KR20240018465A - Optical moisture curable resin composition, adhesive for electronic components, cured body, and electronic components - Google Patents

Abstract

An optical moisture-curable resin composition contains a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having three or more isocyanate groups in the molecule.

Description

Optical moisture curable resin composition, adhesive for electronic components, cured body, and electronic components

The present invention relates to an optical moisture curable resin composition, an adhesive for electronic components, a cured body, and electronic components.

Recently, there has been a demand for high integration and miniaturization in electronic components such as semiconductor chips. For example, there are cases where a plurality of thin semiconductor chips are bonded through an adhesive layer to form a stack of semiconductor chips. In addition, in modern times when mobile devices equipped with various display elements are becoming widespread, a method of miniaturizing display elements is to make the image display portion into a narrow frame (hereinafter also referred to as “narrow frame design”). In these applications, attempts are being made to use optical moisture curing type adhesives instead of double-sided tapes in conjunction with miniaturization and narrower frames.

As an optical moisture-curable adhesive, for example, Patent Document 1 discloses an optical moisture-curable resin composition characterized by containing a radically polymerizable compound, a moisture-curable urethane resin, a radical photopolymerization initiator, and a moisture remover. It is done. Here, the moisture remover is blended to improve storage stability, etc., and a compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group is exemplified.

International Publication No. 2015/111567

An optical moisture curable adhesive generally is in a B-stage state by light curing, and the adherends are bonded and provisionally bonded using the optical moisture curable adhesive in the B stage state, and then the adherends are bonded by moisture curing. It is common to bond them together.

Moreover, depending on the usage environment, the optical moisture curable adhesive may be required to maintain high adhesive strength (final heat-resistant adhesive strength) even under a high temperature environment after main adhesion. For example, when used for electronic components, it may be heated to a high temperature due to the heat emitted by the electronic component, so it may be necessary to increase the final heat-resistant adhesive strength.

However, depending on the formulation, the optical moisture-curable adhesive may not have sufficient final heat-resistant adhesive strength after main adhesion. For example, since the adhesive strength (initial adhesive strength) in the B-stage state immediately after photocuring is often insufficient for light moisture curing adhesives, it is considered to increase the initial adhesive strength by, for example, increasing the molecular weight of the contained prepolymer. there is. However, as the molecular weight of the prepolymer increases, the bulk strength of the cured product tends to decrease and the final heat-resistant adhesive strength tends to decrease.

Therefore, the subject of this invention is to provide an optical moisture hardening type resin composition which improves heat-resistant adhesive force after moisture hardening.

As a result of intensive study, the present inventors found that, in addition to the radically polymerizable compound (A), the moisture-curable resin (B) and the photopolymerization initiator (C), the light moisture-curable resin composition contains a compound having three or more isocyanate groups in the molecule ( It was discovered that the above problem could be solved by containing D), and the following present invention was completed. That is, the present invention provides the following [1] to [29].

[1] An optical moisture-curable resin composition containing a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having three or more isocyanate groups in the molecule.

[2] The optical moisture curable resin composition according to [1], wherein the compound (D) contains a compound having five or more isocyanate groups in the molecule.

[3] When applied to an aluminum substrate with a line width of 1.0 mm, photocured by irradiating 1000 mJ/cm ² ultraviolet rays, and pressing a glass plate at 0.08 MPa for 120 seconds, the average width of the adhesive portion on the glass plate side is If a and the average width of the adhesive portion on the aluminum substrate side are b, a/b is 0.5 or more and 0.99 or less, the optical moisture curable resin composition according to the above [1] or [2].

[4] The optical moisture curable resin composition according to any one of the above [1] to [3], wherein the viscosity measured under conditions of 25°C and 5.0 rpm using a cone plate type viscometer is 40 Pa·s or more and 600 Pa·s or less. .

[5] The optical moisture-curable resin composition according to any one of [1] to [4] above, wherein the moisture-curable resin (B) contains a moisture-curable urethane resin.

[6] The optical moisture-curable type according to any one of [1] to [5] above, wherein the moisture-curable urethane resin is a moisture-curable urethane resin having at least one of a polycarbonate skeleton, a polyether skeleton, and a polyester skeleton. Resin composition.

[7] The optical moisture-curable resin composition according to any one of [1] to [7], wherein the moisture-curable urethane resin is a moisture-curable urethane resin having a polycarbonate skeleton.

[8] The optical moisture-curable resin composition according to any one of [1] to [7], wherein the moisture-curable resin (B) has a weight average molecular weight of 7500 or more and 24000 or less.

[9] The optical moisture curable resin composition according to any one of [1] to [8] above, wherein the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound.

[10] The optical moisture curable resin composition according to [9] above, which contains 90 parts by mass or more of a monofunctional radically polymerizable compound based on 100 parts by mass of the radically polymerizable compound (A).

[11] The optical moisture curable resin composition according to [9] or [10], wherein the monofunctional radically polymerizable compound contains a nitrogen-containing compound.

[12] The optical moisture curable resin composition according to [11] above, wherein the monofunctional radically polymerizable compound contains a linear nitrogen-containing compound.

[13] The optical moisture curable resin composition according to [11] or [12] above, wherein the monofunctional radically polymerizable compound contains a cyclic nitrogen-containing compound.

[14] The optical moisture curable resin composition according to [13], wherein the mass ratio (cyclic/chain) of the nitrogen-containing compound having a cyclic structure to the chain-shaped nitrogen-containing compound is 0.1 or more and 2.0 or less.

[15] Any one of [11] to [14] above, wherein the content of the nitrogen-containing compound, which is a monofunctional radically polymerizable compound, relative to 100 parts by mass of the radically polymerizable compound (A), is 10 parts by mass or more and 95 parts by mass or less. The optical moisture curable resin composition described in the clause.

[16] The optical moisture curable resin composition according to any one of the above [11] to [15], wherein the monofunctional radically polymerizable compound includes a monofunctional (meth)acrylic acid ester compound in addition to the nitrogen-containing compound.

[17] The monofunctional (meth)acrylic acid ester compound is at least one selected from the group consisting of alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates. The optical moisture curable resin composition described in [16].

[18] The total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate is 5 parts by mass or more based on 100 parts by mass of radically polymerizable compound (A). The optical moisture curable resin composition according to [17] above, which is 90 parts by mass or less.

[19] Any one of [1] to [18] above, wherein the mass ratio (B/A) of the moisture-curable resin (B) to the radically polymerizable compound (A) is 30/70 or more and 90/10 or less. The described optical moisture curable resin composition.

[20] The optical moisture curable resin composition according to any one of [1] to [19] above, further comprising a filler (E).

[21] The photopolymerization initiator (C) is a benzophenone-based compound, an acetophenone-based compound, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based compound, a titanocene-based compound, an oxime ester-based compound, and a benzoin ether-based compound. The optical moisture curable resin composition according to any one of the above [1] to [20], which is at least one selected from the group consisting of , and thioxanthone.

[22] The compound (D) is at least one selected from the group consisting of biuret modified polyisocyanate, isocyanurate modified polyisocyanate, polyol modified polyisocyanate, and polymeric MDI, as described above [1 The optical moisture curable resin composition according to any one of ] to [21].

[23] The light moisture curing type according to any one of [1] to [22] above, wherein the compound (D) is at least one member selected from the group consisting of an isocyanurate modified product of polyisocyanate and polymeric MDI. Resin composition.

[24] The optical moisture curable resin composition according to any one of [1] to [23] above, wherein the initial adhesive strength is 0.1 MPa or more.

[25] The optical moisture curable resin composition according to any one of [1] to [24] above, wherein the final heat-resistant adhesive strength is 1.0 MPa or more.

[26] The content of the compound (D) is 0.1 part by mass or more and 10 parts by mass or less, based on a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture curable resin (B). The optical moisture curable resin composition according to any one of [25].

[27] An adhesive for electronic components comprising the optical moisture curable resin composition according to any one of [1] to [26] above.

[28] A cured product of the optical moisture curable resin composition according to any one of [1] to [26] above.

[29] An electronic component comprising the hardened body described in [28] above.

ADVANTAGE OF THE INVENTION According to this invention, the optical moisture hardening type resin composition which improves heat-resistant adhesive force after moisture hardening can be provided.

1 is a conceptual diagram showing a method of measuring the inner-outer ratio a/b.
Figure 2 is a schematic diagram showing an adhesion test method, Figure 2(a) is a top view, and Figure 2(b) is a side view.

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

<Light moisture curable resin composition>

The optical moisture-curable resin composition of the present invention contains a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having three or more isocyanate groups in the molecule. .

Hereinafter, each component contained in the optical moisture hardening type resin composition is explained in more detail.

[Radically polymerizable compound (A)]

The optical moisture hardening type resin composition of this invention contains a radically polymerizable compound (A). The photomoisture-curable resin composition is provided with photocurability by containing a radically polymerizable compound (A). Since the optical moisture curable resin composition has photocurability, it can provide a certain amount of adhesive force just by irradiating it with light, and thus can ensure a certain initial adhesive force.

