JP2019065309A - Photo-moisture curable resin composition cured body - Google Patents

Abstract

To provide a photo-moisture curable resin composition cured body having excellent flexibility, adhesiveness, and reliability under a high-temperature and high-humidity environment.SOLUTION: A photo-moisture curable resin composition cured body is obtained by photo-moisture curing a photo-moisture curable resin composition containing a radical polymerizable compound, a moisture-curable urethane resin, and a photoradical polymerization initiator, the photo-moisture curable resin composition cured body having a sea-island structure composed of a sea portion and an island portion.SELECTED DRAWING: None

Description

The present invention relates to a cured product of a light moisture-curable resin composition which is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment.

In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is usually used to seal liquid crystals and light emitting layers, and to bond substrates, optical films, protective films and various members.
By the way, in the modern world where mobile devices with various display elements such as mobile phones and portable game machines are in widespread use, miniaturization of the display elements is the most sought-after issue, and as a method of miniaturization, narrowing the image display section Frame formation is performed (hereinafter, also referred to as narrow frame design). However, in the narrow frame design, the photocurable resin composition may be applied to the part where light does not sufficiently reach, and as a result, the photocurable resin composition applied to the part where light does not reach is cured. Was insufficient. Therefore, a photo-thermosetting resin composition is used as a resin composition that can be sufficiently cured even when applied to a portion to which light does not reach, and it is also practiced to use photocuring and thermosetting together. There was a possibility that the elements and the like were adversely affected by heating.

As a method of curing a resin composition without heating at high temperature, Patent Document 1 discloses a light containing a urethane prepolymer having at least one isocyanate group and at least one (meth) acryloyl group in the molecule. There is disclosed a method of using light curing and moisture curing in combination using a moisture curable resin composition. However, the light moisture-curable resin composition as disclosed in Patent Document 1 has a cured product that is flexible, adhesive, and reliable (especially creep resistance) under a high temperature and high humidity environment. It was difficult to make everything excellent.

JP 2008-274131 A

An object of the present invention is to provide a light moisture-curable resin composition cured body which is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment.

The present invention is a sea-island consisting of a sea part and an island part which is formed by photo-moisture curing of a light-moisture-curable resin composition containing a radically polymerizable compound, a moisture-curable urethane resin, and a photoradical polymerization initiator. It is a light moisture-curable resin composition cured body having a structure.
The present invention will be described in detail below.

The present inventors have surprisingly found that, in a light and moisture curable resin composition containing a radically polymerizable compound and a moisture curable urethane resin, a cured product obtained by light and moisture curing the composition is uniform. It has been found that the cured product is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment by making it have a sea-island structure instead of the above, and the present invention It came to complete.

The cured product of the light and moisture curable resin composition of the present invention has a sea-island structure comprising a sea part and an island part. The sea-island structure is formed by the light-cured component and the moisture-cured component when the light and moisture-curable resin composition is cured by light and moisture.
By having the sea-island structure, the cured light and moisture curable resin composition of the present invention is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment.
In the present specification, the “sea-island structure” means a phase separation structure in which a phase (island portion) composed of one component is dispersed in a phase (sea portion) composed of the other component.

As a shape of the said island part, spherical shape, rod shape, tube shape, plate shape etc. are mentioned, for example. Especially, spherical shape is preferable.

The preferable lower limit of the dispersion diameter of the island portion is 0.1 μm, and the preferable upper limit is 20 μm. When the dispersion diameter of the island portion is less than 0.1 μm, excellent flexibility may not be obtained. When the dispersion diameter of the above-mentioned island portion exceeds 20 μm, sufficient adhesion may not be obtained. The more preferable lower limit of the dispersion diameter of the island portion is 0.5 μm, and the more preferable upper limit is 10 μm.
In addition, the dispersion diameter of the said island part can be calculated | required by averaging the major axis of 100 island parts selected arbitrarily when the cross section of a hardening body is observed using an electron microscope.

