TWI666285B - Light and moisture curing resin composition, adhesive for electronic parts, and adhesive for display elements - Google Patents

Abstract

An object of the present invention is to provide a light and moisture-curable resin composition having excellent initial adhesion. Another object of the present invention is to provide an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition. The present invention is a light and moisture-curable resin composition containing a radical polymerizable compound, a moisture-curable amine ester resin, and a photo-radical polymerization initiator. The moisture-curable amine ester resin contains: A compound having an urethane bond, an isocyanate group, and a reactive double bond at the terminal.

Description

Light and moisture curing resin composition, adhesive for electronic parts, and adhesive for display elements

The present invention relates to a light and moisture-curable resin composition having excellent initial adhesion. The present invention also relates to an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition.

In recent years, liquid crystal display elements or organic EL display elements have been widely used as display elements having characteristics such as thinness, light weight, and low power consumption. Among these display elements, a photocurable resin composition is usually used for sealing of a liquid crystal or a light-emitting layer, bonding of a substrate, an optical film, a protective film, or various members.

However, mobile devices with display elements, such as mobile phones and portable game consoles, are becoming more and more popular these days, and miniaturization of display elements is the most sought after problem. As a method of miniaturization, the image display portion is narrowed (see below). , Also known as narrow edge design) processing. However, in a narrow-edge design, the light-curable resin composition may be applied to a portion where light cannot reach sufficiently. As a result, there is a problem that the light-curable resin composition applied to a portion where light cannot reach reaches has insufficient curing . Therefore, a light and thermosetting resin composition is used as a resin composition that can be sufficiently hardened even when applied to a part where light cannot reach, and also uses light curing and heat curing, but it may be affected by heating at high temperature. Components, etc. have adverse effects.

As a method of hardening the resin composition without using high-temperature heating, Patent Document 1 or Patent Document 2 discloses the use of light and moisture-curable resin compositions. The light and moisture hardening resin composition contains an amine ester prepolymer having at least one isocyanate group and at least one (meth) acrylfluorene group in the molecule. However, when the light and moisture-curable resin composition disclosed in Patent Document 1 or Patent Document 2 is used, the light and moisture-curable resin composition are light-cured and then bonded immediately after the adherend. In the later stage, the adhesion may become insufficient.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-274131

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-63406

An object of the present invention is to provide a light and moisture-curable resin composition having excellent initial adhesion. Another object of the present invention is to provide an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition.

The present invention is a light and moisture-curable resin composition containing a radical polymerizable compound, a moisture-curable amine ester resin, and a photo-radical polymerization initiator. The moisture-curable amine ester resin contains: A compound having an urethane bond, an isocyanate group, and a reactive double bond at the terminal.

Hereinafter, the present invention will be described in detail.

For example, when a light- and moisture-curable resin composition is used for adhering an adherend such as a substrate, in order to shorten the working time of the step, the light and moisture-curable resin may be irradiated with light. Immediately after the resin composition is light-cured and then adhered, the process proceeds to the next step. At this time, if the initial bonding force immediately after the bonding is insufficient, the bonded body may be peeled off due to stress caused by the undulation or flatness of the bonded body such as a substrate, or a force applied from the outside during processing. . Therefore, the light and moisture-curable resin composition needs to have sufficient initial adhesion to the adherend.

The inventors have surprisingly discovered that in light and moisture-curable resin compositions containing a radical polymerizable compound, a moisture-curable amine ester resin, and a photo-radical polymerization initiator, a resin having an amine ester bond and an isocyanate is used. A compound having a reactive double bond at the end as a moisture-curable amine ester resin, which contributes to the light-hardening of the compound, thereby obtaining a light- and moisture-curable resin composition having excellent initial adhesion. So as to complete the present invention.

The light and moisture-curable resin composition of the present invention contains a moisture-curable urethane resin. The isocyanate group in the moisture-curable amine ester resin-based molecule reacts with moisture in the air or the adherend to be hardened.

The moisture-curable amine ester resin contains a compound having an amine ester bond, an isocyanate group, and a reactive double bond at the terminal (hereinafter, also referred to as "reactive double bond-containing amine ester resin"). The light and moisture-curable resin composition of the present invention contains the above-mentioned reactive double bond-containing amine ester resin as a moisture-curable amine ester resin, whereby the reactive double bond-containing amine ester resin and a radical polymerizable compound Together, it contributes to photo-hardening, and becomes a light- and moisture-curable resin composition that is excellent in initial adhesion.

In addition, in this specification, the said "terminal" means the terminal of a main chain.

In addition, the reactive double bond is a radically polymerizable group, but in the present specification, the reactive double bond-containing amine ester resin is not regarded as a radically polymerizable compound but is considered as a moisture-curable type. Urethane resin.

The reactive double bond-containing amine ester resin preferably has a ratio of isocyanate groups in the structure of 0.8% by weight or less. When the ratio of the isocyanate group in the structure exceeds 0.8% by weight, even if the amine ester resin and the radical polymerizable compound containing a reactive double bond react by light irradiation, the photocurability may be insufficient, and the initial adhesiveness may not be developed. . The reactive double bond-containing amine ester resin is more preferably such that the ratio of isocyanate groups in the structure is 0.5% by weight or less.

In addition, from the viewpoint of moisture curability, it is preferable that the ratio of the isocyanate group in the structure of the amine ester resin containing a reactive double bond is 0.1% by weight or more.

The reactive double bond-containing amine ester resin is preferably obtained by reacting a polyol compound, a polyisocyanate compound, and a compound having an isocyanate group and a reactive double bond at the terminal. A reactive double bond-containing amine ester resin obtained using such a raw material is more reactive than a compound containing a polyol compound, a polyisocyanate compound, and a compound having a hydroxyl group and a reactive double bond at a terminal, for example. The double bond amine ester resin is excellent in the effect of achieving both initial adhesion and flexibility.

The reason is considered to be that in the latter synthesis method, a compound having a hydroxyl group and a reactive double bond at the end is reacted in a state of high viscosity, so it is difficult to uniformly introduce the double bond, but in the former synthesis method, the In an initial state with a low viscosity, a compound having an isocyanate group and a reactive double bond at the terminal is reacted, so that the double bonds can be uniformly introduced.

