KR20230010619A - Optical moisture curable resin composition, adhesive for electronic parts, cured body, and electronic parts - Google Patents

Abstract

The optical moisture-curable resin composition of the present invention includes a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C), and is photocured by irradiation with 1000 mJ/cm ² ultraviolet rays. , the storage modulus (G') at 25°C when measured at 1 Hz with a dynamic viscoelasticity measuring device is 250 kPa or more, and tan δ at 75°C is 1.0 or more.

Description

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

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

In recent years, high integration and miniaturization are required for electronic components such as semiconductor chips. For example, there are cases in which a plurality of thin semiconductor chips are bonded together through an adhesive layer to form a laminated body of semiconductor chips. Also, in modern times when mobile devices with various display elements are widespread, narrowing the image display unit is being performed as a method of miniaturizing the display element (hereinafter, also referred to as "narrow frame design"). In these applications, along with downsizing and frame narrowing, attempts have been made to use optical moisture curing type adhesives instead of double-sided tapes.

As an optical moisture-curable adhesive, for example, Patent Document 1 contains a radical polymerizable compound, a moisture-curable urethane resin, and an optical radical polymerization initiator, and the moisture-curable urethane resin has a weight average molecular weight of 2000 or more. An optical moisture curable resin composition containing a urethane resin is disclosed. Further, Patent Document 2 discloses a reactive hot melt adhesive composition comprising a urethane prepolymer, a urethane (meth)acrylate having a (meth)acryloyl group, and a photopolymerization initiator.

Japanese Patent Publication No. 2016-074781 Japanese Patent Publication No. 2019-006854

However, since optical moisture-curing adhesives do not develop adhesive strength (initial adhesive strength) immediately after bonding, unlike double-sided tapes, it takes time to adhere members to each other, resulting in a problem in workability. For example, in Patent Documents 1 and 2, it is shown that adhesive strength of a certain level or more is expressed after light irradiation, but the initial adhesive strength may not be sufficient.

Then, this invention makes it a subject to provide the optical moisture hardening type resin composition which expresses the outstanding adhesive force immediately after photocuring, and can improve workability|operativity etc.

As a result of intensive examination, the inventors of the present invention have found that the above problems can be solved by setting the storage modulus (G') at 25°C and tanδ at 75°C of the photocured optical moisture curable resin composition within a certain range. completed the present invention. That is, the present invention provides the following [1] to [25].

[1] a radical polymerizable compound (A), a moisture curable resin (B), and a photopolymerization initiator (C),

The storage modulus (G') at 25°C is 250 kPa or more, and the tanδ at 75°C is 1.0 or more when measured at 1 Hz with a dynamic viscoelasticity measuring device in a state of photocuring by irradiation with 1000 mJ/cm ² ultraviolet rays. , Light moisture curable resin composition.

[2] In the above [1],

In the case where the glass plate is applied to an aluminum substrate with a line width of 1.0 mm and photocured by irradiation with ultraviolet rays of 1000 mJ/cm ² , and the glass plate is pressed at 0.08 MPa for 120 seconds, the average width of the adhesive portion on the glass plate side is a, aluminum When b is the average width of the bonded portion on the substrate side, a/b is 0.58 or more and 0.99 or less, the optical moisture curing type resin composition.

[3] In the above [1] or [2],

The optical moisture-curable resin composition in which the said moisture-curable resin (B) contains a moisture-curable urethane resin.

[4] In the above [3],

The moisture-curable urethane resin is a moisture-curable urethane resin having at least any one of a polycarbonate skeleton, a polyether skeleton, and a polyester skeleton.

[5] In the above [3] or [4],

An optical moisture-curable resin composition in which the moisture-curable urethane resin is a moisture-curable urethane resin having a polycarbonate skeleton.

[6] The method of any one of the above [1] to [5],

The light moisture curable resin composition whose weight average molecular weight of the said moisture curable resin (B) is 7500 or more and 24000 or less.

[7] The method of any one of the above [1] to [6],

The optical moisture-curable resin composition in which the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound.

[8] In the above [7],

A light moisture curing type resin composition containing 90 parts by mass or more of a monofunctional radically polymerizable compound with respect to 100 parts by mass of radically polymerizable compound (A).

[9] In the above [7] or [8],

The light moisture curing type resin composition in which the said monofunctional radically polymerizable compound contains a nitrogen-containing compound.

[10] In the above [9],

The light moisture curing type resin composition in which the said monofunctional radically polymerizable compound contains a chain nitrogen containing compound.

[11] In the above [9] or [10],

The light moisture curing type resin composition in which the said monofunctional radically polymerizable compound contains the nitrogen containing compound which has a cyclic structure.

[12] In the above [11],

The mass ratio (cyclic/chain) of the nitrogen-containing compound having the cyclic structure to the chain nitrogen-containing compound is 0.1 or more and 2.0 or less, the optical moisture-curable resin composition.

[13] The method of any one of the above [9] to [12],

The light moisture curing type resin composition whose content of the nitrogen-containing compound which is a monofunctional radically polymerizable compound with respect to 100 mass parts of said radically polymerizable compound (A) is 10 mass parts or more and 95 mass parts or less.

[14] The method of any one of the above [9] to [13],

The light moisture curing type resin composition in which the said monofunctional radically polymerizable compound contains a monofunctional (meth)acrylic acid ester compound other than the said nitrogen-containing compound.

[15] In the above [14],

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. resin composition.

[16] In the above [15],

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 and 90 parts by mass with respect to 100 parts by mass of radically polymerizable compound (A). The light moisture curing type resin composition which is the following.

[17] The method of any one of the above [1] to [16],

A 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 optical moisture-curable resin composition.

[18] The method of any one of the above [1] to [17],

The light moisture curing type resin composition which further contains a filler (D).

[19] The method of any one of the above [1] to [18],

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, a benzoin ether-based compound, and thioxanthone At least one selected from the group consisting of, light moisture curable resin composition.

[20] The method of any one of the above [1] to [19],

An optical moisture curable resin composition having an initial adhesive force of 0.25 MPa or more.

[21] The method of any one of the above [1] to [20],

An optical moisture curable resin composition having a final adhesive force of 2.0 MPa or more.

[22] The method of any one of the above [1] to [21],

An optical moisture curable resin composition having a viscosity of 35 Pa·s or more and 600 Pa·s or less as measured using a cone plate viscometer at 25° C. and 5.0 rpm.

[23] An adhesive for electronic parts comprising the optical moisture curable resin composition according to any one of [1] to [22] above.

[24] A cured product of the optical moisture-curable resin composition according to any one of [1] to [22].

[25] An electronic component comprising the cured product according to [24] above.

ADVANTAGE OF THE INVENTION According to this invention, the optical moisture hardening type resin composition which expresses excellent adhesive force even immediately after photocuring and can improve workability|operativity etc. is provided.

1 is a conceptual diagram showing a method for measuring the internal/external ratio a/b.
2 : is a schematic diagram which shows the adhesiveness test method, FIG. 2 (a) is a top view, and FIG. 2 (b) is a side view.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail, referring an embodiment.

<Light moisture curable resin composition>

The optical moisture-curable resin composition of the present invention contains a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C).

The optical moisture-curable resin composition of the present invention has a storage modulus (G') at 25°C of 250 kPa when measured at 1 Hz using a dynamic viscoelasticity measuring device in a state of photocuring by irradiation with ultraviolet rays of 1000 mJ/cm ² . or more, and tan δ at 75°C is 1.0 or more.