The light and moisture curable resin composition cured product of the present invention is formed by light and moisture curing of a light and moisture curable resin composition containing a radically polymerizable compound, a moisture curable urethane resin, and a photo radical polymerization initiator. . Hereinafter, the light and moisture curable resin composition to be a cured product of the light and moisture curable resin composition of the present invention by light and moisture curing is also referred to as “a light and moisture curable resin composition according to the present invention”.

The light and moisture curable resin composition according to the present invention contains a radically polymerizable compound.
The radically polymerizable compound is not particularly limited as long as it is a radically polymerizable compound having photopolymerizability, and a compound having a radically polymerizable group in the molecule, but an unsaturated double bond as a radically polymerizable group Compounds having a (meth) acryloyl group (hereinafter, also referred to as "(meth) acrylic compounds") are preferable from the viewpoint of reactivity.
In the present specification, the above "(meth) acrylic" means acrylic or methacrylic.

Examples of the (meth) acrylic compound include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meth) obtained by reacting (meth) acrylic acid with an epoxy compound. And (iii) acrylate and urethane (meth) acrylate obtained by reacting an isocyanate with a (meth) acrylic acid derivative having a hydroxyl group.
In the present specification, the above "(meth) acrylate" means acrylate or methacrylate. Moreover, all the isocyanate groups of the isocyanate used as the raw material of the said urethane (meth) acrylate are used for formation of a urethane bond, and the said urethane (meth) acrylate does not have a residual isocyanate group.

Among the above ester compounds, as monofunctional ones, for example, phthalimido acrylates such as N-acryloyloxyethyl hexahydrophthalimide, various imido acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl ) Acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethyl carbitol ( Meta) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxy Ethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate and the like can be mentioned.

Moreover, as a bifunctional thing among the said ester compounds, 1, 3- butanediol di (meth) acrylate, 1, 4- butane diol di (meth) acrylate, 1, 6- hexanediol di (meth), for example Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (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, dimethylol dicyclopentadienyl di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate ) Acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate Etc. The.

Further, among the above ester compounds, as trifunctional or higher functional ones, for example, 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, ethylene oxide adducted isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide adducted glycerin tri (meth) acrylate, tris (meth) acryloyl Oxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrelay , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

As said epoxy (meth) acrylate, what is obtained by making an epoxy compound and (meth) acrylic acid react in presence of a basic catalyst according to a conventional method etc. are mentioned, for example.

As an epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meta) acrylate, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A epoxy resin Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, ortho cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphth Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.

Among the above epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3800, EBECRYL L 40 40.degree. ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all from Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40 EM, epoxy ester 70 PA, Epoxy ester 200 PA, epoxy ester 80 MF , Epoxy ester 3002 M, epoxy ester 3002 A, epoxy ester 1600 A, epoxy ester 3000 M, epoxy ester 3000 A, epoxy ester 200 EA, epoxy ester 400 EA (all from Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314 And Denacol acrylate DA-911 (all of which are manufactured by Nagase ChemteX).

The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with a compound having an isocyanate group in the presence of a catalytic amount of a tin-based compound.

As an isocyanate used as a raw material of the said urethane (meth) acrylate, For example, isophorone diisocyanate, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4 ' -Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl ) Thiophosphate, tetramethylxylene diisocyanate, 1,6,11-undecanetriisocyanate Doors and the like.

Also, as the above-mentioned isocyanate, for example, reaction of a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. with excess isocyanate The resulting chain extended isocyanate compounds can also be used.

Examples of the hydroxyl group-containing (meth) acrylic acid derivative which is a raw material of the above urethane (meth) acrylate include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol and 1,4-butane, for example. Mono (meth) acrylates of dihydric alcohols such as diol and polyethylene glycol, mono (meth) acrylates or di (meth) acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type Epoxy (meth) acrylates, such as epoxy (meth) acrylate, etc. are mentioned.