The reaction of the polyol compound, the polyisocyanate compound, and the compound having an isocyanate group and a reactive double bond at the terminal is generally a hydroxyl (OH) in the polyol compound and the polyisocyanate compound and the isocyanate group and The molar ratio of the isocyanate group (NCO) in a compound having a reactive double bond at the terminal becomes [NCO] / [OH] = 2.0 ~ 2.5.

As the polyol compound, a well-known polyol compound generally used in the production of polyurethanes can be used, and examples thereof include polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols. Among them, polyester polyols and / or polyether polyols are preferred. These polyol compounds may be used alone or in combination of two or more.

Examples of the polyester polyol include a polyester polyol obtained by reacting a polycarboxylic acid and a polyol, or a polyε-caprolactone polyol obtained by subjecting ε-caprolactone to ring-opening polymerization. Alcohol and so on.

Examples of the polycarboxylic acid used as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecanedioic acid, and the like.

Examples of the polyol that serves as a raw material for the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol. , 1,6-hexanediol, diethylene glycol, cyclohexanediol and the like.

Examples of the polyether polyols include ring-opening polymerization compounds of ethylene glycol, propylene glycol, tetrahydrofuran, 3-methyltetrahydrofuran, and random or block copolymers of these or their derivatives, or Polyoxyalkylene modified body of phenol type and the like.

The above-mentioned bisphenol-type polyoxyalkylene modification system makes alkylene oxides (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and active hydrogen of the bisphenol-type molecular skeleton The polyether polyol obtained by partial addition reaction may be a random copolymer or a block copolymer. The bisphenol type polyoxyalkylene modified body is preferably added to both ends of the bisphenol type molecular skeleton. There are 1 or more kinds of alkylene oxides. The bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and a bisphenol A type is preferred.

Examples of the polyalkylene polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and the like.

Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol, polycyclohexanedimethylene carbonate polyol, and the like.

Examples of the polyisocyanate compound include liquid improvements of diphenylmethane diisocyanate, diphenylmethane diisocyanate, polymerized MDI (methane diisocyanate), toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like. . Among these, an aromatic isocyanate compound is preferable because it has high reactivity. In addition, from the viewpoints of low vapor pressure or toxicity and ease of handling, diphenylmethane diisocyanate and its modified product are preferred. These polyisocyanate compounds may be used alone or in combination of two or more.

Examples of the compound having an isocyanate group and a reactive double bond at the terminal include a compound represented by the following formula (1), a vinyl isocyanate, and the like. In addition, compounds synthesized by reacting various diisocyanate compounds and compounds having a hydroxyl group and a (meth) acrylfluorene group at an isocyanate group / hydroxyl (mole ratio) of 2 can also be used. Among them, a compound represented by the following formula (1) is preferable in terms of easy availability.

In the formula (1), R ¹ represents hydrogen or a methyl group, and R ² represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond.

The content of the reactive double bond-containing amine ester resin is 100 parts by weight with respect to the total of the radically polymerizable compound and the moisture-curable amine ester resin. . If the content of the reactive double bond-containing amine ester resin is less than 0.5 parts by weight, the effect of improving initial adhesion may not be sufficiently exhibited in some cases. If the content of the reactive double bond-containing amine ester resin exceeds 20 parts by weight, the cured product of the obtained light and moisture-curable resin composition may become a cured product having poor flexibility or failing to exhibit initial adhesion. . A more preferable lower limit of the content of the reactive double bond-containing amine ester resin is 1 part by weight, and a more preferable upper limit is 15 parts by weight.

The content of the reactive double bond-containing amine ester resin is 100 parts by weight of the moisture-curable amine ester resin, and the preferred lower limit is 1 part by weight, and the preferred upper limit is 35 parts by weight. If the content of the reactive double bond-containing amine ester resin is less than 1 part by weight, the effect of improving initial adhesion may not be sufficiently exhibited in some cases. If the content of the reactive double bond-containing amine ester resin exceeds 35 parts by weight, the cured product of the obtained light and moisture-curable resin composition may become a cured product having poor flexibility or failing to exhibit initial adhesion. . The more preferable lower limit of the content of the reactive double bond-containing amine ester resin is 2 parts by weight, and the more preferable upper limit is 30 parts by weight.

The light and moisture-curable resin composition of the present invention preferably further contains a moisture-curable amine ester resin other than the amine ester resin containing a reactive double bond. The moisture-curable amine ester resin other than the amine ester resin containing a reactive double bond is preferably a moisture-curable amine ester resin having no reactive double bond. By containing a moisture-curable amine ester resin other than the amine ester resin containing a reactive double bond, it becomes easy to achieve both adhesiveness and flexibility.

The other moisture-curable urethane resin is not particularly limited, and has high adhesion and high temperature. From the viewpoint of reliability (especially creep resistance) in a wet environment, compounds having an amine ester bond, a group represented by the following formula (2), and an isocyanate group (hereinafter, also referred to as "containing Silicone-based amine ester resins ").

In formula (2), R ³ and R ⁴ are hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group, and each R ³ and each R ⁴ may be the same or different. x represents an integer from 0 to 2.

In the formula (2), when R ³ and / or R ⁴ is an aryl group, examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group.

In the formula (2), x is preferably 1 or 2 from the viewpoint of more excellent adhesiveness.

In addition, the case where x in the formula (2) is 0 refers to a case where a silicon atom is not bonded to an atom or a group represented by R ³ but is bonded to three -OR ⁴ groups.

The silicone-containing amine ester resin has a group represented by the formula (2).

Among the groups represented by the formula (2), R ³ and R ^{4 are} preferably an alkyl group having 1 to 5 carbon atoms in terms of excellent effects of improving adhesion and reliability under high-temperature and high-humidity environments. Methyl and ethyl are preferred.

The silicone-based amine ester resin has an isocyanate group.

The organosilicon group-containing amine ester resin may have only one isocyanate group in one molecule, or may have two or more.

It is preferable that the silicone-based amine ester resin has the above formula at each end (2) a group represented by the above-mentioned isocyanate group.

The organosilicon group-containing amine ester resin can be obtained by reacting a polyhydric alcohol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. A compound having an amine ester bond and an isocyanate group, and reacting the obtained compound with a compound having a reactive functional group and a group represented by the formula (2). The "reactive functional group" means a group capable of reacting with a compound having the amine ester bond and the isocyanate group.

As the polyol compound and the polyisocyanate compound which are the raw materials of the compound having an amine ester bond and an isocyanate group, the same compounds as those listed as the raw materials of the reactive double bond-containing amine ester resin can be used.