In the optical moisture-curable resin composition of the present invention, when both the storage modulus (G') at 25 ° C. and tan δ at 75 ° C. in the photocured state as described above are above a certain value, an appropriate pressure is applied immediately after photocuring. When this is applied, a certain amount of crushing becomes easy to adhere to the adherend, and a certain cohesive force is expressed even when shear stress is applied. Therefore, the adhesive strength immediately after photocuring (initial stage adhesive strength) can be made excellent.

[Storage modulus (G')]

The optical moisture-curable resin composition of the present invention has a storage modulus (G') of 250 kPa or more at 25°C measured in a state photocured as described above. When the storage elastic modulus (G') at 25°C is lower than 250 kPa, the bulk strength after photocuring is low, and it becomes difficult to increase the initial adhesive strength accordingly.

From the viewpoint of increasing the bulk strength and improving the initial adhesive strength, the storage modulus (G') at 25°C is preferably 350 kPa or more, more preferably 500 kPa or more, still more preferably 600 kPa or more, and even more preferably 700 kPa or more. Do.

The storage elastic modulus (G') at 25°C is preferably 4000 kPa or less, more preferably 3500 kPa or less, still more preferably 3000 kPa or less, and more preferably 2500 kPa or less, from the viewpoint of facilitating the expression of constant adhesiveness even immediately after photocuring. more preferable

[tanδ]

The optical moisture-curable resin composition of the present invention has a tan δ at 75°C of 1.0 or more when measured at 1 Hz using a dynamic viscoelasticity measuring device in a state of photocuring by irradiation with ultraviolet rays at 1000 mJ/cm ² . When the tan δ at 75°C is less than 1.0, the photocurable optical moisture curing type resin composition tends to repel when compressed, becomes difficult to collapse, and makes it difficult to increase the initial adhesive force.

From the standpoint of increasing the initial adhesive force, tan δ at 75°C is preferably 1.05 or more, more preferably 1.1 or more, and still more preferably 1.2 or more. Also, from the viewpoint of preventing the initial adhesive force from deteriorating due to excessive crushing when compressed, tan δ at 75°C is preferably 2.0 or less, more preferably 1.8 or less, and still more preferably 1.6 or less.

The storage modulus (G') at 25°C and tanδ at 75°C can be adjusted by the type, molecular weight, and amount of the moisture-curable resin (B), and the type and amount of the radical polymerizable compound (A). . For example, when the molecular weight of the moisture-curable resin (B) is increased, the storage modulus (G') at 25°C tends to increase. Moreover, when the radically polymerizable compound (A) contains many homopolymers having a large tan δ at 75°C, the tan δ of the light moisture curing type resin composition tends to increase. Moreover, when many monofunctional monomers are blended as the radically polymerizable compound (A), the tan δ tends to increase. In addition, when the molecular weight of the moisture-curable resin (B) is within a certain range, tan δ tends to fall within a certain range.

In addition, the storage elastic modulus (G') and tan-delta of an optical moisture-curable resin composition can be measured as follows.

The optical moisture-curable resin composition is applied to a jig for measuring viscoelasticity, and is photocured by irradiating ultraviolet rays at 1000 mJ/cm ² using a 1000 mW UV-LED lamp to prepare a sample for evaluation. The sample for evaluation was set in a dynamic viscoelasticity measuring device within 30 seconds after irradiation with ultraviolet rays, 10 to 100 ° C, temperature increase rate = 5 ° C / min, frequency F = 1 Hz, storage modulus (G ') in shear mode, and tan δ to measure

[Viscosity at 25°C]

The optical moisture-curable resin composition of the present invention preferably has a viscosity (hereinafter, also referred to as "25°C viscosity") of 35 Pa·s or more and 600 Pa·s or less as measured using a cone plate viscometer at 25°C and 5.0 rpm. Do.

The 25°C viscosity of the moisture-curable resin composition described above is measured under a high shear of 5.0 rpm without photo-curing or moisture-curing, and is a viscosity that is hardly affected by the filler. Therefore, when the viscosity at 25 ° C. is 35 Pa s or more, the low molecular weight component contained in the moisture-curable resin (B) or the like tends to decrease, and the moisture-curable resin (B) or the like becomes difficult to seep through the interface after light irradiation. It becomes easy to improve initial adhesion. That is, when the low molecular weight moisture-curable resin (B) or the like is less likely to permeate into the interface after light irradiation, slippage with the adherend is less likely to occur, adhesive force is easier to develop, and initial adhesive force is easier to improve. In addition, even if the viscosity at 25 ° C. is 600 Pa·s or less, the adhesive properties originally possessed by the moisture-curable resin (B) tend to develop, thereby easily improving the initial adhesive strength and the final adhesive strength described later.

In addition, by setting the 25°C viscosity to 35 Pa·s or more and 600 Pa·s or less, problems such as spillage or inability to apply at normal temperature are less likely to occur, and workability is improved.

The 25°C viscosity of the optical moisture-curable resin composition is more preferably 40 Pa·s or more, more preferably 45 Pa·s or more, still more preferably 90 Pa·s or more, still more preferably 110 Pa·s or more, and , 500 Pa·s or less is more preferable, 350 Pa·s or less is still more preferable, and 230 Pa·s or less is still more preferable. When the 25°C viscosity is within the above range, it is easy to improve workability and initial adhesive strength.

Moreover, since it can prevent that the molecular weight of moisture-curable resin (A) becomes excessively high when below the said upper limit, it becomes easy to improve initial adhesive force, and by extension, adhesive force becomes high enough by moisture hardening, and final adhesive force etc. also improve. it becomes easier to do In addition, the final adhesive force means the adhesive force of the optical moisture hardening type resin composition after photocuring and moisture hardening, and a detail is mentioned later.

[Internal and external secret a/b]

The optical moisture-curable resin composition of the present invention is linearly applied to an aluminum substrate under predetermined conditions described later, and further photocured by UV, and then, when the glass plate is further pressed, the average width of the adhesive portion on the glass plate side is a , when the average width of the bonded portion on the aluminum substrate side is b, it is preferable that a/b (also referred to as "inside/outside ratio a/b") is 0.58 or more and 0.99 or less.

When the internal/external ratio a/b of the present invention is set to 0.58 or more, the internal/external ratio a/b is larger than that of the conventional optical moisture curable resin composition, and the optical moisture curable resin composition is easily crushed immediately after photocuring, and the adherend The adhesion to the interface of is increased, and the initial adhesive force to the adherend is easily increased. Moreover, by setting the internal/external ratio a/b to 0.99 or less, it is possible to prevent the cohesive force of the optical moisture curing type resin composition immediately after photocuring from being reduced, or being too crushed and the initial adhesive force from being lowered.

The internal/external ratio a/b is more preferably 0.63 or more, still more preferably 0.66 or more, more preferably 0.95 or less, and still more preferably 0.93 or less. When the internal/external ratio a/b is within these ranges, it becomes easy to improve the initial adhesive force.

In the present invention, the internal/external 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 have 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 irradiated with ultraviolet rays of 1000 mJ/cm ² to cure the moisture-curable resin composition 10. Immediately thereafter (within 10 seconds), as shown in FIG. 1(c), the glass plate 12 is overlaid on the moisture-curable resin composition 10, and the glass plate 12 is applied to the application area of the moisture-curable resin composition 10. for 120 seconds at 0.08 MPa. After crimping, 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 thereof is taken as the average width a. Moreover, the width b1 of the adhesive part of the moisture-curable resin composition 10 with the aluminum substrate 11 is measured. The width b1 is measured at 5 points, the average value thereof is taken as the average width b, and the inside/outside ratio a/b is calculated from the average widths a and b. In addition, crimping|bonding is performed using a weight, and what is necessary is just to measure the width|variety a1 and b1 5 minutes after removing a weight.