Among the above urethane (meth) acrylates, commercially available ones are, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8413, EBECRYL 8104, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL 1290, EBECRYL5129, EBECRYL4842, EBECRYL 4827, EBECRYLL 7300h Echyl ), Art resin UN-9000H, Art resin UN-9000A, Art resin UN-7100, Art resin UN-1255, Art resin UN-330, Art resin UN-3320 HB, Art resin UN-1200TPK, Art resin SH-500 B ( All are Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U- 122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all are new Nakamura Manabu Industries, Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).

In addition, other radically polymerizable compounds other than those described above can also be used appropriately.
Examples of the other radically polymerizable compounds include N, N-dimethyl (meth) acrylamide, N- (meth) acryloyl morpholine, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N (Meth) acrylamide compounds such as -isopropyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide, and vinyl compounds such as styrene, α-methylstyrene, N-pyropidone, and N-vinyl caprolactone .

It is preferable that the said radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from a viewpoint of adjusting curability. When only a monofunctional radically polymerizable compound is used, the resulting light and moisture curable resin composition may be poor in curability, and when only a polyfunctional radically polymerizable compound is used, the resulting light and moisture curable The mold resin composition may be inferior in tackiness. Especially, it is more preferable to use combining the compound which has a nitrogen atom in a molecule | numerator as said monofunctional radically polymerizable compound, and urethane (meth) acrylate as said polyfunctional radically polymerizable compound. Moreover, it is preferable that it is bifunctional or trifunctional, and, as for the said polyfunctional radically polymerizable compound, it is more preferable that it is bifunctional.

When the radically polymerizable compound contains the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound, the content of the polyfunctional radically polymerizable compound is the same as that of the monofunctional radically polymerizable compound and the polybasic radically polymerizable compound. The preferable lower limit is 2 parts by weight and the preferable upper limit is 30 parts by weight with respect to 100 parts by weight in total with the functional radically polymerizable compound. When the content of the polyfunctional radically polymerizable compound is less than 2 parts by weight, the resulting light moisture-curable resin composition may be inferior in curability. When content of the said polyfunctional radically polymerizable compound exceeds 30 weight part, the optical moisture hardening type resin composition obtained may become inferior to tackiness. A more preferable lower limit of the content of the polyfunctional radically polymerizable compound is 5 parts by weight, and a more preferable upper limit is 20 parts by weight.

The light and moisture curable resin composition according to the present invention contains a moisture curable urethane resin. The moisture-curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with the moisture in the air or in the adherend to be cured. The moisture-curable urethane resin preferably has the isocyanate group at the end of the molecule.

The moisture-curable urethane resin preferably has a group containing an ethylenically unsaturated double bond and / or an alkoxysilyl group, and a group containing an ethylenically unsaturated double bond and / or an alkoxysilyl group is It is more preferable to have at the end.
In addition, even if it has a radically polymerizable group, the said moisture curable urethane resin is not contained in the said radically polymerizable compound, but is handled as a moisture curable urethane resin.

The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. Among them, urethane prepolymers having an isocyanate group at both ends are preferable.
The urethane prepolymer can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

In the reaction of the polyol compound with the polyisocyanate compound, the molar ratio of hydroxyl group (OH) in the polyol compound to isocyanate group (NCO) in the polyisocyanate compound is usually [NCO] / [OH] = 1 It is performed in the range of 0.5 to 2.5.

As said polyol compound, the well-known polyol compound normally used for manufacture of a polyurethane can be used, For example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol etc. are mentioned. These polyol compounds may be used alone or in combination of two or more.

As said polyester polyol, the polyester polyol obtained by reaction of polyhydric carboxylic acid and a polyol, the poly- (epsilon) -caprolactone polyol etc. which are obtained by ring-opening-polymerizing (epsilon) -caprolactone etc. are mentioned, for example.

Examples of the polyvalent carboxylic acid as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberin Acids, azelaic acids, sebacic acids, decamethylene dicarboxylic acids, dodecamethylene dicarboxylic acids and the like can be mentioned.