The radically polymerizable compound (A) may have a radically polymerizable functional group in the molecule. Suitable radically polymerizable functional groups include compounds having an unsaturated double bond, and include (meth)acryloyl group, vinyl group, styryl group, and allyl group.

Among the above, from the viewpoint of adhesiveness, a (meth)acryloyl group is suitable, that is, it is preferable that the radically polymerizable compound (A) contains a compound having a (meth)acryloyl group. In addition, the compound having a (meth)acryloyl group is hereinafter also referred to as a “(meth)acrylic compound.” In addition, in this specification, “(meth)acryloyl group” means an acryloyl group or (meth)acryloyl group, “(meth)acryl” means acrylic or methacryl, and other similar terms are also used. Same thing.

The radically polymerizable compound (A) is one or both of a monofunctional radically polymerizable compound having one radically polymerizable functional group in one molecule and a polyfunctional radically polymerizable compound having two or more radically polymerizable functional groups in one molecule. Although it may be included, it is preferable to include a monofunctional radically polymerizable compound from the viewpoint of improving the initial adhesive strength of the light moisture curable resin composition. Moreover, the radically polymerizable compound (A) is a monofunctional radically polymerizable compound, and it is more preferable that it contains at least a monofunctional (meth)acrylic compound. In addition, the monofunctional radically polymerizable compound may be a prepolymer that is polymerized and has a repeating unit, but usually a monofunctional monomer that does not have a repeating unit may be used.

In the optical moisture-curable resin composition, the monofunctional radically polymerizable compound may be, for example, 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound (A).

Moreover, in order for the optical moisture hardening type resin composition to improve the initial adhesive force of the light moisture hardening type resin composition, it is preferable to contain a large amount of monofunctional radically polymerizable compounds. Specifically, the optical moisture-curable resin composition preferably contains 90 parts by mass or more of the monofunctional radically polymerizable compound, and preferably contains 95 parts by mass or more, with respect to 100 parts by mass of the radically polymerizable compound (A). , it is more preferable to contain 100 parts by mass.

[Monofunctional radically polymerizable compound]

(nitrogen-containing compounds)

The radically polymerizable compound (A) is a monofunctional radically polymerizable compound and preferably contains a nitrogen-containing compound. By using a nitrogen-containing compound, the initial adhesion of the light moisture curable resin composition becomes good. After being applied to an adherend, the optical moisture curable resin composition is photocured by irradiating active energy rays such as ultraviolet rays. At this time, it is generally photocured in the presence of oxygen as will be described later in many cases. It is presumed that when the radically polymerizable compound (A) contains a nitrogen-containing compound, it can be appropriately photocured even in the presence of oxygen, thereby improving the initial adhesion.

The nitrogen-containing compound may contain one or both of a linear nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure. However, from the viewpoint of improving the initial adhesion of the light moisture curable resin composition, the nitrogen-containing compound having a cyclic structure It is preferable that it contains, and it is more preferable to use a chain-shaped nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure in combination.

Nitrogen-containing compounds having a cyclic structure include nitrogen-containing compounds having a lactam structure such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam, morpholine skeleton-containing compounds such as N-acryloylmorpholine, Cyclic imide compounds, such as N-(meth)acryloyloxyethyl hexahydrophthalimide, etc. are mentioned. Among these, amide group-containing compounds such as N-vinylcaprolactam are more preferable. In this specification, nitrogen-containing compounds having a cyclic structure are also referred to as cyclic nitrogen-containing compounds, radically polymerizable compounds in which nitrogen atoms are contained in atoms constituting the ring itself are referred to as cyclic nitrogen-containing compounds, and other nitrogen-containing compounds. is a linear nitrogen-containing compound.

Examples of chain nitrogen-containing compounds include dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. ) Containing chain-shaped amino groups such as acrylates (meth)acrylates, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacryl Examples include chain-shaped (meth)acrylamide compounds such as amide, acrylamide, and methacrylamide, and N-vinylacetamide.

Additionally, the linear nitrogen-containing compound may be monofunctional urethane (meth)acrylate. By using monofunctional urethane (meth)acrylate, when a urethane resin, especially a urethane resin having a polycarbonate skeleton, is used as the moisture-curable resin (B), compatibility with the moisture-curable resin (B) becomes good, Easy to improve initial adhesion. In addition, since urethane (meth)acrylate has relatively high polarity, it is easy to increase the adhesive force to glass.

Monofunctional urethane (meth)acrylate can be used, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group.

Examples of the (meth)acrylic acid derivative having the hydroxyl group include monohydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Examples include (meth)acrylates, mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin.

Isocyanate compounds used to obtain urethane (meth)acrylate include alkane monoisocyanates such as butane isocyanate, hexane isocyanate, and decane isocyanate, and cyclic aliphatic monoisocyanates such as cyclopentane isocyanate, cyclohexane isocyanate, and isophorone monoisocyanate. and aliphatic monoisocyanate.

The monofunctional urethane (meth)acrylate is, more specifically, preferably urethane (meth)acrylate obtained by reacting the above-mentioned monoisocyanate compound with the mono(meth)acrylate of a dihydric alcohol, and its appropriate specification. Examples include 1,2-ethanediol 1-acrylate 2-(N-butylcarbamate).

Among the above, the linear nitrogen-containing compound preferably contains monofunctional urethane (meth)acrylate, and also includes monofunctional urethane (meth)acrylate and (meth)acrylamide compounds. It is also preferable to use compounds other than meth)acrylate together.

The content of the nitrogen-containing compound as a monofunctional radically polymerizable compound with respect to 100 parts by mass of the radically polymerizable compound (A) in the optical moisture-curable resin composition is from the viewpoint of making the initial adhesion of the optical moisture-curable resin composition good. , Preferably it is 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and most preferably 75 parts by mass or more. In addition, the content of the nitrogen-containing compound as the monofunctional radically polymerizable compound is preferably 95 parts by mass or less, more preferably 95 parts by mass or less, in order to contain an appropriate amount of the radically polymerizable compound (A) other than the nitrogen-containing compound. It is 90 parts by mass or less, more preferably 85 parts by mass or less.

When the monofunctional radically polymerizable compound has a chain-shaped nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, the nitrogen-containing compound having a cyclic structure relative to the chain-shaped nitrogen-containing compound in the monofunctional radically polymerizable compound. The mass ratio (ring/chain) of the compound is preferably 0.1 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less, and still more preferably 0.4 or more and 1.2 or less. By keeping the annular/chain mass ratio within the above range, the initial adhesion of the light moisture curable resin composition can be improved.

(Monofunctional radically polymerizable compounds other than nitrogen-containing compounds)

The monofunctional radically polymerizable compound contained in the radically polymerizable compound (A) preferably contains compounds other than the nitrogen-containing compounds described above (hereinafter also referred to as nitrogen-free compounds). When the radically polymerizable compound (A) contains a nitrogen-free compound as a monofunctional radically polymerizable compound, adhesion, etc. can be easily improved.

The nitrogen-free compound is not particularly limited as long as it is a compound having a radically polymerizable functional group, but monofunctional (meth)acrylic compounds are preferable, and among these, (meth)acrylic acid ester compounds are more preferable.

Monofunctional (meth)acrylic acid ester compounds include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates. These may be used individually or in combination of two or more types, but among these, it is preferable to use one or both of alkyl (meth)acrylate and aromatic ring-containing (meth)acrylate.

The total content of alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic ring-containing (meth)acrylate in the radically polymerizable compound (A) is 100 mass of radically polymerizable compound (A). With respect to parts, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. Moreover, the content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, even more preferably 40 parts by mass or less, and most preferably 25 parts by mass or less. am.

Examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth) Alkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms include acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, and stearyl (meth)acrylate.

Examples of (meth)acrylates containing an alicyclic structure include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and isobornyl ( (meth)acrylate having an alicyclic structure such as meth)acrylate and dicyclopentenyl (meth)acrylate. Additionally, the alicyclic structure is a ring structure in which the ring constituent elements are carbon atoms.

Examples of aromatic ring-containing (meth)acrylates include phenylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. phenoxyalkyl (meth)acrylate, etc. are mentioned.

Monofunctional (meth)acrylic acid ester compounds other than alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates can be used, for example, cyclic ether groups. Containing (meth)acrylates can also be used.

Examples of the cyclic ether group-containing (meth)acrylate include (meth)acrylates having an epoxy ring, oxetane ring, tetrahydrofuran ring, dioxolane ring, dioxane ring, etc.

Examples of epoxy ring-containing (meth)acrylate include glycidyl (meth)acrylate. Examples of the oxetane ring-containing (meth)acrylate include (3-ethyloxetan-3-yl)methyl (meth)acrylate. Examples of the tetrahydrofuran ring-containing (meth)acrylate include tetrahydrofurfuryl (meth)acrylate and (meth)acrylic acid multimer ester of tetrahydrofurfuryl alcohol. Examples of dioxolane ring-containing (meth)acrylates include (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate, (2,2-cyclohexyl-1, 3-dioxolane-4-yl)methyl (meth)acrylate, etc. can be mentioned. Examples of (meth)acrylate having a dioxane ring include cyclic trimethylolpropane formal (meth)acrylate.

