Light / moisture-curable resin composition, cured product, method for using light / moisture-curable resin composition, and method for protecting end surface of light / moisture-curable resin composition

Abstract

Provided is a light / moisture-curable resin composition which contains a moisture-curable resin, a radical-polymerizable compound, a photopolymerization initiator, and a colorant, and which has a viscosity value of 80 gf or less as determined by a probe viscosity test after irradiation with ultraviolet light of 3000 mJ / cm2 for 30 seconds.

Description

Technical Field

[0001] The present invention relates to an optical moisture curing type resin composition, a cured product of the optical moisture curing type resin composition, and a method for protecting an end surface of a plate-like member or the like using the optical moisture curing type resin composition. Background Art

[0002] Sometimes, edge protection is performed by applying a curable resin to the outer peripheral side of a plate-like member such as a display member. As a resin composition used for such edge protection, a thermosetting resin or a UV curable resin is generally used.

[0003] For example, Patent Document 1 describes that in order to protect the unstrengthened portion of the outer peripheral side surface of a cover glass for a display device, an uncured resin is applied and then cured, and the cured protective resin is arranged on the outer peripheral side surface. Patent Document 1 describes that as the curable resin, a UV curable resin is preferred, and specifically, a polyene-polythiol resin is preferred.

[0004] Patent Document 2 describes that in a plastic film substrate for a flat-panel display, a UV curable resin or a thermosetting resin is used as a side protective film covering the boundary between the plastic film substrate and the surface protective film. Specifically, it is shown that acrylic resin, epoxy resin, polyurethane resin, polyamide resin, urea resin, polyester resin, etc. can be used as the resin.

[0005] Patent Document 3 discloses a sealing device for applying a resin to an end surface of a bonded substrate having a groove. Patent Document 3 discloses the use of a UV curable resin resistant to etching liquid as the resin.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-182910

[0009] Patent Document 2: Japanese Patent Application Publication No. 2002-178423

[0010] Patent Document 3: Japanese Patent Application Publication No. 2020-204640 Summary of the invention

[0011] Problems to be solved by the invention

[0012] For the resin composition used in protecting the end face of the display component, in order to prevent the display performance of the display component from being reduced due to light leakage, etc., it is sometimes necessary to have light-shielding properties. In addition, for the resin composition used in the end face protection, it is sometimes necessary to color it in the same color as the frame of the surrounding component, etc. Therefore, it has been studied to mix a colorant in the resin composition for end face protection to perform blackening, etc.

[0013] However, if a colorant is added to a UV curable resin, the ultraviolet transmittance is generally reduced, and the curability is reduced. Therefore, when a UV curable resin is used in a resin composition for edge protection, as disclosed in Patent Documents 1 to 3, there is a problem that it is difficult to color the composition by the colorant, such as blackening. In addition, there is also a problem that the UV curable resin is generally prone to insufficient adhesiveness.

[0014] On the other hand, as disclosed in Patent Documents 1 and 2, if a thermosetting resin is used in a resin composition for end face protection, a device having a heating chamber is required to cure the thermosetting resin, and there is also the problem that parts and the like are damaged during the resin curing process. Furthermore, there is the problem that the time from the start of curing to the disappearance of viscosity is long, other undesirable parts may adhere to the applied resin layer, dust may adhere to the resin layer, and the workability is poor.

[0015] The present invention has been completed in view of the above problems, and its object is to provide a curable resin composition that does not require the introduction of large-scale equipment for a curable resin composition containing a colorant, and in addition, does not cause damage to parts etc. due to heat during the resin curing process, and has good adhesion and workability.

[0016] Means of solving the problem

[0017] The present inventors have conducted intensive research and have found that the above-mentioned problems can be solved by making the curable resin composition containing a colorant include a moisture-curable resin, a radical polymerizable compound and a photopolymerization initiator to form a light moisture-curable resin composition, and on this basis, formulating it so that the viscosity value after 30 seconds of ultraviolet irradiation is less than a specified value, thereby completing the following invention. That is, the present invention provides the following [1] to

[20] .

[0018] [1] A light moisture curable resin composition comprising a moisture curable resin, a radical polymerizable compound, a photopolymerization initiator and a colorant, and irradiated with 3000 mJ / cm 2 The viscosity value based on the probe viscosity test after 30 seconds of ultraviolet light is less than 80gf.

[0019] [2] The optical moisture curable resin composition according to [1] above, wherein the radically polymerizable compound includes a radically polymerizable compound having a homopolymer glass transition temperature (Tg) of 40° C. or higher.

[0020] [3] The optical moisture curable resin composition according to [2] above, wherein the content of the radically polymerizable compound having a homopolymer having a glass transition temperature (Tg) of 40° C. or higher is 40 parts by mass or more relative to 100 parts by mass of the radically polymerizable compound contained in the optical moisture curable resin composition.

[0021] [4] The optical moisture curable resin composition according to any one of [1] to [3] above, wherein a cured product of the optical moisture curable resin composition has a maximum glass transition temperature (Tgm) of 40° C. or higher.

[0022] [5] The optical moisture curable resin composition according to any one of [1] to [4] above, wherein the radical polymerizable compound includes a difunctional or higher-functional radical polymerizable compound.

[0023] [6] The optical moisture curable resin composition according to any one of [1] to [5] above, wherein the viscosity at 25° C. is 100 mPa·s or more and 300 Pa·s or less.

[0024] [7] The optical moisture curable resin composition according to any one of [1] to [6] above, wherein the OD value of a cured product having a thickness of 1 mm of the optical moisture curable resin composition is 2 or more.

[0025] [8] The optical moisture-curable resin composition according to any one of [1] to [7] above, wherein the moisture-curable resin is a moisture-curable polyurethane resin.

[0026] [9] The optical moisture-curable resin composition according to [8] above, wherein the moisture-curable polyurethane resin is at least one of moisture-curable polyurethane resins having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton.

[0027]

[10] The optical moisture-curable resin composition according to [9] above, wherein the moisture-curable polyurethane resin having a polyether skeleton comprises a component obtained by using a polyol compound having a structure represented by the following formula (1).

[0028]

[0029] In formula (1), 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, and n is an integer of 1 to 10. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5. It should be noted that the case where l is 0 means that the carbon bonded to R is directly bonded to oxygen.

[0030]

[11] The optical moisture curable resin composition according to any one of [1] to

[10] above, wherein the radical polymerizable compound includes a compound having a (meth)acryloyl group.

[0031]

[12] The optical moisture-curable resin composition according to any one of [1] to

[11] above, wherein the mass ratio of the moisture-curable resin to the radically polymerizable compound (moisture-curable resin / radical polymerizable compound) is 10 / 90 or more and 60 / 40 or less.

[0032]

[13] The optical moisture-curable resin composition according to any one of [1] to

[12] above, wherein the total content of the radical polymerizable compound and the moisture-curable resin is 50% by mass or more.

[0033]

[14] The reactive hot-melt resin composition according to any one of [1] to

[13] , wherein the colorant is a black colorant.

[0034]

[15] The reactive hot-melt resin composition according to any one of [1] to

[14] , wherein the content of the colorant is 0.05 parts by mass or more and 2 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.

[0035]

[16] The reactive hot-melt resin composition according to any one of [1] to

[15] , wherein the colorant is at least one selected from titanium black and zirconium nitride.

[0036]

[17] The optical moisture curable resin composition according to any one of [1] to

[16] above, which is used for edge surface protection.

[0037]

[18] A cured product, which is a cured product of the optical moisture curable resin composition according to any one of [1] to

[17] .

[0038]

[19] Use of the optical moisture curable resin composition according to any one of [1] to

[17] above for protecting the end surface of a plate-like member.

[0039]

[20] A method for protecting an end surface of a plate-like member, comprising the step of applying the optical moisture curable resin composition according to any one of [1] to

[17] above to the end surface of the plate-like member.

[0040] Effects of the Invention

[0041] According to the present invention, a curable resin composition containing a colorant can be provided, which does not require the introduction of a large-scale device, and does not cause damage to parts or the like due to heat during the resin curing process, and has good adhesion and workability. DETAILED DESCRIPTION

[0042] Hereinafter, the present invention will be described in detail with reference to embodiments.

[0043] <Light moisture curing resin composition>

[0044] The optical moisture curable resin composition of the present invention comprises a moisture curable resin, a radical polymerizable compound, a photopolymerization initiator and a colorant, and is irradiated with 3000 mJ / cm 2 The viscosity value based on the probe viscosity test after 30 seconds of ultraviolet light is less than 80gf.

[0045] The light-moisture-curable resin composition of the present invention, by having the above constitution, can be cured by light and moisture without heating, so it can be cured without introducing a large-scale device or without damaging the surrounding parts and the like due to heat during the resin curing process. In addition, since it contains a moisture-curable resin in addition to the free radical polymerizable compound, even if it contains a colorant, it can show high bonding strength by curing with light and moisture. Moreover, the viscosity value (i.e., viscosity) is low after irradiation with ultraviolet rays for 30 seconds, so the stickiness of the surface is immediately reduced after light curing, and the operability becomes good.

