B) is preferably a compound having an unsaturated double bond as a radically polymerizable functional group, and in particular, a compound having a (meth) acryloyl group (hereinafter, also referred to as “(meth) acrylic compound”). Is preferable.
  • the (meth) acrylic compound it becomes easy to adjust the above-mentioned storage elastic modulus and breaking elongation within a predetermined range.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like.
  • a (meth) acrylic acid ester compound is preferable, and it is also preferable to use a (meth) acrylic acid ester compound and a urethane (meth) acrylate in combination.
  • the urethane (meth) acrylate does not have a residual isocyanate group.
  • (meth) acryloyl group means an acryloyl group or a methacryloyl group
  • (meth) acrylate means an acrylate or a methacrylate
  • the (meth) acrylic acid ester compound may be monofunctional, bifunctional, or trifunctional or higher, but is preferably monofunctional.
  • monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth).
  • -Alicyclic (meth) acrylates such as trimethylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 2-hydroxybutyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, 2-methoxyethyl (meth) acrylates.
  • 2-ethoxyethyl (meth) acrylate alkoxyalkyl (meth) acrylate such as 2-butoxyethyl (meth) acrylate, alkoxyethylene glycol (meth) such as methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate.
  • Acrylate methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, Acrylate polyethylene Examples thereof include polyoxyethylene-based (meth) acrylates such as recall (meth) acrylates.
  • the (meth) acrylic acid ester compound may have an aromatic ring, for example, phenylalkyl (meth) acrylate such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate, and phenoxyethyl (meth).
  • phenylalkyl (meth) acrylate such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate
  • phenoxyethyl (meth) acrylates such as acrylates.
  • it may be a (meth) acrylate having a plurality of benzene rings such as a fluorene skeleton and a biphenyl skeleton, and specific examples thereof include fluorene type (meth) acrylate and ethoxylated o-phenylphenol acrylate.
  • phenoxypolyoxyethylene-based (meth) acrylates such as phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxydiethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate can also be mentioned.
  • examples of the monofunctional (meth) acrylic acid ester compound include tetrahydrofurfuryl (meth) acrylate, alkoxylated tetrahydrofurfuryl (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, and 3-ethyl-3-.
  • (Meta) acrylates having a heterocyclic structure such as oxetanylmethyl (meth) acrylates, phthalimide acrylates such as N-acryloyloxyethyl hexahydrophthalimide, various imide (meth) acrylates, 2,2,2-trifluoroethyl ( Meta) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2 -(Meta) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (me
  • bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ().
  • those having trifunctionality or higher include, for example, trimethylol propanetri (meth) acrylate, ethylene oxide-added trimethylol propanetri (meth) acrylate, and propylene oxide-added trimethylol propanetri (meth) acrylate.
  • Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid.
  • the reaction between the epoxy compound and (meth) acrylic acid may be carried out according to a conventional method in the presence of a basic catalyst or the like.
  • the epoxy (meth) acrylate may be monofunctional or polyfunctional such as bifunctional.
  • Examples of the epoxy compound used as a raw material for synthesizing the above epoxy (meth) acrylate include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a 2,2'-diallyl bisphenol A type epoxy resin.
  • Hydrophobic bisphenol type epoxy resin propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin , Glycidyl ester compound, bisphenol A type episulfide resin and the like.
  • epoxy (meth) acrylates commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL370 ), EA-1010, EA-1020, EA-5323, EA-5520, EACHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester.
  • Denacol Acrylate DA-141 examples thereof include denacole acrylate DA-314 and denacole acrylate DA-911 (both manufactured by Nagase ChemteX Corporation).
  • urethane (meth) acrylate for example, an isocyanate compound reacted with a (meth) acrylic acid derivative having a hydroxyl group can be used.
  • a tin-based compound having a catalytic amount it is preferable to use a tin-based compound having a catalytic amount as a catalyst.
  • the urethane (meth) acrylate may be monofunctional or polyfunctional such as bifunctional.
  • Examples of the isocyanate compound used to obtain urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polypeptide MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Examples thereof include polyisocyanate compounds such as isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecantryisocyanate.
  • MDI 4'-di
  • the isocyanate compound a chain-extended polyisocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.