As said polyol used as the raw material of said polyester polyol, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 4- butanediol, neopentyl glycol, 1, 5- pentanediol, 1, 6- hexane, for example Diol, diethylene glycol, cyclohexanediol and the like can be mentioned.

Examples of the polyether polyols include ring-opening polymers of ethylene glycol, propylene glycol, tetrahydrofuran, 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or their derivatives, and bisphenol-type polyoxy acids. Alkylene modification etc. are mentioned.

The bisphenol type polyoxyalkylene modified substance is a polyether polyol obtained by subjecting an active hydrogen portion of a bisphenol type molecular skeleton to an addition reaction of an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) It may be a random copolymer or a block copolymer.
It is preferable that the said bisphenol type polyoxyalkylene modified body is 1 type or 2 types or more of alkylene oxides being added to the both terminal of bisphenol type molecular frame. It does not specifically limit as a bisphenol type, A-type, F-type, S-type etc. are mentioned, Preferably it is bisphenol A-type.

As said polyalkylene polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol etc. are mentioned, for example.

Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol and polycyclohexane dimethylene carbonate polyol.

Examples of the polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymeric MDI (methane diisocyanate), tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like. Among them, diphenylmethane diisocyanate and its modified products are preferred in view of low vapor pressure, low toxicity and ease of handling. The said polyisocyanate compound may be used independently, and may be used in combination of 2 or more type.

Moreover, it is preferable that the said moisture-curable urethane resin has a structure represented by following formula (1). By having a structure represented by the following formula (1), it is possible to obtain a composition having excellent adhesion and a cured product which is flexible and has a good elongation, and is excellent in the compatibility with the above radical polymerizable compound. .
Among them, polyether-type urethane prepolymers using a polyetherpolyol consisting of a ring-opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, and a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as methyl group are preferable. .

In formula (1), R represents hydrogen, a methyl group, or an ethyl group, n is an integer of 1-10, L is an integer of 0-5, m is an integer of 1-500. n is preferably 1 to 5, L is preferably 0 to 4, and m is preferably 50 to 200.
When L is 0, it means that the carbon bonded to R is directly bonded to oxygen.

The preferable lower limit of the weight average molecular weight of the moisture-curable urethane resin is 800, and the preferable upper limit is 10,000. When the weight average molecular weight of the moisture-curable urethane resin is less than 800, the crosslink density may be high, and the flexibility may be impaired. When the weight-average molecular weight of the moisture-curable urethane resin exceeds 10,000, the resulting light-moisture curable resin composition may be inferior in coatability. The lower limit of the weight average molecular weight of the moisture-curable urethane resin is more preferably 1000, more preferably 6500, still more preferably 2000, and still more preferably 4500.
In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography (GPC) and converted to polystyrene. As a column at the time of measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko) etc. are mentioned, for example.

The preferable lower limit of the content of the moisture-curable urethane resin is 30 parts by weight and the preferable upper limit is 80 parts by weight with respect to 100 parts by weight in total of the radically polymerizable compound and the moisture-curable urethane resin. When the content of the moisture-curable urethane resin is less than 30 parts by weight, the resulting light-moisture-curable resin composition may be inferior in moisture curing property. When the content of the moisture curable urethane resin exceeds 80 parts by weight, the resulting light moisture curable resin composition may be inferior in photocurability. The lower limit of the content of the moisture-curable urethane resin is preferably 35 parts by weight, more preferably 70 parts by weight, still more preferably 40 parts by weight, and still more preferably 65 parts by weight.

The light and moisture curable resin composition according to the present invention contains a photo radical polymerization initiator.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, α-hydroxyalkylphenone compounds, acyl phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like. Can be mentioned.

Among the above photo radical polymerization initiators, commercially available ones are IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF Co., Ltd.), benzoin methyl ether And benzoin ethyl ether and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

The preferable lower limit of the content of the photo radical polymerization initiator is 0.01 parts by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the radical polymerizable compound. When the content of the photo radical polymerization initiator is less than 0.01 parts by weight, the resulting light and moisture curable resin composition may not be sufficiently photocured. When the content of the photo radical polymerization initiator exceeds 10 parts by weight, the storage stability of the resulting light moisture-curable resin composition may be lowered. A more preferable lower limit of the content of the photo radical polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.