Examples of the compound having a reactive functional group and a group represented by the formula (2) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Didiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3 -(2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (meth) acrylic acid Propyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (methyl) Acryl) propyloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-mercaptopropylmethyldimethylsiloxane Oxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropane Methylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Among them, from the reactive From a viewpoint, the compound which has a thiol group as a reactive functional group is preferable.

Hereinafter, the matters common to the entire moisture-curable urethane resin containing an amine ester resin containing a reactive double bond are regarded as "moisture-curable urethane resin".

The moisture-curable amine ester resin is preferably obtained by using a polyol compound having a structure represented by the following formula (3). By using a polyhydric alcohol compound having a structure represented by the following formula (3), a composition having excellent adhesion or a hardened material having good flexibility and good extensibility can be obtained, and it has excellent compatibility with the above radical polymerizable compound. By. The moisture-curable urethane resin preferably has a branched chain.

Among them, it is preferred to use a polyether polyol composed of propylene glycol, a ring-opening polymer compound of a tetrahydrofuran (THF) compound, or a ring-opening polymer compound of a tetrahydrofuran compound having a substituent such as a methyl group.

In formula (3), R represents hydrogen, methyl, or ethyl, n is an integer of 1 to 10, L is an integer of 0 to 5, and m is an integer of 1 to 500. n is preferably 1 to 5, L is preferably 0 to 4, and m is preferably 50 to 200.

The case where L is 0 refers to the case where the carbon bonded to R is directly bonded to oxygen.

The preferable lower limit of the weight-average molecular weight of the moisture-curable amine ester resin is 800, and the preferable upper limit is 10,000. If the weight-average molecular weight of the moisture-curable amine ester resin is less than 800, the cross-linking density becomes high, and flexibility may be impaired. If the weight-average molecular weight of the moisture-curable amine ester resin exceeds 10,000, the obtained light and moisture-curable resin composition may sometimes It will be a poor coating. A more preferable lower limit of the weight-average molecular weight of the moisture-curable amine ester resin is 2000, a more preferable upper limit is 8000, a more preferable lower limit is 2500, and a more preferable upper limit is 6000.

In addition, in this specification, the said weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated | required by polystyrene conversion. Examples of the column used when measuring the weight-average molecular weight based on polystyrene by GPC include Shodex LF-804 (manufactured by SHOWA DENKO). Examples of the solvent used in GPC include tetrahydrofuran.

Content of the said moisture-hardening amine ester resin is 100 weight part with respect to the total of the said radically polymerizable compound and the said moisture-hardening amine ester resin, A preferable minimum is 20 weight part, and a preferable upper limit is 90 weight part. If the content of the moisture-curable urethane resin is less than 20 parts by weight, the obtained light and moisture-curable resin composition may become poor in moisture-curability. When the content of the moisture-curable urethane resin is more than 90 parts by weight, the obtained light and moisture-curable resin composition may become poor in photo-curability. The more preferable lower limit of the content of the moisture-curable amine ester resin is 30 parts by weight, the more preferable upper limit is 75 parts by weight, the more preferable lower limit is 41 parts by weight, and the more preferable upper limit is 70 parts by weight.

The light and moisture-curable resin composition of the present invention contains a radical polymerizable compound. The light and moisture-curable resin composition of the present invention is a resin after coating by using the above radical polymerizable compound in combination with the above-mentioned moisture-curable amine ester resin containing an amine ester resin containing a reactive double bond. The composition is excellent in shape retention and excellent in adhesion to an adherend such as a substrate.

As said radically polymerizable compound, as long as it is a radically polymerizable polymer having photopolymerization The compound is not particularly limited as long as it has a radically polymerizable group in the molecule, and a compound having an unsaturated double bond as a radically polymerizable group is preferred. In terms of reactivity, it is particularly preferably A compound having a (meth) acrylfluorenyl group (hereinafter, also referred to as "(meth) acrylic compound").

In addition, in this specification, the "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl, and "(meth) acryl" means acrylic acid or methacryl.

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 ester compound obtained by reacting a (meth) acrylic acid with an epoxy compound. Epoxy (meth) acrylate, amine ester (meth) acrylate, etc. obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound.

In addition, in this specification, the "(meth) acrylate" means an acrylate or a methacrylate. In addition, all isocyanate groups of the isocyanate compound that is a raw material of the amine ester (meth) acrylate are used to form an amine ester bond, and the amine ester (meth) acrylate does not have a residual isocyanate group.

Examples of the monofunctional compound in the ester compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (formyl) Base) stearyl acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate Ester, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Alcohol ester, (meth) acrylic acid-2,2,2-trifluoroethyl ester, (meth) acrylic acid-2,2,3,3-tetrafluoropropyl ester, (meth) acrylic acid-1H, 1H, 5H -Octafluoropentyl ester, ammonium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, ( Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, dicyclopentene (meth) acrylate, isodecyl (meth) acrylate, (methyl) ) Diethylaminoethyl acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloxyethyl succinate, 2- (methyl hexahydrophthalate) (Meth) acrylic acid ethoxyethyl, phthalic acid 2- (meth) acrylic acid oxyethyl-2-hydroxypropyl, (meth) acrylic epoxy Esters, 2- (meth) acryloxyethyl phosphate, N-acryloxyethyl hexahydrophthalimide, phthalimide acrylates, etc. Acrylate, etc.

In addition, examples of the bifunctional ones among the ester compounds include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 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, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (methyl) Acrylate), diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide addition bisphenol A di (Meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylic acid Ester, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, cyclic Ethylene oxide modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, carbonate diol di (meth) acrylic acid Ester, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) ) Acrylate, etc.

In addition, examples of the tri- or more functional group among the above-mentioned ester compounds include neopentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and propylene oxide addition trimethylol. Propane tri (meth) acrylate, ethylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide Alkane addition tris (meth) acrylate isotricyanate, dineopentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (Meth) acrylate, neopentyl tetraol (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, tri (meth) acrylic acid Ethyl phosphate and the like.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst by a conventional method.

Examples of the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, Phenolic novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, ring Oxypropylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, propylene oxide compound, bisphenol A episulfide resin, etc.

Examples of commercially available products of the bisphenol A-type epoxy resin include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850-S (manufactured by DIC Corporation), and the like.

Examples of commercially available products of the bisphenol F-type epoxy resin include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).