The internal/external ratio a/b can be adjusted within the above range by adjusting the type of radical polymerizable compound or the like. For example, when the light moisture curable resin composition contains a large amount of monofunctional radical polymerizable compounds as radical polymerizable compounds, the ratio of crosslinked structures formed after photocuring decreases, so the internal/external ratio a/b can be increased. there is. Moreover, for example, since the hardened|cured material after photocuring becomes soft even when many radically polymerizable compounds with a low glass transition point of a homopolymer are included as a radically polymerizable compound in a light moisture curable resin composition, internal/external ratio a/ b can be increased. Furthermore, it can adjust also with the weight average molecular weight of moisture-curable resin (B).

[Adhesion]

It is preferable that the initial stage adhesive strength of the optical moisture hardening type resin composition of this invention is 0.25 Mpa or more. Moreover, it is preferable that the final adhesive force of the optical moisture hardening type resin composition of this invention is 2.0 Mpa or more.

In addition, the initial adhesive force means the adhesive force at 25 degreeC immediately after photocuring the optical moisture hardening type resin composition, and the final adhesive force means the adhesive force at 25 degreeC, 50RH% after photocuring the optical moisture hardening type resin composition. It means the adhesive strength after leaving it for 24 hours. The details of the method for measuring the initial adhesive force and the final adhesive force are as described in Examples to be described later.

If the optical moisture-curable resin composition has an initial adhesive strength of 0.25 MPa or more at 25°C, it is possible to temporarily bond adherends with relatively high adhesive strength immediately after photocuring, and the workability at the time of temporary bonding is improved. do. In addition, if the final adhesive strength is 2.0 MPa or more, adherends can be firmly bonded to each other by final adhesion by moisture curing after temporary bonding.

The optical moisture-curable resin composition more preferably has an initial adhesive strength of 0.4 MPa or more in order to further enhance the adhesive stability at the time of temporary bonding. In addition, the initial adhesive strength is not particularly limited, but may be, for example, less than 1.5 MPa in order to facilitate reattachment and the like at the time of temporary bonding.

In addition, the final adhesive strength of the optical moisture-curable resin composition is more preferably 3.5 MPa or more in order to more firmly bond the adherends to each other after main bonding. In addition, the final adhesive strength is preferably as high as possible, and is not particularly limited, but is, for example, 20 MPa or less, and may be 10 MPa or less.

Hereinafter, each component contained in the optical moisture curing type resin composition will be described in more detail.

[Radically polymerizable compound (A)]

The optical moisture-curable resin composition of the present invention contains a radically polymerizable compound (A). Photocurability is imparted to the optical moisture-curable resin composition by containing a radically polymerizable compound (A). Since the optical moisture-curable resin composition can provide a certain adhesive force only by light irradiation by having photocurability, appropriate initial stage adhesive force can be ensured.

As the radically polymerizable compound (A), it is only necessary to have a radically polymerizable functional group in the molecule. As the radically polymerizable functional group, a compound having an unsaturated double bond is suitable, and examples thereof include a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group.

Among the above, from an adhesive viewpoint, 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 which has a (meth)acryloyl group is hereinafter also called a "(meth)acrylic compound." In addition, in this specification, "(meth)acryloyl group" means an acryloyl group or (meth)acryloyl group, "(meth)acryl" means an acryl or methacryl, and other similar terms also 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. may include However, it is preferable to include a monofunctional radically polymerizable compound from the viewpoint of increasing the tan δ after photocuring described above and improving the initial adhesive strength of the optical moisture curing type resin composition. Moreover, it is more preferable that the radically polymerizable compound (A) contains at least a monofunctional (meth)acrylic compound which is a (meth)acrylic compound as a monofunctional radically polymerizable 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 having no repeating unit may be used.

The optical moisture-curable resin composition preferably contains a large amount of a monofunctional radical polymerizable compound in order to increase tan δ after photocuring of the optical moisture-curable resin composition and improve initial adhesive strength. Specifically, the light moisture curable resin composition preferably contains 90 parts by mass or more of a monofunctional radical polymerizable compound, preferably 95 parts by mass or more, based on 100 parts by mass of the radical polymerizable compound (A). , It is more preferable to include 100 parts by mass.

[Monofunctional Radical Polymerizable Compound]

(nitrogen containing compound)

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 stage adhesive strength of the light moisture curing type resin composition becomes good. The optical moisture-curable resin composition is photocured by irradiating active energy rays such as ultraviolet rays after being applied to an adherend, and at that time, it is often photocured in the presence of oxygen as will be described later. It is presumed that when the radically polymerizable compound (A) contains a nitrogen-containing compound, it is appropriately photocured even in the presence of oxygen, and thereby the initial adhesive strength becomes good.

The nitrogen-containing compound may contain one or both of a nitrogen-containing compound having a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, but from the viewpoint of improving the initial adhesive strength of the light moisture curable resin composition, a nitrogen-containing compound having a cyclic structure It is preferable to include, and it is more preferable to use together a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure.

Examples of 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, N - Cyclic imide compounds, such as (meth)acryloyloxyethyl hexahydrophthalimide, etc. are mentioned. Among these, amide group-containing compounds such as N-vinyl caprolactam are more preferable. In this specification, a nitrogen-containing compound having a cyclic structure is also referred to as a cyclic nitrogen-containing compound, and a radical polymerizable compound in which a nitrogen atom is included in an atom constituting the ring itself is used as a cyclic nitrogen-containing compound, and other nitrogen-containing compounds Silver is a chain nitrogen-containing compound.

As a chain nitrogen-containing compound, for example, dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, dimethylaminoethyl (meth) chain amino group-containing (meth)acrylates such as acrylates, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide , chain-like (meth)acrylamide compounds such as acrylamide and methacrylamide, and N-vinylacetamide.

Moreover, monofunctional urethane (meth)acrylate may be sufficient as a chain nitrogen-containing compound. When a urethane resin, especially a urethane resin having a polycarbonate skeleton is used as the moisture-curable resin (B) by using a monofunctional urethane (meth)acrylate, compatibility with the moisture-curable resin (B) becomes good , easy to improve the initial adhesion. Moreover, since urethane (meth)acrylate has comparatively high polarity, it becomes easy to raise the adhesive force with respect to glass.

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

As the (meth)acrylic acid derivative having the above hydroxyl group, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, mono ( meth)acrylates, mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; and the like.

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

More specifically, the monofunctional urethane (meth)acrylate is preferably a urethane (meth)acrylate obtained by reacting the above-described monoisocyanate compound with a mono(meth)acrylate of a dihydric alcohol, and suitable spheres thereof As an example, 1,2-ethanediol-1-acrylate-2-(N-butyl carbamate) is mentioned.

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

The content of the nitrogen-containing compound as a monofunctional radical polymerizable compound relative to 100 parts by mass of the radical polymerizable compound (A) in the optical moisture curable resin composition is from the viewpoint of improving the initial adhesive strength of the optical moisture curable resin composition. , It is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and most preferably 60 parts by mass or more. The content of the nitrogen-containing compound as the monofunctional radically polymerizable compound is preferably 95 parts by mass or less, more preferably 90 It is 85 parts by mass or less, more preferably 85 parts by mass or less.