  • the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
  • monoisocyanate for example, in order to obtain a monofunctional urethane (meth) acrylate, monoisocyanate may be used.
  • the monoisocyanate include alkane monoisocyanates such as butane isocyanate, hexane isocyanate and decane isocyanate, and aliphatic monoisocyanates such as cyclic aliphatic monoisocyanates such as cyclopentane isocyanate, cyclohexane isocyanate and isophorone monoisocyanate.
  • the isocyanate compound for obtaining urethane (meth) acrylate may be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid derivative 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.
  • the (meth) acrylic acid derivative for obtaining urethane (meth) acrylate may be used alone or in combination of two or more.
  • polyfunctional urethane (meth) acrylate a polyisocyanate compound reacted with a (meth) acrylic acid derivative having a hydroxyl group may be used.
  • monofunctional urethane (meth) acrylate one obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with a monoisocyanate compound may be used, but the monoisocyanate compound and a dihydric alcohol mono (mono) Urethane (meth) acrylate obtained by reacting with a meta) acrylate is preferable, and preferred specific examples thereof include 1,2-ethanediol 1-acrylate 2- (N-butylcarbamate).
  • urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Synthetic Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411.
  • a (meth) acrylic compound or a vinyl compound other than the above-mentioned (meth) acrylic acid ester compound may be used in combination.
  • examples of such compounds include (meth) acrylic compounds having a cyclic structure such as (meth) acryloylmorpholine, and vinyl compounds having a cyclic structure such as N-vinyl-2-pyrrolidone and N-vinyl- ⁇ -caprolactam. Can be used.
  • the radically polymerizable compound (B) at least one selected from urethane (meth) acrylate and alkyl (meth) acrylate is used from the viewpoint of facilitating the increase in shear adhesive strength. These are preferable, and these may be used in combination, but it is more preferable to use at least an alkyl (meth) acrylate.
  • the urethane (meth) acrylate is not particularly limited, but is, for example, 1 part by mass or more and 30 parts by mass or less, preferably 5 parts by mass, based on 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). It is contained in an amount of 25 parts by mass or less.
  • the alkyl (meth) acrylate is not particularly limited, but is preferably 5 parts by mass or more and 40 parts by mass or less, for example, with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). Is contained in an amount of 10 parts by mass or more and 30 parts by mass or less.
  • the radically polymerizable compound (B) may be appropriately selected and adjusted so that the cured product does not have a glass transition point within the temperature range of 10 ° C. or higher.
  • the radically polymerizable compound (B) is a compound having a low glass transition point (Tg) when it is homopolymer (a low Tg compound, for example, the above Tg is less than 0 ° C., preferably ⁇ 10 ° C. or lower, more preferably. It is preferable to contain a compound having a temperature of ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower).
  • a compound having a high glass transition point (Tg) when made into a homopolymer so that the cured product does not have a glass transition point in the temperature range of 10 ° C. or higher. It is also preferable to use, for example, a Tg of 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher).
  • Tg glass transition point
  • the shear adhesive strength is likely to be improved.
  • the Tg in parentheses of each of the above compounds is the glass transition temperature when the homopolymer of each compound is used.
  • the radically polymerizable compound (B) contains urethane (meth) acrylate as described above.
  • the urethane (meth) acrylate may be monofunctional or polyfunctional, but preferably contains at least monofunctional. By using a monofunctional urethane (meth) acrylate, it becomes easy to increase the shear adhesive strength. Further, the urethane (meth) acrylate may be the above-mentioned low Tg compound or a high Tg compound.
  • the content of the moisture-curable resin (A) in the moisture-curable resin composition is, for example, 50 parts by mass or more with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). However, it is preferably 60 parts by mass or more. When it is 60 parts by mass or more, the elongation at break tends to be high, and the impact resistance is easily improved.
  • the content of the moisture-curable resin (A) may be 100 parts by mass or less, preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and further preferably 70 parts by mass or less.
  • the content of the moisture-curable resin (A) By setting the content of the moisture-curable resin (A) to 80 parts by mass or less, the content of the radically polymerizable compound (B) becomes a certain amount or more, the viscosity is lowered, and the coatability is improved. In addition, the shape retention after application tends to be good.
  • the content of the radically polymerizable compound (B) may be, for example, 50 parts by mass or less with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). , 40 parts by mass or less is preferable.