Examples of commercially available products of the bisphenol S-type epoxy resin include EPICLON EXA1514 (manufactured by DIC Corporation).

As a commercial item in the said 2,2'- diallyl bisphenol A type epoxy resin, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As a commercial item among the said hydrogenated bisphenol-type epoxy resin, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said propylene oxide addition bisphenol A type epoxy resin, EP-4000S (made by ADEKA CORPORATION) is mentioned, for example.

Examples of commercially available products of the resorcinol-type epoxy resin include EX-201 (manufactured by Nagase ChemteX Corporation).

As a commercial item among the said biphenyl type epoxy resins, jERYX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

Examples of commercially available products among the sulfide-type epoxy resins include YSLV-50TE (NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.).

Examples of commercially available products of the diphenyl ether epoxy resin include YSLV-80DE (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.).

As a commercial item among the said dicyclopentadiene-type epoxy resins, EP-4088S (made by ADEKA CORPORATION) etc. are mentioned, for example.

Examples of commercially available products of the aforementioned naphthalene-type epoxy resins include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).

As a commercial item among the said phenolic novolak-type epoxy resin, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

Examples of commercially available products of the o-cresol novolac-type epoxy resin include EPICLON N-670-EXP-S (manufactured by DIC Corporation).

As a commercial item among the said dicyclopentadiene novolak-type epoxy resins, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item of the said biphenol novolak-type epoxy resin, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As a commercial item in the said naphthol novolak-type epoxy resin, ESN-165S (made by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) Etc. are mentioned, for example.

Examples of commercially available products of the aforementioned epoxy amine-type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.), And the like.

Examples of commercially available products of the above-mentioned alkyl polyol type epoxy resins include ZX-1542 (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) And EPICLON 726 (DIC Corporation), EPOLIGHT 80MFA (manufactured by KYOEISHA CHEMICAL Co., LTD.), DENACOL EX-611 (manufactured by Nagase ChemteX Corporation), and the like.

Examples of commercially available products of the rubber-modified epoxy resin include YR-450, YR-207 (both manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.), EPOLEAD PB (manufactured by Daicel Corporation), and the like.

As a commercial item among the said propylene oxide ester compounds, DENACOL EX-147 (made by Nagase ChemteX Corporation) etc. are mentioned, for example.

Examples of commercially available products of the bisphenol A-type epivulcanized resin include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).

Examples of other commercially available epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), and the like.

Examples of commercially available products among the above epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYLDAL6363 ( LTD.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by KYOEISHA CHEMICAL Co., LTD.), DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all of Nagase ChemteX Corporation).

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

Examples of the isocyanate compound used as a raw material of the amine ester (meth) acrylate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. , Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, ditoluidine Diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) phosphorothioate, tetramethylxylene diisocyanate, 1 , 6,11-undecane triisocyanate and so on.

In addition, as the isocyanate compound, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, poly A chain-extended isocyanate compound obtained by reacting a polyhydric alcohol such as caprolactone diol with an excess of an isocyanate compound.

Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material of the amine ester (meth) acrylic acid ester include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1 Mono (meth) acrylates of diols such as 4-butanediol and polyethylene glycol, or mono (meth) acrylic acid of diols such as trimethylolethane, trimethylolpropane, and glycerol Ester or Di (methyl) propane Epoxy esters, epoxy (meth) acrylates such as bisphenol A epoxy (meth) acrylates, and the like.

Examples of commercially available products among the amine ester (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by TOAGOSEI CO., LTD.), EBCRYL230, and EBCRYL270. , EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4K, EBECRYL4RM, EBECRYL2K, EBECRYL4K, EBECRYL4K , Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all are Negami Chemical Industrial Co., Ltd .Manufactured), 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 manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by KYOEISHA CHEMICAL Co., LTD.) And the like.

In addition, other radical polymerizable compounds other than those described above may be appropriately used.

Examples of the other radically polymerizable compound include N, N-dimethyl (meth) acrylamide, N- (meth) acrylamide, morpholine, and N-hydroxyethyl (meth) acryl Amidoamine, N, N-diethyl (meth) acrylamidonium, N-isopropyl (meth) acrylamidoamine, N, N-dimethylamino (Meth) acrylamide compounds such as propyl (meth) acrylamide, or vinyl compounds such as styrene, α-methylstyrene, N-vinylpyrrolidone, N-vinylcaprolactone, and the like.

From the viewpoint of adjusting the hardenability, it is preferable that the radical polymerizable compound contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. When using only a monofunctional radically polymerizable compound, the obtained light and moisture-curable resin composition may become poor in hardenability. When using only a multifunctional radically polymerizable compound, the obtained light and The moisture-curable resin composition may become poor in adhesion. Among them, it is more preferable to use a compound having a nitrogen atom in the molecule as the monofunctional radical polymerizable compound and an amine ester (meth) acrylate as the polyfunctional radical polymerizable compound. The polyfunctional radical polymerizable compound is preferably difunctional or trifunctional, and more preferably difunctional.

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 greater than that of the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound. The total amount of the functional radical polymerizable compound is 100 parts by weight, and the preferred lower limit is 2 parts by weight, and the preferred upper limit is 45 parts by weight. If the content of the polyfunctional radically polymerizable compound is less than 2 parts by weight, the obtained light and moisture-curable resin composition may become inferior in curability. When the content of the above-mentioned polyfunctional radical polymerizable compound exceeds 45 parts by weight, the obtained light and moisture-curable resin composition may become poor in adhesion. A more preferable lower limit of the content of the polyfunctional radical polymerizable compound is 5 parts by weight, and a more preferable upper limit is 35 parts by weight.

Content of the said radically polymerizable compound is 100 weight part with respect to the total of the said radically polymerizable compound and the said moisture-hardening amine ester resin, Preferably a minimum is 10 weight part, and a preferable upper limit is 80 weight part. If the content of the radical polymerizable compound is less than 10 weight In some cases, the obtained light and moisture-curable resin composition may be poor in photocurability. When the content of the radically polymerizable compound exceeds 80 parts by weight, the obtained light and moisture-curable resin composition may become poor in moisture-curability. A more preferable lower limit of the content of the radical polymerizable compound is 25 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 59 parts by weight.

The light and moisture-curable resin composition of the present invention contains a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin-ether-based compounds, 9 -Oxysulfur Wait.