When the monofunctional radically polymerizable compound has a chain nitrogen-containing compound and a nitrogen-containing compound having a cyclic structure, the monofunctional radically polymerizable compound contains nitrogen having a cyclic structure relative to the chain nitrogen-containing compound The mass ratio (cyclic/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 setting the cyclic/chain mass ratio within the above range, the initial stage adhesive strength of the optical 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 non-nitrogen-containing compounds). When the radically polymerizable compound (A) contains a non-nitrogen-containing compound as a monofunctional radically polymerizable compound, it becomes easy to improve adhesive strength and the like.

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 preferred, and (meth)acrylic acid ester compounds are more preferred among them.

Examples of monofunctional (meth)acrylic acid ester compounds include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates. Although these may be used individually by 1 type and may be used together 2 or more types, it is preferable to use one or both of alkyl (meth)acrylate and aromatic ring containing (meth)acrylate in these.

The total content of the alkyl (meth)acrylate, the alicyclic structure-containing (meth)acrylate, and the aromatic ring-containing (meth)acrylate in the radically polymerizable compound (A) is 100 masses of the radically polymerizable compound (A). It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. The content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and most preferably 40 parts by mass or less.

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

Examples of the alicyclic structure-containing (meth)acrylate include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl ( and (meth)acrylates having alicyclic structures such as meth)acrylate and dicyclopentenyl (meth)acrylate.

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. A phenoxyalkyl (meth)acrylate etc. are mentioned.

As the monofunctional (meth)acrylic acid ester compound, other than alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates can be used, for example, cyclic ether group-containing compounds. (meth)acrylates can also be used.

As a cyclic ether group containing (meth)acrylate, the (meth)acrylate which has an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a dioxolane ring, a dioxane ring, etc. is mentioned.

As an epoxy ring containing (meth)acrylate, glycidyl (meth)acrylate is mentioned, for example. 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. As the dioxolane ring-containing (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2,2-cyclohexyl-1,3- Dioxolan-4-yl) methyl (meth)acrylate etc. are mentioned. As (meth)acrylate which has a dioxane ring, cyclic trimethylol-propane formal (meth)acrylate etc. are mentioned.

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

Moreover, as a monofunctional (meth)acrylic acid ester compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyl Hydroxyalkyl (meth)acrylates such as butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, etc. Alkoxyethylene glycol (meth)acrylates such as alkoxyalkyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methyl Toxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, You may also use polyoxyethylene type (meth)acrylates, such as ethoxy polyethylene glycol (meth)acrylate.

Moreover, you may use carboxyl-containing (meth)acrylic compounds, such as acrylic acid and methacrylic acid, etc. as a monofunctional (meth)acrylic compound.

[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 polyfunctional radically polymerizable compound include bifunctional (meth)acrylic acid ester compounds, trifunctional or higher functional (meth)acrylic acid ester compounds, and bifunctional or higher functional urethane (meth)acrylates.

Examples of the bifunctional (meth)acrylic acid ester compound include 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, and 1,6-hexanedioldi(meth)acrylate. rate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi(meth)acrylate , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tri Propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyl di(meth)acrylate, neopentylglycoldi(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate , carbonatedioldi(meth)acrylate, polyetherdioldi(meth)acrylate, polyesterdioldi(meth)acrylate, polycaprolactonedioldi(meth)acrylate, polybutadienedioldi(meth)acrylate etc. can be mentioned.

In addition, as a trifunctional or more than trifunctional (meth)acrylic acid ester compound, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition 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)acrylate ) Acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. can

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

As the (meth)acrylic acid derivative having the above hydroxyl group, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, mono ( Epoxy (meth)acrylate, mono(meth)acrylate or di(meth)acrylate of trihydric alcohols such as meth)acrylate, trimethylolethane, trimethylolpropane, and glycerin, and bisphenol A type epoxy (meth)acrylate ) Acrylate etc. are mentioned.

Examples of the isocyanate compound used to obtain urethane (meth)acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. , diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogen and polyisocyanate compounds such as added XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

Moreover, as an isocyanate compound, the chain-extended polyisocyanate compound obtained by reaction of a polyol and excessive isocyanate compound can also be used. 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 resins, hydrolyzable silyl group-containing resins, and moisture-curable cyanoacrylate resins. Among them, moisture-curable urethane resins and Any of hydrolyzable silyl group-containing resins are preferred, and moisture-curable urethane resins are more preferred. These may be used individually by 1 type, and may use 2 or more types together.

(moisture curing urethane resin)

A moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule. The moisture-curable urethane resin only needs to have an isocyanate group in its molecule, and the isocyanate group in the molecule reacts with moisture in the air or in an adherend to cure it. The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more, but it is preferable that the moisture-curable urethane resin has one or two isocyanate groups in one molecule. Moreover, although an isocyanate group is not specifically limited, What is necessary is just to form the terminal of a moisture curable urethane resin.

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 as 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 used as a raw material of 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 polyol etc. can be mentioned. These polyol compounds may be used individually by 1 type, or may be used in combination of 2 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 at least one of a moisture-curable urethane resin having a polycarbonate skeleton or a polyether skeleton. is more preferable, and a moisture-curable urethane resin having a polycarbonate skeleton is still more preferable. Moisture-curable urethane resins are excellent in both initial adhesive force and final adhesive force by having a polycarbonate skeleton. Furthermore, an optical moisture-curable resin composition excellent in weather resistance, heat resistance, moisture resistance and the like of the cured product can also be provided.

(moisture curable urethane resin having a polycarbonate skeleton)

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

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

In Formula (1), R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 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 be improved. In addition, yellowing and the like are less likely to occur due to thermal deterioration and the like, and weather resistance is also improved. R consisting of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but from the viewpoint of easily improving stress relaxation properties and flexibility, it is preferable to have a chain structure. Further, R in the chain structure may be linear or branched.

n is preferably 5 to 200, more preferably 10 to 150, and still more preferably 20 to 50.

Moreover, R contained in the polycarbonate polyol which comprises a moisture-curing urethane resin may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that at least one part is a C6 or more chain aliphatic saturated hydrocarbon group, more preferably, at least one part is a C7 or more chain aliphatic saturated hydrocarbon group.

By including a chain-shaped saturated aliphatic hydrocarbon group having 7 or more carbon atoms, it becomes easy to improve stress relaxation properties and flexibility. When the polycarbonate diol is a compound represented by the above formula (1), the ratio of chain-shaped saturated aliphatic hydrocarbon groups having 7 or more carbon atoms is preferably 20 mol% or more and 100 mol% or less with respect to R contained in the total polycarbonate diol 30 mol% or more and 100 mol% or less are more preferable, and 50 mol% or more and 100 mol% or less are still more preferable.

The chain-like saturated aliphatic hydrocarbon group having 7 or more carbon atoms preferably has 8 or more and 12 or less carbon atoms, and more preferably has 8 or more and 10 or less carbon atoms.

Specific examples of R may be linear, such as a tetramethylene group, a pentylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and the like. Branched phases, such as a rene group and a methyl octamethylene group, may be sufficient. A plurality of R's in one molecule may be the same as or different from each other. Therefore, two or more types of R may be included in one molecule, and in that case, preferably two or three types of R are included in one molecule. For example, the polycarbonate polyol may be a copolymer containing R of 6 or less carbon atoms and R of 7 or more carbon atoms in one molecule, and in this case, any R may be a chain-shaped saturated aliphatic hydrocarbon group.

Further, R may include a linear saturated aliphatic hydrocarbon group or may include a branched saturated aliphatic hydrocarbon group. As for R in the polycarbonate polyol, branched and linear R may be used together, or linear R may be used alone.