As the cyclic ether group-containing (meth)acrylate, it is preferable to use either oxetane ring-containing (meth)acrylate or tetrahydrofuran ring-containing (meth)acrylate, but it is also preferable to use them in combination.

In addition, monofunctional (meth)acrylic acid ester compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxyacrylate. Hydroxyalkyl (meth)acrylate such as oxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate Alkoxyalkyl (meth)acrylate such as alkoxyalkyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate etc. Alkoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, Methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate , polyoxyethylene-based (meth)acrylates such as ethoxypolyethylene glycol (meth)acrylate, etc. may also be used.

Additionally, as the monofunctional (meth)acrylic compound, carboxyl-containing (meth)acrylic compounds such as acrylic acid and methacrylic acid may be used.

[Compounds other than monofunctional radically polymerizable compounds]

The radically polymerizable compound (A) may contain a polyfunctional radically polymerizable compound as long as the effect of the present invention is exhibited. Examples of the multifunctional radically polymerizable compound include bifunctional (meth)acrylic acid ester compounds, trifunctional or higher (meth)acrylic acid ester compounds, and bifunctional or higher urethane (meth)acrylate.

Bifunctional (meth)acrylic acid ester compounds include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate Rate, 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, dimethylol dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate Latex, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutanedienediol di(meth)acrylate Rates, etc. can be mentioned.

In addition, examples of trifunctional or higher (meth)acrylic acid ester compounds include trimethylolpropane tri(meth)acrylate, ethylene oxide added trimethylolpropane tri(meth)acrylate, and propylene oxide added trimethylolpropane tri. (meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, pentaerythritol 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) Acrylates, etc. can be mentioned.

For example, bifunctional or higher urethane (meth)acrylate can be used by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group.

Examples of the (meth)acrylic acid derivative having the hydroxyl group include monohydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. (meth)acrylates, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin, and epoxies such as bisphenol A type epoxy (meth)acrylates ( Meta)acrylate, etc. can be mentioned.

Isocyanate compounds used to obtain urethane (meth)acrylate include, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylenedi. Isocyanate, diphenylmethane diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate , polyisocyanate compounds such as triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

Additionally, as the isocyanate compound, a chain-extended polyisocyanate compound (polyol modified product) obtained by reaction of a polyol and an excess isocyanate compound can also be used. Here, examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

By using these polyisocyanate compounds, polyfunctional urethane (meth)acrylate can be obtained.

[Moisture curable resin (B)]

Examples of the moisture-curable resin (B) used in the present invention include moisture-curable urethane resin, hydrolyzable silyl group-containing resin, and moisture-curable cyanoacrylate resin. Among them, moisture-curable urethane resin and One of the hydrolyzable silyl group-containing resins is preferable, and moisture-curable urethane resin is more preferable. These may be used individually, or two or more types may be used together.

(Moisture curable urethane resin)

Moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule. Moisture-curable urethane resins just need to have an isocyanate group in the molecule, and the isocyanate group in the molecule reacts with moisture in the air or in the adherend to harden. The moisture-curable urethane resin may have only one isocyanate group per molecule, or may have two or more isocyanate groups. However, the moisture-curable urethane resin preferably has one or two isocyanate groups per molecule, and more preferably has two isocyanate groups. desirable. In addition, the isocyanate group is not particularly limited, but may be formed at the terminal of the moisture-curable urethane resin, for example, at both terminals.

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

As the polyol compound that serves as the raw material for the moisture-curable urethane resin, known polyol compounds commonly used in the production of polyurethane can be used, such as polyester polyol, polyether polyol, polyalkylene polyol, and polycarbonate. Polyols, etc. can be mentioned. These polyol compounds may be used individually, or may be used in combination of two or more types.

The moisture-curable urethane resin is preferably at least one of a moisture-curable urethane resin having a polycarbonate skeleton, a polyether skeleton, or a polyester skeleton, and is preferably at least one of a moisture-curable urethane resin having a polycarbonate skeleton or a polyether skeleton. This is more preferable, and a moisture-curable urethane resin having a polycarbonate skeleton is more preferable. By having a polycarbonate skeleton, the moisture-curable urethane resin has increased heat resistance, mechanical strength, etc., and can easily be made excellent in both initial and final heat-resistant adhesive forces. In addition, an optical moisture curable resin composition having excellent weather resistance, moisture resistance, etc. of the cured product can also be provided.

(Moisture-curable urethane resin with polycarbonate skeleton)

The moisture-curable urethane resin having a polycarbonate skeleton is one in which the polycarbonate skeleton is introduced into the urethane resin by using polycarbonate polyol as the polyol compound. Moisture-curable urethane resin having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule.

As polycarbonate polyol, polycarbonate diol is preferable, and a preferable specific example of polycarbonate diol includes a compound represented by the following formula (1).

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

In formula (1), R is preferably an aliphatic saturated hydrocarbon group. When R is an aliphatic saturated hydrocarbon group, heat resistance tends to improve. Additionally, yellowing, etc., is less likely to occur due to thermal deterioration, etc., and weather resistance is also improved. R, which consists of an aliphatic saturated hydrocarbon group, may have a chain structure or a cyclic structure, but it is preferable to have a chain structure from the viewpoint of easy stress relaxation and flexibility. Additionally, R in the chain structure may be either linear or branched.

It is preferable that n is 5-200, it is more preferable that it is 10-150, and it is still more preferable that it is 20-50. R is preferably 5 to 12.

In addition, R contained in the polycarbonate polyol constituting the moisture-curable urethane resin may be used individually or in combination of two or more types. When two or more types are used together, it is preferable that at least part of the group is a chain-shaped aliphatic saturated hydrocarbon group having 6 or more carbon atoms.

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

Specific examples of R may be linear, such as tetramethylene group, pentylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group, for example, 3-methylpentylene group, etc. It may be a branched phase such as a methylpentylene group or a methyloctamethylene group. A plurality of R in one molecule may be the same or different from each other. Therefore, one molecule may contain two or more types of R, and in that case, two or three types of R are preferably included in one molecule. For example, polycarbonate polyol may be a copolymer containing R with 6 or less carbon atoms and R with 7 or more carbon atoms in one molecule, and in this case, any R may be a chain-shaped saturated aliphatic hydrocarbon group.

Moreover, R may contain a linear aliphatic saturated hydrocarbon group or a branched aliphatic saturated hydrocarbon group. In polycarbonate polyol, branched and linear R may be used in combination, or linear R may be used singly.

In addition, polycarbonate polyol may be used individually, or may be used in combination of two or more types.

As polyisocyanate compounds that serve as raw materials for moisture-curable urethane resins, aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds are suitably used.

Examples of aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.

Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, and hydrogenated polyisocyanate. Silylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane, dicyclohexylmethane diisocyanate, etc. are mentioned.

As the polyisocyanate compound, aromatic polyisocyanate compounds are preferable, especially from the viewpoint of increasing the adhesive strength after overall curing, and diphenylmethane diisocyanate is more preferable among them. Moreover, from a viewpoint of making it easy to provide stress relaxation property, flexibility, etc. to the hardened|cured material of an optical moisture hardening resin composition, an aliphatic polyisocyanate compound is preferable.

The polyisocyanate compound may be used individually, or may be used in combination of two or more types.

(Moisture-curable urethane resin with a polyester skeleton)

The moisture-curable urethane resin having a polyester skeleton is one in which the polyester skeleton is introduced into the urethane resin by using polyester polyol as the polyol compound. Moisture-curable urethane resin having a polyester skeleton can be obtained by reacting a polyester polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule.

Examples of the polyester polyol include polyester polyol obtained by reaction between a polyhydric carboxylic acid and a polyol, and poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone.

Examples of the polyhydric carboxylic acids that serve as raw materials for polyester polyol include phthalic acid, telephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, and phthalic acid. Examples include melic acid, suberic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and dodecamethylenedicarboxylic acid. Among these, phthalic acid or adipic acid is preferable from the viewpoint of easier adhesion at high temperatures.

The polyols that serve as raw materials for polyester polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Hexanediol, diethylene glycol, cyclohexanediol, etc. can be mentioned. Among these, 1,6-hexanediol or 1,4-butanediol is preferable from the viewpoint of easier adhesion at high temperatures.

Moreover, as a polyisocyanate compound, the polyisocyanate compound mentioned above can be used.

In addition, polyester polyol may be used individually, or may be used in combination of two or more types.

(Moisture-curable urethane resin with polyether skeleton)

The moisture-curable urethane resin having a polyether skeleton is one in which the polyether skeleton is introduced into the urethane resin by using polyether polyol as the polyol compound. A urethane resin having a polyether skeleton can be obtained by reacting a polyether polyol having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule.

Polyether polyols include, for example, polyethylene glycol, polypropylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, random copolymers or block copolymers of these or their derivatives, and bisphenol. and polyoxyalkylene-modified products.

Here, the bisphenol-type polyoxyalkylene modified product is obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton. It is a polyether polyol obtained through reaction. This polyether polyol may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified product preferably has one or two or more types of alkylene oxides added to both ends of the bisphenol-type molecular skeleton.