Examples of commercially available products in the photoradical polymerization initiator include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all of which are Manufactured by BASF Corporation), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

Content of the said photo-radical polymerization initiator is 100 weight part with respect to the said radically polymerizable compound, Preferably a minimum is 0.01 weight part, and a preferable upper limit is 10 weight part. If the content of the photo-radical polymerization initiator is less than 0.01 part by weight, the obtained light and moisture-curable resin composition may not be sufficiently photo-cured. When the content of the photo-radical polymerization initiator exceeds 10 parts by weight, the storage stability of the obtained light and moisture-curable resin composition may sometimes decrease. A more preferable lower limit of the content of the photoradical polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.

From the standpoint of improving adhesion or creep resistance, the light and moisture of the present invention are hard The chemical resin composition may contain a coupling agent.

The coupling agent preferably has a reactive functional group capable of reacting with a radical polymerizable compound and / or a moisture-curable amine ester resin. By having the said reactive functional group, the said coupling agent is introduce | transduced into the hardened | cured material obtained by hardening the light and moisture hardening resin composition of this invention, As a result, adhesiveness and creep resistance are improved further.

Examples of the reactive functional group included in the coupling agent include a group having an unsaturated double bond such as a (meth) acrylfluorenyl group, an epoxy group, an isocyanate group, a thiol group, and an amino group. Among them, a group having an unsaturated double bond, an epoxy group, or an isocyanate group is preferable in terms of excellent effect of improving adhesion and creep resistance.

Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, and a zirconate-based coupling agent. Among them, a silane coupling agent is preferred because the effect of improving adhesion and creep resistance is particularly excellent. These coupling agents may be used alone or in combination of two or more.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-Aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyl Methylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (methyl) Acrylic methoxypropylmethyldimethoxysilane, 3- (meth) acrylic methoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3 -Isocyanatepropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like.

Examples of the titanate-based coupling agent include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, and tetra-tert-butyl Titanate, tetrastearyl titanate, titanium acetylacetonate and the like.

Examples of the aluminate-based coupling agent include aluminum acetoacetate diisopropoxide and the like.

Examples of the zirconate-based coupling agent include n-propyl zirconate and ethyl zirconate.

The content of the coupling agent is preferably 5 parts by weight based on 100 parts by weight of the total of the radically polymerizable compound and the moisture-curable amine ester resin. If the content of the coupling agent is more than 5 parts by weight, the obtained light and moisture-curable resin composition may sometimes be inferior in storage stability. A more preferable upper limit of the content of the coupling agent is 1.5 parts by weight.

The content of the coupling agent is preferably 0.05 parts by weight based on 100 parts by weight of the total of the radically polymerizable compound and the moisture-curable amine ester resin. If the content of the coupling agent is less than 0.05 parts by weight, the effect of improving adhesion and creep resistance may not be sufficiently exhibited in some cases. A more preferable lower limit of the content of the coupling agent is 0.5 part by weight.

The light and moisture-curable resin composition of the present invention may contain a filler from the viewpoint of adjusting the coatability or shape retention of the obtained light and moisture-curable resin composition.

The preferred lower limit of the primary particle size of the filler is 1 nm, and the preferred upper limit is 50 nm. If the primary particle diameter of the filler is less than 1 nm, the obtained light and moisture-curable resin composition may become poor in coating properties. If the primary particle diameter of the filler exceeds 50 nm, the obtained light and moisture-curable resin composition may become a poor shape-retaining property after coating. The lower limit of the primary particle diameter of the filler is more preferably 5 nm, and the more preferable upper limit is 30 nm, and the more preferable lower limit is 10 nm, and more preferably, the upper limit is 20 nm.

The primary particle diameter of the filler can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) to disperse the filler in a solvent (water, organic solvent, etc.).

In addition, the filler mentioned above may exist in the form of secondary particles (composed of a plurality of primary particles) in the light and moisture-curable resin composition of the present invention. The particle size of such secondary particles is preferred. The lower limit is 5 nm, the preferred upper limit is 500 nm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 100 nm. The particle diameter of the secondary particles of the filler can be measured by observing the light and moisture-curable resin composition of the present invention or a cured product thereof using a transmission electron microscope (TEM).

Examples of the filler include silica, talc, titanium oxide, and zinc oxide. Among these, silicon dioxide is preferred in that the obtained light and moisture-curable resin composition is excellent in UV light transmission. These fillers may be used alone or in combination of two or more.

The filler is preferably subjected to a hydrophobic surface treatment. By the above-mentioned hydrophobic surface treatment, the obtained light and moisture-curable resin composition becomes more excellent in shape retention after coating.

Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Among them, in terms of the effect of improving the shape retention property, a silicidation treatment is preferred, and a trimethylsilication treatment is more preferred.

Examples of the method for the hydrophobic surface treatment of the filler include a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent.

Specifically, for example, the above trimethyl silylated silicon dioxide can be obtained by, for example, the following method Production method: sol-gel method is used to synthesize silicon dioxide, and hexamethyldisilazane is sprayed in a mist state while the silicon dioxide is flowing; or silicon dioxide is added to organic solvents such as alcohol and toluene Then, after adding hexamethyldisilazane and water, the water and the organic solvent are evaporated and dried by an evaporator to make the product.

In 100 parts by weight of the entire light and moisture-curable resin composition of the present invention, the preferred lower limit of the content of the filler is 1 part by weight, and the preferred upper limit is 20 parts by weight. If the content of the filler is less than 1 part by weight, the obtained light and moisture-curable resin composition may sometimes be inferior in shape retention after coating. When the content of the filler exceeds 20 parts by weight, the obtained light and moisture-curable resin composition may become poor in coating properties. The more preferable lower limit of the content of the filler is 2 parts by weight, the more preferable upper limit is 15 parts by weight, the more preferable lower limit is 3 parts by weight, the more preferable upper limit is 10 parts by weight, and the more preferable lower limit is 4 parts by weight.

The light and moisture-curable resin composition of the present invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the light and moisture-curable resin composition of the present invention is excellent in light-shielding properties, and light leakage of a display element can be prevented.

In addition, in the present specification, the "shielding agent" means a material having the ability to make it difficult to penetrate light in the visible light region.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. In addition, the above-mentioned light-shielding agent may not show black. As long as the material has the ability to make it difficult to transmit light in the visible light region, the materials listed as silica, talc, titanium oxide, etc. as fillers are also included in the light-shielding agent in. Among these, titanium black is preferred.