In addition, polycarbonate polyol may be used individually by 1 type, and may be used in combination of 2 or more type.

As a polyisocyanate compound used as a raw material of a moisture-curable urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are used suitably.

Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, a liquid modified product of diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, and naphthalene-1,5-diisocyanate.

Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylyl Rendiisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like are exemplified.

As a polyisocyanate compound, especially, from a viewpoint which can make the adhesive force after total hardening high, an aromatic polyisocyanate compound is preferable, and among these, diphenylmethane diisocyanate and its modified product are more preferable. Moreover, from a viewpoint of making it easy to impart stress relaxation property, flexibility, etc. to the hardened|cured material of an optical moisture curable resin composition, an aliphatic polyisocyanate compound is preferable.

A polyisocyanate compound may be used independently or may be used in combination of 2 or more types.

(moisture curable urethane resin having a polyester skeleton)

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

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

Examples of the polyhydric carboxylic acid used as a raw material of polyester polyol include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, and dodecamethylene dicarboxylic acid. Among these, phthalic acid or adipic acid is preferable from the viewpoint of increasing the adhesive force at high temperature more easily.

As the polyol used as a raw material of the polyester polyol, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexane Diol, diethylene glycol, cyclohexanediol, etc. are mentioned. Among these, 1,6-hexanediol or 1,4-butanediol is preferable from the viewpoint of increasing the adhesive strength at high temperatures more easily.

In addition, polyester polyol may be used individually by 1 type, and may be used in combination of 2 or more type.

(moisture curable urethane resin having a polyether skeleton)

A moisture-curable urethane resin having a polyether skeleton is obtained by introducing a polyether skeleton into the urethane resin by using a 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 in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

Examples of the polyether polyol include 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 type. A polyoxyalkylene modified form of , etc. are mentioned. Among these, a ring-opening polymer of polypropylene glycol, tetrahydrofuran, or a ring-opening polymer of 3-methyltetrahydrofuran is preferred from the viewpoint of facilitating the coating properties of the light and moisture-curable resin composition.

Here, the modified bisphenol-type polyoxyalkylene is obtained by adding an alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen moiety of the bisphenol-type molecular skeleton. It is a polyether polyol obtained by making it react. The polyether polyol may be a random copolymer or a block copolymer. In the bisphenol-type polyoxyalkylene modified body, it is preferable that one or two or more alkylene oxides are added to both ends of the bisphenol-type molecular skeleton.

It does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, Preferably it is bisphenol A type.

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

It is preferable that the moisture-curable urethane resin which has a polyether skeleton further contains what was obtained using the polyol compound which has a structure represented by following formula (2). By using a polyol compound having a structure represented by the following formula (2), it is possible to obtain an optical moisture-curable resin composition with excellent adhesiveness and a cured product that is flexible and has good elongation, and is compatible with the radically polymerizable compound (A). The castle becomes something outstanding.

Among them, it is preferable to use a polyether polyol composed of a ring-opening polymerization compound of polypropylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group, and polypropylene glycol and A ring-opening polymerization compound of a tetrahydrofuran (THF) compound is more preferred. The ring-opening polymerization compound of a tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol.

In addition, polyether polyol may be used individually by 1 type, and may be used in combination of 2 or more type.

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. In addition, when l is 0, it means the case where 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 to 3 are still more preferable. Moreover, it is more preferable that R is a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

The moisture-curable urethane resin having a polycarbonate, polyester, or polyether skeleton described above may have two or more kinds of skeletons in the molecule, and may have, for example, a polycarbonate skeleton and a polyester skeleton. In that case, a polycarbonate polyol and a polyester polyol may be used as the polyol compound used as the raw material. Similarly, a moisture-curable urethane resin 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 one having an isocyanate group, as described later in the hydrolyzable silyl group-containing urethane resin, may be continued

(Hydrolyzable silyl group-containing resin)

In the resin containing a hydrolyzable silyl group used in the present invention, the hydrolyzable silyl group in the molecule reacts with moisture in the air or in an adherend to cure it.

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

Moreover, as said hydrolyzable silyl group-containing resin, what has an isocyanate group is not included.

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

In Formula (3), R ¹ is each independently an 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 which may be substituted. (R ² is each independently a hydrocarbon group having 1 or more and 20 or less carbon atoms). Moreover, in Formula (3), X is a hydroxyl group or a hydrolysable group each independently. Moreover, in Formula (3), a is an integer of 1-3.

The hydrolyzable group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mer A capto group etc. are mentioned. Especially, a halogen atom, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable at a point with high activity. Further, from the viewpoint of mild hydrolysis and easy handling, an alkoxy group such as a methoxy group and an ethoxy group is more preferred, and a methoxy group and an ethoxy group are still more preferred. Further, from the viewpoint of safety, an ethoxy group or an isopropenoxy group in which the compound released by the reaction is ethanol or acetone, respectively, is preferable.

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

It is preferable that it is 2 or 3, and, as for a in said Formula (3), it is especially preferable that it is 3 from a viewpoint of hardenability. Moreover, it is preferable that a is 2 from a viewpoint of storage stability.

In addition, as R ¹ in the formula (3), 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, a trimethylsiloxy group, A chloromethyl group, a methoxymethyl group, etc. are mentioned. Especially, 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 A methyl) dimethoxysilyl group, (acetoxymethyl) dimethoxysilyl group, (acetoxymethyl) diethoxysilyl group, etc. are mentioned.

Examples of the hydrolysable silyl group-containing resin include a hydrolysable silyl group-containing (meth)acrylic resin, a molecular chain terminal or an organic polymer having a hydrolysable silyl group at the molecular chain terminal portion, a hydrolyzable silyl group-containing polyurethane resin, and the like. can be heard

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 a (meth)acrylic acid alkyl ester in the main chain.

Examples of the hydrolyzable silyl group-containing (meth)acrylic acid ester include (meth)acrylic acid 3-(trimethoxysilyl)propyl, (meth)acrylic acid 3-(triethoxysilyl)propyl, (meth)acrylic acid 3- (methyldimethoxysilyl)propyl, (meth)acrylic acid 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 (methyldimethoxysilyl)methyl, etc. are mentioned.

Examples of the alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. ) Isobutyl acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n- (meth)acrylate Octyl, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and stearyl (meth)acrylate.

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

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

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

Examples of the polyoxyalkylene-based polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, and a polyoxypropylene-poly The polymer etc. which have an oxybutylene copolymer structure are mentioned.

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

As a method for producing the above hydrolyzable silyl group-containing polyurethane resin, for example, when producing a polyurethane resin by reacting a polyol compound and a polyisocyanate compound, further reacting a silyl group-containing compound such as a silane coupling agent How to do it, etc. Specifically, the method of synthesizing a urethane oligomer having a hydrolyzable silyl group described in Japanese Unexamined Patent Publication No. 2017-48345, etc. are exemplified.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, and β-(3,4-epoxycyclohexyl)-ethyltrimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethine Toxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethyne Toxysilane, (gamma)-aminopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. Especially, (gamma)-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.

Moreover, the moisture-curable urethane resin may have both an isocyanate group and a hydrolysable 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 above method, and further reacting the silane coupling agent with the raw material urethane resin It is desirable to manufacture

In addition, the detail of the moisture curable urethane resin which has an isocyanate group is as above-mentioned. As the silane coupling agent reacted with the raw material urethane resin, it may be appropriately selected and used from those listed above, 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-aminopropyltrimethoxysilane. Toxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-aminopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, etc. are mentioned.

