WO2022230820A1

WO2022230820A1 - Light/moisture-curable adhesive composition, and cured body

Info

Publication number: WO2022230820A1
Application number: PCT/JP2022/018760
Authority: WO
Inventors: 坤徐; 彰結城; 拓身木田; 智一玉川; 康平萩原
Original assignee: 積水化学工業株式会社
Priority date: 2021-04-28
Filing date: 2022-04-25
Publication date: 2022-11-03
Also published as: TW202309214A; CN117203300A; JPWO2022230820A1; KR20240004322A

Abstract

This light/moisture-curable adhesive composition contains: a urethane prepolymer containing a polyurethane having a polycarbonate skeleton and a silicone skeleton in a molecule; and a radically polymerizable compound.

Description

Light-moisture-curable adhesive composition and cured product

The present invention relates to a light and moisture-curable adhesive composition and a cured product of the light and moisture-curable adhesive composition.

Conventionally, moisture-curable adhesives containing moisture-curable resins that are cured by external moisture have been widely used. A moisture-curable urethane prepolymer may be used as the moisture-curable resin. Generally, as a urethane prepolymer, a polyurethane obtained by reacting a polyisocyanate and a polyol is widely known. Polyester polyols and polyether polyols are often used as polyols, which are raw materials for polyurethanes. In recent years, the use of polycarbonate polyols, silicone skeleton-containing polyols, and the like has also been studied.

For example, in Patent Document 1, a carboxyl group characterized by having a structure derived from a silicone-containing diol compound having a hydroxyl value of 5 to 200 mgKOH/g is used as a polyurethane used in solder resist ink or overcoat ink. A contained polyurethane is disclosed. Patent Document 2 describes a composition used for medical devices, implants, etc., containing at least one polysiloxane macrodiol and at least one polyether and/or polycarbonate macrodiol soft segment. A polyurethane elastomer composition is disclosed.
Further, Patent Document 3 describes a one-part moisture-curable polyurethane coating agent useful as a moisture-proof insulation agent, which is obtained by mixing an organic polyisocyanate, a polycarbonate diol having a specific molecular weight, a polyester polyol, and a siloxane-modified polyol in a predetermined ratio. It is disclosed that those obtained by reacting with are used.

JP 2007-100036 A JP 2008-101194 A JP 2008-156501 A

In recent years, the use of moisture-curable adhesives has expanded, and there is a growing demand for higher adhesive strength to various types of adherends. Therefore, it is required to improve the adhesive force.
In addition, moisture-curable adhesives are sometimes required to maintain a certain interval or more between adherends to be adhered. However, when a general moisture-curing adhesive is placed between two adherends and adhered to each other, it is crushed by the pressure during adhesion and cannot maintain its shape, resulting in a constant bond between the adherends. It is difficult to keep the interval.

On the other hand, the polyurethanes disclosed in Patent Documents 1 to 3 are shown to improve various performances by having a silicone skeleton, but they have not been studied for use in adhesives and can be used in various substrates. No specific technique is disclosed for maintaining a constant interval between the adherends while improving the adhesive force to the adherends.

Therefore, the present invention provides a moisture-curable adhesive composition that maintains a certain shape without being crushed even when pressure is applied during adhesion, while improving the adhesive strength to various adherends. The challenge is to ensure that

As a result of intensive studies, the present inventors have found that the above problems can be solved by including a urethane prepolymer having a specific skeleton and a radically polymerizable compound in a moisture-curable adhesive composition. I completed the present invention. That is, the present invention can provide the following [1] to [22].
[1] A light and moisture-curable adhesive composition comprising a urethane prepolymer containing a polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule, and a radically polymerizable compound.
[2] The light and moisture-curable adhesive composition according to [1] above, wherein the cured product has a storage elastic modulus of 0.01 MPa or more and 50 MPa or less at an elongation of 25%.
[3] The light moisture-curable adhesive composition according to the above [1] or [2], wherein the urethane prepolymer is moisture-curable.
[4] The light and moisture-curable adhesive composition according to [3] above, wherein the urethane prepolymer has an isocyanate group.
[5] The light and moisture curable type according to any one of [1] to [4] above, wherein the urethane prepolymer is a reaction product of a polyol compound containing a polycarbonate polyol and a silicone polyol and a polyisocyanate compound. adhesive composition.
[6] The light and moisture-curable adhesive composition according to [5] above, wherein the silicone polyol is a silicone diol having two hydroxyl groups.
[7] The light and moisture-curable adhesive composition according to [5] or [6] above, wherein the polycarbonate polyol is a polycarbonate diol.
[8] The light and moisture-curable adhesive composition according to any one of [5] to [7] above, wherein the polyisocyanate compound is a diisocyanate compound.
[9] In the polyol compound, the ratio (Si/PC) of the compounding amount (Si) of the silicone polyol to the compounding amount (PC) of the polycarbonate polyol is 5/95 or more and 95/5 or less on a mass basis. The light and moisture-curable adhesive composition according to any one of [5] to [8] above.
[10] The light and moisture-curable adhesive composition according to any one of [1] to [9] above, wherein the urethane prepolymer has a weight-average molecular weight of 800 or more and 20,000 or less.
[11] The light and moisture-curable adhesive composition according to any one of [1] to [10] above, wherein the radically polymerizable compound contains a compound having a (meth)acryloyl group.
[12] The above [11], wherein the compound having a (meth)acryloyl group is at least one selected from the group consisting of (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. ].
[13] The (meth)acrylic acid ester compound is selected from the group consisting of a (meth)acrylic acid ester compound having an alicyclic structure, a (meth)acrylic acid ester compound having an aromatic ring, and an alkyl (meth)acrylate. The light and moisture-curable adhesive composition according to [12] above, which contains at least one monofunctional (meth)acrylic acid ester compound.
[14] The content of the radical polymerizable compound is 5 parts by mass or more and 70 parts by mass or less with respect to the total amount of 100 parts by mass of the urethane prepolymer and the radical polymerizable compound, above [11] to [ 13], the optical and moisture-curable adhesive composition according to any one of the above items.
[15] The light and moisture-curable adhesive composition according to any one of [1] to [14] above, further comprising a photopolymerization initiator.
[16] The above [1] to [15], wherein the ratio by mass of the content of the silicone skeleton portion to the content of the polycarbonate skeleton portion in the urethane prepolymer is 5/95 or more and 95/5 or less. The optical moisture-curable adhesive composition according to any one of the above.
[17] The light and moisture-curable adhesive composition according to any one of [1] to [16] above, wherein the urethane prepolymer has an isocyanate group at its terminal.
[18] Any one of the above [1] to [17], wherein the total amount of the urethane prepolymer and the radically polymerizable compound is 70% by mass or more based on the total amount of the light moisture-curable adhesive composition. A light and moisture-curable adhesive composition.
[19] A cured product of the light and moisture-curable adhesive composition according to any one of [1] to [18] above.
[20] An electronic device comprising the cured product of [19] above.
[21] Use of the optical moisture-curable adhesive composition according to any one of [1] to [18] above for bonding between adherends.
[22] The use according to [21] above, wherein the adherend is a part constituting an electronic device.