The average transmittance of the above titanium blacks with respect to light with a wavelength of 300 to 800 nm For substances in the vicinity of the ultraviolet region, especially for materials having a higher transmittance with respect to light having a wavelength of 370 to 450 nm. That is, the above-mentioned titanium black has the property of providing light-shielding properties to the light and moisture-curable resin composition of the present invention by sufficiently shielding light of a wavelength in the visible light region, and transmitting light of a wavelength near the ultraviolet region on the other hand. Sunscreen. Therefore, as the photo-radical polymerization initiator, the light and the moisture-curable resin of the present invention can be used by those who can start the reaction by using the wavelength (370 to 450 nm) at which the transmittance of the titanium black is increased. The photocurability of the composition is further increased. On the other hand, as the light-shielding agent contained in the light and moisture-curable resin composition of the present invention, a highly insulating substance is preferable, and as a light-shielding agent with high insulation, titanium black is preferable.

The optical density (OD value) of the titanium black is preferably 3 or more, and more preferably 4 or more. The blackness (L value) of the titanium black is preferably 9 or more, and more preferably 11 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black does not particularly have a preferable upper limit, but it is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even without surface treatment, but it can also be treated with organic components such as coupling agents on the surface, or silicon oxide, titanium oxide, germanium oxide, alumina, zirconia, magnesium oxide, etc. Titanium black after surface treatment of inorganic component coatings. Among them, those treated with an organic component are preferred in terms of further improving the insulation properties.

In addition, a display element manufactured using the light and moisture-curable resin composition of the present invention has sufficient light-shielding properties, so it has no light leakage, has a high contrast ratio, and has an excellent figure. Like display quality.

Examples of commercially available products in the titanium black include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), and Tilack D (manufactured by Ako Kasei Co., Ltd.).

The preferred lower limit of the specific surface area of the titanium black is 5 m ² / g, the preferred upper limit is 40 m ² / g, the more preferred lower limit is 10 m ² / g, and the more preferred upper limit is 25 m ² / g.

In addition, the lower limit of the sheet resistance of the titanium black is preferably limited to 10 ⁹ Ω / □ when mixed with the resin (70% blending), and a more preferable lower limit is 10 ¹¹ Ω / □.

In the light and moisture-curable resin composition of the present invention, the primary particle diameter of the above-mentioned light-shielding agent is equal to or less than the distance between the substrates of the display element, etc., and can be appropriately selected according to the application. The preferred lower limit is 30 nm and the preferred upper limit is 500 nm. . If the primary particle diameter of the light-shielding agent is less than 30 nm, the viscosity or shake of the obtained light and the moisture-curable resin composition may be greatly increased, and the workability may be deteriorated. If the primary particle diameter of the above-mentioned light-shielding agent exceeds 500 nm, the dispersibility of the light-shielding agent in the obtained light and the moisture-curable resin composition may decrease, and the light-shielding property may decrease. A more preferable lower limit of the primary particle diameter of the above-mentioned sunscreen is 50 nm, and a more preferable upper limit is 200 nm.

The particle diameter of the light-shielding agent was measured by calculating the average particle diameter by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The content of the above-mentioned light-shielding agent in the entire light and moisture-curable resin composition of the present invention is not particularly limited, and the preferred lower limit is 0.05% by weight, and the preferred upper limit is 10% by weight. If the content of the light-shielding agent is less than 0.05% by weight, sufficient light-shielding properties may not be obtained. When content of the said light-shielding agent exceeds 10 weight%, the adhesiveness of the obtained light and moisture-curable resin composition with respect to a board | substrate etc., or the intensity | strength after hardening may fall, or drawability may fall. The more preferable lower limit of the content of the above-mentioned sunscreen agent is 0.1% by weight, the more preferable upper limit is 2% by weight, and the more preferable upper limit is 1% by weight.

The light and moisture-curable resin composition of the present invention may further contain There are additives such as colorants, ionic liquids, solvents, metal-containing particles, and reactive diluents.

Examples of the method for producing the light and moisture-curable resin composition of the present invention include the following methods: using a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill A mixer is used to mix a radically polymerizable compound, a moisture-curable urethane resin, a photoradical polymerization initiator, and additives added as needed.

In the light and moisture-curable resin composition of the present invention, a preferable lower limit of the viscosity measured using a cone-plate viscosity meter at 25 ° C and 1 rpm is 50 Pa. s, the preferred upper limit is 500Pa. s. If the above viscosity does not reach 50Pa. s or more than 500Pa. s, when the light and moisture-curable resin composition is used for an adhesive for electronic parts or an adhesive for display elements, workability may be deteriorated when it is applied to an adherend such as a substrate. The better lower limit of the above viscosity is 80Pa. s, the better upper limit is 300Pa. s, and further preferably the upper limit is 200Pa. s.

A preferred lower limit of the shake index of the light and moisture-curable resin composition of the present invention is 1.3, and a preferred upper limit is 5.0. If the above-mentioned shake index is less than 1.3 or more than 5.0, the workability when the light and moisture-curable resin composition is used for an adhesive for electronic parts or an adhesive for display elements when it is applied to a substrate such as a substrate Sometimes it gets worse. The lower limit of the shake index is more preferably 1.5. A better upper limit is 4.0.

In addition, in the present specification, the above-mentioned shake index means a viscosity obtained by using a cone-plate viscosity meter measured at 25 ° C and 1 rpm divided by a viscosity measured by using a cone plate viscosity meter at 25 ° C and 10 rpm. value.

The lower limit of the tensile elastic modulus of the cured product of the light and moisture-curable resin composition of the present invention at 25 ° C is preferably 0.5 kgf / cm ² , and the upper limit thereof is preferably 6 kgf / cm ² . When the said tensile elasticity modulus is less than 0.5 kgf / cm <^2> , it will become too soft, the cohesion force may become weak, and the adhesive force may fall. When the tensile elastic modulus exceeds 6 kgf / cm ² , flexibility may be impaired. The more preferable lower limit of the above-mentioned tensile elastic modulus is 1 kgf / cm ² , and the more preferable upper limit is 4 kgf / cm ² .

In addition, in the present specification, the "tensile elastic modulus" means that a hardened product is stretched at a speed of 10 mm / min using a tensile tester (for example, "EZ-Graph" manufactured by Shimadzu Corporation), and is set to elongation. 50% force measured.

Examples of the adherend that can be adhered using the light and moisture-type resin composition of the present invention include various adherends such as metal, glass, and plastic.