In addition, moisture-curable resin may have a radically polymerizable functional group. As the 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 from a particularly reactive surface. In addition, moisture-curable resin which has a radically polymerizable functional group is handled as moisture-curable resin (B), not included in the above-mentioned radically polymerizable compound.

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

The weight average molecular weight of the moisture-curable resin (B) is preferably 7500 or more and 24000 or less. By setting the weight average molecular weight within the above range, the storage modulus (G′) at 25° C. and tan δ at 75° C. of the optical moisture-curable resin composition are within a predetermined range, and the initial adhesive strength is easily increased. Moreover, it becomes easy to make final adhesive force favorable by using below the said upper limit. From these viewpoints, the weight average molecular weight of the moisture-curable resin (B) is more preferably 7800 or more, more preferably 10000 or more, still more preferably 11500 or more, more preferably 20000 or less, and 16000 or less. More preferably, 15000 or less is even more preferable.

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

Moisture-curable resin may be subjected to chain extension in order to make the weight average molecular weight more than a certain value as described above.

For example, in a moisture-curable urethane resin, a polyol compound and a urethane resin having an isocyanate group obtained by reacting a polyisocyanate compound having two or more isocyanate groups in one molecule (hereinafter also referred to as "raw material urethane resin") are added A chain extender may be reacted with . At this time, the chain extension agent should just adjust the amount used appropriately so that the isocyanate group remains in the moisture-curable urethane resin without allowing the chain extension agent to react with all the isocyanate groups of the raw material urethane resin. Further, 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 resins is preferably a polyol compound. Details of the polyol compound are as described above. Moreover, what is necessary is just to use the polyol compound similar to the polyol compound used in order to synthesize|combine the raw material urethane resin for the polyol compound as a chain extension agent. Therefore, if the polyol compound used to synthesize the raw material urethane resin is polycarbonate polyol, the chain extender may also use polycarbonate polyol.

When the amount of use of the chain extension agent is 100 parts by mass of the total amount of the raw material urethane resin and the chain extension agent,

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, and 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 radical polymerizable compound (A) is preferably 30/70 or more and 90/10 or less, and is 40/60 or more and 80/60 or more. 20 or less is more preferable, and 50/50 or more and 70/30 or less are still more preferable. When the mass ratio falls within these ranges, photocurability and moisture curability can be imparted to the optical moisture-curable resin composition in a well-balanced manner, and both the initial adhesive force and the final adhesive force can be easily adjusted within a desired range.

The optical moisture-curable resin composition may contain a resin component other than the radical polymerizable compound (A) and the moisture-curable resin (B) as a resin component within a range not impairing the effects of the present invention. You may contain resin components (for example, acrylic resin, urethane resin, etc.), thermosetting resin, etc., such as a thermoplastic resin which does not have. The ratio of the resin components other than the radical polymerizable compound (A) and the moisture-curable urethane resin (B) is, for example, 50 Part by mass or less, preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[Photoinitiator (C)]

The optical moisture-curable resin composition of the present invention contains a photopolymerization initiator. Photocurability is appropriately imparted to the optical moisture-curable resin composition by containing a photopolymerization initiator.

Examples of the photopolymerization initiator 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, thioxanthone, etc. can be heard

Examples of commercially available photopolymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, IRGACURE TPO (all manufactured by BASF), benzoin methyl ether, benzoin Phosphate ethyl ether, benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.), and the like are exemplified.

The content of the photopolymerization initiator in the optical moisture-curable resin composition is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A). below When the content of the photopolymerization initiator is within these ranges, the resulting optical moisture-curable resin composition has excellent photocurability and storage stability. Moreover, by setting it in the said range, the radical photopolymerization compound hardens suitably and it becomes easy to make adhesive force favorable.

[Filler (D)]

The light moisture curable resin composition of the present invention may contain a filler (D). By containing the filler (D), the optical moisture-curable resin composition of the present invention has a suitable thixotropic property, and can sufficiently maintain the shape after application. As a filler, a particulate thing may be used.

As the filler (D), inorganic fillers are preferable, and examples thereof include silica, talc, titanium oxide, zinc oxide, and calcium carbonate. Among them, silica is preferable in view of the obtained optical moisture curable resin composition having excellent ultraviolet transmittance. In addition, the filler (D) may be subjected to a hydrophobic surface treatment such as silylation treatment, alkylation treatment, or epoxidation treatment.

A filler (D) may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of the filler (D) is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 2 parts by mass, based on 100 parts by mass of the total amount of the radical polymerizable compound (A) and the moisture curable urethane resin (B). 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less.

(moisture curing accelerator catalyst)

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

As a moisture curing acceleration catalyst, an amine-type compound, a metal-type catalyst, etc. are mentioned specifically,. Examples of the amine compound include compounds having a morpholine skeleton such as di(methylmorpholino)diethyl ether, 4-morpholinopropylmorpholine, and 2,2'-dimorpholinodiethyl ether, and bis(2-dimethyl Aminoethyl) ether, amine compounds containing dimethylamino groups having two dimethylamino groups such as 1,2-bis(dimethylamino)ethane, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6 ,7-trimethyl-1,4-diazabicyclo[2.2.2]octane, etc. are mentioned.

Examples of the metal catalyst include tin compounds such as din-butyltin dilaurylate, din-butyltin diacetate, and tin octylate; zinc compounds such as zinc octylate and zinc naphthenate; zirconium tetraacetylacetonate; copper naphthenate; and other metal compounds such as cobalt naphthenate.

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

(coloring agent)

The optical moisture curable resin composition of the present invention may contain a coloring agent. Examples of the colorant include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Light-shielding property etc. become favorable by containing a coloring agent in an optical moisture hardening type resin composition. Among these, titanium black is preferable. Titanium black sufficiently blocks light of a wavelength in the visible light region and transmits light of a wavelength in the vicinity of the ultraviolet region, so that the photocurable property of the optical moisture curing type resin composition is prevented from deteriorating.

The content of the coloring agent in the optical moisture curable resin composition is preferably 0.05 parts by mass or more and 8 parts by mass or less, more preferably 100 parts by mass of the total amount of the radical polymerizable compound (A) and the moisture curable urethane resin (B) It is 0.1 mass part or more and 2 mass parts or less. Appropriate light-shielding property can be provided, maintaining the adhesiveness of an optical moisture hardening type resin composition favorably by content of a coloring agent being in these ranges.

The optical moisture curing type resin composition may contain other additives, such as a coupling agent, a wax particle, an ionic liquid, expanded particle|grains, expanded particle|grains, and a reactive diluent, in addition to the component mentioned above. Moreover, as a coupling agent, a silane coupling agent, a titanate type coupling agent, a zirconate type coupling agent, etc. are mentioned, Among these, a silane coupling agent is preferable.

The optical moisture curing type resin composition may be diluted with a solvent as needed. When the optical moisture-curable resin composition is diluted with a solvent, the mass part of the optical moisture-curable resin composition is a solid content standard, that is, it means a mass part excluding the solvent.

As a method for producing the optical moisture curable resin composition of the present invention, a radical polymerizable compound (A), a moisture curable resin (B), and a photopolymerization initiator (C) are further blended as necessary using a mixer, A method of mixing other additives, such as a filler, a moisture curing accelerator, and a colorant, etc. are mentioned. As a mixer, a homodisper, a homomixer, a universal mixer, a planetary mixer, a planetary stirring device, a kneader, a three roll etc. are mentioned, for example.

