KR20210052344A - Curable composition - Google Patents

Abstract

The present invention aims to provide a curable composition which has excellent photocurable properties and excellent thermosetting properties, has a low viscosity, and has a small cure shrinkage rate. The curable composition comprises the following components (1) to (4): (1) a compound having a (meth)acryloyl group; (2) a polythiol compound having two or more mercapto groups in one molecule; (3) a photo-radical generator; and (4) a latent curing agent, wherein the component (1) contains a component (1-1) which is a compound having a poly(oxyalkylene) chain and having a (meth)acryloyl group equivalent of 300 or more.

Description

Curable composition {CURABLE COMPOSITION}

The present invention relates to a curable composition.

BACKGROUND ART In recent years, as portable devices such as smart phones have become more functional, camera modules mounted on portable devices such as smart phones have become high pixels. Further, with the miniaturization and high functionality of the camera module, for example, the positional accuracy of the lens and the image sensor is becoming very important.

On the other hand, the adhesive used for assembling the camera module requires low temperature curing properties to avoid thermal damage due to high temperature treatment on the image sensor, etc., and also, from the viewpoint of improving production efficiency, the ability to cure at low temperatures and in a short time. (Low temperature-short time curing property) is also required at the same time. From this point of view, as a low-temperature-low-temperature short-time curable adhesive, ultraviolet-curable adhesives and thermosetting epoxy resin-based adhesives are widely used (for example, Patent Documents 1 and 2). However, while the ultraviolet curable adhesive is capable of rapid curing, curing shrinkage is large, and the position of the part is displaced after curing. On the other hand, thermosetting epoxy resin-based adhesives, even if they are low-temperature-short-time curing adhesives, need to be fixed with a jig or device to maintain the bonding posture during bonding, and the viscosity decreases due to temperature increase due to heating. As a result, there is a possibility that the position of the parts may be displaced, and this was not necessarily satisfactory.

Therefore, in order to solve the above problems, in order to arrange each component constituting the camera module with high precision, it is temporarily fixed by curing (pre-curing) by irradiation of light (ultraviolet rays, visible light), and the effect of heat (main curing). As a result, several types of adhesives that adhere (fix) are proposed (for example, Patent Documents 3 and 4).

Japanese Unexamined Patent Application Publication No. 2004-140497 Japanese Unexamined Patent Application Publication No. 2013-88525 Japanese Unexamined Patent Application Publication No. 2009-51954 Japanese Unexamined Patent Application Publication No. 2009-79216

Even when a light and thermosetting adhesive as described in Patent Documents 3 and 4 is used, when the curing shrinkage of the adhesive is large, there has been a problem that the position of the part due to shrinkage is displaced. In addition, when the viscosity of the adhesive is high, the workability (ease of application, etc.) of the adhesive decreases.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition having both excellent photocurability and excellent thermosetting property, low viscosity, and low cure shrinkage.

The present invention capable of achieving the above object is as follows.

[1] The following components (1) to (4):

(1) a compound having a (meth)acryloyl group,

(2) a polythiol compound having two or more mercapto groups in one molecule,

(3) a photo radical generator, and

(4) Latent hardener

As a curable composition comprising a,

Component (1) is the following component (1-1):

(1-1) A compound having a poly(oxyalkylene) chain and a (meth)acryloyl group, and having a (meth)acryloyl group equivalent of 300 or more

Containing, curable composition.

[2] The curable composition according to [1], wherein the poly(oxyalkylene) chain contains at least one selected from the group consisting of an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit.

[3] The curable composition according to [1] or [2], wherein the amount of the component (1-1) is 15 to 100 parts by weight per 100 parts by weight of the component (1).

[4] The curable composition according to any one of [1] to [3], wherein the component (2) contains a polythiol compound having 2 to 6 mercapto groups in one molecule.