There is no particular limitation on the bisphenol type, and examples include A-type, F-type, and S-type, and bisphenol A-type is preferred.

Moreover, as a polyisocyanate compound, the polyisocyanate compound mentioned above can be used.

It is preferable that the moisture-curable urethane resin having a polyether skeleton further includes one obtained using a polyol compound having a structure represented by the following formula (2). By using a polyol compound having a structure represented by the following formula (2), an optical moisture curable resin composition with excellent adhesiveness and a cured product that is flexible and has good elongation can be obtained, and is compatible with the radical polymerizable compound (A). The castle becomes excellent.

Among them, from the viewpoint of making it easy to increase applicability by setting the viscosity of the light moisture curable resin composition to an appropriate range, polypropylene glycol, a ring-opening polymerization compound of tetrahydrofuran (THF), or methyl groups such as 3-methyltetrahydrofuran It is preferable to use a polyether polyol composed of a ring-opening polymerization compound of tetrahydrofuran having a substituent such as polypropylene glycol, and a ring-opening polymerization compound of tetrahydrofuran (THF). The ring-opening polymerization compound of the tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol.

In addition, polyether polyol may be used individually, or may be used in combination of two or more types.

In formula (2), R represents a hydrogen atom, a methyl group, or an ethyl group, l is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5. Additionally, when l is 0, it means that the carbon bonded to R is directly bonded to oxygen.

Among the above, it is more preferable that the sum of n and l is 1 or more, and 1-3 is more preferable. Moreover, R is more preferably a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

The moisture-curable urethane resin having the above-mentioned polycarbonate, polyester, or polyether skeleton may have two or more types of skeleton in the molecule, for example, may have a polycarbonate skeleton and a polyester skeleton. In that case, polycarbonate polyol and polyester polyol may be used as the polyol compound serving as the raw material. Similarly, moisture-curable urethane resins having a polyester skeleton and a polyether skeleton may also be used.

In addition, the moisture-curable urethane resin may be one containing an isocyanate group as described above, but is not limited to having an isocyanate group. As explained in the hydrolyzable silyl group-containing resin described later, the urethane resin containing a hydrolyzable silyl group may be used. It's okay.

(Hydrolyzable silyl group-containing resin)

The hydrolyzable silyl group-containing resin used in the present invention is cured by the hydrolyzable silyl group in the molecule reacting with moisture in the air or in the adherend.

The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more hydrolyzable silyl groups. Among them, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule.

Additionally, the hydrolyzable silyl group-containing resin does not include those having an isocyanate group.

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

In formula (3), R ¹ is each independently an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or -OSiR ² ₃ ( R ² is a triorganosiloxy group represented by (each independently, a hydrocarbon group having 1 to 20 carbon atoms). Moreover, in formula (3), X is each independently a hydroxy group or a hydrolyzable group. Additionally, in formula (3), a is an integer of 1 to 3.

The hydrolyzable group is not particularly limited and includes, for example, a halogen atom, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mer Kaptogi, etc. can be mentioned. Among them, halogen atoms, alkoxy groups, alkenyloxy groups, and acyloxy groups are preferred because of their high activity. Moreover, from the viewpoint of easy hydrolysis and easy handling, alkoxy groups such as methoxy groups and ethoxy groups are more preferable, and methoxy groups and ethoxy groups are more preferable. Also, from the viewpoint of safety, ethoxy groups and isopropenoxy groups, where the compounds released by the reaction are ethanol and acetone, respectively, are preferable.

The hydroxy group or the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3. When two or more of the hydroxy groups or the hydrolyzable groups are bonded to one silicon atom, these groups may be the same or different.

From the viewpoint of curability, a in the formula (3) is preferably 2 or 3, and is particularly preferably 3. Moreover, from the viewpoint of storage stability, a is preferably 2.

Moreover, R ¹ in the above formula (3) includes, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or a trimethylsiloxy group. A chloromethyl group, a methoxymethyl group, etc. are mentioned. Among them, a methyl group is preferable.

Examples of the hydrolyzable silyl group include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, (chloromethyl) Dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (dichloromethyl)dimethoxysilyl group, (1-chloroethyl)dimethoxysilyl group, (1-chloropropyl)dimethoxysilyl group, (methoxymethyl) Dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (ethoxymethyl)dimethoxysilyl group, (1-methoxyethyl)dimethoxysilyl group, (aminomethyl)dimethoxysilyl group, (N,N -dimethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, (N-(2-aminoethyl)amino Examples include methyl)dimethoxysilyl group, (acetoxymethyl)dimethoxysilyl group, and (acetoxymethyl)diethoxysilyl group.

Examples of the hydrolyzable silyl group-containing resin include (meth)acrylic resin containing a hydrolyzable silyl group, an organic polymer having a hydrolyzable silyl group at the end of the molecular chain or at the terminal portion of the molecular chain, and a urethane resin containing a hydrolyzable silyl group. I can hear it.

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

Hydrolyzable silyl group-containing (meth)acrylic acid esters include, for example, 3-(trimethoxysilyl)propyl (meth)acrylic acid, 3-(triethoxysilyl)propyl (meth)acrylic acid, and 3-(meth)acrylic acid. -(Methyldimethoxysilyl)propyl, 2-(trimethoxysilyl)ethyl (meth)acrylic acid, 2-(triethoxysilyl)ethyl (meth)acrylic acid, 2-(methyldimethoxysilyl)ethyl (meth)acrylic acid , trimethoxysilylmethyl (meth)acrylic acid, triethoxysilylmethyl (meth)acrylic acid, and (methyldimethoxysilyl)methyl (meth)acrylic acid.

Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( (meth)acrylic acid isobutyl, (meth)acrylic acid tert-butyl, (meth)acrylic acid n-pentyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid n-heptyl, (meth)acrylic acid n -octyl, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, etc.

As a method for producing a hydrolyzable silyl group-containing (meth)acrylic resin, specifically, for example, a method for synthesizing a hydrolyzable silicon group-containing (meth)acrylic acid ester-based polymer described in International Publication No. 2016/035718. etc. can be mentioned.

The organic polymer having a hydrolyzable silyl group at the molecular chain terminal or molecular chain terminal portion has a hydrolyzable silyl group at at least one of the terminal of the main chain and the terminal of the side chain.

The skeletal structure of the main chain is not particularly limited, and examples include saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth)acrylic acid ester-based polymers.

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

The method for producing an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or molecular chain terminal portion specifically includes, for example, the molecular chain terminal or molecular chain terminal described in International Publication No. 2016/035718. A method for synthesizing an organic polymer having a crosslinkable silyl group only at the site is included. In addition, as another method for producing an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or molecular chain terminal portion, for example, a polyoxyalkylene-based reactive silicon group-containing method described in International Publication No. 2012/117902 and polymer synthesis methods.

As a method of producing the hydrolyzable silyl group-containing urethane resin, for example, when producing a urethane resin by reacting a polyol compound and a polyisocyanate compound, a method of reacting a silyl group-containing compound such as a silane coupling agent is also used. etc. can be mentioned. Specifically, for example, the method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in Japanese Patent Application Laid-Open No. 2017-48345.

The silane coupling agent includes, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, and β-(3,4-epoxycyclohexyl)-ethyltrimethyl. Toxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltri Methoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, etc. are mentioned. Among them, γ-mercaptopropyltrimethoxysilane, 3-isocyanate propyltrimethoxysilane, and 3-isocyanate propyltriethoxysilane are preferable. These silane coupling agents may be used individually, or two or more types may be used in combination.

Additionally, the moisture-curable urethane resin may have both an isocyanate group and a hydrolyzable silyl group. The moisture-curable urethane resin having both an isocyanate group and a hydrolyzable silyl group is obtained by first obtaining a moisture-curable urethane resin (raw material urethane resin) having an isocyanate group by the method described above and further reacting the raw material urethane resin with a silane coupling agent. It is desirable to manufacture.

In addition, the details of the moisture-curable urethane resin having an isocyanate group are as described above. The silane coupling agent reacted with the raw material urethane resin may be appropriately selected from those listed above and used, but it is preferable to use a silane coupling agent having an amino group or a mercapto group from the viewpoint of reactivity with an isocyanate group. Preferred specific examples include N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, and N-phenyl-γ-aminopropyl. Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanate propyltrimethoxysilane, etc. are mentioned.

Additionally, the moisture-curable resin may have a radically polymerizable functional group. As a radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferable, and a (meth)acryloyl group is more preferable, especially from the viewpoint of reactivity. In addition, moisture-curable resin having a radically polymerizable functional group is not included in the above-mentioned radically polymerizable compounds and is handled as moisture-curable resin (B).

The moisture-curable resin (B) may be appropriately selected from the various resins described above and used individually or in combination of two or more types.