Moreover, as mentioned above, the molecular weight of moisture-curable resins, such as a moisture-curable urethane resin, may be increased by a chain extension agent. In that case, for example, a raw material resin such as a raw material urethane resin and a chain extension agent are reacted in advance to obtain a moisture-curable resin (B), and then, as described above, other raw materials such as a radical polymerizable compound (A) to be mixed with

In addition, by mixing raw resin, chain extension agent, and radical polymerizable compound (A), and heating the mixture as necessary, the chain extension agent is reacted with raw resin to synthesize moisture-curable resin (B) You can do it. In this case, since a mixture of the moisture curable resin (B) and the radical polymerizable compound (A) is obtained, a photopolymerization initiator (C) and other additives further blended as necessary are added to the mixture to form a light moisture curing type. A resin composition may be obtained.

<Using Method of 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 may first be photocured by light irradiation, for example, in a B-stage state (semi-cured state), and then cured by moisture to fully cure the composition. .

Here, the optical moisture-curable resin composition is placed between adherends, and when bonding the adherends, it is applied to one adherend, and then photocured by light irradiation, for example, in a B-stage state. Then, the other adherend is superimposed on the light moisture curable resin composition in a photocured state, and the adherends are temporarily bonded with appropriate adhesive strength (initial adhesive strength). Then, the moisture-curable urethane resin in the B-stage state is fully cured by curing the moisture-curable urethane resin with moisture, and through the optical moisture-curable resin composition, the overlapped adherends are bonded together with sufficient adhesive strength. .

Although application|coating of the optical moisture hardening type resin composition to an adherend may be performed, for example with a dispenser, it is not specifically limited. Although the light irradiated at the time of photocuring is not specifically limited as long as it is light which hardens a radically polymerizable compound, ultraviolet rays are preferable. Moreover, what is necessary is just to leave a predetermined time in air|atmosphere, when fully hardening an optical moisture-curable resin composition with moisture after photocuring.

The application of the optical moisture-curable resin composition to the adherend is not particularly limited, but may be performed at around room temperature, specifically, at a temperature of about 10 to 35°C. Since the optical moisture-curable resin composition of the present invention has a viscosity at 25° C. within the above-described predetermined range, it can be easily applied even when applied at around room temperature, and dripping does not occur.

In addition, since the optical moisture curable resin composition of the present invention develops initial adhesive strength of a certain value or more immediately after light irradiation, temporary bonding can be performed immediately after photocuring, resulting in good workability.

The optical moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic parts. That is, this invention also provides the adhesive agent for electronic parts which consists of the said light moisture curable resin composition.

Therefore, the adherend described above is preferably various electronic components constituting electronic equipment. As various electronic components constituting electronic devices, various electronic components provided in display elements, substrates on which electronic components are attached, semiconductor chips, and the like are exemplified.

Moreover, any of metal, glass, plastic, etc. may be sufficient as a material of an adherend. In addition, the shape of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod shape) shape, a box shape, a housing shape, and the like. .

As described above, the optical moisture-curable resin composition of the present invention is preferably used for bonding electronic parts constituting electronic devices. Moreover, the optical moisture curable resin composition of this invention is used also in order to bond an electronic component to another component preferably. With these configurations, the electronic component has the cured body of the present invention.

In addition, the optical moisture-curable resin composition of the present invention is used, for example, for bonding substrates to substrates to obtain assembled parts inside electronic devices and the like. The assembly component obtained in this way has a first substrate, a second substrate, and the 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. Also, the first substrate and the second substrate are preferably each equipped with at least one electronic component.

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 smart phones, an adhesive is applied on a base of a narrow square frame (ie, narrow frame), and the adhesive is applied to the display panel, Although a touch panel etc. are attached, what is necessary is just to use the optical moisture hardening type resin composition of this invention as the adhesive agent. Moreover, it is preferable to use the optical moisture hardening type resin composition of this invention for the use of a semiconductor chip. The optical moisture-curable resin composition of the present invention is used for bonding semiconductor chips to each other in the use of semiconductor chips, for example.

Example

Although the present invention will be described in more detail by examples, the present invention is not limited in any way by these examples.

Various physical properties were measured and evaluated 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 in terms of polystyrene. For the GPC measurement, Shodex KF-806L (manufactured by Showa Denko) was used as a column. Moreover, tetrahydrofuran (THF) was used as a solvent and a mobile phase. In addition, as the measurement conditions of GPC, the flow rate was 1.0 ml/min and the measurement temperature was 40°C.

In each Example and Comparative Example, the weight average molecular weight was measured using a mixture of a radically polymerizable compound and a moisture-curable resin (B) as a sample. In this mixture, the peak of the radical polymerizable compound 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) can be obtained from the peak on the high molecular weight side. there is.

(viscosity at 25°C)

The 25°C viscosity was measured under conditions of 5.0 rpm and 25°C using a cone plate viscometer (trade name: TVE-35, manufactured by Donggi Industry Co., Ltd.).

(Storage modulus (G') at 25°C and tanδ at 75°C)

As a dynamic viscoelasticity measuring device, a trade name "DVA-200" manufactured by Haiti Measurement & Control Co., Ltd. was used. As the viscoelasticity measurement jig, a shear test jig was used. A 0.6 mm × 6 mm × 9 mm optical moisture-curable resin composition was set on a viscoelasticity measurement jig, and 1000 mJ/cm ² of ultraviolet rays having a wavelength of 405 nm was irradiated, and the photocured sample was measured by the method described in the specification.

(Internal and external secret a/b)

The internal/external ratio a/b was measured by the method described in the specification. In addition, as an aluminum substrate and a glass plate, the aluminum alloy "A6063S" whose size is 2 mm x 25 mm x 60 mm, and the glass plate with the smooth surface which ultrasonically cleaned for 5 minutes were used, respectively. The application of the moisture-curable resin composition was performed at room temperature (25° C.) using a dispensing device, “SHOTMASTER300SX” manufactured by Musashi Engineering, in a straight line such that the width was 1.0±0.1 mm, the length was 25 mm, and the thickness was 0.4±0.1 mm. applied to an aluminum substrate. Next, about the applied optical moisture curable resin composition, 1000 mJ/cm ² of ultraviolet rays having a wavelength of 405 nm was irradiated with a line type LED irradiator (manufactured by HOYA Corporation, 1000 mW). The pressure bonding of the glass plate to the aluminum substrate was performed using a weight as a weight, and the widths a1 and b1 were measured 5 minutes after the weight was removed. The measurement of the widths a1 and b1 after crimping was performed by observing the crimped surface from the glass plate side using a microscope.

(initial adhesion)

As shown in Fig. 2 (a), (b), using the dispensing device described above, the optical moisture curing type resin is applied to the aluminum substrate 21 so that the width is 1.0 ± 0.1 mm, the length is 25 mm, and the thickness is 0.4 ± 0.1 mm. Composition 20 was applied at room temperature (25° C.). And it was photocured by irradiating 1000 mJ/cm< ² > of ultraviolet rays of wavelength 405nm with the line type LED irradiation machine (made by HOYA Corporation, 1000mW). Thereafter, the glass plate 22 was bonded to the aluminum substrate 21 via the photocured light moisture curing type resin composition 20, and pressure-bonded for 120 seconds at 0.08 MPa with respect to the applied area using weights to achieve adhesiveness. A sample (23) for evaluation was obtained.