[5] The sum of the acryloyl groups and methacryloyl groups in the component (1) and the molar ratio of the mercapto groups in the component (2) (the sum of the acryloyl groups and methacryloyl groups in the component (1) / component (2) The curable composition according to any one of [1] to [4], wherein the mercapto group) in) is 0.5 to 2.0.

[6] The curable composition according to any one of [1] to [5], wherein the component (4) contains an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound.

[7] An adhesive containing the curable composition according to any one of [1] to [6].

[8] The adhesive according to [7], for bonding between constituent parts of a camera module.

[9] A sealing agent containing the curable composition according to any one of [1] to [6].

[10] A coating agent containing the curable composition according to any one of [1] to [6].

[11] The following steps (I) to (III):

(I) a step of positioning the first adhesive component and the second adhesive component to which the curable composition according to any one of [1] to [6] has been applied,

(II) a step of curing the curable composition by light irradiation to temporarily fix the first adhesive component and the second adhesive component, and

(III) Step of curing the curable composition by heating to fix the first adhesive component and the second adhesive component

Containing, a method of manufacturing a camera module.

Advantageous Effects of Invention According to the present invention, it is possible to obtain a curable composition having both excellent photocurability and excellent thermosetting properties, low viscosity, and small cure shrinkage.

<curable composition>

The curable composition of the present invention includes the following components (1) to (4):

(1) a compound having a (meth)acryloyl group,

(2) a polythiol compound having two or more mercapto groups in one molecule (hereinafter sometimes abbreviated as a ``polythiol compound''),

(3) a photo radical generator, and

(4) It contains a latent hardener.

In the present invention, component (1) is the following component (1-1):

(1-1) It is characterized by containing a compound having a poly(oxyalkylene) chain and a (meth)acryloyl group, and having an equivalent weight of a (meth)acryloyl group of 300 or more. By using the component (1-1), it is possible to obtain a curable composition having both excellent photocurability and excellent thermosetting properties and a small cure shrinkage rate.

The curable composition of the present invention has a feature of low viscosity. The viscosity of the curable composition of the present invention is preferably less than 10 Pa·s, more preferably less than 8 Pa·s from the viewpoint of workability. There is no particular limitation on the lower limit of the viscosity of the curable composition of the present invention, but this viscosity is preferably 0.05 Pa·s or more, and more preferably 0.1 Pa·s or more. In addition, the viscosity of the curable composition is a value measured using an E-type viscometer under the conditions of temperature: 25°C, rotation speed: 20 rpm, and rotor: 3°×R9.7.

All of the components (1) to (4) and the component (1-1) may be used alone or in combination of two or more. When the curable composition of the present invention contains components other than components (1) to (4) and component (1-1), the above components may also be used alone or in combination of two or more. Hereinafter, each component will be described in order.

<(1) a compound having a (meth)acryloyl group>

In the present invention, the compound having a (meth)acryloyl group used as the component (1) mainly plays a role of increasing the adhesive strength. In addition, in this invention, the "(meth)acryloyl group" means one or both of an acryloyl group and a methacryloyl group.

Component (1) is a compound having a poly(oxyalkylene) chain and having a (meth)acryloyl group equivalent of 300 or more (hereinafter, a component which may be abbreviated as ``POA-(meth)acryloyl compound'') (1-1)). In the present invention, "poly(oxyalkylene) chain" means _{a chemical structure represented by the formula: -(OR) n-} (wherein R represents an alkylene group and n represents a number of 2 or more). . The alkylene group in the poly(oxyalkylene) chain may be linear or branched. Further, the number of oxyalkylene units represented by the formula: -(OR)-, n, may be a small number. In addition, a compound having only an oxyalkylene unit in which n is 1 and not a poly(oxyalkylene) chain (for example, ethylene glycol di(meth)acrylate) is a POA-(meth)acryloyl compound. not included.

The (meth)acryloyl group equivalent of a POA-(meth)acryloyl compound means a value obtained by dividing the weight average molecular weight of the compound by the number of (meth)acryloyl groups in one molecule of the compound ((meth) Acryloyl group equivalent = weight average molecular weight/1 number of (meth)acryloyl groups in a molecule).