Examples of the shape of the adherend include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod shape) shape, a box shape, a frame shape, and the like.

Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.

Examples of the glass include alkaline glass, non-alkali glass, and quartz glass.

Examples of the plastic include polyolefin resins such as high-density polyethylene, ultra-high molecular weight polyethylene, in-row polypropylene, opposite-row polypropylene, and ethylene-propylene copolymer resin, or nylon 6 (N6) and nylon 66 (N66 ), Nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 Copolymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer and other polyamide resins, or polyparaphenylene Butyl dicarboxylate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polynaphthalene dicarboxylic acid Aromatic polyester resins such as succinate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid / polybutylene terephthalate copolymer, or polyacrylonitrile (PAN), polymer Methacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / Polystyrene resins such as styrene copolymers, methacrylonitrile / styrene / butadiene copolymers, or polycarbonates, or polymethyl methacrylate (PMMA), polyethyl methacrylate / vinyl acetate ( EVA) and other polymethacrylate resins, or polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene Polyethylene resins such as vinyl chloride copolymers, vinylidene chloride / methyl acrylate copolymers, and the like.

In addition, as the adherend, a composite material having a metal plating layer on the surface may be mentioned, and as a plating base material of the composite material, the above-mentioned metals, glass, plastic, etc. may be mentioned, for example.

In addition, examples of the adherend include a material in which a passive film is formed by inactivating a metal surface. Examples of the passive treatment include heat treatment and anodizing. In particular, in the case of an aluminum alloy such as the 6000 series made of the international aluminum alloy, the adhesion can be improved by performing a sulfuric acid alumite treatment or a phosphoric acid alumite treatment as the passivation treatment.

The light and moisture-curable resin composition of the present invention is particularly suitable for use as an adhesive for electronic parts or an adhesive for display elements. The adhesive for electronic parts using the light and moisture-curing resin composition of the present invention and the adhesive for display elements using the light and moisture-curing resin composition of the present invention are each one of the present invention.

According to the present invention, a light and moisture-curable resin composition having excellent initial adhesion can be provided. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition.

1‧‧‧ polycarbonate substrate

2‧‧‧Light and moisture hardening resin composition

3‧‧‧ glass plate

FIG. 1 (a) is a schematic diagram showing a case where the sample for adhesion evaluation is viewed from above, and (b) is a schematic diagram showing a case where the sample for adhesion evaluation is viewed from the side.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples.

(Synthesis example 1 (production of amine ester prepolymer A))

100 parts by weight of polytetramethylene ether glycol ("PTMG-2000", manufactured by Mitsubishi Chemical Corporation), which is a polyol compound, and 0.01 parts by weight of dibutyltin dilaurate were placed in a separable flask having a volume of 500 mL. The mixture was stirred and mixed at 100 ° C. for 30 minutes under vacuum (less than 20 mmHg). Thereafter, it was set to normal pressure, and 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI" manufactured by NISSO SHOJI CO., LTD.) As a polyisocyanate compound was placed therein, and the reaction was carried out by stirring at 80 ° C for 3 hours. To obtain an amine ester prepolymer A (weight average molecular weight: 2700).

(Synthesis example 2 (production of amine ester prepolymer B))

100 parts by weight of polypropylene glycol ("EXCENOL 2020" manufactured by ASAHI GLASS CO., LTD.), Which is a polyol compound, and 0.01 parts by weight of dibutyltin dilaurate were placed in a separable flask having a volume of 500 mL. Stir and mix at 100 ° C for 30 minutes under vacuum (less than 20 mmHg). Thereafter, it was set to normal pressure, and 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI" manufactured by NISSO SHOJI CO., LTD.) As a polyisocyanate compound was placed therein, and the reaction was carried out at 80 ° C with stirring for 3 hours. To obtain an amine ester prepolymer B (weight average molecular weight: 2900).

(Synthesis example 3 (production of amine ester prepolymer C))

100 parts by weight of polypropylene glycol (ASAHI GLASS CO., LTD. ("EXCENOL 2020"), 0.01 part by weight of dibutyltin dilaurate, and 13 parts by weight of 2-methacryloxyethyl isocyanate as a compound having an isocyanate group and a reactive double bond at the terminal ( SHOWA DENKO Co., Ltd. ("Karenz MOI") was placed in a separable flask with a volume of 500 mL, and stirred and mixed at 100 ° C for 30 minutes under vacuum (20 mmHg or less). Thereafter, it was set to normal pressure, and 4.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI" manufactured by NISSO SHOJI CO., LTD.) As a polyisocyanate compound was placed therein, and the reaction was stirred at 80 ° C for 3 hours. An amine ester prepolymer C (weight average molecular weight: 3000) having a reactive double bond at the terminal and a ratio of isocyanate groups in the structure of about 0.4% by weight was obtained.

(Synthesis example 4 (production of amine ester prepolymer D))

Instead of 2-methacryloxyethyl isocyanate (manufactured by SHOWA DENKO, "Karenz MOI"), 2-methacryloxy ethoxyethyl isocyanate (manufactured by SHOWA DENKO, "Karenz MOI-EG") was used. ”) Except for 13.5 parts by weight, synthesis was performed in the same manner as in Synthesis Example 3 to obtain an amine ester prepolymer D (weight by weight) having a reactive double bond at the terminal and a ratio of isocyanate groups in the structure of about 0.4% by weight. (The average molecular weight is 3100).

(Examples 1 to 13, Comparative Examples 1 to 3)

According to the blending ratios described in Tables 1 and 2, each material was stirred with a planetary agitation device (manufactured by THINKY CORPORATION, "defoaming stirring Taro"), and then uniformly mixed with a ceramic three-roller to obtain Examples 1 to 4. 3. The light and moisture-curable resin compositions of Comparative Examples 1 to 3. In addition, the "amine ester prepolymer A" in Tables 1 and 2 is an amine ester prepolymer having isocyanate groups at both ends described in Synthesis Example 1, and the "amine ester prepolymer B" is in Synthesis Example 2. The amine ester prepolymer having isocyanate groups at both ends is described, and "amine ester prepolymer C" is the ratio of the isocyanate groups having a reactive double bond at the terminals and the structure described in Synthesis Example 3 to about 0.4% by weight of amine ester The prepolymer, "amine ester prepolymer D", is an amine ester prepolymer described in Synthesis Example 4 having a reactive double bond at the terminal and having a ratio of isocyanate groups in the structure of about 0.4% by weight.