The weight average molecular weight of the moisture-curable resin (B) is preferably 7,500 or more and 24,000 or less. By setting the weight average molecular weight within the above range, it becomes easy to increase the initial adhesive force of the optical moisture hardening type resin composition. Moreover, by setting it below the above upper limit, it becomes easy to achieve good final heat-resistant adhesive strength. From these viewpoints, the weight average molecular weight of the moisture-curable resin (B) is more preferably 7,800 or more, more preferably 10,000 or more, even more preferably 11,500 or more, more preferably 20,000 or less, and 16,000 or less. It is more preferable, and 15000 or less is even more preferable.

In addition, in this specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion.

As described above, the moisture-curable resin may be chain-extended in order to increase the weight average molecular weight to a certain value or more.

For example, in the case of moisture-curable urethane resin, it is added to a urethane resin having an isocyanate group (hereinafter also referred to as “raw material urethane resin”) obtained by reacting a polyol compound with a polyisocyanate compound having two or more isocyanate groups in one molecule. You may react with a chain extender. At this time, the chain extender does not cause the chain extender to react with all of the isocyanate groups contained in the raw material urethane resin, but the amount used can be appropriately adjusted so that the isocyanate groups remain in the moisture-curable urethane resin. Additionally, the raw material urethane resin may be reacted with the chain extender reacted with the raw material urethane resin.

The chain extender used in moisture-curable urethane resin is preferably a polyol compound. Details of the polyol compound are as described above. Additionally, the polyol compound as the chain extender may be the same polyol compound as the polyol compound used to synthesize the raw material urethane resin. Therefore, if the polyol compound used to synthesize the raw material urethane resin is polycarbonate polyol, polycarbonate polyol may also be used as the chain extender.

The amount of chain extender used is when the total amount of raw material urethane resin and chain extender is 100 parts by mass.

For example, it is 5 parts by mass or more and 40 parts by mass or less, preferably 10 parts by mass or more and 35 parts by mass or less, more preferably 15 parts by mass or more and 30 parts by mass or less.

In the optical moisture-curable resin composition, the mass ratio (B/A) of the moisture-curable resin (B) to the radically polymerizable compound (A) is preferably 30/70 or more and 90/10 or less, and is preferably 40/60 or more and 80/10 or more. 20 or less is more preferable, and 50/50 or more and 70/30 or less is more preferable. When the mass ratio falls within these ranges, photo-curability and moisture-curability can be imparted to the light-moisture-curable resin composition in a balanced manner, and it becomes easy to adjust both the initial adhesive force and the final heat-resistant adhesive force within the desired range.

The optical moisture-curable resin composition may contain resin components other than the radically polymerizable compound (A) and the moisture-curable resin (B) as resin components within a range that does not impair the effects of the present invention, for example, to provide curability. It may contain resin components such as thermoplastic resins (for example, acrylic resins, urethane resins, etc.), thermosetting resins, etc. that it does not have. The ratio of resin components other than the radically polymerizable compound (A) and the moisture-curable resin (B) is, for example, 50 parts by mass with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). Below, preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[Photopolymerization initiator (C)]

The optical moisture hardening type resin composition of this invention contains a photopolymerization initiator. The photomoisture-curable resin composition is appropriately provided with photocurability by containing a photopolymerization initiator.

Examples of photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and Ti. Oxanthone, etc. can be mentioned.

Among the photopolymerization initiators, commercially available ones include, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF SE), benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether (all manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), etc. can be mentioned.

The content of the photopolymerization initiator in the optical moisture hardening type resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the radically polymerizable compound (A). It is below wealth. When the content of the photopolymerization initiator is within these ranges, the obtained optical moisture curable resin composition becomes excellent in photocurability and storage stability. Moreover, by setting it within the said range, the radical photopolymerization compound hardens appropriately and it becomes easy to improve adhesive force.

[Compound (D)]

The optical moisture curable resin composition of the present invention contains a compound (D) (hereinafter sometimes simply referred to as compound (D)) having three or more isocyanate groups in the molecule. By containing the compound (D), the optical moisture-curable resin composition forms a crosslinked structure in the moisture-cured product, thereby increasing the bulk strength and improving heat-resistant adhesive strength (final heat-resistant adhesive strength) after moisture curing. Therefore, as described above, for example, even if the molecular weight of the moisture-curable resin (B) is increased, the bulk strength of the cured product does not decrease, and the final heat-resistant adhesive strength can be excellent.

The compound (D) may be a compound other than the moisture-curable resin (B) described above and may be a compound having three or more isocyanate groups. Compound (D) may be, for example, a compound whose molecular weight (weight) is 1500 or less. Examples of the compound (D) include polyisocyanate modified products obtained by reacting a polyisocyanate compound with another compound.

Polyisocyanate modified products include biuret modified products of polyisocyanate compounds, isocyanurate modified products of polyisocyanate compounds, glycerin, trimethylolpropane, or polyols obtained by addition polymerizing these with alkylene oxides such as propylene oxide and ethylene oxide. , polyol modified product, which is an adduct obtained by reacting a polyisocyanate compound, and polymethylene polyphenyl polyisocyanate, also called polymeric MDI.

In addition, at least some of the isocyanate groups contained in compound (D) may be temporarily protected by a blocking agent, urethedione structure, etc. In this case, when using the light moisture curable resin composition, the isocyanate group contained in the compound (D) is regenerated due to dissociation of the blocking agent, cleavage of the urethione structure, etc.

Examples of the polyisocyanate compound used as a raw material in the modified product include monomers that do not have a repeating unit. The polyisocyanate compound is preferably a diisocyanate compound, and specifically, aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, isophorone diisocyanate, and hexamethylenedi. and aliphatic isocyanate compounds such as isocyanate, trimethylhexamethylene diisocyanate, hydrogenated MDI, norbornane diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, and tetramethylxylylene diisocyanate.

Additionally, as the compound (D), products other than the above-mentioned polyisocyanate modifications may be used, and polyisocyanate compounds such as triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, and 1,6,11-undecane triisocyanate may be used. do.

Among the above, polyisocyanate modified products are preferable, and among them, isocyanurate modified products and polymeric MDI are more preferable.

In addition, the compound (D) may have three or more isocyanate groups, and may be a compound having three isocyanate groups. However, in order to increase the crosslinking density and further improve the heat-resistant adhesive strength after moisture curing, a compound having four or more isocyanate groups may be used. is preferable, and it is more preferable that it contains a compound having 5 or more isocyanate groups. The upper limit of the number of isocyanate groups in compound (D) is not particularly limited, but is, for example, 10 or less, preferably 8 or less.

Among the compounds having three isocyanate groups, a biuret-modified product, an isocyanurate-modified product, and a polyol-modified product are included, and the isocyanurate-modified product is preferable. Additionally, a suitable specific example of a compound having 4 or 5 or more isocyanate groups includes polymeric MDI.

Compound (D) having three or more isocyanate groups may be a mixture of compounds with different numbers of isocyanate groups, and therefore, the number of isocyanate groups in compound (D) may be expressed by the average number of isocyanate groups. The average number of isocyanate groups in the compound (D) may be 3 or more, but in order to further improve heat-resistant adhesive strength, 4 or more is preferable, and 5 or more is more preferable.

The upper limit of the average number of isocyanate groups in compound (D) is not particularly limited, but is, for example, 10 or less, preferably 8 or less, and more preferably 6.5 or less.

The content of the compound (D) in the optical moisture-curable resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B). . If the amount is above the lower limit, the compound (D) can form a sufficient cross-linked structure in the cured product after moisture curing, and the final heat-resistant adhesive strength can be easily increased. Moreover, by setting it to 10 parts by mass or less, it is possible to prevent the initial adhesive strength from decreasing due to the influence of the compound (D). From these viewpoints, the content of compound (D) is more preferably 0.2 parts by mass or more, and more preferably 0.3 parts by mass or more, relative to a total of 100 parts by mass of the radically polymerizable compound (A) and the moisture-curable resin (B). It is preferable, and 5 parts by mass or less is more preferable, and 3 parts by mass or less is still more preferable.

In addition to the compound (D) having three or more isocyanate groups in the molecule, the optical moisture curable resin composition may contain a diisocyanate compound having two isocyanate groups. Specific examples of the diisocyanate compound used here include the diisocyanate compounds listed as raw materials for polyisocyanate modifications.

In the production process of the above-described polyisocyanate modified product, the diisocyanate compound as a raw material does not react, and there are cases where it remains as an unreacted diisocyanate compound. Such unreacted diisocyanate compound is together with compound (D). , may be blended into an optical moisture curable resin composition.

For example, polymethylene polyphenyl polyisocyanate (polymeric MDI) having three or more isocyanate groups may be blended with the light moisture curable resin composition as a mixture with MDI, which is a diisocyanate compound.

In addition, the content of the diisocyanate compound in the optical moisture hardening type resin composition is not particularly limited, but, for example, it may be less than the content of the compound (D) on a mass basis.

[Filler (E)]

The optical moisture hardening type resin composition of this invention may contain a filler (E). By containing the filler (E), the optical moisture curable resin composition of the present invention has appropriate thixotropy and can sufficiently maintain the shape after application. As a filler, a particle-type filler may be used.