  • the radically polymerizable compound (B) does not have to be contained in the moisture-curable resin composition. Therefore, the content of the radically polymerizable compound (B) may be 0 parts by mass or more, which is preferable. Is 20 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more.
  • the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B) is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 75% by mass, based on the total amount of the moisture-curable resin composition. % Or more and 100% by mass or less, but preferably 99% by mass or less, more preferably 97% by mass or less in order to contain other components such as a photopolymerization initiator.
  • the moisture-curable resin composition total amount standard means that the total amount of solid content contained in the moisture-curable resin composition is used as a standard. For example, when the moisture-curable resin composition contains a solvent for diluting the composition, the amount of the component excluding the solvent is the total amount of the moisture-curable resin composition.
  • the moisture-curable resin composition of the present invention may contain a cross-linking agent (X).
  • a cross-linking agent (X) By containing the cross-linking agent (X), the elongation at break and the storage elastic modulus are enhanced, and the adhesive performance and the impact resistance are easily improved.
  • the cross-linking agent (X) is preferably a compound having a functional group capable of reacting with at least one of the above-mentioned moisture-curable resin (A) and radically polymerizable compound (B) when the moisture-curable resin composition is cured. Specific examples thereof include compounds having an isocyanate group. Examples of such a compound include polyisocyanate compounds having two or more isocyanate groups in one molecule.
  • the cross-linking agent (X) is preferably contained in the moisture-curable resin composition when the moisture-curable resin composition contains the radically polymerizable compound (B).
  • polyisocyanate compound used as the cross-linking agent (X) examples include aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds.
  • aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polypeptide MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like.
  • Examples of the aliphatic polyisocyanate compound 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 (isocyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate and the like.
  • an aromatic polyisocyanate compound is preferable, a diphenylmethane diisocyanate and a modified product thereof, and a polypeptide MDI are more preferable, and a diphenylmethane diisocyanate is further preferable, from the viewpoint of increasing the storage elastic modulus and improving the adhesive performance.
  • the polyisocyanate compound may be used alone or in combination of two or more.
  • the content of the cross-linking agent (X) in the moisture-curable resin composition is 0.4 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). It is preferably less than or equal to a part.
  • the content of the moisture-curable resin (A) and the radically polymerizable compound (B) can be secured in a certain amount or more, so that the elongation at break can be easily increased and the impact resistance can be increased. You can improve the sex.
  • the content of the cross-linking agent is more preferably 0.8 parts by mass or more, further preferably 1.0 part by mass or more, still more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less.
  • the moisture-curable resin composition of the present invention preferably contains a photopolymerization initiator (Y) in order to ensure photocurability.
  • a photopolymerization initiator (Y) include a photoradical polymerization initiator. Specifically, benzophenone compounds, acetphenone compounds such as ⁇ -aminoalkylphenone and ⁇ -hydroxyalkylphenone, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like are used. Can be mentioned.
  • photopolymerization initiators include, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, and IRGACURE OX01.
  • examples thereof include ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
  • the content of the photopolymerization initiator (Y) in the moisture-curable resin composition is preferably 0.01 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. More than 5 parts by mass or less.
  • the content of the photopolymerization initiator (Y) is within this range, the obtained moisture-curable resin composition has excellent photocurability and storage stability.
  • the radically polymerizable compound (B) is appropriately cured, and the above-mentioned shear adhesive strength, breaking elongation and the like can be easily adjusted within the predetermined range.
  • the moisture-curable resin composition of the present invention may contain a filler.
  • the moisture-curable resin composition of the present invention has suitable thixo property and can sufficiently retain the shape after coating.
  • a particulate material may be used.
  • the filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Among them, silica is preferable because the obtained moisture-curable resin composition has excellent ultraviolet transparency.
  • the filler may be subjected to a hydrophobic surface treatment such as a silylation treatment, an alkylation treatment and an epoxidation treatment. The filler may be used alone or in combination of two or more.
  • the content of the filler is, for example, 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). It is 5 parts by mass or less, more preferably 5 parts by mass or more and 15 parts by mass or less.
  • the moisture-curable resin composition may contain a coupling agent.
  • a coupling agent By containing a coupling agent, it becomes easy to improve the adhesive strength.