Since the POA-(meth)acryloyl compound is a compound having a poly(oxyalkylene) chain composed of an oxyalkylene unit, the weight average molecular weight is used as the molecular weight for calculating the (meth)acryloyl group equivalent thereof. use. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. Specifically, LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Corporation as a column, and chloroform as a mobile phase And the like, and the weight average molecular weight can be calculated using a calibration curve of standard polystyrene.

The weight average molecular weight of the POA-(meth)acryloyl compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably from the viewpoint of curability, viscosity and cure shrinkage of the curable composition. It is preferably 4,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.

When the POA-(meth)acryloyl compound is a mixture, the number of (meth)acryloyl groups in one molecule of the compound represents an average value per molecule. In addition, when both acryloyl groups and methacryloyl groups are present in one molecule of the compound, the number means the total number of acryloyl groups and methacryloyl groups in one molecule.

The number of (meth)acryloyl groups in one molecule of the POA-(meth)acryloyl compound can be calculated by, for example, a weight average molecular weight and an iodine value measured by a method specified in JIS K0070.

The number of (meth)acryloyl groups in one molecule of the POA-(meth)acryloyl compound is from the viewpoint of curability, viscosity and cure shrinkage of the curable composition, preferably 1 to 6, more preferably 2 to 5 , More preferably 2 to 4.

The (meth)acryloyl group equivalent of the POA-(meth)acryloyl compound needs to be 300 or more. The (meth)acryloyl group equivalent is preferably 320 or more, more preferably 350 or more from the viewpoint of curability, viscosity, and cure shrinkage of the curable composition. On the other hand, from the viewpoint of curability and viscosity, the (meth)acryloyl group equivalent is preferably 1,000 or less, more preferably 800 or less.

The poly(oxyalkylene) chain of the POA-(meth)acryloyl compound preferably contains at least one selected from the group consisting of an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit, and more preferably , At least one selected from the group consisting of an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Here, the oxypropylene unit may be a straight chain (i.e., -O-(CH ₂ ) ₃ -) or a branched chain (eg -O-CH ₂ -CH(CH ₃ )-). In addition, the oxybutylene unit may be a straight chain (ie, -O-(CH ₂ ) ₄ -) or a branched chain (eg, -O-CH ₂ -CH(CH ₂ CH ₃ )-).

Examples of the POA-(meth)acryloyl compound include the following compounds. In addition, all of the following compounds may be used alone or in combination of two or more.

(POA-(meth)acryloyl compound having one acryloyl group or methacryloyl group in one molecule)

Methoxy polyethylene glycol (meth)acrylate

Methoxypolypropylene glycol (meth)acrylate

Methoxypolytetramethylene glycol (meth)acrylate

Phenoxy polyethylene glycol (meth)acrylate

Nonylphenoxy polyethylene glycol (meth)acrylate

In addition, in this invention, "(meth)acrylate" means one or both of an acrylate and a methacrylate.

(POA-(meth)acryloyl compound having two (meth)acryloyl groups in one molecule)

Polyethylene glycol di(meth)acrylate

Polypropylene glycol di(meth)acrylate

Polytetramethylene glycol di(meth)acrylate

EO modified bisphenol A di(meth)acrylate

PO modified bisphenol A di(meth)acrylate

EO modified bisphenol F di(meth)acrylate

PO modified bisphenol F di(meth)acrylate

In addition, in this invention, "EO modification" means what was modified by addition of ethylene oxide (EO). In addition, "PO modification" means a thing modified by addition of propylene oxide (PO).

(Compound having three or more (meth)acryloyl groups in one molecule)

Ethoxylated pentaerythritol tetra(meth)acrylate

Here, the ethoxylated pentaerythritol tetra(meth)acrylate means a compound having a structure obtained by ester bonding between pentaerythritol having a poly(oxyethylene) chain and four (meth)acrylates.