[0046] <Viscosity value>

[0047] As described above, the optical moisture curable resin composition of the present invention is irradiated with 3000 mJ / cm 2 The viscosity value of the probe viscosity test after irradiation with ultraviolet rays for 30 seconds is 80 gf or less. If the viscosity value after irradiation with ultraviolet rays for 30 seconds exceeds 80 gf, the viscosity will not be immediately reduced after photocuring, so in the curing process, other undesired parts will be adhered to the light moisture curable resin composition, or dust will be attached, making it difficult to improve the workability.

[0048] In order to further improve the workability, the above viscosity value is preferably 60 gf or less, more preferably 50 gf or less, and further preferably 40 gf or less. In addition, in terms of workability, the lower the viscosity value, the better, and it can be 0 gf or more. In terms of easy moisture curing after light irradiation to improve the bonding strength, it is preferably 5 gf or more, more preferably 10 gf or more, and further preferably 20 gf or more.

[0049] It should be noted that the viscosity value can be obtained as follows: under an environment of 25°C and 50% RH, for a sample irradiated with 3000 mJ / cm 2 The light moisture curing resin composition of ultraviolet light with a wavelength of 365nm is subjected to ultraviolet irradiation for 30 seconds. After the ultraviolet irradiation ends, a probe (SUS, 5mm in diameter) is pressed into the composition with a force of 10gf for 1 second using a probe viscosity tester, and the load when the probe is lifted at a speed of 10mm / second is measured to obtain the viscosity. In more detail, the measurement can be performed according to the method described in the examples.

[0050] For example, the viscosity value can be adjusted to the above-specified range by appropriately adjusting the type and content of the radical polymerizable compound and the moisture curable resin. Specifically, the viscosity value can be easily reduced by using a compound with a high glass transition temperature (Tg) of a homopolymer as a radical polymerizable compound, or by using a specific nitrogen-containing compound such as a cyclic nitrogen-containing compound as a monofunctional radical polymerizable compound. In addition, the viscosity value can also be easily reduced by reducing the ratio of the moisture curable resin to the radical polymerizable compound.

[0051] Hereinafter, each component contained in the optical moisture curing type resin composition is demonstrated in detail.

[0052] [Moisture curing resin]

[0053] As the moisture-curable resin used in the present invention, for example, moisture-curable polyurethane resin, hydrolyzable silyl group-containing resin, moisture-curable cyanoacrylate resin, etc. can be cited. Among them, moisture-curable polyurethane resin and hydrolyzable silyl group-containing resin are preferred, and moisture-curable polyurethane resin is more preferred. These can be used alone or in combination of two or more.

[0054] (Moisture curable polyurethane resin)

[0055] Moisture-curable polyurethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in each molecule with a polyisocyanate compound having two or more isocyanate groups in each molecule. The moisture-curable polyurethane resin can have 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 polyurethane resin can have only one isocyanate group in each molecule, or it can have two or more, preferably one or two isocyanate groups in each molecule, and more preferably two isocyanate groups. In addition, the isocyanate group is not particularly limited and can be provided at the end of the moisture-curable polyurethane resin, for example, it can be provided at both ends.

[0056] The reaction of the polyol compound and the polyisocyanate compound is usually carried out in a molar ratio of hydroxyl group (OH) in the polyol compound to isocyanate group (NCO) in the polyisocyanate compound within the range of [NCO] / [OH]=2.0 to 2.5.

[0057] As the polyol compound of the raw material of the moisture-curable polyurethane resin, known polyol compounds commonly used in the preparation of polyurethane can be used, for example, polyester polyols, polyether polyols, polyalkylene polyols, polycarbonate polyols, etc. These polyol compounds can be used alone or in combination of two or more.

[0058] As the polyisocyanate compound as a raw material of the moisture-curable polyurethane resin, an aromatic polyisocyanate compound or an aliphatic polyisocyanate compound is preferably used.

[0059] Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymeric MDI, toluene diisocyanate, and naphthalene-1,5-diisocyanate.

[0060] Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatemethyl)cyclohexane, and dicyclohexylmethane diisocyanate.

[0061] As the polyisocyanate compound, aromatic polyisocyanate compounds are preferred, and diphenylmethane diisocyanate is more preferred, from the viewpoint of accelerating the moisture curing speed and improving the bonding strength after full curing. In addition, aliphatic polyisocyanate compounds are also preferred from the viewpoint of easily imparting stress relaxation and flexibility to the cured product of the light moisture curing resin composition.

[0062] The polyisocyanate compound may be used alone or in combination of two or more.

[0063] The moisture-curable polyurethane resin is preferably at least one of a moisture-curable polyurethane resin having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, and more preferably a moisture-curable polyurethane resin having a polyether skeleton. The moisture-curable polyurethane resin has a polyether skeleton, which makes it easy to improve the adhesive strength after moisture curing. In addition, it is also easy to improve the softness of the cured product of the light moisture curable resin composition.

[0064] (Moisture-curable polyurethane resin having a polyether skeleton)

[0065] The moisture-curable polyurethane resin having a polyether skeleton is a resin in which a polyether skeleton is introduced into a polyurethane resin by using a polyether polyol as the above-mentioned polyol compound. The polyurethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule. The polyisocyanate compound is as described above.

[0066] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, ring-opening polymers of 2-methyltetrahydrofuran, random copolymers or block copolymers thereof or derivatives thereof, and bisphenol-type polyoxyalkylene-modified products.

[0067] Here, the bisphenol type polyoxyalkylene modified product is a polyether polyol obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen part of the bisphenol type molecular skeleton. The polyether polyol can be a random copolymer or a block copolymer. For the above-mentioned bisphenol type polyoxyalkylene modified product, it is preferred that one or more alkylene oxides are added to both ends of the bisphenol type molecular skeleton.

[0068] The bisphenol type is not particularly limited, and examples thereof include A type, F type, S type, etc., and bisphenol A type is preferred.

[0069] The moisture-curable polyurethane resin having a polyether skeleton preferably comprises a substance obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyol compound having a structure represented by the following formula (1), a light moisture-curable resin composition having excellent adhesion and a cured product having softness and good elongation can be obtained, and the compatibility with free radical polymerizable compounds is also excellent.

[0070] Among them, from the perspective of making the viscosity of the optical moisture curing resin composition reach an appropriate range and easily improving the coating property, it is preferred to use a polyether polyol formed by a ring-opening polymer compound of polypropylene glycol, polytrimethylene glycol, tetrahydrofuran (THF), or a ring-opening polymer compound of tetrahydrofuran having a methyl group or the like such as 3-methyltetrahydrofuran, and more preferably a polypropylene glycol and a ring-opening polymer compound of tetrahydrofuran (THF). The ring-opening polymer compound of the tetrahydrofuran (THF) compound is usually polytetramethylene ether glycol.

[0071] In addition, the polyether polyol may be used individually by 1 type, or may use 2 or more types together.

[0072]

[0073] In formula (1), 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, and n is an integer of 1 to 10. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5. It should be noted that when l is 0, it means that the carbon bonded to R is directly bonded to oxygen.

[0074] In the above, the total of n and 1 is more preferably 1 or more, and further preferably 1 to 3. In addition, R is more preferably a hydrogen atom or a methyl group.

[0075] (Moisture-curable polyurethane resin having a polycarbonate skeleton)

[0076] The moisture-curable polyurethane resin having a polycarbonate skeleton is a resin in which a polycarbonate skeleton is introduced into a polyurethane resin by using a polycarbonate polyol as the above-mentioned polyol compound. The moisture-curable polyurethane resin having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule. The polyisocyanate compound is as described above.

[0077] As the polycarbonate polyol, polycarbonate diol is preferred, and specific preferred examples of the polycarbonate diol include compounds represented by the following formula (2).

[0078]

[0079] In formula (2), R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 2 to 500.

[0080] In formula (2), R is preferably an aliphatic saturated hydrocarbon group. By making R an aliphatic saturated hydrocarbon group, it is easy to improve heat resistance. In addition, it is not easy to yellow due to thermal degradation, etc., and weather resistance is also improved. R consisting of an aliphatic saturated hydrocarbon group can have a chain structure or a cyclic structure, but it is preferably a chain structure from the perspective of easily making stress relaxation and flexibility good. In addition, the chain structure R can be any one of a straight chain or a branched chain.

[0081] n is preferably 5 to 200, more preferably 10 to 150, and even more preferably 20 to 50. R is preferably 5 to 12.

[0082] The R contained in the polycarbonate polyol constituting the moisture-curable polyurethane resin may be used alone or in combination of two or more. When two or more are used in combination, at least a portion of them is preferably a chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms.

[0083] The chain aliphatic saturated hydrocarbon group having 6 or more carbon atoms preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

[0084] As a specific example of R in formula (2), it can be a straight chain such as tetramethylene, pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc., or a branched chain such as methylpentylene such as 3-methylpentylene, methyloctamethylene, etc. The multiple Rs in each molecule can be the same as or different from each other. Therefore, more than two kinds of R can be included in each molecule, in which case, it is preferred to include two or three kinds of R in each molecule. For example, a polycarbonate polyol can be a copolymer containing R with a carbon number of less than 6 and R with a carbon number of more than 7 in each molecule, in which case any one of R can be a chain-like aliphatic saturated hydrocarbon group.