  • the coupling agent include a silane coupling agent, a titanate-based coupling agent, a zirconate-based coupling agent, and the like. Of these, a silane coupling agent is preferable because it is excellent in the effect of improving the adhesiveness.
  • the coupling agent may be used alone or in combination of two or more.
  • the content of the coupling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, preferably 0.2 parts by mass, based on 100 parts by mass of the total amount of the moisture-curable resin (A) and the radically polymerizable compound (B). More than parts and 2 parts by mass are more preferable, and 0.5 parts by mass or more and 1.5 parts by mass or less are further preferable. By setting the content of the coupling agent within these ranges, the adhesive strength can be improved without significantly affecting other physical properties.
  • the moisture-curable resin composition of the present invention may be diluted with a solvent, if necessary.
  • the parts by mass of the moisture-curable resin composition are based on the solid content, that is, the parts by mass excluding the solvent.
  • the moisture-curable resin composition contains wax particles, metal-containing particles, light-shielding agents, colorants, reactive diluents, additives such as moisture-curing accelerators, and the like. May be good.
  • the components constituting the moisture-curable resin composition may be mixed using a mixer.
  • a moisture-curable resin (A), a radically polymerizable compound (B), and a cross-linking agent (X), a photopolymerization initiator (Y), a filler, a coupling agent, and a coupling agent which are blended as needed.
  • the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer (planetary stirrer), a kneader, a three-roll, and the like.
  • the moisture-curable resin composition of the present invention is cured and used as a cured product.
  • the moisture-curable resin composition of the present invention has photocurability, thermosetting, or both, first, it is cured by photocuring, thermosetting, or both by light irradiation or heating. For example, it is good to put it in a B stage state (semi-cured state), and then further cure it with moisture to completely cure it.
  • the moisture-curable resin composition of the present invention is preferably light-moisture-curable. Therefore, it is preferable to photo-cure by light irradiation to obtain a B stage state (semi-cured state), and then further cure by moisture to fully cure.
  • the moisture-curable resin composition is arranged between the adherends, and when the adherends are bonded to each other, the moisture-curable resin composition is applied to one of the adherends, and then photocured by light irradiation or the like.
  • the other adherend is superposed on the moisture-curable resin composition cured to the B stage state, and the adherends are temporarily bonded with an appropriate adhesive force (initial adhesive force). It is good.
  • the moisture-curable resin composition in the B stage state is completely cured by being cured by moisture, and the adherends laminated via the moisture-curable resin composition are joined with sufficient adhesive force. ..
  • the light irradiated at the time of photocuring is not particularly limited as long as it is the light at which the radically polymerizable compound (B) is cured, but ultraviolet rays are preferable.
  • the thermosetting is not particularly limited as long as it is the temperature at which the thermosetting resin is cured, but for example, it may be heated to a temperature of 60 ° C. or higher and lower than 120 ° C., more preferably a temperature of lower than 100 ° C. Further, when the moisture-curable resin composition is cured by moisture, it may be left in the air for a predetermined time.
  • the moisture-curable resin composition is applied to the adherend by using a dispenser.
  • the dispenser include an air dispenser, a jet dispenser, a mono pump dispenser, a screw dispenser, a hand gun dispenser, and the like, and among these, a jet dispenser is preferable.
  • the moisture-curable resin composition is formed into a fine line of, for example, 1 mm or less, preferably about 0.1 to 0.7 mm, with good coatability. It can be applied with a jet dispenser. Further, in the jet dispenser, for example, the moisture-curable resin composition may be heated to about 70 to 100 ° C. and applied.
  • the moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic devices.
  • the moisture-curable resin composition of the present invention is more preferably used as an adhesive for portable electronic devices. More specific examples of the portable electronic device include a mobile phone such as a smartphone, a tablet terminal, and the like.
  • the constituent members that are adherends may be detached if they are accidentally dropped during use, but the moisture-curable resin composition of the present invention is used as an adhesive for portable electronic devices. If so, the cured product of the moisture-curable resin composition of the present invention has excellent impact resistance, so that the adherend is less likely to come off.
  • the adherend is not particularly limited, but is, for example, various parts constituting the electronic device.