Component (1-1) is preferably polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylic It contains at least one selected from the group consisting of a rate, and more preferably, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and ethoxylated It is at least one selected from the group consisting of pentaerythritol tetra(meth)acrylate.

The amount of component (1-1) is, from the viewpoint of curability, viscosity and cure shrinkage of the curable composition, per 100 parts by weight of component (1), preferably 15 to 100 parts by weight, more preferably 19.5 to 100 parts by weight, further It is preferably 19.5 to 99.5 parts by weight.

Next, a compound having a (meth)acryloyl group other than the POA-(meth)acryloyl compound (hereinafter sometimes abbreviated as "(meth)acryloyl compound") will be described. The number of (meth)acryloyl groups in one molecule of the (meth)acryloyl compound may be 1 or more. When the (meth)acryloyl compound is a mixture, the number represents an average value per molecule. In addition, when both acryloyl groups and methacryloyl groups are present in one molecule, the number means the total number of acryloyl groups and methacryloyl groups in one molecule. The number of (meth)acryloyl groups in one molecule of the (meth)acryloyl compound (however, excluding phosphoric acid-modified (meth)acrylate described later) is preferably 1 to 6, more preferably 2 to 6, more preferably 2 to 4.

The molecular weight of the (meth)acryloyl compound (however, excluding phosphoric acid-modified (meth)acrylate described later) is preferably 50 to 5,000, more preferably 70 to 4,000, and even more preferably 100 to 2,000. . When this molecular weight is less than 50, the volatility is high, and it is not preferable in terms of odor and handling properties, and when the molecular weight exceeds 5,000, the viscosity of the composition increases, and the coating property of the composition tends to decrease. In addition, a molecular weight of 1,000 or more means a weight average molecular weight, and can be measured by gel permeation chromatography (GPC). Molecular weights of less than 1,000 can be measured with a gravimetric apparatus (eg ESI-MS).

As a (meth)acryloyl compound, the following compounds are mentioned, for example. In addition, all of the following compounds may be used alone or in combination of two or more.

((Meth)acryloyl compound having one acryloyl group or methacryloyl group per molecule)

β-carboxyethyl (meth)acrylate

Isobornyl (meth)acrylate

Octyl/decyl(meth)acrylate

Ethoxylated phenyl (meth)acrylate

N-(meth)acryloyloxyethylhexahydrophthalimide

ω-carboxy-polycaprolactone mono (meth)acrylate

Monohydroxyethyl phthalate (meth)acrylate

2-hydroxy-3-phenoxypropyl (meth)acrylate

((Meth)acryloyl compound having two (meth)acryloyl groups in one molecule)

1,6-hexanediol di(meth)acrylate

Ethylene glycol di(meth)acrylate

Propylene glycol di(meth)acrylate

Tetramethylene glycol di(meth)acrylate

Tricyclodecanedimethanol di(meth)acrylate

Neopentyl glycol hydroxypivalic acid ester di(meth)acrylate

Polyurethane having two (meth)acryloyl groups in one molecule

Polyester having two (meth)acryloyl groups in one molecule

Bisphenol A type epoxy (meth)acrylate

Caprolactone modified epoxy (meth)acrylate

Here, caprolactone-modified epoxy (meth)acrylate having two (meth)acryloyl groups in one molecule (in this specification, it may be abbreviated as ``caprolactone-modified epoxy (meth)acrylate'') means ( It means a compound which can be produced by reacting meth)acrylic acid with ε-caprolactone to prepare a carboxylic acid compound, and then reacting this carboxylic acid compound with a bifunctional epoxy compound.