According to the light and moisture-curable adhesive composition of the present invention, it is possible to secure shape retention while improving adhesive strength to various adherends.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows an adhesive test method, Fig.1 (a) is a top view, FIG.1(b) is a side view.

<Light Moisture Curing Adhesive Composition>
The light and moisture-curable adhesive composition of the present invention contains a urethane prepolymer containing polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule, and a radically polymerizable compound.

The light-moisture-curable adhesive composition of the present invention has moisture-curable properties by containing a moisture-curable resin. Any type of moisture-curable resin may be used in the light moisture-curable adhesive composition as long as it contains a moisture-curable resin, but as described below, the urethane prepolymer is moisture-curable. is preferred.

[Urethane prepolymer]
The urethane prepolymer used in the present invention contains polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule. The moisture-curable adhesive composition of the present invention secures wettability to various adherends by incorporating both a polycarbonate skeleton with high mechanical strength and a silicone skeleton with low surface free energy into the urethane prepolymer. At the same time, the mechanical strength of the cured product is improved. Therefore, high adhesive strength can be ensured for various types of adherends. Moreover, heat resistance is improved, and good adhesiveness can be secured even in a high-temperature environment.
Moreover, the urethane prepolymer preferably has a moisture-curable functional group, and more preferably a urethane prepolymer containing an isocyanate group.

In addition, in the urethane prepolymer of the present invention, the content of the silicone skeleton portion may be greater than, less than or equal to the content of the polycarbonate skeleton portion on a mass basis. , the content of the silicone skeleton is preferably higher than the content of the polycarbonate skeleton on a mass basis. When the content of the silicone skeleton portion is large, the adhesive force to various types of adherends can be further improved.
In the urethane prepolymer, as described later, a polycarbonate skeleton and a silicone skeleton are introduced by using both a silicone polyol and a polycarbonate polyol as polyol compounds that are raw materials. Therefore, in the present invention, the silicone skeleton portion is a portion derived from a silicone polyol, and the polycarbonate skeleton portion is a portion derived from a polycarbonate polyol. Moreover, a silicone skeleton means an organopolysiloxane skeleton.

The urethane prepolymer of the present invention is a reaction product of a polyol compound and a polyisocyanate compound. Specifically, it 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 between the polyol compound and the polyisocyanate compound, the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound is usually [NCO]/[OH]=1.9 to 2. .5 range.

Here, both polycarbonate polyol and silicone polyol are used as the polyol compound that is the raw material of the urethane prepolymer. That is, the urethane prepolymer is a reaction product of a mixture of polycarbonate polyol and silicone polyol and a polyisocyanate compound. As a result, at least part of the polyurethane constituting the urethane prepolymer can contain both a polycarbonate skeleton and a silicone skeleton in the molecule.

As described above, the polyurethane constituting the urethane prepolymer contains isocyanate groups by increasing [NCO]/[OH], and preferably contains a plurality of isocyanate groups in the molecule.
Moreover, the polyol compound used to obtain the urethane prepolymer is preferably a diol compound, and the polyisocyanate compound is preferably a diisocyanate compound. Therefore, the polyurethane constituting the urethane prepolymer preferably has two isocyanate groups. Also, each isocyanate group is preferably contained at the end of the molecule.

In addition, in the polyol compound used as the raw material, the amount of the silicone polyol blended may be greater, lesser, or the same than the blended amount of the polycarbonate on a mass basis. More is preferable. For example, if the blending amount of the silicone polyol is greater than the blending amount of the polycarbonate, the content of the silicone skeleton portion in the urethane prepolymer will be greater than the content of the polycarbonate skeleton portion.