From the viewpoint of forming a suitable sea-island structure, the light and moisture curable resin composition according to the present invention contains 20 to 70 parts by weight of urethane acrylate as a radically polymerizable compound, and a polyether urethane prepolymer as a moisture curable urethane resin. It is preferable to contain 30 to 80 parts by weight of an acyl phosphine oxide compound or an α-hydroxyalkylphenone compound as a photo radical polymerization initiator in a ratio of 0.1 to 5 parts by weight.

The light and moisture curable resin composition according to the present invention may contain a filler from the viewpoint of adjusting the coatability and the shape retention of the resulting light and moisture curable resin composition.
The preferable lower limit of the particle diameter of the filler is 1 nm, and the preferable upper limit is 100 nm. When the particle diameter of the filler is less than 1 nm, the resulting light moisture-curable resin composition becomes inferior in coatability. When the particle diameter of the filler exceeds 100 nm, the resulting light moisture-curable resin composition becomes inferior in shape retention after application. The more preferable lower limit of the particle diameter of the filler is 3 nm, the more preferable upper limit is 50 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 45 nm.
The preferable lower limit of the primary particle diameter of the filler is 1 nm, and the preferable upper limit is 50 nm.
In addition, the particle diameter of the said filler can be measured by calculating | requiring an average particle diameter using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS company).

Examples of the filler include silica, talc, titanium oxide, zinc oxide and the like. Among them, silica is preferable because the resulting light and moisture curable resin composition is excellent in UV light transmittance. These fillers may be used alone or in combination of two or more.

The filler is preferably subjected to hydrophobic surface treatment. By the said hydrophobic surface treatment, the optical moisture hardening type resin composition obtained becomes what is excellent by the shape-retaining property after application | coating.
Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, epoxidation treatment and the like. Among them, silylation treatment is preferable, and trimethylsilylation treatment is more preferable, because it is excellent in the effect of improving shape retention.

As a method of hydrophobic-surface-treating the said filler, the method of processing the surface of a filler, etc. are mentioned using surface treating agents, such as a silane coupling agent, for example.
Specifically, for example, the above-mentioned trimethylsilylation-treated silica is a method of synthesizing silica by a sol-gel method or the like, spraying hexamethyldisilazane in a state of flowing silica, or an organic solvent such as alcohol or toluene Silica can be added to the inside, hexamethyldisilazane and water can be further added, and then water and an organic solvent can be produced by evaporation and drying using an evaporator.

The preferable lower limit of the content of the filler is 1 part by weight and the preferable upper limit is 20 parts by weight in 100 parts by weight of the entire light and moisture curable resin composition according to the present invention. When the content of the filler is less than 1 part by weight, the obtained light and moisture curable resin composition may be inferior in shape retention after application. When the content of the filler exceeds 20 parts by weight, the resulting light and moisture curable resin composition may be inferior in coatability. The lower limit of the content of the filler is preferably 2 parts by weight, more preferably 15 parts by weight, still more preferably 3 parts by weight, still more preferably 10 parts by weight, particularly preferably 4 parts by weight. .

The light and moisture curable resin composition according to the present invention may contain a light shielding agent. By containing the light shielding agent, the light and moisture curable resin composition according to the present invention is excellent in the light shielding property, and light leakage of the display element can be prevented.
In the present specification, the above-mentioned "light shielding agent" means a material having the ability to hardly transmit light in the visible light region.

Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like.
Further, the light shielding agent does not have to have a black color, and as long as it is a material having the ability to hardly transmit light in the visible light region, the materials mentioned as the filler such as silica, talc, titanium oxide etc. Included in sunscreens. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance whose transmittance to light in the vicinity of the ultraviolet region, particularly to light having a wavelength of 370 to 450 nm is higher than the average transmittance to light having a wavelength of 300 to 800 nm.
That is, while sufficiently shielding light of wavelengths in the visible light region, the titanium black imparts a light-shielding property to the light moisture-curable resin composition according to the present invention, while transmitting light of wavelengths near the ultraviolet light region. It is a light shielding agent having a property. Therefore, the photo moisture-curable resin composition according to the present invention can be obtained by using, as the photo radical polymerization initiator, one capable of initiating a reaction by light of a wavelength (370 to 450 nm) at which the transmittance of titanium black increases. Photocurability can be further increased. On the other hand, as the light shielding agent contained in the light moisture-curable resin composition according to the present invention, a substance having a high insulating property is preferable, and titanium black is also preferable as a light shielding agent having a high insulating property.
The titanium black preferably has an optical density (OD value) of 3 or more, and more preferably 4 or more. The higher the light shielding property of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide It is also possible to use surface-treated titanium black, such as those coated with inorganic components such as zirconium and magnesium oxide. Especially, what is processed by the organic component is preferable at the point which can improve insulation more.
In addition, the display device manufactured using the light and humidity curable resin composition according to the present invention has high light contrast and high contrast since the light and moisture curable resin composition has a sufficient light shielding property. It has excellent image display quality.

Among the titanium blacks, commercially available ones include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilac D (manufactured by Akao Kasei Co., Ltd.), and the like.

In the light-moisture-curable resin composition according to the present invention, the particle diameter of the light-shielding agent is appropriately selected according to the application, such as the distance between the substrates of the display element or less, but the preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. It is. When the particle diameter of the light shielding agent is less than 1 nm, the viscosity and thixotropy of the resulting light moisture-curable resin composition may be greatly increased, and the workability may be deteriorated. When the particle diameter of the light shielding agent exceeds 5 μm, the coatability of the resulting light moisture-curable resin composition to a substrate may be deteriorated. The more preferable lower limit of the particle diameter of the light shielding agent is 10 nm, the more preferable upper limit is 2 μm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1.5 μm.
In addition, the particle diameter of the said light shielding agent can be measured by calculating | requiring an average particle diameter using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS company).

The content of the light shielding agent in the entire light and moisture curable resin composition according to the present invention is not particularly limited, but a preferable lower limit is 0.05% by weight and a preferable upper limit is 10% by weight. When the content of the light shielding agent is less than 0.05% by weight, sufficient light shielding properties may not be obtained. When the content of the light shielding agent exceeds 10% by weight, the adhesion to the substrate or the like of the obtained light and moisture curable resin composition and the strength after curing may be reduced, or the drawability may be reduced. A more preferable lower limit of the content of the light shielding agent is 0.1% by weight, a more preferable upper limit is 2% by weight, and a still more preferable upper limit is 1% by weight.

The light and moisture curable resin composition according to the present invention may further contain additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent, as necessary.

As a method for producing the light moisture-curable resin composition according to the present invention, for example, a radically polymerizable compound may be used using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader or a 3-roll mill. And a method of mixing a moisture-curable urethane resin, a radical photopolymerization initiator, and an additive added as required.

In the light and moisture curable resin composition according to the present invention, the preferable lower limit of the viscosity measured under the conditions of 25 ° C. and 1 rpm using a cone-plate viscometer is 50 Pa · s, and the preferable upper limit is 500 Pa · s. When the viscosity is less than 50 Pa · s or exceeds 500 Pa · s, the workability at the time of applying the light and humidity curable resin composition to an adherend such as a substrate may be deteriorated. A more preferable lower limit of the viscosity is 80 Pa · s, a more preferable upper limit is 300 Pa · s, and a further preferable upper limit is 200 Pa · s.
In addition, when the viscosity of the optical moisture hardening type resin composition concerning this invention is too high, coatability can be improved by heating at the time of application | coating.