The filler (E) is preferably an inorganic filler, and examples include silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Among these, silica is preferable because the obtained optical moisture curable resin composition is excellent in ultraviolet ray permeability. Additionally, the filler (E) may be subjected to hydrophobic surface treatment such as silylation treatment, alkylation treatment, or epoxidation treatment.

The filler (E) may be used individually, or two or more types may be used in combination.

The content of the filler (E) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 2 parts by mass or more, relative to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture curable resin (B). It is 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less.

(Moisture Curing Acceleration Catalyst)

The optical moisture-curable resin composition may contain a moisture-curing acceleration catalyst that promotes the moisture-curing reaction of the moisture-curable resin (B). By using a moisture curing accelerator catalyst, the optical moisture curable resin composition becomes more excellent in moisture curing properties and becomes easy to increase adhesive strength.

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

Metal catalysts include tin compounds such as din-butyltin dilaurate, din-butyltin diacetate, and tin octylate, zinc compounds such as zinc octylate and zinc naphthenate, zirconium tetraacetylacetonate, and naphthenic acid. Other metal compounds such as copper and cobalt naphthenate can be mentioned.

The content of the moisture curing acceleration catalyst is preferably 0.01 parts by mass or more and 8 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the moisture curable resin (B). When the content of the moisture curing acceleration catalyst is within the above range, the effect of promoting the moisture curing reaction becomes excellent without worsening the storage stability of the optical moisture curing type resin composition, etc.

(coloring agent)

The optical moisture hardening type resin composition of this invention may contain a coloring agent. Colorants include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. The light-moisture-curable resin composition also improves light-shielding properties and the like by containing a colorant. Among these, titanium black is preferable. Since titanium black has the property of sufficiently shielding light with a wavelength in the visible light region and transmitting light with a wavelength near the ultraviolet region, it can prevent the photocurability of the light moisture-curable resin composition from decreasing.

The content of the colorant in the optical moisture-curable resin composition is preferably 0.05 parts by mass or more and 8 parts by mass or less, with respect to 100 parts by mass of the total amount of the radically polymerizable compound (A) and the moisture-curable resin (B). is 0.1 parts by mass or more and 2 parts by mass or less. By keeping the content of the colorant within these ranges, appropriate light-shielding properties can be provided while maintaining good adhesiveness of the light moisture-curable resin composition.

In addition to the components mentioned above, the optical moisture curable resin composition may contain other additives such as a coupling agent, wax particles, ionic liquid, foamed particles, expanded particles, and a reactive diluent. Furthermore, examples of the coupling agent include silane coupling agents, titanate coupling agents, zirconate coupling agents, etc. Among these, silane coupling agents are preferable. Although the optical moisture hardening type resin composition generally does not contain a solvent, it may contain a solvent as needed in the range which does not impair the effect of this invention.

[25℃ viscosity]

The optical moisture curable resin composition of the present invention preferably has a viscosity (hereinafter also referred to as "25°C viscosity") of 40 Pa·s or more and 600 Pa·s or less, as measured using a cone plate type viscometer under conditions of 25°C and 5.0 rpm. do.

The 25°C viscosity of the moisture-curable resin composition was measured under high shear of 5.0 rpm, and is a viscosity that is unlikely to be affected by fillers. Therefore, if the viscosity at 25°C is 40 Pa·s or more, the low molecular weight components contained in the moisture-curable resin (B), etc. tend to decrease, and it becomes difficult for the moisture-curable resin (B), etc. to penetrate into the interface after light irradiation, and the initial It becomes easier to improve adhesion. That is, if the low molecular weight moisture-curable resin (B) or the like becomes difficult to penetrate into the interface after light irradiation, slippage between the adhesive and the adherend becomes difficult, adhesive force is easily developed, and initial adhesion becomes easy to improve. Furthermore, in the present invention, by increasing the 25°C viscosity, the moisture-curable resin composition contains a large amount of high molecular weight components, and the content of the functional group having moisture-curability tends to decrease. As a result, there is a risk that the bulk strength after moisture curing may be lowered, but by containing the above-mentioned compound (D), the bulk strength after moisture curing increases and the final heat-resistant adhesive strength also becomes good.

In addition, even if the viscosity at 25°C is 600 Pa·s or less, the inherent adhesiveness of the moisture-curable resin (B) tends to develop, and thereby the initial adhesive strength and final heat-resistant adhesive strength are easily improved.

In addition, by setting the viscosity at 25°C to 40 Pa·s or more and 600 Pa·s or less, problems such as liquid sagging or inability to apply at room temperature are less likely to occur, and workability is improved.

The 25°C viscosity of the optical moisture curable resin composition is more preferably 45 Pa·s or more, more preferably 90 Pa·s or more, more preferably 110 Pa·s or more, and more preferably 500 Pa·s or less, 350 Pa·s or less is more preferable, and 230 Pa·s or less is even more preferable. If the viscosity at 25°C is within the above range, it becomes easy to improve workability and initial adhesion.

In addition, if it is set below the above upper limit, the molecular weight of the moisture-curable resin (A) can be prevented from becoming excessively high, so the initial adhesive strength is easily improved, and the adhesive strength is sufficiently increased by moisture curing, and the final heat-resistant adhesive strength, etc. is also improved. It becomes easier to do.

[Internal and external ratio a/b]

The optical moisture curable resin composition of the present invention is applied in a linear shape to an aluminum substrate under the predetermined conditions described later, and photocured with UV, and then further pressed against a glass plate, the average width of the adhesive portion on the glass plate side is When a and the average width of the adhesive portion on the aluminum substrate side are b, a/b (also referred to as “inner/outer ratio a/b”) is, for example, 0.5 or more and 0.99 or less.

When the inside-outside ratio a/b of the optical moisture-curable resin composition of the present invention is set to 0.5 or more, the inside-outside ratio a/b becomes large, becomes prone to crushing immediately after photocuring, and the adhesion to the interface of the adherend increases, The initial adhesion to the adherend becomes easier to increase. Moreover, by setting the inner-outer ratio a/b to 0.99 or less, it can be prevented that the cohesive force of the light moisture-curable resin composition immediately after photocuring becomes small or is too distorted and the initial adhesive strength falls.

The inner/outer ratio a/b is more preferably 0.58 or more, more preferably 0.63 or more, more preferably 0.7 or more, more preferably 0.95 or less, and still more preferably 0.93 or less. If the inner/outer ratio a/b is within these ranges, it becomes easy to improve the initial adhesive strength.

In the present invention, the inner-outer ratio a/b is measured as follows. First, as shown in FIG. 1(a), the moisture-curable resin composition 10 is applied to the aluminum substrate 11 with a line width of 1.0 mm. Here, the line width of 1.0 mm does not need to be strictly 1.0 mm, and there may be an error of 1.0 ± 0.1 mm. Next, as shown in FIG. 1(b), the moisture-curable resin composition 10 is cured by irradiating ultraviolet rays of 1000 mJ/cm ² to the moisture-curable resin composition 10. Immediately thereafter (within 10 seconds), as shown in FIG. 1(c), the glass plate 12 is overlapped on the moisture-curable resin composition 10, and the glass plate 12 is covered with the moisture-curable resin composition 10 in an area covered by the moisture-curable resin composition 10. For , compress it at 0.08 MPa for 120 seconds. After compression, the width (a1) of the adhesive portion of the moisture-curable resin composition 10 with the glass plate 12 is measured. The width (a1) is measured at 5 points, and the average value is taken as the average width (a). Additionally, the width (b1) of the adhesive portion of the moisture-curable resin composition 10 and the aluminum substrate 11 is measured. The width (b1) is measured at 5 points, the average value is taken as the average width (b), and the inside-outside ratio a/b is calculated from the average widths (a, b). Additionally, compression may be performed using a weight, and the widths (a1, b1) may be measured 5 minutes after the weight is removed.

The inner/outer ratio a/b can be adjusted within the above range by adjusting the type of radically polymerizable compound, etc. For example, when the photomoisture curable resin composition contains a large amount of monofunctional radically polymerizable compounds as radically polymerizable compounds, the proportion of crosslinked structures formed after photocuring decreases, so the inside-outside ratio a/b can be increased. there is. Moreover, for example, even when the photomoisture curable resin composition contains a large number of radically polymerizable compounds with a low glass transition point of the homopolymer as a radically polymerizable compound, the cured product after photocuring becomes soft, so that the internal/external ratio a/ b can be made larger. In addition, it can also be adjusted depending on the weight average molecular weight of the moisture-curable resin (B).

[Adhesion]

The initial adhesive strength of the optical moisture-curable resin composition of the present invention may be, for example, 0.05 MPa or more, but is preferably 0.1 MPa or more. Moreover, it is preferable that the optical moisture hardening type resin composition of this invention has a final heat-resistant adhesive force of 1.0 MPa or more.

In addition, the initial adhesive strength means the adhesive strength at 25°C immediately after photocuring the light moisture-curable resin composition, and the final heat-resistant adhesive strength means photocuring the light moisture-curable resin composition, and then 25°C and 50RH%. This means the adhesive force measured in a 70°C environment after being left for 24 hours. Details of the method for measuring the initial adhesive force and final heat-resistant adhesive force are as described in the Examples described later.