Here, in the polyol compound used as the raw material, the ratio (Si/PC) of the compounding amount (Si) of the silicone polyol to the compounding amount (PC) of the polycarbonate polyol is preferably 5/95 or more and 95 on a mass basis. /5 or less, more preferably 10/90 or more and 90/10 or less, and still more preferably 15/85 or more and 85/15 or less. Further, the lower limit is more preferably greater than 50/50, and even more preferably 60/40 or more. By setting the blending ratio within the above range, the light and moisture-curable adhesive composition has good adhesion to various materials. Further, when the Si/PC ratio is greater than 50/50, the adhesion to various types of adherends becomes even better.
In addition, as described above, the silicone skeleton portion is a portion derived from a silicone polyol, and the polycarbonate skeleton portion is a portion derived from a polycarbonate polyol. Therefore, the preferred range of the mass-based ratio of the content of the silicone skeleton portion to the content of the polycarbonate skeleton portion in the urethane prepolymer is as described in the above ratio (Si/PC).

Moreover, the polyol compound used as a raw material may consist of a polycarbonate polyol and a silicone polyol, but may contain polyols other than these as long as the effects of the present invention are not impaired. For example, the urethane prepolymer may be a reaction product of polycarbonate polyols, silicone polyols, and mixtures with other polyols and polyisocyanate compounds.
The blending ratio of polyols other than polycarbonate polyols and silicone polyols (other polyols) is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and most preferably 10% by mass or less, based on the total polyol compound. is 0% by mass.
Therefore, the urethane prepolymer may have other polyol-derived moieties in addition to the silicone skeleton and the polycarbonate skeleton, and the preferred range of the content of the other polyol-derived moieties in the urethane prepolymer is the above. It is the same as the blending ratio derived from other polyols.

The urethane prepolymer may be used singly or as a mixture of two or more. When two or more types of urethane prepolymers are used, each urethane prepolymer is preferably a reaction product obtained by reacting a polyol compound with a polyisocyanate compound. For example, at least one of the polyol compound and the polyisocyanate compound used as raw materials may be different from each other. Even when two or more kinds of urethane prepolymers are used, it is preferable that the polyol compound used as a raw material in each urethane prepolymer contains both a polycarbonate polyol and a silicone polyol.
However, any one of the two or more urethane prepolymers may use both polycarbonate polyol and silicone polyol as raw material polyol compounds. It is not necessary to use both polyols.

(silicone polyol)
Examples of silicone polyols include hydroxy group-modified organopolysiloxane compounds having an organopolysiloxane skeleton and hydroxy groups. Moreover, the silicone polyol is preferably a silicone diol having two hydroxyl groups.
Specific examples of hydroxy group-modified organopolysiloxane compounds include a compound having an organopolysiloxane skeleton and hydroxyl groups at both ends thereof, and a compound having an organopolysiloxane skeleton and two hydroxyl groups at one end thereof. etc.
The terminal hydroxy group may be directly bonded to the Si atom constituting the organopolysiloxane skeleton, or may be bonded via a hydrocarbon group or a hydrocarbon group having an ether bond. The hydrocarbon group has, for example, about 2 to 50 carbon atoms, preferably about 2 to 30 carbon atoms.
Silicone polyols may be used singly or in combination of two or more.

The weight average molecular weight of the silicone polyol is preferably from 100 to 10,000, more preferably from 500 to 5,000, and even more preferably from 800 to 3,000. By setting the weight average molecular weight within the above range, the compatibility of the silicone polyol with the polycarbonate polyol is improved. Therefore, by using a mixture of a polycarbonate polyol and a silicone polyol as a raw material for producing a urethane prepolymer, a urethane prepolymer containing a polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule can be produced appropriately. be able to. Then, by adjusting the elastic modulus of the cured product within an appropriate range, the adhesion and the like can be improved.

(polycarbonate polyol)
Polycarbonate diols are preferred as polycarbonate polyols, and specific examples of polycarbonate diols include compounds represented by the following formula (1).

In formula (1), R is a divalent hydrocarbon group having 4 or more and 16 or less carbon atoms, and n is an integer of 2 or more and 500 or less.

In formula (1), R is preferably an aliphatic saturated hydrocarbon group. When R is an aliphatic saturated hydrocarbon group, the heat resistance tends to be good. In addition, yellowing or the like due to heat deterioration or the like is less likely to occur, and weather resistance is improved. Although R composed of an aliphatic saturated hydrocarbon group may have a cyclic structure, it preferably has a chain structure from the viewpoint of easily improving flexibility and the like. In addition, R in the chain structure may be linear or branched. n is preferably 5 or more and 200 or less, more preferably 5 or more and 100 or less, and even more preferably 5 or more and 50 or less.
Moreover, R contained in polycarbonate polyol may be used individually by 1 type, and may be used in combination of 2 or more types. When two or more divalent hydrocarbon groups having 4 to 16 carbon atoms are used in combination, at least a portion thereof is preferably a chain aliphatic saturated hydrocarbon group having 6 to 16 carbon atoms. Here, the chain aliphatic saturated hydrocarbon group having 6 or more and 16 or less carbon atoms preferably has 6 or more and 12 or less carbon atoms, more preferably 6 or more and 10 or less carbon atoms.
When two or more kinds of divalent hydrocarbon groups having 4 to 16 carbon atoms are used in combination, and at least a part thereof is a chain aliphatic saturated hydrocarbon group having 6 to 16 carbon atoms, further 4 carbon atoms or 5 divalent hydrocarbon groups.
Specific examples of R may be linear groups such as a tetramethylene group, pentylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and, for example, a 3-methylpentylene group. It may be branched such as a methylpentylene group such as a methylpentylene group or a methyloctamethylene group. Plural R's in one molecule may be the same or different. Furthermore, from the viewpoint of increasing the elastic modulus to a certain value or more, R preferably contains a branched saturated aliphatic hydrocarbon group, and from the viewpoint of weather resistance, R contains a linear saturated aliphatic hydrocarbon group. is preferred. Branched R and linear R may be used in combination in the polycarbonate polyol.
Polycarbonate polyols may be used singly or in combination of two or more.