The preferable lower limit of the thixotropic index of the light and moisture-curable resin composition according to the present invention is 1.5, and the preferable upper limit is 5.0. When the thixotropic index is less than 1.5 or exceeds 5.0, the workability at the time of applying the photo-moisture-curable resin composition to an adherend such as a substrate may be deteriorated. The more preferable lower limit of the thixotropic index is 2.0, and the more preferable upper limit is 4.0.
In the present specification, the above-mentioned thixotropic index is a viscosity measured at 25 ° C. and 1 rpm using a cone and plate viscometer, and was measured at 25 ° C. and 10 rpm using a cone and plate viscometer It means the value divided by the viscosity.

As a method for producing the cured product of the light and moisture curable resin composition of the present invention by curing the light and moisture curable resin composition according to the present invention by light and moisture, for example, to the photo moisture curable resin composition of the present invention The step of photocuring by irradiation with light of 100 to 50000 mJ / cm ² and the photo-moisture curable resin composition according to the present invention cured at 15 to 100 ° C. under an environment of 10 to 90% RH for 1 to 120 And the like, and a method including the steps of exposing to time and curing with moisture.

According to the present invention, it is possible to provide a light moisture-curable resin composition cured body which is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment.

It is an observation image obtained by observing the optical humidity hardening type resin composition hardening object obtained in Example 1 with a scanning electron microscope by magnification of 5000 times. (A) is a schematic diagram which shows the case where the sample for adhesive evaluation is seen from the top, (b) is a schematic diagram which shows the case where the sample for adhesive evaluation is seen from the side.

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

Synthesis Example 1 (Preparation of Urethane Prepolymer A)
In a 500 mL separable flask, 100 parts by weight of polytetramethylene ether glycol ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation) and 0.01 parts by weight of dibutyltin dilaurate as a polyol compound are placed under vacuum (20 mmHg) Below, it stirred for 30 minutes at 100 degreeC, and mixed. Thereafter, under normal pressure, 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI", manufactured by Nippon Soda Co., Ltd.) is added as a polyisocyanate compound, and stirred at 80 ° C for 3 hours for reaction to react. Urethane prepolymer A (weight average molecular weight 2700).

Synthesis Example 2 (Preparation of Urethane Prepolymer B)
100 parts by weight of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., "EXCENOL 2020") and 0.01 parts by weight of dibutyltin dilaurate as a polyol compound are placed in a 500 mL separable flask, and 100 ° C under vacuum (20 mmHg or less). The mixture was stirred for 30 minutes and mixed. Thereafter, under normal pressure, 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI", manufactured by Nippon Soda Co., Ltd.) is added as a polyisocyanate compound, stirred at 80 ° C for 3 hours, and reacted, Urethane prepolymer B (weight average molecular weight 2900).

(Example 1, Comparative Example 1)
After stirring each material with a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.) according to the compounding ratio described in Table 1, it is uniformly mixed with a ceramic three-roll and light humidity curing The mold resin composition was obtained. Each of the obtained light and moisture curable resin compositions is photocured by irradiating UV light at 1000 mJ / cm ² using a UV-LED (wavelength 365 nm), and then moisture cured by standing overnight A cured product of the light and moisture curable resin composition of Example 1 and Comparative Example 1 was obtained.
In addition, "urethane prepolymer A" in Table 1 is the urethane prepolymer having an isocyanate group at both ends described in Synthesis Example 1, and "urethane prepolymer B" is the isocyanate described at Synthesis Example 2 It is a urethane prepolymer having a group.

<Evaluation>
The following evaluation was performed about each optical moisture-curable resin composition obtained by the Example and the comparative example and the optical moisture-curable resin composition hardened | cured material. The results are shown in Table 1.