<Evaluation>

The following evaluations were performed on each of the light and moisture-curable resin compositions obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

(Initial adhesion)

Using a dispensing device, each light and moisture-curable resin composition obtained in the examples and comparative examples was coated on a polycarbonate substrate so as to have a width of about 2 mm and a length of 30 mm. Thereafter, 500 mJ / cm ² of ultraviolet rays were irradiated with a high-pressure mercury lamp to light-harden the light and the moisture-curable resin composition. Then, a glass plate was bonded to a polycarbonate substrate, and a weight of 100 g was placed for 5 seconds to obtain a sample for initial adhesiveness evaluation.

The glass substrate of the initial adhesiveness evaluation sample produced was fixed with a clip, the sample was hung perpendicularly to the ground, and a weight of 10 g was hung on the end of the polycarbonate substrate, and the time until the polycarbonate substrate dropped was measured. When the polycarbonate substrate is dropped within 10 minutes, it is set to "×". When the polycarbonate substrate is dropped within 10 minutes and less than 30 minutes, it is set to "△". When the polycarbonate substrate is dropped within 30 minutes, it is set to "△". If it does not fall, set it to "○".

(Adherence)

Using a dispensing device, each of the light and moisture-curable resin compositions obtained in the examples and comparative examples was coated on a polycarbonate substrate with a width of about 2 mm. Thereafter, 500 mJ / cm ² of ultraviolet rays were irradiated with a high-pressure mercury lamp to light-harden the light and the moisture-curable resin composition. After that, a glass plate was bonded to the polycarbonate substrate, a weight of 100 g was placed thereon, and it was left to stand for moisture curing overnight to obtain a sample for adhesion evaluation.

FIG. 1 is a schematic diagram (FIG. 1 (a)) showing a case where the sample for adhesion evaluation is viewed from above, and a schematic diagram (FIG. 1 (b)) showing a case where the sample for adhesion evaluation is viewed from the side.

Using a tensile tester ("Ez-Graph" manufactured by Shimadzu Corporation), the produced adhesive evaluation sample was stretched at a speed of 5 mm / sec in the shear direction, and the peeling of the polycarbonate substrate and the glass plate was measured. The strength of the time.

(Softness)

The light obtained in the Examples and Comparative Examples and the moisture-curable resin composition were light-cured by irradiating 500 mJ / cm ² of ultraviolet rays using a high-pressure mercury lamp, and then moisture-cured by standing overnight. A tensile tester ("EZ-Graph" manufactured by Shimadzu Corporation) was used to stretch at a speed of 10 mm / sec. The obtained hardened product was punched in a dumbbell shape (No. 6 shape specified in "JIS K 6251") and punched. The obtained test piece was calculated | required by the force at 50% elongation as an elasticity modulus.

[Industrial availability]

According to the present invention, a light and moisture-curable resin composition having excellent initial adhesion can be provided. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition.

Claims (16)

A light and moisture-curable resin composition containing a radically polymerizable compound, a moisture-curable amine ester resin, and a photo-radical polymerization initiator. The moisture-curable amine ester resin contains: A compound having an isocyanate group and a reactive double bond at the terminal, the light and moisture-curable resin composition further containing a compound that has an amine ester bond, an isocyanate group, and a reactive double bond at the terminal. Type amine ester resin. For example, the light and moisture-curable resin composition of the scope of application for a patent, wherein the moisture-curable amine ester resin further contains: a moisture-curable amine ester resin that does not contain a reactive double bond, as the reaction-free A moisture-curable amine ester resin having a double bond, containing a compound having an amine ester bond, a group represented by the following formula (2), and an isocyanate group, In the formula (2), R ³ and R ⁴ are hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group. Each R ³ and each R ⁴ may be the same or different, and x represents an integer of 0 to 2. A light and moisture-curable resin composition containing a radically polymerizable compound, a moisture-curable amine ester resin, and a photo-radical polymerization initiator. The moisture-curable amine ester resin contains: A compound having an isocyanate group and a reactive double bond at the end has a viscosity of 50 to 500 Pa · s measured at 25 ° C and 1 rpm using a cone-plate viscometer for the light and moisture-curable resin composition. For example, the light and moisture-curable resin composition of item 1 or 3 of the patent application range, wherein the ratio of isocyanate groups in the structure of the compound having an amine ester bond, an isocyanate group, and a reactive double bond at the terminal is 0.8 weight %the following. For example, the light and moisture-curable resin composition of item 1 or 3 of the scope of patent application, wherein the content of the compound having an amine ester bond, an isocyanate group, and a reactive double bond at the terminal is relative to the radically polymerizable compound and the moisture content. A total of 100 parts by weight of the gas-curable amine ester resin is 0.5 to 20 parts by weight. For example, the light and moisture-curable resin composition according to item 1 or claim 3, wherein the compound having an amine ester bond, an isocyanate group, and a reactive double bond at the terminal is a polyol compound, a polyisocyanate compound, and It is obtained by reacting a compound having an isocyanate group and a reactive double bond at the terminal. For example, the light and moisture-curable resin composition according to item 6 of the patent application, wherein the polyol compound is a polyester polyol and / or a polyether polyol. For example, the light and moisture-curable resin composition of item 6 of the patent application scope, wherein the polyisocyanate compound is an aromatic isocyanate compound. For example, the light and moisture-curable resin composition according to item 1 or 3 of the patent application scope, wherein the radical polymerizable compound contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. For example, the light and moisture-curable resin composition of item 9 of the patent application range, wherein the content of the polyfunctional radical polymerizable compound is 100 weight relative to the total of the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound. Part is 2 to 45 parts by weight. For example, the light and moisture hardening resin composition of the scope of patent application No. 1 or 3 contains a coupling agent. For example, the light and moisture-curable resin composition of item 1 or 3 of the patent application scope contains a filler having a primary particle diameter of 1 to 50 nm. For example, the light and moisture-curable resin composition of item 1 or 3 of the patent application scope contains a sunscreen. For example, the light and moisture-curable resin composition of item 1 or 3 of the patent scope has a shake index of 1.3 to 5.0. An adhesive for electronic parts is made by using a light and moisture-curable resin composition according to any one of claims 1 to 14. An adhesive for display elements, which is made by using a light and moisture-curable resin composition according to any one of claims 1 to 14.