The weight average molecular weight of the polycarbonate polyol is preferably 100 or more and 10000 or less, more preferably 500 or more and 5000 or less, and even more preferably 800 or more and 3000 or less. By setting the weight average molecular weight within the above range, the compatibility of the silicone polyol with the polycarbonate polyol is improved. Therefore, a urethane prepolymer containing polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule can be easily produced.

(Polyisocyanate compound)
Examples of polyisocyanate compounds used as raw materials for urethane prepolymers include aliphatic polyisocyanate compounds and aromatic polyisocyanate compounds.
Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate. , bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like. Aliphatic polyisocyanate compounds may be those obtained by increasing these.
Examples of aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene-1,5-diisocyanate. The aromatic polyisocyanate compound may be a multimer of these compounds, polymeric MDI, or the like.
Also, the polyisocyanate compound is preferably a diisocyanate compound.
A polyisocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Although the weight average molecular weight of the urethane prepolymer is not particularly limited, it is preferably 800 or more and 20,000 or less. By setting the weight-average molecular weight within the above range, the elastic modulus of the cured product can be adjusted within an appropriate range while improving the applicability of the light and moisture-curable adhesive composition.
The weight average molecular weight of the urethane prepolymer is more preferably 1500 or more, more preferably 2000 or more, and more preferably 18000 or less, still more preferably 15000 or less.
In addition, in this specification, a weight average molecular weight is a value which measures by a gel permeation chromatography (GPC), and is calculated|required by polystyrene conversion. Shodex LF-804 (manufactured by Showa Denko KK) can be used as a column for measuring the weight average molecular weight in terms of polystyrene by GPC. Moreover, tetrahydrofuran is mentioned as a solvent used in GPC.

[Radical polymerizable compound]
The light moisture-curable adhesive composition of the present invention contains a radically polymerizable compound. By containing a radically polymerizable compound, the light and moisture-curable adhesive composition of the present invention is imparted with photocurability and becomes a light and moisture-curable adhesive composition. Further, in a semi-cured state after photocuring and before moisture curing, it has hardness of a certain level or more, and shape retention can be ensured. If the shape retainability in the semi-cured state can be secured, it becomes easier to secure a constant space between adherends by the cured body formed from the light and moisture-curable adhesive composition.
In addition, since the light and moisture-curable adhesive composition contains a radically polymerizable compound, a certain amount of adhesive strength is imparted only by light irradiation, so even in a semi-cured state after light curing and before moisture curing. A certain level of adhesive strength can be secured.

The radically polymerizable compound is not particularly limited as long as it is a radically polymerizable compound having photopolymerizability, and is a compound having a radically polymerizable functional group in the molecule. A compound having an unsaturated double bond is suitable as the radically polymerizable functional group, and the radically polymerizable functional group includes a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, and the like.
Among the above, a (meth)acryloyl group is preferable from the viewpoint of reactivity. Therefore, the radically polymerizable compound is a compound having a (meth)acryloyl group (hereinafter, also referred to as "(meth)acrylic compound" ) is preferred.

Specific examples of (meth)acrylic compounds include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, urethane (meth)acrylates, and the like. In addition, urethane (meth)acrylate does not have a residual isocyanate group.
In the present specification, "(meth)acryloyl group" means acryloyl group or (meth)acryloyl group, "(meth)acrylate" means acrylate or methacrylate, and the same applies to other similar terms. be.

The (meth)acrylic acid ester compound may be monofunctional, bifunctional, or trifunctional or more.
Examples of monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylates, alkyl (meth)acrylates such as stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl ( meth)acrylates, (meth)acrylates having an alicyclic structure such as dicyclopentenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, etc. ) acrylate, methoxyethylene glycol (meth)acrylate, alkoxyethylene glycol (meth)acrylate such as ethoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate polyoxyethylene-based (meth)acrylates such as acrylates, ethyl carbitol (meth)acrylates, ethoxydiethylene glycol (meth)acrylates, ethoxytriethylene glycol (meth)acrylates, and ethoxypolyethylene glycol (meth)acrylates;

In addition, the (meth)acrylic acid ester compound may have an aromatic ring. and phenoxyalkyl (meth)acrylates such as Furthermore, it may be a (meth)acrylate having a plurality of benzene rings such as a fluorene skeleton or a biphenyl skeleton, and specific examples thereof include fluorene-type (meth)acrylates and ethoxylated o-phenylphenol acrylates.
Phenoxypolyoxyethylene-based (meth)acrylates such as phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, nonylphenoxydiethyleneglycol (meth)acrylate and nonylphenoxypolyethyleneglycol (meth)acrylate are also included.

Further, monofunctional (meth)acrylic acid ester compounds include tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-ethyl-3- (Meth)acrylates having a heterocyclic structure such as oxetanylmethyl (meth)acrylate, various imide (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoro Propyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-( meth) acryloyloxyethyl hexahydrophthalic acid, N-acryloyloxyethyl hexahydrophthalimide, 2-(meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(meth) acryloyloxy Also included are ethyl phosphate and the like.

Examples of bifunctional (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyl di(meth) Acrylates, neopentyl 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, polyesterdiol di(meth)acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate and the like.