((Meth)acryloyl compound having 3 or more (meth)acryloyl groups in one molecule)

Trimethylolpropane tri(meth)acrylate

Pentaerythritol (tri/tetra) (meth)acrylate

Glycerin propoxytri(meth)acrylate

Ditrimethylolpropane tetra(meth)acrylate

Dipentaerythritol (penta/hexa) (meth)acrylate

Dipentaerythritol hexa(meth)acrylate

Polyurethane having 3 or more (meth)acryloyl groups in one molecule

Polyester having 3 or more (meth)acryloyl groups in one molecule

Pentaerythritol (tri/tetra)(meth)acrylate is a mixture of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate. This mixing ratio (pentaerythritol tri(meth)acrylate/pentaerythritol tetra(meth)acrylate) is a weight ratio, preferably 5/95 to 95/5, more preferably 30/70 to 70/30.

Dipentaerythritol (penta/hexa) (meth)acrylate is a mixture of dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa(meth)acrylate. This mixing ratio (dipentaerythritol penta(meth)acrylate/dipentaerythritol hexa(meth)acrylate) is by weight, preferably 5/95 to 95/5, more preferably 30/70 to 70/30 to be.

Among the (meth)acryloyl compounds, tricyclodecanedimethanol di(meth)acrylate, bisphenol A type epoxy (meth)acrylate, caprolactone-modified epoxy (meth)acrylate, and dipentaerythritol hexa(meth)acrylic Rate is preferable, and bisphenol A type epoxy (meth)acrylate is more preferable.

From the viewpoint of storage stability, component (1) preferably contains a phosphoric acid-modified (meth)acrylate. Here, "phosphoric acid modification" means a thing modified by an ester bond with phosphoric acid. Phosphoric acid-modified (meth)acrylate may be used alone or in combination of two or more. The phosphoric acid-modified (meth)acrylate is preferably a phosphoric acid-modified methacrylate.

The phosphoric acid-modified (meth)acrylate can be produced, for example, by the following method (i), but the present invention is not limited thereto.

(i) A method of reacting a compound having a (meth)acryloyl group and a hydroxy group with phosphoric acid.

A compound having a (meth)acryloyl group and a hydroxy group in one molecule that can be used in the method (i) can be prepared, for example, by the following method (ii) or (iii), but the present invention It is not limited to these.

(ii) A method of reacting (meth)acrylic acid or (meth)acrylate with a polyhydric alcohol (eg, alkylene glycol, glycerin, etc.) in an amount ratio in which the hydroxy group of the polyhydric alcohol remains.

(iii) A method of adding an alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) to (meth)acrylic acid.

As for the phosphoric acid-modified (meth)acrylate, you may use a commercial item. Examples of commercially available products include "EBECRYL168" manufactured by Allnex Corporation, "KAYAMER PM-2" manufactured by Nippon Kayaku Corporation, "KAYAMER PM-21", manufactured by Kyoeisha Kagaku Corporation. "Light ester P-1M", "Light ester P-2M", "Light acrylate P-1A(N)", and "JPA-514" manufactured by Johoku Chemical Co., Ltd. are mentioned.

The number of (meth)acryloyl groups in one molecule of the phosphoric acid-modified (meth)acrylate is preferably 0.5 to 3, more preferably 1 to 2, and still more preferably 1 to 1.5. In addition, when phosphoric acid-modified (meth)acrylate is a mixture, the number represents an average value per molecule.

The molecular weight of the phosphoric acid-modified (meth)acrylate is preferably 100 to 1,000, more preferably 150 to 800, and still more preferably 200 to 600.

When using a phosphoric acid-modified (meth)acrylate, from the viewpoint of storage stability, the amount thereof is per 100 parts by weight of component (1), preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, even more preferably It is 0.05 to 2 parts by weight.

Component (1) preferably contains a compound having two or more (meth)acryloyl groups in one molecule from the viewpoint of curability of the curable composition. As the compound having two or more (meth)acryloyl groups in one molecule, the POA-(meth)acryloyl compound may be used, or other (that is, the (meth)acryloyl compound) may be used. When using a compound having two or more (meth)acryloyl groups in one molecule, from the viewpoint of curability of the curable composition, the amount thereof is per 100 parts by weight of component (1), preferably 10 to 100 parts by weight, more preferably It is preferably 20 to 100 parts by weight, more preferably 30 to 99.5 parts by weight.