[0085] In addition, R in formula (2) may contain a linear aliphatic saturated hydrocarbon group or a branched aliphatic saturated hydrocarbon group. R in the polycarbonate polyol may contain a combination of a branched and a linear R, or a linear R alone may be used.

[0086] In addition, the polycarbonate polyol may be used individually by 1 type, or may use 2 or more types together.

[0087] (Moisture-curable polyurethane resin having a polyester skeleton)

[0088] The moisture-curable polyurethane resin having a polyester skeleton is a resin in which a polyester skeleton is introduced into a polyurethane resin by using a polyester polyol as the above-mentioned polyol compound. The moisture-curable polyurethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule.

[0089] Examples of the polyester polyol include polyester polyols obtained by reaction between polycarboxylic acid and polyol, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone.

[0090] The polycarboxylic acid as a raw material of the polyester polyol includes, for example, phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid, etc. Among them, phthalic acid or adipic acid is preferred from the viewpoint of being easy to further improve the adhesive force at high temperature.

[0091] Examples of the polyols as raw materials of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanediol. Among them, 1,6-hexanediol or 1,4-butanediol is preferred because it is easy to further improve the adhesive force at high temperatures.

[0092] Moreover, as a polyisocyanate compound, the above-mentioned polyisocyanate compounds can be used.

[0093] In addition, the polyester polyol may be used individually by 1 type, or may use 2 or more types together.

[0094] The above-mentioned moisture-curable polyurethane resin with polycarbonate, polyester or polyether skeleton can have two or more skeletons in the molecule, for example, can have a polycarbonate skeleton and a polyester skeleton. At this time, as the above-mentioned polyol compound as a raw material, polycarbonate polyol and polyester polyol can be used. Similarly, moisture-curable polyurethane resin with a polyester skeleton and a polyether skeleton etc. can also be used.

[0095] The moisture-curable polyurethane resin may be an isocyanate group-containing resin as described above, but is not limited to the isocyanate group-containing resin and may be a hydrolyzable silyl group-containing polyurethane resin as described in the hydrolyzable silyl group-containing resin described later.

[0096] (Hydrolyzable silyl group-containing resin)

[0097] The hydrolyzable silyl group-containing resin used in the present invention is cured by the reaction of the hydrolyzable silyl group in the molecule with moisture in the air or in the adherend.

[0098] The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group per molecule, or may have two or more hydrolyzable silyl groups. Among them, it is preferred that the resin has hydrolyzable silyl groups at both ends of the main chain of the molecule.

[0099] It should be noted that the hydrolyzable silyl group-containing resin does not include a resin having an isocyanate group.

[0100] The hydrolyzable silyl group is represented by the following formula (3).

[0101] -SiR 1 3-a X a (3)

[0102] In formula (3), R 1Each independently represents 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(R 2 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms. In the formula (3), each X independently represents a hydroxyl group or a hydrolyzable group. In the formula (3), a represents an integer of 1 to 3.

[0103] The hydrolyzable group is not particularly limited, and examples thereof include halogen atoms, alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, ketoxime ester groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfhydryl groups, etc. Among them, from the perspective of high activity, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferred. In addition, from the perspective of stable hydrolysis and easy handling, alkoxy groups such as methoxy groups and ethoxy groups are more preferred, and methoxy groups and ethoxy groups are further preferred. In addition, from the perspective of safety, the compounds separated by the reaction are ethanol and acetone, respectively, preferably ethoxy groups and isopropyleneoxy groups.

[0104] The hydroxyl group or the hydrolyzable group may be bonded to one silicon atom in a range of 1 to 3. When two or more hydroxyl groups or the hydrolyzable groups are bonded to one silicon atom, these groups may be the same or different.

[0105] From the viewpoint of curability, 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.

[0106] In addition, as R in the above formula (3), 1 Examples thereof include methyl, alkyl groups such as ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, trimethylsilyloxy, chloromethyl, methoxymethyl, etc. Among them, methyl is preferred.

[0107] Examples of the hydrolyzable silyl group include methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, tri(2-propenyloxy)silyl, triacetoxysilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (dichloromethyl)dimethoxysilyl, (1-chloroethyl)dimethoxysilyl, (1-chloropropyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl. alkyl, (ethoxymethyl)dimethoxysilyl, (1-methoxyethyl)dimethoxysilyl, (aminomethyl)dimethoxysilyl, (N,N-dimethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl, (N-(2-aminoethyl)aminomethyl)dimethoxysilyl, (acetoxymethyl)dimethoxysilyl, (acetoxymethyl)diethoxysilyl and the like.

[0108] Examples of the hydrolyzable silyl group-containing resin include hydrolyzable silyl group-containing (meth)acrylic resins, organic polymers having a hydrolyzable silyl group at or at a molecular chain terminal, and hydrolyzable silyl group-containing polyurethane resins.

[0109] The hydrolyzable silyl group-containing (meth)acrylic resin preferably has a repeating structural unit derived from a hydrolyzable silyl group-containing (meth)acrylic acid ester and / or an alkyl (meth)acrylate in the main chain.

[0110] Examples of the (meth)acrylate containing a hydrolyzable silyl group include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 2-(trimethoxysilyl)ethyl (meth)acrylate, 2-(triethoxysilyl)ethyl (meth)acrylate, 2-(methyldimethoxysilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, triethoxysilylmethyl (meth)acrylate, and (methyldimethoxysilyl)methyl (meth)acrylate.

[0111] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and stearyl (meth)acrylate.

[0112] Specific examples of the method for preparing a hydrolyzable silyl group-containing (meth)acrylic resin include a method for synthesizing a hydrolyzable silicon group-containing (meth)acrylic ester polymer described in International Publication No. 2016 / 035718.

[0113] The organic polymer having a hydrolyzable silyl group at a molecular chain terminal or at a molecular chain terminal site has a hydrolyzable silyl group at at least one of a main chain terminal and a side chain terminal.

[0114] The skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth)acrylic acid ester polymers, and the like.

[0115] Examples of the polyoxyalkylene polymer include polymers having a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, and a polyoxypropylene-polyoxybutylene copolymer structure.

[0116] As a method for preparing the above-mentioned organic polymer having a hydrolyzable silyl group at the molecular chain end or at the molecular chain end portion, specifically, for example, the synthesis method of an organic polymer having only a crosslinkable silyl group at the molecular chain end or at the molecular chain end portion described in International Publication No. 2016 / 035718 can be cited. In addition, as other methods for preparing the above-mentioned organic polymer having a hydrolyzable silyl group at the molecular chain end or at the molecular chain end portion, for example, the synthesis method of a polyoxyalkylene polymer containing a reactive silicon group described in International Publication No. 2012 / 117902 can be cited.

[0117] As a method for preparing the above-mentioned polyurethane resin containing a hydrolyzable silyl group, for example, when a polyol compound and a polyisocyanate compound are reacted to prepare a polyurethane resin, a method of further reacting a silyl group-containing compound such as a silane coupling agent, etc. Specifically, for example, a method for synthesizing a polyurethane oligomer having a hydrolyzable silyl group described in Japanese Patent Application Laid-Open No. 2017-48345 can be cited.

[0118] Examples of the silane coupling agent include vinyl trichlorosilane, vinyl triethoxysilane, vinyl tri(β-methoxy-ethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, γ-methacryloxypropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethyl dimethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, γ-chloropropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane. Among them, γ-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferred. These silane coupling agents may be used alone or in combination of two or more.

[0119] In addition, the moisture-curable polyurethane resin may have two groups, an isocyanate group and a hydrolyzable silyl group. The moisture-curable polyurethane resin having two groups, an isocyanate group and a hydrolyzable silyl group, is preferably prepared by the following method: first, a moisture-curable polyurethane resin having an isocyanate group (raw polyurethane resin) is obtained by the above method, and then a silane coupling agent is reacted with the raw polyurethane resin.

[0120] It should be noted that the details of the moisture-curable polyurethane resin with isocyanate groups are as described above. As a silane coupling agent reacting with the raw material polyurethane resin, it is appropriate to select and use from the silane coupling agents listed above. From the perspective of reactivity with isocyanate groups, it is preferred to use a silane coupling agent with an amino group or a mercapto group. As a preferred specific example, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethyl dimethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, etc. can be listed.

[0121] Moreover, the moisture-curable resin may also have a free radical polymerizable functional group. As the free radical polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferred, and in particular, a (meth)acryloyl group is more preferred from the aspect of reactivity. For the moisture-curable resin having a free radical polymerizable functional group, for example, it may be a resin having an unsaturated double bond such as a (meth)acryloyl group and an isocyanate group, or it may be a resin having at least one group selected from two or more unsaturated double bond groups and isocyanate groups. In addition, the moisture-curable resin having a free radical polymerizable functional group may have an unsaturated double bond and an isocyanate group at each end. It should be noted that the moisture-curable resin having a free radical polymerizable functional group is not included in the free radical polymerizable compound described later, and is treated as a moisture-curable resin.

[0122] The moisture-curable resin may be appropriately selected from the above-mentioned various resins and used alone or in combination of two or more.

[0123] The weight average molecular weight of the moisture curable resin is preferably 800 to 30000. By making the weight average molecular weight within the above range, it is easy to improve the adhesive strength of the moisture curable resin composition after moisture curing. In addition, it is also possible to prevent the viscosity of the moisture curable resin composition from becoming higher than necessary.