Further, among the (meth)acrylic acid ester compounds, tri- or higher functional ones include, 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-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, tris (Meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound with (meth)acrylic acid. Here, the reaction between the epoxy compound and (meth)acrylic acid is preferably carried out in the presence of a basic catalyst or the like according to a conventional method. The epoxy (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, but polyfunctional is preferred, and bifunctional is more preferred.
Examples of epoxy compounds that are raw materials for synthesizing the epoxy (meth)acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallylbisphenol A type 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 Novolak type epoxy resin, ortho-cresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin , glycidyl ester compounds, bisphenol A type episulfide resins, and the like.

上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬ　ＲＤＸ６３１８２（いずれもダイセル・オルネクス社製), EA-1010, EA-1020, EA-5323, EA-5520, EACHHD, 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 (both manufactured by Nagase ChemteX Corporation), and the like.

As urethane (meth)acrylate, for example, a product obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group can be used. Here, for the reaction between the isocyanate compound and the (meth)acrylic acid derivative, it is preferable to use a catalytic amount of a tin-based compound or the like as a catalyst. The urethane (meth)acrylate may be monofunctional or polyfunctional such as bifunctional, but bifunctional is preferred.
Examples of isocyanate compounds used to obtain urethane (meth)acrylates include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Polyisocyanate compounds such as isocyanatophenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate and the like can be mentioned.
As the isocyanate compound, a chain-extended polyisocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used. Examples of polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of (meth)acrylic acid derivatives having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. mono (meth) acrylate, trimethylol ethane, trimethylol propane, trihydric alcohol mono (meth) acrylate or di (meth) acrylate such as glycerin, epoxy (meth) acrylate such as bisphenol A type epoxy (meth) ) acrylates and the like.

Examples of commercially available urethane (meth)acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411, ＥＢＥＣＲＹＬ８４１２、ＥＢＥＣＲＹＬ８４１３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２７０、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２２２０（いずれもダイセル・オルネクス社製）、アートレジンＵＮ－９０００Ｈ、アートレジンＵＮ－９０００Ａ、アートレジンＵＮ－７１００、アートResin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Neagari Kogyo 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 Shin Nakamura Chemical Kogyosha), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), CN-902, CN-973, CN-9021, CN-9782, CN-9833 (all manufactured by Arkema) and the like.

As the radically polymerizable compound, radically polymerizable compounds other than those mentioned above can also be used as appropriate. Other radically polymerizable compounds include, for example, N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N- (Meth)acrylamide compounds such as isopropyl (meth)acrylamide and N,N-dimethylaminopropyl (meth)acrylamide, vinyls such as styrene, α-methylstyrene, N-vinyl-2-pyrrolidone and N-vinyl-ε-caprolactam compounds and the like.

Among the above, it is preferable to use a (meth)acrylic acid ester compound as the radically polymerizable compound. The (meth)acrylic acid ester compound is preferably a monofunctional (meth)acrylic acid ester compound. It is more preferable to include at least one selected. Moreover, as a radically polymerizable compound, it is also preferable to use a monofunctional (meth)acrylate compound and a urethane (meth)acrylate together.

When the light moisture-curable adhesive composition contains a radically polymerizable compound, the content of the radically polymerizable compound is preferably 5 parts by mass with respect to 100 parts by mass of the total amount of the urethane prepolymer and the radically polymerizable compound. It is more than 70 mass parts or less. By making the content of the radically polymerizable compound equal to or higher than the above lower limit value, it is possible to appropriately impart photocurability to the light and moisture-curable adhesive composition, and to further improve the above-described shape retention. In addition, it becomes easier to improve the applicability of the adhesive composition. On the other hand, by setting the amount to the above upper limit or less, the amount of the urethane prepolymer can be increased to a certain amount or more, and by making the urethane prepolymer moisture-curable, an appropriate moisture-curable property can be imparted to the light moisture-curable adhesive composition. can be granted.
From these viewpoints, the content of the radical polymerizable compound is more preferably 10 parts by mass or more and 60 parts by mass or less, still more preferably 20 parts by mass or more and 50 parts by mass or less, and even more preferably 25 parts by mass or more and 45 parts by mass or less. is.

The total amount of the urethane prepolymer and the radical polymerizable compound is not particularly limited, but is preferably 70% by mass or more, more preferably 75% by mass or more and 97% by mass or less, based on the total amount of the light moisture-curable adhesive composition. Preferably, it is 80% by mass or more and 95% by mass or less.

[Photoinitiator]
It is preferable that the photo-moisture-curable adhesive composition of the present invention further contains a photopolymerization initiator. By containing a photopolymerization initiator, it is possible to appropriately impart photocurability to the photo-moisture-curable adhesive composition.
Examples of photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone.
Examples of commercially available photopolymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (both manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the like.

The content of the photopolymerization initiator in the light moisture-curable adhesive composition is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. It is more than 5 mass parts or less. When the content of the photopolymerization initiator is within these ranges, the resulting photo-moisture-curable adhesive composition has excellent photocurability and storage stability. Moreover, by setting the content within the above range, the photoradical polymerizable compound is appropriately cured, and the adhesive strength tends to be improved.