When the initial adhesive strength at 25°C of the photomoisture-curable resin composition is equal to or higher than the above lower limit, adherends can be temporarily bonded with a certain or higher adhesive strength immediately after photocuring, and workability during temporary bonding is improved. Moreover, if the final heat-resistant adhesive strength is 1.0 MPa or more, adherends can be firmly joined by permanent adhesion by moisture curing after temporary adhesion, even in a high temperature environment.

In order to further increase the adhesion stability during temporary adhesion, the optical moisture curable resin composition more preferably has an initial adhesion of 0.2 MPa or more. In addition, the initial adhesive force is not particularly limited, but in order to facilitate reattachment during temporary adhesion, it may be, for example, less than 1.5 MPa.

In addition, the optical moisture curable resin composition preferably has a final heat-resistant adhesive strength of 2.0 MPa or more in order to more firmly bond the adherends after main adhesion. The final heat-resistant adhesive strength is not particularly limited, but may be 20 MPa or less, and may be 10 MPa or less.

As a method for producing the light moisture-curable resin composition of the present invention, a radical polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) are added using a mixer. A method of mixing other additives such as fillers, moisture hardening accelerating catalysts, and colorants, which are mixed as needed, can be mentioned. Examples of mixers include homodispers, homomixers, universal mixers, planetary mixers, planetary stirring devices, kneaders, and three-roll mills.

Additionally, as described above, the molecular weight of moisture-curable resins such as moisture-curable urethane resins may be increased by using a chain extender. In that case, for example, a raw material resin such as a raw material urethane resin and a chain extender are reacted in advance to obtain a moisture-curable resin (B), and then, as described above, a radically polymerizable compound (A) is photopolymerized. It can be mixed with other raw materials such as initiator (C) and compound (D).

In addition, the raw material resin, the chain extender, and the radically polymerizable compound (A) are mixed, and the mixture is heated as needed to cause the raw material resin to react with the chain extender to synthesize moisture-curable resin (B). You can do it. In this case, a mixture of the moisture-curable resin (B) and the radically polymerizable compound (A) is obtained, and the photopolymerization initiator (C), the compound (D), and other additives blended as necessary are added to the mixture. , an optical moisture curable resin composition may be obtained.

<Method of using light moisture curable resin composition>

The optical moisture curable resin composition of the present invention is cured and used as a cured body. Specifically, the optical moisture curable resin composition of the present invention is first photocured by light irradiation, for example, in a B stage state (semi-cured state), and then cured with moisture to fully cure the composition. .

Here, the optical moisture curable resin composition is disposed between adherends, and when bonding the adherends, it is applied to one adherend and then photocured by light irradiation, for example, B stage. In this state, the other adherend is piled on top of the photo-moisture curable resin composition in the photocured state, and the adherends are temporarily bonded with an appropriate adhesive force (initial adhesive force). After that, the photo-moisture-curable resin composition in the B-stage state is fully cured by curing the moisture-curable resin with moisture, and the adherends overlapped through the photo-moisture-curable resin composition are permanently bonded, and are joined with sufficient adhesive force.

Application of the optical moisture curable resin composition to the adherend may be performed, for example, using a dispensing device, but is not particularly limited. The light irradiated during photo curing is not particularly limited as long as it is light that cures the radically polymerizable compound, but ultraviolet rays are preferable. In addition, when the photo-moisture-curable resin composition is fully cured with moisture after photo-curing, it may be left to stand in the air for a predetermined period of time.

Although application of the optical moisture hardening type resin composition to a to-be-adhered body is not specifically limited, it may be performed around normal temperature, and, specifically, may be performed at a temperature of about 10 to 35°C. The optical moisture curable resin composition of the present invention has a viscosity within the above-mentioned predetermined range at 25°C, so that it can be applied easily even when applied at around room temperature, and liquid sagging does not occur.

Moreover, since the light moisture hardening type resin composition of this invention develops initial adhesive force of a certain value or more immediately after light irradiation, temporary adhesion can be performed immediately after light curing, and workability|operativity becomes good.

The optical moisture curable resin composition of the present invention is preferably used as an adhesive for electronic components. That is, the present invention also provides an adhesive for electronic components consisting of the optical moisture curable resin composition.

Therefore, the above-described adherend is preferably various electronic components constituting an electronic device. Various electronic components that constitute electronic devices include, for example, various electronic components that are installed in display elements and constitute electronic circuits, boards on which the electronic components are mounted, housings that constitute electronic devices, semiconductor chips, etc. I can hear it.

Additionally, the material of the adherend may be any of metal, glass, plastic, etc. The shape of the adherend is not particularly limited, and examples include film, sheet, plate, panel, tray, rod, box, and housing.

As mentioned above, the optical moisture curable resin composition of the present invention is preferably used for joining electronic components constituting an electronic device. Moreover, the optical moisture curable resin composition of this invention is preferably used also in order to join electronic components to other components. With these structures, the electronic component has the hardened body of the present invention.

Moreover, the optical moisture curable resin composition of this invention is used inside an electronic device etc. to obtain an assembled part by adhering a board|substrate to a board|substrate, for example. The assembled part obtained in this way has a first substrate, a second substrate, and a cured body of the present invention, and at least a part of the first substrate is bonded to at least a part of the second substrate through the cured body. Additionally, the first substrate and the second substrate are preferably each equipped with at least one electronic component constituting an electronic circuit.

Moreover, it is preferable that the optical moisture hardening type resin composition of this invention is used for narrow frame applications. For example, in various display devices such as display devices for mobile phones such as smartphones, adhesive is applied on a base of a narrow square frame shape (i.e., narrow frame), and the display panel and touch panel are formed through the adhesive. etc. can be attached, and the optical moisture curable resin composition of the present invention may be used as the adhesive. Moreover, it is preferable to use the optical moisture hardening type resin composition of this invention for semiconductor chip applications. The optical moisture curable resin composition of the present invention is used in semiconductor chip applications, for example, to bond semiconductor chips.

Example

The present invention will be explained in more detail by way of examples, but the present invention is in no way limited by these examples.

Measurement and evaluation of various physical properties were performed as follows.

(Weight average molecular weight)

The weight average molecular weight of the moisture-curable resin (B) in each Example and Comparative Example was measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion. For the GPC measurement, Shodex KF-806L (manufactured by Showa Denko KK) was used as a column. Additionally, tetrahydrofuran (THF) was used as the solvent and mobile phase. Additionally, the measurement conditions for GPC were a flow rate of 1.0 ml/min and a measurement temperature of 40°C.

In addition, in each Example and Comparative Example, the weight average molecular weight was measured using a sample of a mixture of a radically polymerizable compound (A) and a moisture-curable resin (B). In this mixture, the peak of the radically polymerizable compound (A) appears on the low molecular weight side and the peak of the moisture-curable resin (B) appears on the high molecular weight side, so the weight average molecular weight of the moisture-curable resin (B) is determined from the peak on the high molecular weight side. can be obtained.

(inner/outer ratio a/b)

The inner-outer ratio a/b was measured using the method described in the specification. In addition, as the aluminum substrate and glass plate, aluminum alloy "A6063S" each having a size of 2 mm x 25 mm x 60 mm, and a glass plate with a smooth surface that had been ultrasonic cleaned for 5 minutes were used. The application of the moisture-curable resin composition was performed at room temperature (25°C) using a dispensing device, “SHOTMASTER 300SX” manufactured by Musashi Engineering, in a straight line with a width of 1.0 ± 0.1 mm, a length of 25 mm, and a thickness of 0.4 ± 0.1 mm. Applied to an aluminum substrate. Next, the applied optical moisture curable resin composition was irradiated with 1000 mJ/cm ² of ultraviolet rays with a wavelength of 405 nm at 1000 mW using a line-type LED irradiator (manufactured by HOYA Corporation). The glass plate was pressed against the aluminum substrate using a weight as a weight, and the widths (a1, b1) were measured 5 minutes after the weight was removed. The width (a1, b1) after compression was measured by observing the compression surface from the glass plate side using a microscope.

(25℃ viscosity)

The 25°C viscosity was measured at 5.0 rpm and 25°C using a cone plate type viscometer (trade name: TVE-35, manufactured by Toki Sangyo Co., Ltd.).

(initial adhesion)

2(a) and 2(b), using the above-described dispensing device, an optical moisture curing type coating is applied to the aluminum substrate 21 to have a width of 1.0 ± 0.1 mm, a length of 25 mm, and a thickness of 0.4 ± 0.1 mm. The resin composition (20) was applied at room temperature (25°C). Then, it was photo-cured by irradiating 1000 mJ/cm ² of ultraviolet rays with a wavelength of 405 nm at 1000 mW using a line-type LED irradiator (manufactured by HOYA Corporation). After that, the glass plate 22 is bonded to the aluminum substrate 21 through the light-cured light moisture-curable resin composition 20, and is pressed at 0.08 MPa for 120 seconds using a weight to obtain a sample for adhesion evaluation ( 23) was obtained.