[0124] From these viewpoints, the weight average molecular weight of the moisture-curable resin is more preferably 1,500 or more, further preferably 2,000 or more, and is more preferably 20,000 or less, further preferably 10,000 or less, and further preferably 6,000 or less.

[0125] In addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion measured by gel permeation chromatography (GPC).

[0126] [Radical polymerizable compound]

[0127] The light moisture curable resin composition of the present invention contains a free radical polymerizable compound. The light moisture curable resin composition is given photocurability by containing a free radical polymerizable compound. The light moisture curable resin composition has photocurability, so that a certain adhesive force can be given only by light irradiation, and thus a certain initial adhesive force can be ensured.

[0128] The radical polymerizable compound may have any radical polymerizable functional group in the molecule. The radical polymerizable functional group is preferably a compound having an unsaturated double bond, and examples thereof include (meth)acryloyl, vinyl, styryl, and allyl groups.

[0129] Among the above functional groups, (meth)acryloyl is preferred from the aspect of adhesion, that is, the free radical polymerizable compound preferably contains a compound having a (meth)acryloyl group. It should be noted that the compound having a (meth)acryloyl group is also referred to as a "(meth)acrylic acid compound" below. In addition, in this specification, "(meth)acryloyl" refers to acryloyl or (meth)acryloyl, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and other similar terms are the same.

[0130] The radical polymerizable compound may include one or both of a monofunctional radical polymerizable compound having one radical polymerizable functional group per molecule and a difunctional or higher radical polymerizable compound having two or more radical polymerizable functional groups per molecule (multifunctional radical polymerizable compound). Among them, the radical polymerizable compound preferably contains a multifunctional radical polymerizable compound, and more preferably contains a multifunctional radical polymerizable compound and a monofunctional radical polymerizable compound. For the multifunctional radical polymerizable compound, as long as it is difunctional or higher, there is no particular limitation, preferably 2 to 4 functional, more preferably 2 to 3 functional, and further preferably difunctional.

[0131] The light moisture curable resin composition can easily improve curability by containing a multifunctional free radical polymerizable compound, and can easily reduce viscosity and increase adhesive strength after light curing or moisture curing by containing a monofunctional free radical polymerizable compound.

[0132] In the case where the radical polymerizable compound contains both a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound, the mass ratio of the polyfunctional radical polymerizable compound to the monofunctional radical polymerizable compound (polyfunctional / monofunctional) is preferably 0.01 or more and 1 or less. By being within the above range, both curability and bonding strength are easily improved. The mass ratio of the polyfunctional radical polymerizable compound to the monofunctional radical polymerizable compound (polyfunctional / monofunctional) is more preferably 0.05 or more and 0.5 or less, and further preferably 0.1 or more and 0.3 or less.

[0133] (Monofunctional radical polymerizable compound)

[0134] The monofunctional radical polymerizable compound may be a nitrogen-containing compound containing nitrogen in the molecule or a nitrogen-free compound containing no nitrogen in the molecule. In addition, a nitrogen-containing compound and a nitrogen-free compound may be used in combination as the monofunctional radical polymerizable compound.

[0135] In the case of a light moisture curable resin composition, by containing a nitrogen-containing compound as a monofunctional free radical polymerizable compound, the viscosity of the light moisture curable resin composition immediately after photocuring can be further reduced. On the other hand, in the case of a light moisture curable resin composition, by containing a non-nitrogen-containing compound as a monofunctional free radical polymerizable compound, the adhesive strength of the cured product can be easily improved.

[0136] The monofunctional radical polymerizable compound may be a prepolymer having a repeating unit after polymerization, or a monofunctional monomer having no repeating unit may be used. The use of a monofunctional radical polymerizable compound having no repeating unit makes it easier to reduce the viscosity at 25° C. described below.

[0137] In addition, the monofunctional radical polymerizable compound may be used individually by 1 type, or may use 2 or more types together.

[0138] As the nitrogen-containing compound used as the monofunctional free radical polymerizable compound, both a chain nitrogen-containing compound and a nitrogen-containing compound having a ring structure may be used, and a nitrogen-containing compound having a ring structure is preferably used. By using a nitrogen-containing compound having a ring structure, it is easy to reduce the viscosity of the light moisture curable resin composition immediately after light curing. In addition, it is easy to reduce the viscosity of the light moisture curable resin composition and adjust the viscosity at 25°C described later to a desired range.

[0139] In this specification, nitrogen-containing compounds having a ring structure are also referred to as cyclic nitrogen-containing compounds, radical polymerizable compounds containing nitrogen atoms in atoms constituting the ring itself are regarded as cyclic nitrogen-containing compounds, and other nitrogen-containing compounds are regarded as chain nitrogen-containing compounds.

[0140] Examples of the nitrogen-containing compound having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam, compounds containing a morpholine skeleton such as N-acryloylmorpholine, and cyclic imide compounds such as N-(meth)acryloyloxyethylhexahydrophthalimide.

[0141] Examples of the chain nitrogen-containing compound include chain amino-containing (meth)acrylates such as dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; chain (meth)acrylamide compounds such as diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, and methacrylamide; and N-vinylacetamide.

[0142] The chain nitrogen-containing compound may be a monofunctional urethane (meth)acrylate. As the monofunctional urethane (meth)acrylate, for example, one obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be used.

[0143] Examples of the (meth)acrylic acid derivative having a hydroxyl group include mono(meth)acrylates of diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol and polyethylene glycol; and mono(meth)acrylates of triols such as trimethylolethane, trimethylolpropane and glycerol.

[0144] Examples of the isocyanate compound used to obtain the monofunctional urethane (meth)acrylate include aliphatic monoisocyanates such as alkane monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate, and cyclic aliphatic monoisocyanates such as cyclopentane isocyanate, cyclohexane isocyanate, and isophorone monoisocyanate.

[0145] More specifically, the monofunctional urethane (meth)acrylate is preferably a urethane (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compound with a mono(meth)acrylate of a diol, and a preferred specific example thereof is 1,2-ethylene glycol 1-acrylate 2-(N-butyl carbamate).

[0146] In the case where the optical moisture curable resin composition contains a nitrogen-containing compound as a monofunctional free radical polymerizable compound, from the viewpoint of reducing the viscosity immediately after irradiation with ultraviolet rays, the content of the nitrogen-containing compound is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, and further preferably 50 parts by mass or more relative to 100 parts by mass of the free radical polymerizable compound contained in the optical moisture curable resin composition. In addition, in order to contain an appropriate amount of free radical polymerizable compounds other than the nitrogen-containing compound, the above-mentioned content of the nitrogen-containing compound as a monofunctional free radical polymerizable compound is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less.

[0147] As described above, the nitrogen-containing compound as the monofunctional radical polymerizable compound is preferably a cyclic nitrogen-containing compound. Therefore, the suitable content range of the cyclic nitrogen-containing compound as the monofunctional radical polymerizable compound is the same as the content range of the nitrogen-containing compound described above.

[0148] The nitrogen-free compound used as the monofunctional radical polymerizable compound is not particularly limited as long as it is a compound having a radical polymerizable functional group, but a monofunctional (meth)acrylic compound is preferred, and a (meth)acrylate compound is more preferred.

[0149] Examples of the monofunctional (meth)acrylate compound include alkyl (meth)acrylates, (meth)acrylates containing alicyclic structures, (meth)acrylates containing aromatic rings, and the like. These may be used alone or in combination of two or more. Among the monofunctional (meth)acrylate compounds, (meth)acrylates containing alicyclic structures are preferably used.

[0150] As described below, the alicyclic structure-containing (meth)acrylate easily increases the glass transition temperature of the homopolymer and easily reduces the viscosity immediately after ultraviolet irradiation. In addition, it easily reduces the viscosity of the optical moisture curable resin composition and adjusts the viscosity at 25° C. described below to a desired range.

[0151] In addition, from the viewpoint of being easy to further reduce the viscosity immediately after ultraviolet irradiation, the alicyclic structure-containing (meth)acrylate is more preferably used in combination with the above-mentioned nitrogen-containing compound as a monofunctional radical polymerizable compound.

[0152] The content of the (meth)acrylate containing an alicyclic structure in the radical polymerizable compound is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more, relative to 100 parts by mass of the radical polymerizable compound. In addition, in view of containing a certain amount or more of other radical polymerizable compounds, the content of the (meth)acrylate containing an alicyclic structure is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and further preferably 50 parts by mass or less.

[0153] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 18 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-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, and stearyl (meth)acrylate.

[0154] Examples of (meth)acrylates containing an alicyclic structure include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and adamantyl (meth)acrylate. It should be noted that the alicyclic structure is a ring structure in which the ring constituent elements are composed of carbon atoms.

[0155] Examples of the aromatic ring-containing (meth)acrylate include benzyl (meth)acrylate, phenylalkyl (meth)acrylate such as 2-phenylethyl (meth)acrylate, and phenoxyalkyl (meth)acrylate such as phenoxyethyl (meth)acrylate.

[0156] As the monofunctional (meth)acrylate compound, compounds other than alkyl (meth)acrylates, (meth)acrylates containing an alicyclic structure, and (meth)acrylates containing an aromatic ring may be used. For example, (meth)acrylates containing a cyclic ether group may be used.