[filler]
The light moisture-curable adhesive composition of the present invention may contain a filler. By containing a filler, the light and moisture-curable adhesive composition of the present invention has suitable thixotropic properties, which facilitates good shape retention after application. A particulate filler may be used as the filler.
Preferred fillers include inorganic fillers such as silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Among these, silica is preferable because the light and moisture-curable adhesive composition has excellent ultraviolet transmittance. In addition, the filler may be subjected to hydrophobic surface treatment such as silylation treatment, alkylation treatment, and epoxidation treatment.
A filler may be used individually by 1 type, and 2 or more types may be used in combination.
The content of the filler is preferably 0.5 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less, still more preferably It is 2 parts by mass or more and 15 parts by mass or less.

In addition to the components described above, the photo-moisture-curable adhesive composition of the present invention contains a moisture-curing acceleration catalyst, a coupling agent such as a silane coupling agent, a titanate-based coupling agent, a zirconate-based coupling agent, and a wax. Other additives such as particles, ionic liquids, colorants, expanded particles, expanded particles, reactive diluents, antioxidants, radical scavengers, etc. may be contained.

A moisture-hardening acceleration catalyst is a catalyst that accelerates the moisture-hardening reaction of a moisture-curable resin. By using a moisture-curing acceleration catalyst, the moisture-curing property of the light-moisture-curable adhesive composition becomes more excellent, making it easier to increase adhesive strength. Specific examples of moisture curing acceleration catalysts include amine-based compounds and metal-based catalysts. Examples of amine compounds include compounds having a morpholine skeleton such as di(methylmorpholino) diethyl ether, 4-morpholinopropyl morpholine, 2,2′-dimorpholino diethyl ether, bis(2-dimethylaminoethyl) ether, 1,2 -Dimethylamino group-containing amine compounds having two dimethylamino groups such as bis(dimethylamino)ethane, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4 -diazabicyclo[2.2.2]octane and the like.
Examples of metal-based catalysts include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate and tin octylate; zinc compounds such as zinc octoate and zinc naphthenate; zirconium tetraacetylacetonate; copper naphthenate; Other metal compounds such as cobalt naphthenate are included.
When the light moisture-curable adhesive composition contains a moisture curing acceleration catalyst, the content of the moisture curing acceleration catalyst in the light moisture-curable adhesive composition is relative to 100 parts by mass of the light moisture-curable adhesive composition. , preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, still more preferably 0.3 to 5 parts by mass.

The light-moisture-curable adhesive composition may be diluted with a solvent, if necessary. When the light moisture-curable adhesive composition is diluted with a solvent, each amount (parts by mass, mass%) of the light moisture-curable adhesive composition is based on the solid content, i.e., parts by mass excluding the solvent , means % by weight.

As a method for producing the adhesive composition of the present invention, a mixer is used to prepare a urethane prepolymer, and, if necessary, a radically polymerizable compound, a photopolymerization initiator, a moisture curing acceleration catalyst, and a filler. and a method of mixing with other additives such as an agent and a coupling agent. Examples of mixers include homodispers, homomixers, universal mixers, planetary mixers (planetary stirring devices), kneaders, and three rolls.

[Storage modulus at elongation of 25%]
In the present invention, it is preferable that the cured product of the light and moisture-curable adhesive composition has a storage elastic modulus of 0.01 MPa or more and 50 MPa or less at an elongation of 25%. The light and moisture-curable adhesive composition has a storage elastic modulus of 0.01 MPa or more at an elongation of 25% of the cured product, so that cohesive failure is unlikely to occur even when shearing or the like is applied, and the adhesive strength is sufficiently improved. can be higher. In addition, by setting the pressure to 50 MPa or less, the elasticity of the cured product becomes appropriate, and the adhesive strength to various adherends can be easily improved.
The storage elastic modulus of the cured product of the light moisture-curable adhesive composition at an elongation rate of 25% is preferably 0.05 MPa or more, more preferably 0.1 MPa or more, from the viewpoint of improving the adhesive strength to various adherends. 0.2 MPa or more is more preferable, 25 MPa or less is preferable, 15 MPa or less is more preferable, and 8 MPa or less is even more preferable.

In the present invention, the storage elastic modulus at 25% elongation of the cured product is the storage elastic modulus measured at 23° C. in a state in which the cured product is elongated by 25%. The storage elastic modulus of the cured product at an elongation of 25% can be measured by the following method.
The light and moisture-curable adhesive composition is poured into a Teflon (registered trademark) mold having a width of 2 mm, a length of 10 mm, and a thickness of 1 mm, and cured to obtain a cured body sample. The obtained cured body sample is pulled up to 100% elongation using a tensile tester, and the storage elastic modulus at 25% elongation is determined from the resulting tensile curve. The measurement conditions are 25° C. and a tensile speed of 50 mm/min.
Curing of the light and moisture-curable adhesive composition for obtaining a cured product sample may be carried out by the following method depending on the curing mechanism, as long as the light and moisture-curable adhesive composition can be completely cured. For example, in the case of light moisture curing type, UV-LED (wavelength 365 nm) is used to photo-cure by irradiating 1000 mJ/cm ² of ultraviolet rays, and then for 24 hours in an environment of 23 ° C. and 50% RH. Moisture hardening is carried out by leaving it to stand. Moreover, in the case of a moisture-curing type that does not have photo-curing properties, it is preferable to carry out in the same manner as described above, except that the step of photo-curing is omitted.

[Hardened body]
The light and moisture-curable adhesive composition of the present invention is preferably cured and used as a cured product. The cured product is preferably obtained by curing a light and moisture-curable adhesive composition with light and moisture. The photo-moisture-curable adhesive composition of the present invention can be used by being photo-cured by light irradiation to, for example, a B-stage state (semi-cured state), and then further cured by moisture to be fully cured. preferable.