Afterwards, the aluminum substrate 21 was stretched in the shear direction S at a speed of 10 mm/min using a tensile tester (“Tensile Compression Tester SVZ-50NB”, manufactured by Imada-SS Corporation) in an atmosphere of 25°C. and the maximum stress when the glass plate 22 peels off was measured and set as the initial adhesive force. In addition, the period from the end of photocuring to the start of the tensile test was conducted within 150 seconds. Initial adhesion was evaluated based on the following evaluation criteria.

A: 0.2MPa or more

B: 0.1 MPa or more but less than 0.2 MPa

C: Less than 0.1MPa

(Final heat-resistant adhesion)

In the same manner as the initial adhesion, the glass plate was bonded to the aluminum substrate through the photocured light moisture curable resin composition. After that, it was moisture-cured by leaving it at 25°C and 50RH% for 24 hours to obtain a sample for evaluating adhesiveness. Using a sample for adhesion evaluation, the sample was stretched in the shear direction in the same manner as the initial adhesive strength measurement method except that the ambient temperature was changed from 25°C to 70°C, and the maximum stress when the aluminum substrate and the glass plate peeled off was determined. was measured and used as the final heat-resistant adhesive strength.

A: 2.0MPa or more

B: 1.0 MPa or more but less than 2.0 MPa

C：Less than 1.0MPa

The urethane resin raw material used in each Example and Comparative Example was produced by the following method.

[Synthesis Example 1]

(PC urethane resin raw material)

100 parts by mass of polycarbonate diol (compound represented by formula (1)) as a polyol compound, 90 mol% of R is a 3-methylpentylene group, 10 mol% is a hexamethylene group, manufactured by Kuraray Co., Ltd., brand name “Kuraraypolyol” C-1090") and 0.01 parts by mass of dibutyltin dilaurate were placed in a separable flask with a capacity of 500 mL. 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 was brought to normal pressure, 50 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., brand name "Pure MDI") was added as a polyisocyanate compound, and the reaction was stirred at 80°C for 3 hours to form a polycarbonate skeleton. A moisture-curable urethane resin (PC urethane resin raw material) having isocyanate groups at both ends was obtained. The weight average molecular weight of the obtained urethane resin raw material was 6700.

[Synthesis Example 2]

(ET urethane resin raw material)

As a polyol compound, 100 parts by mass of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, brand name "PTMG-3000") and 0.01 part by mass of dibutyltin dilaurate were placed in a separable flask with a capacity of 500 mL. 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 was brought to normal pressure, 17.5 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., brand name "Pure MDI") was added as a polyisocyanate compound, and the reaction was stirred at 80°C for 3 hours to form a polyether skeleton. and a moisture-curable urethane resin (ET urethane resin raw material) having isocyanate groups at both ends was obtained. The weight average molecular weight of the obtained urethane resin raw material was 3500.

[Example 1]

As shown in Table 5, 60 parts by mass of each raw material constituting the moisture-curable resin (PC-L25) was added to 40 parts by mass of Acrylic B. Acrylic B was obtained by mixing each compound in the mixing ratio shown in Table 2. As a moisture-curable resin (PC-L25), PC urethane resin raw material and PC polyol were sequentially added to acrylic B in the mass ratio shown in Table 3 to obtain a mixture. As the PC polyol, the polycarbonate diol used in Synthesis Example 1 was used.

By stirring the obtained mixture at 50°C, PC polyol is reacted with a part of the urethane resin raw material to synthesize a moisture-curable urethane resin that is chain-extended and has isocyanate groups at both ends, and is combined with acrylic B (radically polymerizable compound) and moisture-curable urethane resin. A mixture of urethane resins was obtained.

To the obtained mixture of acrylic B and moisture-curable urethane resin, polyfunctional isocyanate a, a photopolymerization initiator, and a filler were added and mixed according to the composition in Table 5, and an optical moisture-curable resin composition was obtained. About the obtained optical moisture curable resin composition, the 25°C viscosity, inner/outer ratio a/b, initial adhesive strength, and final heat-resistant adhesive strength were measured.

[Example 2, 3, 5]

The same procedure as in Example 1 was carried out, except that polyfunctional isocyanate b was used instead of polyfunctional isocyanate a, and the mixing amount was changed as shown in Table 5.

[Example 4]

Examples except that polyfunctional isocyanate b, a photopolymerization initiator, a filler, and a colorant were added and mixed to the obtained mixture of acrylic B and moisture-curable urethane resin according to the formulation in Table 5 to obtain an optical moisture-curable resin composition. The same procedure as in 3 was carried out.

[Example 6]

As the moisture-curable resin, the moisture-curable resin (PC-L25) was replaced with a moisture-curable resin (ET-L25), as shown in Tables 4 and 5, and the same procedure as in Example 3 was used. That is, the mixing ratio and type of urethane resin raw material and polyol added to acrylic B were changed as shown in Table 4, and a mixture of acrylic B and moisture-curable urethane resin was obtained, in the same manner as in Example 3. carried out. In addition, as the ET polyol in Table 4, polytetramethylene ether glycol used in Synthesis Example 2 was used.

[Example 7, 8, 9]

The same procedure as Example 3 was performed except that acrylics C, D, and A were used instead of acrylic B. Additionally, each of acrylics C, D, and A was obtained by mixing each compound in the mixing ratio shown in Table 2.

[Comparative Examples 1 to 5]

Comparative Examples 1 to 5 were conducted in the same manner as Examples 1 and 6 to 9, except that polyfunctional isocyanate was not added.

[Comparative Example 6]

The same procedure as Example 1 was carried out, except that difunctional isocyanate (MDI) was used instead of polyfunctional isocyanate.

[Comparative Example 7]

The same procedure as Example 6 was carried out, except that difunctional isocyanate (MDI) was used instead of polyfunctional isocyanate.

※ In addition, polyfunctional isocyanate a is an isocyanurate modified form and is a compound having three isocyanate groups in the molecule.

Polyfunctional isocyanate b is a mixture of MDI (bifunctional isocyanate) and polymeric MDI (polymethylene polyphenyl polyisocyanate: compound (D)) having three or more isocyanate groups, and the proportion of MDI is 40% by mass, and the polymeric MDI is The ratio is 60% by mass. The average number of isocyanate groups in polymeric MDI is 5 to 6.

Acrylics A to D used in Examples and Comparative Examples were as follows.

The moisture-curable resin (B) used in the examples and comparative examples was as shown in Tables 3 and 4 below. As described above, the reaction product of the following urethane resin raw materials and polyol was used as the moisture-curable resin (B).

The optical moisture-curable resin compositions of Examples 1 to 9, in addition to the radically polymerizable compound (A), the moisture-curable resin (B), and the photopolymerization initiator (C), include a compound (D) having three or more isocyanate groups in the molecule. Since it contains, the final heat-resistant adhesive strength after moisture curing was increased, and high adhesive strength could be maintained even in a high temperature environment.

In contrast, the optical moisture-curable resin compositions of Comparative Examples 1 to 5 do not contain the compound (D) having three or more isocyanate groups in the molecule, so the final heat-resistant adhesive strength after moisture curing is low, and high adhesive strength cannot be secured in a high temperature environment. I couldn't.

This tendency was the same in Comparative Examples 6 and 7 in which a diisocyanate compound was used instead of compound (D) having three or more isocyanate groups.

Claims (12)

An optical moisture-curable resin composition containing a radically polymerizable compound (A), a moisture-curable resin (B), a photopolymerization initiator (C), and a compound (D) having three or more isocyanate groups in the molecule. In claim 1,
The said compound (D) is an optical moisture hardening type resin composition containing a compound which has 5 or more isocyanate groups in a molecule|numerator. In claim 1 or claim 2,
When applying a line width of 1.0 mm to an aluminum substrate and photocuring it by irradiating 1000 mJ/cm ² ultraviolet rays, the glass plate is pressed at 0.08 MPa for 120 seconds. The average width of the bonded portion on the glass plate side is a, aluminum If the average width of the adhesive portion on the substrate side is b, a/b is an optical moisture curable resin composition of 0.5 or more and 0.99 or less. The method according to any one of claims 1 to 3,
An optical moisture curable resin composition having a viscosity of 40 Pa·s or more and 600 Pa·s or less as measured under conditions of 25°C and 5.0 rpm using a cone plate type viscometer. The method according to any one of claims 1 to 4,
An optical moisture-curable resin composition in which the moisture-curable resin (B) contains a moisture-curable urethane resin. The method according to any one of claims 1 to 5,
An optical moisture-curable resin composition in which the weight average molecular weight of the moisture-curable resin (B) is 7,500 or more and 24,000 or less. The method according to any one of claims 1 to 6,
An optical moisture-curable resin composition in which the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound. In claim 7,
An optical moisture-curable resin composition containing 90 parts by mass or more of a monofunctional radically polymerizable compound with respect to 100 parts by mass of a radically polymerizable compound (A). The method according to any one of claims 1 to 8,
An optical moisture curable resin composition further comprising a filler (E). An adhesive for electronic components comprising the optical moisture curable resin composition according to any one of claims 1 to 9. A cured body of the optical moisture curable resin composition according to any one of claims 1 to 1O. An electronic component comprising the hardened body according to claim 11.