[0157] Examples of the cyclic ether group-containing (meth)acrylate include (meth)acrylates having an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a dioxolane ring, a dioxane ring, and the like.

[0158] As (meth)acrylates containing epoxy rings, for example, glycidyl (meth)acrylate can be cited. As (meth)acrylates containing oxetane rings, (meth)acrylate (3-ethyloxetane-3-yl)methyl can be cited. As (meth)acrylates containing tetrahydrofuran rings, (meth)acrylate tetrahydrofurfuryl, (meth)acrylate polymers of tetrahydrofurfuryl alcohol can be cited. As (meth)acrylates containing dioxolanes, (meth)acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl, (meth)acrylate (2,2-cyclohexyl-1,3-dioxolan-4-yl)methyl, etc. can be cited. As (meth)acrylates having dioxane rings, cyclic trimethylolpropane formal (meth)acrylate can be cited.

[0159] As the cyclic ether group-containing (meth)acrylate, it is preferred to use either an oxetane ring-containing (meth)acrylate or a tetrahydrofuran ring-containing (meth)acrylate, and it is also preferred to use them in combination.

[0160] In addition, as the monofunctional (meth)acrylate compound, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 2-butoxyethyl (meth)acrylate, alkoxyethylene glycol (meth)acrylates such as methoxyethylene glycol (meth)acrylate and ethoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethylcarbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, and polyoxyethylene (meth)acrylates such as ethoxypolyethylene glycol (meth)acrylate can be used.

[0161] As the monofunctional (meth)acrylic acid compound, a carboxyl group-containing (meth)acrylic acid compound such as acrylic acid or methacrylic acid can be used.

[0162] (Multifunctional radical polymerizable compound)

[0163] Examples of the polyfunctional radical polymerizable compound include bifunctional (meth)acrylate compounds, trifunctional or higher functional (meth)acrylate compounds, bifunctional or higher functional urethane (meth)acrylates, etc. Among them, urethane (meth)acrylates are preferred because they can easily improve the flexibility of the cured product.

[0164] In addition, the polyfunctional radical polymerizable compound may be used individually by 1 type, or may use 2 or more types together.

[0165] Examples of the bifunctional (meth)acrylate compound include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate. di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dihydroxymethyl dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylate 2-hydroxy-3-(meth)acryloyloxypropyl, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, and the like.

[0166] Examples of trifunctional or higher-functional (meth)acrylate 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, glycerol tri(meth)acrylate, propylene oxide-added glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0167] As for the bifunctional or higher-functional urethane (meth)acrylate, for example, what is obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be used.

[0168] Examples of the (meth)acrylic acid derivative having a hydroxyl group include mono(meth)acrylates of diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol; mono(meth)acrylates or di(meth)acrylates of triols such as trimethylolethane, trimethylolpropane, and glycerol; and epoxy(meth)acrylates such as bisphenol A epoxy(meth)acrylate.

[0169] Examples of the isocyanate compound used to obtain the urethane (meth)acrylate include polyisocyanate compounds such as isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)phosphorothioate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

[0170] In addition, as the isocyanate compound, a chain-extended polyisocyanate compound (modified polyol) obtained by reacting a polyol with an excess of an isocyanate compound may also be used. Here, as the polyol, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. may be cited.

[0171] By using the above polyisocyanate compound, a polyfunctional urethane (meth)acrylate can be obtained.

[0172] (Radical polymerizable compound having a Tg of 40°C or higher)

[0173] The radical polymerizable compound of the present invention preferably includes a radical polymerizable compound (hereinafter sometimes referred to as a "high Tg compound") having a homopolymer glass transition temperature (hereinafter sometimes referred to as "Tg") of 40°C or higher. In the present invention, the radical polymerizable compound contains a high Tg compound, which makes it easy to reduce the viscosity immediately after ultraviolet irradiation.

[0174] For the high Tg compound, the glass transition temperature of the homopolymer is more preferably 50° C. or higher. The upper limit of the glass transition temperature of the high Tg compound is not particularly limited, and is, for example, 260° C. or lower, 200° C. or lower, or 160° C. or lower.

[0175] It should be noted that the glass transition temperature (Tg) of a homopolymer of a radical polymerizable compound is generally known, and the values ​​described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) etc. may be referred to. In addition, for substances not described in the above literature, a homopolymer of a radical polymerizable compound may be prepared and measured by the same measuring method as the measuring method of the glass transition temperature (Tgm) described later.

[0176] As the high Tg compound, a compound having a Tg of 40°C or above among the above-mentioned free radical polymerizable compounds can be appropriately selected and used. The high Tg compound can be a monofunctional free radical polymerizable compound or a polyfunctional free radical polymerizable compound, preferably a monofunctional free radical polymerizable compound. In addition, among the monofunctional free radical polymerizable compounds, cyclic nitrogen-containing compounds, (meth)acrylates containing alicyclic structures, and the like are preferred. Specifically, as cyclic nitrogen-containing compounds, compounds containing a morpholine skeleton such as N-acryloylmorpholine (Tg: 145°C), N-acryloyloxyethylhexahydrophthalimide (Tg: 56°C), and the like can be cited.

[0177] In addition, as the (meth)acrylate containing an alicyclic structure, acrylate containing an alicyclic structure such as 3,3,5-trimethylcyclohexyl acrylate (Tg: 52°C), isobornyl acrylate (Tg: 97°C), dicyclopentenyl acrylate (Tg: 120°C), 1-adamantyl acrylate (Tg: 153°C), and 4-tert-butylcyclohexyl acrylate (Tg: 80°C) can be preferably used, among which 3,3,5-trimethylcyclohexyl acrylate and isobornyl acrylate are more preferred.

[0178] The high Tg compound may be used alone or in combination of two or more.

[0179] When the free radical polymerizable compound contains a high Tg compound, the content of the high Tg compound is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, further preferably 55 parts by mass or more, and further preferably 70 parts by mass or more relative to 100 parts by mass of the free radical polymerizable compound contained in the light moisture curable resin composition. The free radical polymerizable compound contains a large amount of the high Tg compound, which makes it easy to reduce the viscosity just after irradiation with ultraviolet rays.

[0180] The higher the content of the high Tg compound in the radical polymerizable compound, the better. The content of the high Tg compound may be 100 parts by mass or less based on 100 parts by mass of the radical polymerizable compound, and may be 90 parts by mass or less in view of the inclusion of other compounds.

[0181] The mass ratio of the moisture-curable resin in the light moisture-curable resin composition to the free radical polymerizable compound (moisture-curable resin / free radical polymerizable compound) is preferably 10 / 90 or more and 60 / 40 or less. By making the mass ratio above the above lower limit, it is easy to make the bonding strength of the light moisture-curable resin composition after moisture curing reach a certain value or more. In addition, by setting it below the above upper limit, it is easy to reduce the viscosity just after ultraviolet irradiation, and then it is easy to adjust the viscosity to the desired range. Considering these aspects, the above mass ratio is more preferably 15 / 85 or more, more preferably 20 / 80 or more, and more preferably 25 / 75 or more. In addition, it is more preferably 50 / 50 or less, more preferably 45 / 55 or less, and more preferably 40 / 60 or less.

[0182] The total content of the radical polymerizable compound and the moisture curable resin in the light moisture curable resin composition is not particularly limited, and is based on the total amount of the light moisture curable resin composition, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. By making their total amount above the above lower limit, it is easy to give appropriate light curing and moisture curing properties to the moisture curable resin composition. In addition, the above total content can be less than 100% by mass, but in order to appropriately contain other components, it is preferably 99% by mass or less, and more preferably 98% by mass or less.

[0183] The optical moisture curable resin composition may contain a resin component other than a radical polymerizable compound and a moisture curable resin as a resin component within the range not impairing the effects of the present invention, for example, a resin component such as a thermoplastic resin that is not curable (for example, an acrylic resin, a polyurethane resin, etc.), a thermosetting resin, etc. The proportion of the resin component other than the radical polymerizable compound and the moisture curable resin relative to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture curable resin is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less.

[0184] [Photopolymerization initiator]

[0185] The optical moisture curable resin composition of the present invention contains a photopolymerization initiator. The optical moisture curable resin composition is appropriately given photocurability by containing a photopolymerization initiator. Therefore, it is easy to make the viscosity value after the ultraviolet irradiation below a certain value.

[0186] Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, alkylphenone photopolymerization initiators, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.

[0187] Examples of commercially available photopolymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and IRGACURE TPO (all manufactured by BASF), benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0188] The content of the photopolymerization initiator in the light moisture curable resin composition is preferably 0.1 mass part or more and 10 mass parts or less, more preferably 0.3 mass part or more and 5 mass parts or less, and further preferably 0.5 mass part or more and 3 mass parts or less, relative to 100 mass parts of the free radical polymerizable compound. By setting the content of the photopolymerization initiator to above the above lower limit, the photocurability of the obtained light moisture curable resin composition becomes excellent, and it is easy to make the viscosity value after ultraviolet irradiation also below a certain value. In addition, by setting it to below the above upper limit, it becomes easy to exert an effect consistent with the content.