The light and moisture-curable adhesive composition may be used, for example, to bond the adherends together by being placed between the adherends and cured. More specifically, the light-moisture-curable adhesive composition is applied to one adherend, then photo-cured by light irradiation to a B-stage state, and the photo-cured light-moisture-curable adhesive composition It is preferable that the other adherend is superimposed on the object, and the adherends are temporarily adhered with an appropriate adhesive force. After that, the light moisture-curable adhesive composition in the B-stage state was completely cured by curing a moisture-curable resin such as a urethane prepolymer with moisture, and was superimposed via the light moisture-curable adhesive composition. The adherends are joined with sufficient adhesive force.
In the present invention, since the light and moisture-curable adhesive composition contains a radically polymerizable compound, a certain thickness or more can be secured even when the other adherend is superimposed in the B-stage state. Therefore, it is possible to maintain a constant interval between the adherends.

The application of the light moisture-curable adhesive composition to the adherend is preferably carried out, for example, with a dispenser, but is not particularly limited. Moreover, the light to be irradiated during photocuring is not particularly limited as long as it is light that cures the radically polymerizable compound, but ultraviolet rays are preferable. Moreover, when the light moisture-curable adhesive composition is completely cured by moisture, it may be left in the air for a predetermined period of time.

The light-moisture-curable adhesive composition of the present invention is preferably used as an adhesive for electronic devices. Therefore, although the adherend is not particularly limited, it is preferably various parts constituting an electronic device. Examples of various parts that constitute an electronic device include electronic parts, substrates to which electronic parts are attached, semiconductor chips, and the like. Examples of electronic devices include, but are not limited to, display devices such as liquid crystal displays and organic EL displays. Further, the electronic device may be a portable electronic device or the like, or may be a large-sized electronic device or the like.

In addition, the light and moisture-curable adhesive composition of the present invention can ensure high adhesive strength to various materials. Therefore, the material of the adherend is not particularly limited, and may be any of metal, glass, plastic, etc., and can be adhered to various types of plastics with high adhesive strength.
The shape of the adherend is not particularly limited, and examples thereof include film-like, sheet-like, plate-like, panel-like, tray-like, rod-like, box-like, and housing-like shapes.

In addition, the optical moisture-curable adhesive composition of the present invention is used for obtaining assembled parts by bonding substrates together, for example, inside electronic devices. The assembly part thus obtained has a first substrate, a second substrate, and the cured product of the present invention, wherein at least a portion of the first substrate is at least a portion of the second substrate. is joined through a hardened body. At least one electronic component is preferably attached to each of the first substrate and the second substrate.

The present invention will be described in more detail with examples, but the present invention is not limited by these examples.

Various physical properties were measured and evaluated as follows.
<Storage modulus at 25% elongation>
A cured sample was obtained under the conditions described in the specification, and the storage elastic modulus at 25° C. and an elongation of 25% was measured by the method described in the specification for the obtained cured sample. As the tensile tester, a trade name "Autograph AG-X" manufactured by Shimadzu Corporation was used.

<SUS Adhesion>
As shown in FIGS. 1(a) and 1(b), the light moisture-curable resin compositions 10 obtained in Examples and Comparative Examples were placed in an environment of 20 to 25° C. with a width of 1.0±0.05 mm, It was applied to the first plate 11 so as to have a length of 25±2 mm and a thickness of 0.2±0.05 mm. Within 1 minute after the application was completed, the optical moisture-curable adhesive composition 10 was photo-cured by irradiating 1000 mJ/cm ² of ultraviolet rays using a UV-LED (wavelength: 365 nm). After that, the second plate 12 is superimposed, and a weight of 100 g is allowed to stand thereon for 10 seconds in a state where there is no gap material, thereby applying a load of 0.04 MPa to the cured product in the photocured state. Acted for 10 seconds. Next, the weight of 100 g was removed, and the sample 13 for evaluation was prepared by leaving it in an environment of 23° C. and 50 RH% for 3 days for moisture curing (main curing). As the first and

second plates

11 and 12, SUS plates were used.
The prepared evaluation sample 13 is pulled at a speed of 12 mm / min in the shear direction S using a tensile tester in an environment of 20 to 25 ° C. When the first plate 11 and the second plate 12 are peeled off The adhesive force was measured by measuring the strength of the adhesive. The measured adhesive strength was evaluated according to the following evaluation criteria.
However, when the moisture-curable resin composition obtained in the comparative example does not have photocurability, the adhesive strength was measured in the same manner as described above, except that the photocuring by irradiation with ultraviolet rays was omitted. Evaluation was made according to the following evaluation criteria.
AA: 90 N or more A: 75 N or more and less than 90 N B: 65 N or more and less than 75 N C: less than 65 N

<PC adhesion>
The adhesive force was measured in the same manner as described above, except that polycarbonate plates were used as the first and

second plates

11 and 12 instead of the SUS plates. Based on the measured adhesive force, evaluation was made according to the same evaluation criteria as for SUS adhesiveness.

<PMMA adhesion>
The adhesive force was measured in the same manner as described above, except that polymethyl methacrylate resin plates (PMMA plates) were used as the first and

second plates

11 and 12 instead of SUS plates. The measured adhesive strength was evaluated according to the following evaluation criteria.
AA: 150 N or more A: 100 N or more and less than 150 N B: 80 N or more and less than 100 N C: less than 80 N

<Shape retention>
When preparing an evaluation sample in the SUS adhesion test, evaluation was performed by measuring the thickness of the moisture-curable resin composition 10 after removing a 100 g weight. Evaluation criteria are as follows.
A: The thickness of the moisture-curable resin composition is 0.1 mm or more.
C: The thickness of the moisture-curable resin composition is less than 0.1 mm.