(Observation of sea-island structure)
A cross-sectional sample is produced with a cryoultramicrotome, and a silver paste is applied around the cross-sectional sample for each cured product of the light and moisture-curable resin composition obtained in Examples and Comparative Examples, and carbon deposition is performed to produce electrolytic discharge. The presence or absence of the sea-island structure was observed using a scanning electron microscope ("S-4800" manufactured by Hitachi High-Technologies Corporation). When the sea-island structure was confirmed, the dispersion diameter of the island part was determined.
FIG. 1 is an observation image obtained by observing the cured light and humidity curable resin composition obtained in Example 1 with a scanning electron microscope at a magnification of 5,000. As shown in FIG. 1, it was confirmed that the cured product obtained in Example 1 had a sea-island structure. On the other hand, the light moisture-curable resin composition cured product obtained in Comparative Example 1 was a uniform cured product without a sea-island structure.

(Adhesiveness)
Each light and moisture curable resin composition obtained in Examples and Comparative Examples was applied to a polycarbonate substrate with a width of about 2 mm using a dispensing apparatus. Then, the light moisture-curable resin composition was photocured by irradiating UV light at 1000 mJ / cm ² using a UV-LED (wavelength 365 nm). Thereafter, a glass plate was attached to a polycarbonate substrate, a weight of 20 g was placed, and moisture curing was performed by standing overnight, to obtain a sample for evaluating adhesion.
FIG. 2 is a schematic view showing the case of the adhesive evaluation sample viewed from above (FIG. 2 (a)), and a schematic view showing the case of the adhesive evaluation sample viewed from the side (FIG. 2 (b)) showed that.
The prepared adhesive evaluation sample is pulled in the shear direction at a speed of 5 mm / sec using a tensile tester (manufactured by Shimadzu Corporation “Ez-Grapf”), and the strength when the polycarbonate substrate and the glass plate are peeled off Was measured.

(High temperature reliability (creep resistance))
A sample for high temperature reliability evaluation was produced in the same manner as the sample for adhesive evaluation in the evaluation of “(adhesiveness)”. The obtained sample for high temperature reliability evaluation was hung vertically to the ground, placed in a 100 ° C. oven with a 100 g weight hung from the edge of the polycarbonate substrate, and allowed to stand for 24 hours. After standing for 24 hours, the case where the polycarbonate substrate and the glass plate were not peeled is "○", the case where the polycarbonate substrate and the glass plate were partially peeled is "Δ", and the polycarbonate substrate and the glass plate are completely The high temperature reliability (creep resistance) of the light and moisture curable resin composition was evaluated by setting the case where it had been peeled off as “x”.

(Flexibility)
Photocuring the moisture-curable resin composition obtained in Examples and Comparative Examples by irradiating UV light at 1000 mJ / cm ² using a UV-LED (wavelength 365 nm), and then leaving it to stand overnight Moisture cured. A test piece obtained by punching out the obtained cured product in the shape of a dumbbell (No. 6 type specified by "JIS K 6251") using a tensile tester ("EZ-Graph" manufactured by Shimadzu Corporation) The tensile force at a speed of 10 mm / sec and the force at 50% elongation were determined as the elastic modulus.

According to the present invention, it is possible to provide a light moisture-curable resin composition cured body which is excellent in flexibility, adhesiveness, and reliability in a high temperature and high humidity environment.

1 Polycarbonate substrate 2 Light moisture-curable resin composition 3 Glass plate

Claims (3)

A light and moisture curable resin composition containing a radically polymerizable compound, a moisture curable urethane resin, and a photo radical polymerization initiator is cured by light and moisture,
What is claimed is: 1. A cured product of a light-moisture-curable resin composition having a sea-island structure comprising a sea part and an island part. The dispersion diameter of an island part is 0.1-20 micrometers, The optical moisture hardening type resin composition hardening body of Claim 1 characterized by the above-mentioned. The light moisture-curable resin composition contains 20 to 70 parts by weight of urethane acrylate as a radically polymerizable compound, 30 to 80 parts by weight of a polyether urethane prepolymer as a moisture-curable urethane resin, and acyl phosgene as a light radical polymerization initiator. The photo moisture-curable resin composition cured product according to claim 1 or 2, characterized in that it contains 0.1 to 5 parts by weight of a fin oxide compound or an α-hydroxyalkylphenone compound.