  • the various components constituting the electronic device include electronic components or a substrate on which the electronic components are mounted, and more specifically, various electronic components provided on the display element, a substrate on which the electronic components are mounted, a semiconductor chip, and the like. Can be mentioned. That is, the present invention also provides an electronic component provided with a cured product of a moisture-curable resin composition.
  • the material of the adherend may be any of metal, glass, plastic and the like.
  • the shape of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod shape, a box shape, and a housing shape. ..
  • the moisture-curable resin composition of the present invention does not have a glass transition point in the temperature range of 10 ° C. or higher while the cured product of the moisture-curable resin composition has a shear adhesive strength and breaking elongation of a predetermined value or more. As a result, the impact resistance becomes excellent. Therefore, in the moisture-curable resin composition of the present invention, even when the coating width and the adhesive area of the moisture-curable resin composition are small, the adherend may be peeled off, for example, when a large impact is applied to the adherend. Is prevented.
  • an adhesive used to bond semiconductor chips having a small adhesive area or an adhesive used in a display device, for example, a display device for a portable electronic device in which the coating width tends to be small, particularly a display device for a mobile phone such as a smartphone. It is suitably used as an agent.
  • a cured product sample is prepared from the moisture-curable resin composition according to the method described in the specification, and the cured product sample is prepared at 25 ° C. by a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., trade name “DVA-200”).
  • the storage elastic modulus in. The measurement conditions were that the deformation mode was pulled, the set strain was 1%, the measurement frequency was 1 Hz, and the temperature rising rate was 5 ° C./min.
  • a test piece is prepared from the moisture-curable resin composition according to the method described in the specification, and is broken at a speed of 50 mm / min using a tensile tester (manufactured by A & D Co., Ltd., trade name "TENSILON"). The elongation at break was measured at 25 ° C.
  • FIG. 2A The outline of the impact resistance adhesion test is shown in FIG.
  • a 2 mm-thick polycarbonate plate 3 having a 38 mm ⁇ 50 mm rectangular hole 2 in the central portion was prepared.
  • the moisture-curable resin composition 1 was applied to the polycarbonate plate 3 in a square frame shape so that the outer diameter was 46 mm ⁇ 61 mm and the inner diameter was 44 mm ⁇ 59 mm, and the coating width was 1 mm and the rectangular hole 2 was surrounded.
  • the moisture-curable resin composition 1 was photocured by irradiating 1000 mJ / cm 2 of ultraviolet rays in an environment of 25 ° C. and 50% RH using a UV-LED (wavelength 365 nm).
  • a polycarbonate plate 4 having a thickness of 50 mm ⁇ 75 mm and a thickness of 4 mm was attached to the polycarbonate plate 3 via the semi-cured moisture-curable resin composition 1 to assemble a test piece.
  • the center positions of the polycarbonate plate 4 and the moisture-curable resin composition 1 having a square frame shape are aligned with each other. Then, it was inverted from the state of FIG. 2A and arranged so that the polycarbonate plate 3 was placed on the polycarbonate plate 4.
  • the moisture-curable resin composition 1 was moisture-cured by leaving it at room temperature (23 ° C.) for 24 hours at room temperature (23 ° C.) and 50% RH under a pressure of 5 kgf applied from the polycarbonate plate 3 side to moisture-cure the polycarbonate plate 4 and the polycarbonate plate 3. , The completely cured moisture-curable resin composition 1 was used for adhesion.
  • the prepared test piece is fixed to the support base 5, and an iron ball 6 having a weight of 300 g and passing through the rectangular hole 2 is passed through the rectangular hole 2. Dropped from a height of 20 mm. The iron ball was repeatedly dropped under the same conditions, and the impact resistance was judged according to the following evaluation criteria.
  • AA The polycarbonate plate did not peel off even when the iron ball was dropped 80 times.
  • A The polycarbonate plate was peeled off when the iron ball was dropped 40 times or more and less than 80 times.
  • B The polycarbonate plate was peeled off when the number of times the iron ball was dropped was 20 times or more and less than 40 times.
  • B The polycarbonate plate was peeled off when the iron ball was dropped less than 20 times.