Urethane prepolymers used in Examples and Comparative Examples were produced according to the following Synthesis Examples.
[Synthesis Example 1]
As polyol compounds, 80 parts by mass of silicone diol ("polyol FM-4411" manufactured by JNC), 20 parts by mass of polycarbonate diol ("polyol C-1090" manufactured by Kuraray Co., Ltd.), and 0.01 parts by mass of dibutyltin dilaurate. was placed in a 500 mL separable flask. The inside of the flask was stirred and mixed at 100° C. for 30 minutes under vacuum (20 mmHg or less). After that, the pressure is reduced to normal pressure, and 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., trade name “Pure MDI”) is added as a polyisocyanate compound and stirred at 80 ° C. for 3 hours to react to have a polycarbonate skeleton and a silicone skeleton. , to obtain a urethane prepolymer 1 having isocyanate groups at both ends. The weight average molecular weight of the obtained urethane prepolymer 1 was 10,000.

[Synthesis Example 2]
In the same manner as in Synthesis Example 1, except that the amount of the polyol compound was changed to 85 parts by mass of silicone diol and 15 parts by mass of polycarbonate diol, a urethane having a polycarbonate skeleton and a silicone skeleton and having isocyanate groups at both ends was prepared. A prepolymer 2 was obtained. The weight average molecular weight of the resulting urethane prepolymer 2 was 9,800.

[Synthesis Example 3]
In the same manner as in Synthesis Example 1, except that the amount of the polyol compound was changed to 20 parts by mass of silicone diol and 80 parts by mass of polycarbonate diol, a moisture having a polycarbonate skeleton and a silicone skeleton and having isocyanate groups at both ends A curable urethane resin (urethane prepolymer 3) was obtained. The weight average molecular weight of the resulting urethane prepolymer 3 was 1,200.

[Synthesis Example 4]
A urethane having a polycarbonate skeleton and isocyanate groups at both ends was prepared in the same manner as in Synthesis Example 1, except that the polyol compound was changed to 100 parts by mass of a polycarbonate diol instead of using a silicone diol as the polyol compound. A prepolymer 4 was obtained. The weight average molecular weight of the resulting urethane prepolymer 4 was 14,000.

Components other than the moisture-curable urethane resin used in each example and comparative example were as follows.
(Radical polymerizable compound)
Acrylic 1: urethane acrylate, manufactured by Daicel Allnex, trade name “EBECRYL8411”, bifunctional, weight average molecular weight 12000, diluted with 20% by mass isobornyl acrylate (IBOA), urethane acrylate content 80% by mass
Acrylic 2: Phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light acrylate PO-A”, monofunctional acrylic 3: Lauryl acrylate: manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light acrylate LA”, monofunctional acrylic 4: Cyclohexyl acrylate: Osaka Organic, trade name "Viscoat #155"
Filler: trimethylsilylated silica, trade name "R812" manufactured by Nippon Aerosil Co., Ltd., primary particle size 7 nm
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, manufactured by BASF, trade name "IRGACURE 369"
Other additives: Moisture curing acceleration catalyst, silane coupling agent, antioxidant

[Examples 1 to 4, Comparative Examples 1 to 3]
According to the compounding ratio shown in Table 1, each material was stirred at a temperature of 50°C with a planetary stirrer (manufactured by Thinky Co., Ltd., "Awatori Mixer"), and then at a temperature of 50°C with three ceramic rolls. They were uniformly mixed to obtain light moisture-curable adhesive compositions or moisture-curable adhesive compositions of Examples 1 to 4 and Comparative Examples 1 to 3.

As shown in Table 1, in each example, a urethane prepolymer containing a polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule and a light and moisture-curable adhesive composition containing a radically polymerizable compound were used. By doing so, it was possible to secure a constant adhesive strength to adherends made of various materials, and to achieve good shape retention.
On the other hand, the moisture-curable adhesive compositions of Comparative Examples 1 and 2 contained a urethane prepolymer containing a polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule, but did not contain a radically polymerizable compound. I didn't. Therefore, although a certain level of adhesive strength could be ensured for adherends made of various materials, shape retention could not be ensured. In addition, in Comparative Example 3, since a urethane prepolymer having a silicone skeleton in the molecule and containing no urethane was used, it was not possible to secure a constant adhesive strength to adherends made of various materials.

Claims

A light and moisture-curable adhesive composition containing a urethane prepolymer containing polyurethane having a polycarbonate skeleton and a silicone skeleton in the molecule, and a radically polymerizable compound.
The light and moisture-curable adhesive composition according to claim 1, wherein the cured product has a storage elastic modulus of 0.01 MPa or more and 50 MPa or less at an elongation of 25%.
The light moisture-curable adhesive composition according to claim 1 or 2, wherein the urethane prepolymer is moisture-curable.
The light and moisture-curable adhesive composition according to claim 3, wherein the urethane prepolymer has an isocyanate group.
The light and moisture-curable adhesive composition according to any one of claims 1 to 4, wherein the urethane prepolymer is a reaction product of a polyol compound containing polycarbonate polyol and silicone polyol, and a polyisocyanate compound.
The light and moisture-curable adhesive composition according to any one of claims 1 to 5, wherein the urethane prepolymer has a weight average molecular weight of 800 or more and 20,000 or less.
agent composition.
A cured product of the light and moisture-curable adhesive composition according to any one of claims 1 to 6.