[0189] [Colorant]

[0190] The optical moisture curable resin composition of the present invention contains a colorant. The optical moisture curable resin composition contains a colorant, and is blackened, so that light shielding properties are easily imparted. In addition, it is easy to color it to a desired color, thereby improving design properties.

[0191] As the colorant, black colorants such as titanium black, aniline black, cyanine black, carbon black, black iron oxide, and zirconium nitride can be cited. In addition, as the colorant, colorants other than black colorants can also be used. As colorants other than black colorants, known pigments, dyes, etc. can be used, specifically, the "Cromashine" series and "Cosmicolor" series manufactured by Toyo Almi Co., Ltd., and the "Dipilogistic" series manufactured by Dainichi Seika Industries, Ltd. can be used.

[0192] The coloring agent may be used alone or in combination of two or more.

[0193] As a colorant, a colorant that can make the OD value of the cured product of the light moisture curable resin composition greater than the specified value described below by being contained in the light moisture curable resin composition can be preferably used. Specifically, from the perspective of light shielding, a black colorant is preferably used, among which at least one selected from titanium black and zirconium nitride is more preferably used.

[0194] For the colorant content in the light moisture curable resin composition, it is preferably 0.01 mass parts or more and 3 mass parts or less relative to 100 mass parts of the total amount of the free radical polymerizable compound and the moisture curable resin. By setting the content of the colorant to above the above lower limit, it is easy to increase the OD value described later and also easy to ensure light shielding. In addition, it is easy to color the light moisture curable resin composition to a desired color. On the other hand, by making the content of the colorant below the above upper limit, the photocurability is not easily reduced by the colorant.

[0195] From the above aspects, the content of the colorant relative to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture curable resin is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and more preferably 2 parts by mass or less, further preferably 1 part by mass or less, further preferably 0.8 parts by mass or less.

[0196] [Bulking Agent]

[0197] The optical moisture curable resin composition of the present invention may contain fillers other than colorants. The optical moisture curable resin composition of the present invention easily has suitable thixotropy by containing fillers, and can fully maintain the shape of the coating film after coating. Therefore, even if it is applied to the end surface of a plate-like member described later, a coating film with a uniform film thickness can be appropriately formed without generating dripping, etc.

[0198] As the filler, a particulate filler can be used. As the filler, an inorganic filler is preferred, for example, silicon dioxide, talc, titanium oxide, zinc oxide, calcium carbonate, etc. can be cited. Among them, silicon dioxide is preferred from the perspective of the excellent ultraviolet transmittance of the obtained light moisture curing resin composition. In addition, the filler can be subjected to hydrophobic surface treatment such as organosiliconization, silylation, alkylation, epoxidation, etc.

[0199] The primary particle size of the filler is preferably 1 nm or more and 50 nm or less, more preferably 2 nm or more and 30 nm or less, and further preferably 3 nm or more and 20 nm or less. By making the primary particle size of the filler within the above range, the coating property and shape retention of the light moisture curing type resin composition become good. In addition, it is not easy to hinder ultraviolet curing due to the filler. The primary particle size of the filler can be measured by using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS company) by dispersing the above filler in a solvent (water, organic solvent, etc.).

[0200] The filler may be used alone or in combination of two or more.

[0201] The content of the filler relative to 100 parts by mass of the total amount of the radical polymerizable compound and the moisture curable resin 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, and further preferably 3 parts by mass or more and 15 parts by mass or less.

[0202] [Moisture curing catalyst]

[0203] The optical moisture curing resin composition may contain a moisture curing accelerating catalyst for accelerating the moisture curing reaction of the moisture curable resin. By using a moisture curing accelerating catalyst, the moisture curing property of the optical moisture curing resin composition becomes better and the adhesive strength after moisture curing is easily improved.

[0204] Specific examples of moisture curing accelerators include amine compounds, metal catalysts, etc. Examples of amine compounds include compounds having a morpholine skeleton such as di(methylmorpholino)diethyl ether, 4-morpholinopropylmorpholine, and 2,2'-dimorpholinodiethyl ether, dimethylamino-containing amine compounds having two dimethylamino groups such as bis(2-dimethylaminoethyl)ether and 1,2-bis(dimethylamino)ethane, triethylamine, 1,4-diazabicyclo[2.2.2]octane, and 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane.

[0205] Examples of the metal catalyst include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octylate; zinc compounds such as zinc octylate and zinc naphthenate; and other metal compounds such as zirconium tetraacetylacetonate, copper naphthenate, and cobalt naphthenate.

[0206] The content of the moisture curing accelerating catalyst relative to 100 parts by mass of the moisture curing resin is preferably 0.01 parts by mass or more and 8 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. By making the content of the moisture curing accelerating catalyst within the above range, the storage stability of the optical moisture curing type resin composition will not be deteriorated, and the effect of promoting the moisture curing reaction becomes excellent.

[0207] The light moisture curable resin composition may contain, in addition to the above-mentioned components, other additives such as coupling agents, wax particles, ionic liquids, foamed particles, expanded particles, reactive diluents, etc. In addition, as coupling agents, silane coupling agents, titanate coupling agents, zirconate coupling agents, etc. may be cited, among which silane coupling agents are preferred.

[0208] The optical moisture curable resin composition generally does not contain a solvent, but may be diluted with a solvent as needed within a range that does not impair the effects of the present invention. When the optical moisture curable resin composition is diluted with a solvent, the amount of the optical moisture curable resin composition mentioned above refers to the solid content, that is, the mass after removing the solvent.

[0209] <Viscosity at 25°C>

[0210] The optical moisture curing resin composition of the present invention preferably has a viscosity measured at 25°C and 1.0 rpm using a cone-plate viscometer (hereinafter also referred to as "25°C viscosity") of 100 mPa·s or more and 300 Pa·s or less. For the optical moisture curing resin composition, by making the 25°C viscosity 100 mPa·s or more, dripping is not easy to occur, and it is easy to apply with a coating thickness of a certain thickness or more, for example, it can also be appropriately applied to the end surface of a plate-like member, etc.

[0211] On the other hand, by making the viscosity 300 Pa·s or less, the coating property is improved, and it is easy to properly coat even when coating is performed using a dispenser, etc. In addition, by making the 25°C viscosity of the optical moisture curable resin composition within the above range, it is easy to contain a certain amount or more of both a free radical polymerizable compound and a certain amount or more of a moisture curable resin.

[0212] From the perspective of being easy to contain a certain amount of moisture-curable resin and being less likely to produce dripping, the viscosity at 25°C is more preferably 500 mPa·s or more, more preferably 5 Pa·s or more, and more preferably 15 Pa·s or more. In addition, from the perspective of being easy to contain a certain amount of free radical polymerizable compound and further improving coating properties, the viscosity at 25°C is more preferably 200 Pa·s or less, more preferably 100 Pa·s or less, more preferably 80 Pa·s or less, and particularly preferably 45 Pa·s or less.

[0213] <OD value>

[0214] The optical moisture curable resin composition of the present invention preferably has an optical density (OD value) of 1 mm thick cured product of 2 or more. If the OD value is 2 or more, the light shielding property becomes good, and a high level of blackening can also be achieved. Therefore, in the case of end face protection for display components, light leakage can be prevented and the display performance of the display components can be improved. In addition, for the optical moisture curable resin composition, by making the OD value above 2, it becomes difficult to photocuring, but by containing a moisture curable resin in addition to the free radical polymerizable compound, it can be properly cured by light and moisture curing, so that the bonding strength after curing can be improved.

[0215] From the perspective of achieving good light-shielding properties and a higher level of blackening, the OD value is preferably 2.5 or more, more preferably 3 or more. From the perspective of light-shielding properties, the higher the OD value, the better. However, from the perspective of keeping the content of the colorant below a certain value, improving the photocurability, and making the optical moisture curable resin composition have an appropriate viscosity, the OD value is preferably 7 or less, more preferably 6 or less, and even more preferably 5.5 or less.

[0216] It should be noted that the OD value of the cured product of the above-mentioned moisture-curable resin composition can be measured using an optical densitometer. For the above-mentioned OD value, a sample with a thickness of 1 mm obtained by curing the moisture-curable resin composition by ultraviolet irradiation can be used for measurement. It should be noted that the thickness can also be appropriately changed according to the measurement limit of the optical densitometer for measurement, and the extrapolated value at a thickness of 1 mm can be used for judgment. Here, ultraviolet irradiation can be performed according to the conditions described in the embodiment.

[0217] <Glass transition temperature (Tgm)>

[0218] The optical moisture curable resin composition of the present invention preferably has a maximum glass transition temperature (hereinafter also referred to as "Tgm") of 40° C. or higher of a cured product formed by curing the composition.

[0219] When the optical moisture curable resin composition of the present invention measures the glass transition temperature, the glass transition temperature of the cured product of the moisture curable resin detected on the low temperature side and the glass transition temperature of the cured product of the free radical polymerizable compound detected on the high temperature side are typically observed. Therefore, the glass transition temperature (Tgm) can also be said to be the glass transition temperature of the polymer derived from the free radical polymerizable compound. In the present invention, by setting the glass transition temperature Tgm of the polymer derived from the free radical polymerizable compound to 40°C or more, it is easy to reduce the viscosity immediately after irradiation with ultraviolet rays.