Then, in an atmosphere of 25 ° C., pulling at a speed of 10 mm / min in the shear direction (S) using a tensile tester ("tensile compression tester SVZ-50NB" manufactured by Imada Manufacturing Co., Ltd.), the aluminum substrate 21 and the glass plate (22) The maximum stress at the time of peeling off was measured, and it was set as the initial adhesive force. In addition, it was carried out within 150 seconds from the end of photocuring to the start of the tensile test. The initial stage adhesive force was evaluated according to the following evaluation criteria.

A: 0.4 MPa or more

B: 0.25 MPa or more and less than 0.4 MPa

C: Less than 0.25 MPa

(final adhesion)

Similarly to the initial adhesive strength, the glass plate was bonded to the aluminum substrate through the photocured light moisture curable resin composition. Then, it was made to moisture cure by leaving it to stand at 25 degreeC and 50RH% for 24 hours, and the sample for adhesiveness evaluation was obtained. Using the sample for evaluating adhesiveness, the sample was pulled in the shear direction in the same way as the method for measuring initial adhesive force, and the maximum stress when the aluminum substrate and the glass plate were peeled off was measured and set as the final adhesive force.

A: 3.5 MPa or more

B: 2.0 MPa or more and less than 3.5 MPa

C: Less than 2.0 MPa

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)

As a polyol compound, 100 parts by mass of polycarbonate diol (compound represented by formula (1), 90 mol% of R is a 3-methylpentylene group, 10 mol% is a hexamethylene group, manufactured by Kuraray, trade name "Kuraraypolyol C-1090" ) and 0.01 parts by mass of dibutyltin dilaurate were placed in a 500 mL separable flask. The inside of the flask was stirred and mixed at 100°C for 30 minutes under vacuum (20 mmHg or less). After that, under normal pressure, 50 parts by mass of diphenylmethane diisocyanate (trade name "Pure MDI" manufactured by Nisso Corporation) was added as a polyisocyanate compound, stirred at 80 ° C. for 3 hours to react, and had a polycarbonate skeleton, and both ends A moisture-curable urethane resin (PC urethane resin raw material) having an isocyanate group 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, trade name "PTMG-3000") and 0.01 part by mass of dibutyltin dilaurate were placed in a separable flask having 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). Thereafter, under normal pressure, 17.5 parts by mass of diphenylmethane diisocyanate (trade name "Pure MDI", manufactured by Nisso Corporation) was added as a polyisocyanate compound, stirred at 80°C for 3 hours to react, and had a polyether skeleton at both ends. A moisture-curable urethane resin (ET urethane resin raw material) having an isocyanate group was obtained. The weight average molecular weight of the obtained urethane resin raw material was 3500.

[Example 1]

As shown in Table 5, each raw material constituting 60 parts by mass of moisture-curable resin (PC-L25) was added to 40 parts by mass of acrylic A. Acrylic A was obtained by mixing each compound in the compounding ratio shown in Table 2. As the moisture-curable resin (PC-L25), PC urethane resin raw material and PC polyol were sequentially added to acrylic A 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 an isocyanate group remaining, and acrylic A (radical polymerizable compound) and moisture-curable urethane A mixture of resins was obtained.

A photopolymerization initiator and a filler were added to the mixture of the obtained acrylic A and moisture-curable urethane resin according to the formulation in Table 5 and further mixed to obtain an optical moisture-curable resin composition. About the obtained light moisture curing type resin composition, the 25 degreeC viscosity, the storage elastic modulus (G') at 25 degreeC, and tan-delta at 75 degreeC, internal/external ratio a/b, initial adhesive force, and final adhesive force were measured.

[Examples 2 to 4, 7, 8, Comparative Examples 1 and 2]

Except for the fact that acrylic B was used instead of acrylic A, and that moisture-curable resins as shown in Tables 3, 4, and 5 were used instead of moisture-curable resins (PC-L25) as moisture-curable resins. It was carried out in the same way as in Example 1.

That is, acrylic B is used instead of acrylic A, and the mixing ratio and type of the urethane resin raw material and the polyol added to the acrylic B are changed as shown in Tables 3 and 4, and the acrylic B and the moisture-curable urethane resin Except for obtaining a mixture, it was carried out in the same manner as in Example 1. In addition, as the ET polyol in Table 4, the polytetramethylene ether glycol used in Synthesis Example 2 was used. In Comparative Example 1, since only the urethane resin raw material was added to acrylic A and no polyol was added, the urethane resin raw material was used as a moisture curable resin as it was.

[Examples 5, 9 to 11, Comparative Examples 3 to 5]

Instead of acrylic A, it was carried out in the same manner as in Example 1 except that acrylics B to H were used. In addition, each of acrylics B-H was what mixed each compound by the compounding ratio of Table 2.

[Example 6]

A photopolymerization initiator, a filler, and a colorant were added to and mixed with the obtained mixture of acrylic B and moisture-curable urethane resin according to the formulation in Table 5, and the light moisture-curable resin composition was obtained. It was carried out in the same manner as in Example 5. .

Components other than the moisture-curable urethane resin (B) used in each Example and Comparative Example were as showing in Table 1 below.

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

Moisture-curable resins (B) used in Examples and Comparative Examples were as shown in Table 3 below. As described above, in the moisture-curable resin (L0), the urethane resin raw material is used as it is as the moisture-curable resin (B), and other than that, the reaction product of the following urethane resin raw material and polyol is used as the moisture-curable resin (B) used

The optical moisture-curable resin compositions of Examples 1 to 11 contain a radical polymerizable compound (A), a moisture-curable resin (B), and a photopolymerization initiator (C), and have a storage modulus (G') at 25°C. And when tan δ at 75°C was equal to or greater than a predetermined value, the initial adhesive force was excellent. In contrast, in Comparative Examples 1 to 5, since at least either of the storage modulus (G') at 25°C and tanδ at 75°C was less than a predetermined value, the initial adhesive strength could not be improved.

Claims (10)

A radical polymerizable compound (A), a moisture curable resin (B), and a photopolymerization initiator (C) are included,
The storage modulus (G') at 25°C is 250 kPa or more and the tanδ at 75°C is 1.0 or more when measured at 1 Hz with a dynamic viscoelasticity measuring device in a state of photocuring by irradiation with 1000 mJ/cm ² ultraviolet rays. , Light moisture curable resin composition. The method of claim 1,
In the case where the glass plate is applied to an aluminum substrate with a line width of 1.0 mm and photocured by irradiation with ultraviolet rays of 1000 mJ/cm ² , and the glass plate is pressed at 0.08 MPa for 120 seconds, the average width of the adhesive portion on the glass plate side is a, aluminum When b is the average width of the bonded portion on the substrate side, a/b is 0.58 or more and 0.99 or less, the optical moisture curing type resin composition. According to claim 1 or claim 2,
The optical moisture-curable resin composition in which the said moisture-curable resin (B) contains a moisture-curable urethane resin. The method according to any one of claims 1 to 3,
The light moisture curable resin composition whose weight average molecular weight of the said moisture curable resin (B) is 7500 or more and 24000 or less. The method according to any one of claims 1 to 4,
The optical moisture-curable resin composition in which the radically polymerizable compound (A) contains a monofunctional radically polymerizable compound. The method of claim 5,
A light moisture curing type resin composition containing 90 parts by mass or more of a monofunctional radically polymerizable compound with respect to 100 parts by mass of radically polymerizable compound (A). The method according to any one of claims 1 to 6,
The light moisture curing type resin composition which further contains a filler (D). The adhesive for electronic parts which consists of the optical moisture hardening type resin composition in any one of Claims 1-7. The hardened|cured material of the optical moisture hardening type resin composition in any one of Claims 1-8. An electronic component comprising the cured body according to claim 9.

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