  • the moisture-curable resin composition coated on the substrate was exposed to ultraviolet rays of 365 nm with an LED lamp at 25 ° C. and 50% RH at 1000 mJ / cm 5 seconds after the coating was completed. 2 Irradiated. Then, after leaving it in an environment of 25 ° C. and 50% RH for 16 hours, the width (maximum width) and height (maximum height) of the cured product were measured with a laser microscope (trade name "VK-X200", manufactured by KEYENCE CORPORATION). The measurement was performed, and the ratio of the height to the width of the cured product was calculated as the aspect ratio. Based on the calculated aspect ratio, the shape retention was evaluated according to the following evaluation criteria. A: Aspect ratio is 0.4 or more B: Aspect ratio is less than 0.4
  • the components used in the examples and comparative examples were as follows.
  • (Moisture curable resin (A) The moisture-curable urethane resin 1 (PTMG) was produced according to the following Synthesis Example 1.
  • Synthesis Example 1 As a polyol compound, 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG-2000", average molecular weight 2000) and 0.01 parts by mass of dibutyltin dilaurate are placed in a separable flask having a capacity of 500 mL. It was put in, stirred under vacuum (20 mmHg or less) at 100 ° C. for 30 minutes, and mixed.
  • the moisture-curable urethane resin 2 was produced according to the following Synthesis Example 2.
  • Synthesis Example 2 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-3000", average molecular weight 3000) and 0.01 parts by mass of dibutyltin dilaurate as a polyol compound were placed in a separable flask containing 500 mL. Under vacuum (20 mmHg or less), the mixture was stirred at 100 ° C. for 30 minutes and mixed.
  • the moisture-curable urethane resin 3 was produced according to the following Synthesis Example 3.
  • Synthesis Example 3 As a polyol compound, 100 parts by mass of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., "EXCENOL 2020", average molecular weight 2000) and 0.01 parts by mass of dibutyltin dilaurate are placed in a 500 mL separable flask and placed under vacuum (20 mmHg or less). ), Stirred at 100 ° C. for 30 minutes and mixed.
  • the moisture-curable urethane resin 4 (polyester) was produced according to the following Synthesis Example 4.
  • Synthesis Example 4 As a polyol compound, 100 parts by mass of polyester polyol (Kuraray Polyol P-5010 (manufactured by Kuraray), a condensate of adipic acid and 3-methyl-1,5-pentadiol) and 0.01 parts by mass of dibutyltin dilaurate. was placed in a separable flask containing 500 mL, stirred under vacuum (20 mmHg or less) at 100 ° C. for 30 minutes, and mixed.
  • the moisture-curable urethane resin 5 (polycarbonate) was produced according to the following Synthesis Example 5.
  • Synthesis Example 5 As a polyol compound, 100 parts by mass of polycarbonate diol (manufactured by Kuraray, trade name "Kuraraypolyol C-1090") and 0.01 parts by mass of dibutyltin dilaurate were placed in a separable flask having a capacity of 500 mL. The inside of the flask was stirred under vacuum (20 mmHg or less) at 100 ° C. for 30 minutes and mixed.
  • PC polycarbonate
  • PC polycarbonate
  • a PC skeleton aliphatic terminal urethane having both ends being an aliphatic isocyanate group was obtained.
  • the weight average molecular weight of the obtained PC skeletal aliphatic terminal urethane was 7000. 35 parts by mass of the obtained PC skeleton aromatic terminal urethane and 30 parts by mass of the PC skeleton aliphatic terminal urethane were mixed to obtain a moisture-curable urethane resin 5.
  • Isobornyl acrylate Kyoeisha Chemical Co., Ltd., trade name "IB-XA”, monofunctional, Tg: 94 ° C.
  • Tridecyl acrylate manufactured by Sartmer, trade name "SR489D”, monofunctional, Tg: -55 ° C.
  • Stearyl Acrylate Made by Sartmer, trade name "SR257”, monofunctional, Tg: 35 ° C.
  • Aronix M-140 Toagosei Co., Ltd., trade name "Aronix M-140", N-acryloyloxyethyl hexahydrophthalimide
  • Crosslinking agent (X) Diphenylmethane diisocyanate (photopolymerization initiator (Y)) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (BASF, "IRGACURE 369") (Coupling agent) 3-Acryloxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-5103" (filler) Siliconized silica: Made by Aerosil Japan, trade name "RY300"
  • Examples 1 to 9, Comparative Examples 1 to 4 According to the formulation shown in Table 1, each material is stirred at a temperature of 50 ° C. with a planetary stirrer (Sinky Co., Ltd., “Awatori Rentaro”), and then uniformly at a temperature of 50 ° C. with three ceramic rolls. The moisture-curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were obtained.