[0220] The glass transition temperature (Tgm) of the cured product is preferably 40° C. or higher, more preferably 50° C. or higher, and further preferably 60° C. or higher. In addition, there is no particular limitation on the upper limit of the glass transition temperature (Tgm) of the cured product, and for example, it is 150° C. or lower, and may be 120° C. or lower. The glass transition temperature (Tgm) of the cured product can be adjusted by the type (particularly the Tg of each radical polymerizable compound) and the amount of each radical polymerizable compound.

[0221] The glass transition temperature (Tgm) refers to a temperature at which a maximum value due to micro-Brownian motion appears among the maximum values ​​of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement, and can be measured by a method using a dynamic viscoelasticity measuring apparatus.

[0222] As a method for preparing the optical moisture curable resin composition of the present invention, there can be cited a method of mixing a radical polymerizable compound, a moisture curable resin, a photopolymerization initiator and a colorant, and other additives such as a filler and a moisture curing accelerator as required using a mixer, etc. Examples of the mixer include a homodispersor, a homomixer, a universal mixer, a planetary mixer, a planetary stirring device, a kneader, and a three-roll mill.

[0223] <Usage of optical moisture curing resin composition>

[0224] The optical moisture curable resin composition of the present invention is cured and used as a cured product. Specifically, the optical moisture curable resin composition of the present invention can be first photocured by light irradiation to, for example, a B-stage state (semi-cured state), and then fully cured by moisture curing.

[0225] Here, the light moisture curable resin composition is applied to the coated body, and then, it is photocured by light irradiation to form, for example, a B-stage state. Then, the light moisture curable resin composition can be fully cured by further curing it with moisture to form a cured layer of the light moisture curable resin composition on the surface of the coated body. The light moisture curable resin composition of the present invention has high bonding strength to the coated body after light and moisture curing, and can be firmly bonded to the coated body, so as described later, it can be suitably used as a protective layer for protecting end faces, etc.

[0226] The light moisture curable resin composition of the present invention is preferably used for end face protection, more specifically, is preferably used for end face protection of a plate-like member. Therefore, the coated body is a plate-like member, and the light moisture curable resin composition is applied to the end face of the plate-like member constituting the outer peripheral side of the plate-like member to form a coating layer. Moreover, the coating layer formed by the light moisture curable resin composition can be cured by light curing and moisture curing as described above to form a cured layer.

[0227] The end surface of the plate-like member is preferably protected by the applied optical moisture curable resin composition. For example, the applied optical moisture curable resin composition (particularly the cured layer) can prevent scratches or breakage due to external impact.

[0228] In addition, the light moisture curable resin composition (particularly the cured layer) applied to the end surface can also be used as a light shielding layer to prevent light from passing through the peripheral side of the plate-like member. Specifically, it can be used as a light shielding layer to prevent light from leaking from the inside to the outside of the plate-like member, or from the outside to the inside of the plate-like member.

[0229] Furthermore, the cured layer can also be used as a colored layer for improving the design of the outer peripheral side surface of the plate-like member.

[0230] The plate-like member is not particularly limited as long as it is a member with a small thickness, and the concept also includes members generally called films, sheets, etc. The thickness of the plate-like member is, for example, about 0.1 to 5.0 mm, preferably about 0.3 to 3.0 mm.

[0231] For plate-like components, any component formed of various materials such as metal, glass, plastic, ceramic, etc. can be listed. Components composed of single-layer metal plates, glass plates, plastic plates, ceramic plates, etc., or multi-layer components formed by laminating more than two layers of them, and components that are laminated with various components such as adhesive layers, resin layers, conductive layers, liquid crystal layers, organic EL layers, dimming layers, electronic components, light sources, etc. in addition to these components.

[0232] As the plate-like member, it is preferably a member used in various electronic devices. In addition, the plate-like member is also preferably a display member. The display member is a member used for image display, etc., for example, a liquid crystal panel, an organic EL panel, an LED display panel, a segment display panel, a plasma display panel, a backlight panel for a display device, etc. If the above-mentioned solidified layer is formed on the end face of the plate-like member, especially the display member, the end face can be protected by the solidified layer, and the display performance of the display member can be prevented from being reduced due to light leakage, etc., so it is particularly preferred.

[0233] There is no particular restriction on applying the light moisture curing type resin composition on the coated body such as a plate-like member, and for example, a dispenser can be used. As the dispenser, an air dispenser, a jet dispenser, a single pump dispenser, a spiral dispenser, a pistol dispenser, etc. can be listed, among which a jet dispenser is preferred. If a dispenser is used, the light moisture curing type resin composition can be applied with good coating properties even if the width is narrow, so as mentioned above, the end face of a plate-like member with a small thickness can also be coated with high precision. In addition, for the light moisture curing type resin composition of the present invention, by making the viscosity at 25°C reach the above-specified range, it can be appropriately applied using a dispenser.

[0234] There is no particular limitation on the application of the optical moisture curing resin composition to the adherend, and the application may be carried out by heating the optical moisture curing resin composition or at around room temperature, specifically, at a temperature of about 10 to 35° C. For the optical moisture curing resin composition, by setting the viscosity at 25° C. to be within the above-specified range, the application can be easily performed even at around room temperature, and dripping can also be prevented.

[0235] When the light moisture curing resin composition is applied to the end surface of the plate-like member, the plate-like member is preferably arranged so that the thickness direction of the plate-like member is along the vertical direction. It should be noted that the thickness direction along the vertical direction here means that the thickness direction does not need to be parallel to the vertical direction, for example, it can be inclined at an angle of about 30° relative to the vertical direction.

[0236] By disposing the plate-like member as described above for coating, it is not necessary to stand the plate-like member upright for coating the end face, thereby improving operability. On the other hand, although the end face of the plate-like member is disposed vertically or obliquely relative to the horizontal direction, by adjusting the viscosity at 25° C. to a prescribed range or containing a filler, a coating film with a uniform film thickness can be appropriately formed on the end face without causing dripping, etc.

[0237] The light irradiated during photocuring is not particularly limited as long as it cures the radical polymerizable compound, and ultraviolet rays are preferred. In addition, when the light moisture curable resin composition is fully cured by moisture after photocuring, it can be left in the air for a predetermined time.

[0238] In addition, since the optical moisture curable resin composition of the present invention has low viscosity immediately after ultraviolet irradiation, it is possible to prevent undesired adhesion of other components or adhesion of dust to the optical moisture curable resin composition in a B-stage state, thereby improving workability. In addition, since dust adhesion can be prevented, it is also possible to prevent display components and the like from being contaminated by dust.

[0239] Example

[0240] The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0241] The measurement and evaluation of various physical properties were performed as follows. In Comparative Examples 1 and 2, instead of the optical moisture curable resin composition, the measurement and evaluation were performed using a photocurable resin composition and a moisture curable resin composition, respectively.

[0242] (Weight average molecular weight)

[0243] The weight average molecular weight of the moisture curable resin was measured by gel permeation chromatography (GPC) and obtained by polystyrene conversion. Shodex KF-806L (Showa Denko Co., Ltd.) was used as a column for GPC measurement. In addition, tetrahydrofuran (THF) was used as a solvent and a mobile phase. Moreover, the measurement conditions of GPC were a flow rate of 1.0 ml / min and a measurement temperature of 40°C.

[0244] (Viscosity value)

[0245] Under the environment of room temperature 25°C and 50% RH, a frame-shaped spacer is arranged on a glass plate in such a way that the inner dimensions are 10 mm in width, 0.4 mm in thickness, and 30 mm in length. The light moisture curing resin composition is applied within 5 seconds using a dispenser in such a way that the inner side of the frame-shaped spacer is filled. It should be noted that in the case where the light moisture curing resin composition overflows from the inner side of the frame-shaped spacer, a scraper is used to remove it. The end time of coating using the dispenser is regarded as 0 seconds. After 60 seconds of coating, 3000 mJ / cm 2 Ultraviolet rays with a wavelength of 365 nm were applied. 30 seconds after the ultraviolet irradiation, a probe (made of SUS, 5 mm in diameter) was pressed into the center of the applied light moisture curable resin composition with a force of 10 gf using a probe viscosity tester (manufactured by Reska Co., Ltd., "TAC-100") for 1 second, and the load when the probe was lifted at a speed of 10 mm / sec was measured as the viscosity value.

[0246] (Glass transition temperature (Tgm))

[0247] The light moisture curing resin composition was poured into a Teflon (registered trademark) mold with a width of 30 mm, a length of 50 mm, and a thickness of 0.6 mm, and cured to obtain a cured product sample. The light moisture curing resin composition was cured by irradiating with 3000 mJ / cm2 using a UV-LED irradiator (manufactured by CCS Co., Ltd.) at 25°C and 50% RH. 2 After ultraviolet light of 365nm wavelength was used for ultraviolet curing, it was placed in an environment of 25℃ and 50%RH for 7 days to make it moisture-cured. Then, the cured sample was cut into pieces with a width of 3mm, a length of 30mm and a thickness of 0.6mm. For the cut cured sample, a dynamic viscoelasticity measuring device (manufactured by IT Measurement and Control Co., Ltd., "DVA-200") was used to measure the dynamic viscoelasticity in the range of -100℃ to 150℃ under the conditions of deformation mode: stretching, set strain 1%, measurement frequency 1Hz, and heating rate 5℃ / min. The temperature of the maximum value of the loss tangent (tanδ) was calculated as the glass transition temperature. It should be noted that Table 1 only lists the highest glass transition temperature among the observed glass transition temperatures.

[0248] (Viscosity at 25℃)

[0249] The 25°C viscosity of the optical moisture curable resin composition was measured under the conditions of 1.0 rpm and 25°C using a cone-plate viscometer (trade name TVE-35, manufactured by Toki Sangyo Co., Ltd.).

[0250] (OD value)

[0251] The optical moisture curing resin composition was evenly applied between two slide glasses ("S1214", manufactured by Matsunami Glass Industries, Ltd.) so that the thickness after UV curing was 1 mm. The film was irradiated with 3000 mJ / cm2 using a UV-LED irradiator (manufactured by CCS Corporation) at 25°C and 50% RH. 2 The optical moisture curable resin composition was photocured by ultraviolet light of a wavelength of 365 nm to obtain a sample for OD value evaluation. The OD value of the obtained sample for OD value evaluation was measured using an optical densitometer (manufactured by Ihara Electronics Industry Co., Ltd., "T5 Plus").

[0252] (Adhesion Strength)

[0253] The evaluation of the bonding strength is carried out by a cross-cut test on the cured product of the light-curable resin composition cured by light and moisture. Specifically, the light-curable resin composition is applied to the surface of the glass plate in a manner of more than 30 mm in length and more than 30 mm in width, and a thickness of 0.5 mm after moisture curing. The applied light-curable resin composition is irradiated with 3000 mJ / cm2 using a UV-LED irradiator (manufactured by CCS Co., Ltd.) at 25°C and 50% RH. 2 After ultraviolet curing with ultraviolet light of a wavelength of 365nm, it was placed in an environment of 25°C and 50% RH for 7 days to allow it to be wet-cured to obtain a cured layer (cured product). The obtained cured layer was cut in such a way that the cut interval was 3mm and 100 grids of 10×10 were formed. Rub the tape (manufactured by Nichiban Co., Ltd., "Selotime No. 405") with your fingertips so that the tape contacts the entire cured product, thereby sticking the tape to the surface of the cured layer with the cut. Then, the tape was pulled apart at an angle of about 60° within one second, and the bonding strength was evaluated based on the number of squares that remained on the glass plate without being peeled off. It should be noted that the bonding and peeling of the adhesive tape were carried out in an environment of a temperature of 25°C and a humidity of 50% RH.

[0254] (Operability)

[0255] The optical moisture curable resin composition was applied to the glass plate to a thickness of 0.5 mm after UV curing. The applied optical moisture curable resin composition was irradiated with 3000 mJ / cm2 using a UV-LED irradiator (manufactured by CCS Corporation) at 25°C and 50% RH. 2The photocuring was performed by applying ultraviolet light of a wavelength of 365 nm. 30 seconds after the ultraviolet irradiation was completed, JIS test powder 1 (2 kinds) was dropped on the photocured light moisture curing resin composition in a manner covering the entire cured product. Then, the powder attached to the cured product was removed with an air dust collector, and the amount of powder attached to the light moisture curing resin composition was confirmed and evaluated according to the following evaluation criteria. The less the amount of attached powder, the lower the viscosity and the higher the operability.

[0256] A: The powder attached to the solidified material is less than 5% of the total area of ​​the solidified material.

[0257] B: The powder attached to the solidified product accounts for more than 5% and less than 30% of the total area of ​​the solidified product.

[0258] C: The powder attached to the solidified product accounts for more than 30% of the total area of ​​the solidified product.

[0259] The polyurethane resin raw material used in each of the Examples and Comparative Examples was prepared by the following method.

[0260] [Synthesis example 1]

[0261] (Moisture curable polyurethane resin)

[0262] 100 parts by mass of polytetramethylene ether glycol (Mitsubishi Chemical Corporation, trade name "PTMG-2000") as a polyol compound and 0.01 parts by mass of dibutyltin dilaurate were placed in a 500 mL separable flask. The flask was stirred for 30 minutes at 100 ° C under vacuum (below 20 mmHg) to mix. Then, set to normal pressure, 26.5 parts by mass of diphenylmethane diisocyanate (Nissou Shoji Co., Ltd., trade name "Pure MDI") as a polyisocyanate compound was added to the flask, stirred at 80 ° C for 3 hours to react, and a moisture-curable polyurethane resin (polyurethane prepolymer 1) having a polyether skeleton and an isocyanate group at both ends was obtained. The weight average molecular weight of the obtained polyurethane prepolymer 1 is 2700.

[0263] Components other than the moisture-curable polyurethane resin used in Examples and Comparative Examples are as follows.

[0264] (Radical polymerizable compound)

[0265] Acrylic acid 1: Urethane acrylate, manufactured by DAICEL-ALLNEX, "EBECRYL8411", difunctional, Tg: less than 40°C

[0266] Acrylic acid 2: Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "Biscoder #192", monofunctional, Tg: 2°C

[0267] Acrylic acid 3: 3,3,5-trimethylcyclohexyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "Biscoder #196", monofunctional, Tg: 52°C

[0268] Acrylic acid 4: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "IBXA", monofunctional, Tg: 97°C Acrylic acid 5: N-acryloylmorpholine, manufactured by KJ Chemicals, monofunctional, Tg: 145°C

[0269] Filler: Siliconized silica, manufactured by Japan Aerosil Co., Ltd., "RY300", primary particle size 7 nm

[0270] Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-(manufactured by BASF, “IRGACURE 369”)

[0271] Colorant: Titanium black, manufactured by Mitsubishi Material Co., Ltd., "13M-C"

[0272] Moisture curing accelerating catalyst: 2,2'-dimorpholinyl diethyl ether ("U-CAT660M" manufactured by Sanapro)

[0273] [Examples 1 to 3, Comparative Examples 1 to 3]

[0274] According to the ratios described in Table 1, each material was stirred at a temperature of 80° C. using a mixing device (manufactured by Shinky Co., Ltd., “Awato Rirentaro”) until it was uniform, thereby obtaining the light-curable resin compositions of Examples 1 to 3, Comparative Example 3, the light-curable resin composition of Comparative Example 1, and the moisture-curable resin composition of Comparative Example 2.

[0275] Table 1

[0276]

[0277] The light moisture curable resin compositions of Examples 1 to 3 contain a radical polymerizable compound, a moisture curable resin, a photopolymerization initiator, and a colorant, and have a low viscosity value after ultraviolet irradiation for 30 seconds, so that both the workability and the adhesive strength after curing can be improved. In addition, by curing with light and moisture, the curable resin composition can be cured without introducing a large-scale device and without damaging the components or the like due to heat during the resin curing process.

[0278] In contrast, the photocurable resin composition of Comparative Example 1 does not contain a moisture-curable resin, and therefore cannot improve the adhesive strength after curing. The moisture-curable resin composition of Comparative Example 2 does not contain a free radical polymerizable compound, so even if it is irradiated with ultraviolet rays after coating, it does not undergo photocuring, thereby failing to reduce the viscosity and deteriorating the workability. The light moisture-curable resin composition of Comparative Example 3 contains a free radical polymerizable compound, a moisture-curable resin, and a colorant, but since the viscosity value after irradiation with ultraviolet rays for 30 seconds is higher than 80 gf, even if it is photocured, the viscosity is not sufficiently reduced and the workability cannot be improved.

Claims

1. A light moisture curable resin composition comprising a moisture curable resin, a free radical polymerizable compound, a photopolymerization initiator and a colorant, and irradiated with 3000 mJ / cm 2 The viscosity value based on the probe viscosity test after 30 seconds of ultraviolet light is less than 80gf. 2 . The optical moisture curable resin composition according to claim 1 , wherein the radically polymerizable compound comprises a radically polymerizable compound having a homopolymer having a glass transition temperature Tg of 40° C. or higher. 3 . The optical moisture curable resin composition according to claim 1 , wherein a cured product of the optical moisture curable resin composition has a maximum glass transition temperature Tgm of 40° C. or higher. 4 . The optical moisture curable resin composition according to claim 1 , wherein the radical polymerizable compound comprises a difunctional or higher-functional radical polymerizable compound. 5 . The optical moisture curable resin composition according to claim 1 , wherein the viscosity at 25° C. is 100 mPa·s or more and 300 Pa·s or less. 6 . The optical moisture curable resin composition according to claim 1 , wherein the OD value of a cured product of the optical moisture curable resin composition having a thickness of 1 mm is 2 or more. 7 . The optical moisture-curable resin composition according to claim 1 , wherein the moisture-curable resin is a moisture-curable polyurethane resin. 8 . The optical moisture curable resin composition according to claim 1 , which is used for edge protection. 9 . A cured product, which is a cured product of the optical moisture curable resin composition according to claim 1 or 2.

10. Use of the optical moisture curing resin composition according to claim 1 or 2 for protecting an end surface of a plate-like member. 11 . A method for protecting an end surface of a plate-like member, comprising the step of applying the optical moisture curable resin composition according to claim 1 or 2 to an end surface of the plate-like member.

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