  • the impact resistance is excellent by increasing both the shear adhesive strength and the elongation at break of the cured product and having no glass transition point in the temperature range of 10 ° C. or higher. It became a thing.
  • the impact resistance was not sufficiently high because either the shear adhesive strength of the cured product or the elongation at break was not high.
  • Comparative Example 3 although both the shear adhesive strength of the cured product and the elongation at break were high, the impact resistance was not sufficiently high due to having the glass transition point in the temperature range of 10 ° C. or higher.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition de résine durcissable à l'humidité comprenant une résine durcissable à l'humidité, et donnant des objets durcis qui ont une résistance de liaison au cisaillement supérieure ou égale à 4 MPa et un allongement à la rupture supérieur ou égal à 600 % et n'ont pas de point de transition vitreuse à des températures supérieures ou égales à 10 °C.
PCT/JP2021/043650 2020-11-30 2021-11-29 Composition de résine durcissable à l'humidité et adhésif pour appareil électronique WO2022114186A1 (fr)

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JP2008133460A (ja) * 2006-10-27 2008-06-12 Asahi Glass Co Ltd 制振材用ウレタン樹脂の製造方法および制振材用ウレタンプレポリマー
WO2015174371A1 (fr) * 2014-05-13 2015-11-19 積水化学工業株式会社 Composition de resine photopolymerisable et reticulables a l'humidite, adhesif pour pieces electroniques, et adhesif pour element d'affichage
JP2016150974A (ja) * 2015-02-17 2016-08-22 積水化学工業株式会社 光湿気硬化型樹組成物硬化体
WO2016167305A1 (fr) * 2015-04-17 2016-10-20 積水化学工業株式会社 Corps durci, composant électronique, élément d'affichage, et composition de résine durcissable à la lumière/l'humidité
JP2018514599A (ja) * 2015-03-10 2018-06-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリオルガノシロキサンおよびそれを含む湿気および放射線硬化性接着剤組成物
WO2020149379A1 (fr) * 2019-01-18 2020-07-23 積水化学工業株式会社 Composition de résine photodurcissable/durcissable à l'humidité et corps durci
WO2020156802A1 (fr) * 2019-02-01 2020-08-06 Basf Se Polyuréthane et produit thermofusible réactif au pur à double durcissement à l'humidité et aux uv comprenant celui-ci

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KR102323646B1 (ko) 2014-11-13 2021-11-08 세키스이가가쿠 고교가부시키가이샤 경화체, 전자 부품, 및, 표시 소자

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Publication number Priority date Publication date Assignee Title
JPH1135699A (ja) * 1997-07-17 1999-02-09 Toray Ind Inc 湿気硬化樹脂からなる製品の製造方法
JP2008133460A (ja) * 2006-10-27 2008-06-12 Asahi Glass Co Ltd 制振材用ウレタン樹脂の製造方法および制振材用ウレタンプレポリマー
WO2015174371A1 (fr) * 2014-05-13 2015-11-19 積水化学工業株式会社 Composition de resine photopolymerisable et reticulables a l'humidite, adhesif pour pieces electroniques, et adhesif pour element d'affichage
JP2016150974A (ja) * 2015-02-17 2016-08-22 積水化学工業株式会社 光湿気硬化型樹組成物硬化体
JP2018514599A (ja) * 2015-03-10 2018-06-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリオルガノシロキサンおよびそれを含む湿気および放射線硬化性接着剤組成物
WO2016167305A1 (fr) * 2015-04-17 2016-10-20 積水化学工業株式会社 Corps durci, composant électronique, élément d'affichage, et composition de résine durcissable à la lumière/l'humidité
WO2020149379A1 (fr) * 2019-01-18 2020-07-23 積水化学工業株式会社 Composition de résine photodurcissable/durcissable à l'humidité et corps durci
WO2020156802A1 (fr) * 2019-02-01 2020-08-06 Basf Se Polyuréthane et produit thermofusible réactif au pur à double durcissement à l'humidité et aux uv comprenant celui-ci

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