In one aspect of the present invention, component (1) preferably contains component (1-1) and phosphoric acid-modified (meth)acrylate, and more preferably, component (1-1) and phosphoric acid-modified ( It is a mixture of meth)acrylates. In this aspect, the component (1-1) is preferably polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol. Contains at least one selected from the group consisting of tetra (meth) acrylate, more preferably polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) It is at least one selected from the group consisting of acrylate and ethoxylated pentaerythritol tetra(meth)acrylate.

In another aspect of the present invention, component (1) is preferably tricyclodecane dimethanol di (meth) acrylate, bisphenol A type epoxy (meth) acrylate, caprolactone modified epoxy (meth) acrylate and At least one selected from the group consisting of dipentaerythritol hexa(meth)acrylate, component (1-1), and phosphoric acid-modified (meth)acrylate, more preferably tricyclodecanedimethanol di( At least one selected from the group consisting of meth)acrylate, bisphenol A type epoxy (meth)acrylate, caprolactone-modified epoxy (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and component (1-1) And, it is a mixture of phosphoric acid-modified (meth)acrylate. In this aspect, the component (1-1) is preferably polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol. Contains at least one selected from the group consisting of tetra (meth) acrylate, more preferably polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) It is at least one selected from the group consisting of acrylate and ethoxylated pentaerythritol tetra(meth)acrylate.

In another aspect of the present invention, component (1) preferably contains component (1-1), bisphenol A type epoxy (meth)acrylate, and phosphoric acid-modified (meth)acrylate, more preferably Specifically, it is a mixture of component (1-1), bisphenol A type epoxy (meth)acrylate, and phosphoric acid-modified (meth)acrylate. In this aspect, the component (1-1) is preferably polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol. Contains at least one selected from the group consisting of tetra (meth) acrylate, more preferably polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) It is at least one selected from the group consisting of acrylate and ethoxylated pentaerythritol tetra(meth)acrylate.

From the viewpoint of curability, viscosity and cure shrinkage of the curable composition, the amount of component (1) per the total curable composition is preferably 10% by weight or more, more preferably 15% by weight or more, even more preferably 20% by weight or more. And, preferably 80% by weight or less, more preferably 75% by weight or less, and still more preferably 70% by weight or less.

<(2) Polythiol compound>

In the present invention, the "polythiol compound having two or more mercapto groups in one molecule" used as component (2) in the present invention acts as a curing agent to cure the composition by reacting with component (1) mainly by irradiation with light such as ultraviolet rays. In charge of The number of mercapto groups in one molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, and particularly preferably 3 or 4.

As the polythiol compound, a commercially available product may be used, or a product manufactured by a known method (for example, the method described in Japanese Unexamined Patent Publication No. 2012-153794 or International Publication No. 2001/00698) may be used.

Examples of the polythiol compound include partial esters of polyols and mercapto organic acids, and complete esters of polyols and mercapto organic acids. Here, partial ester means that a part of the hydroxy group of a polyol forms an ester bond as an ester of a polyol and a carboxylic acid, and complete ester means that all the hydroxy groups of a polyol form an ester bond.

Examples of the polyol include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

Examples of mercapto organic acids include mercapto aliphatic monos such as mercaptoacetic acid, mercaptopropionic acid (eg 3-mercaptopropionic acid), and mercaptobutyric acid (eg 3-mercaptobutyric acid, 4-mercaptobutyric acid). Carboxylic acid; Esters containing a mercapto group and a carboxy group obtained by esterification of a hydroxy acid and a mercapto organic acid; Mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (eg 2,3-dimercaptosuccinic acid); And mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid). The number of carbon atoms of the mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among the mercapto organic acids, a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is preferable, and mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferable, and 3-mer Captopropionic acid is more preferred.

Specific examples of partial esters of polyols and mercapto organic acids include trimethylolethane bis (mercaptoacetate), trimethylolethane bis (3-mercaptopropionate), trimethylolethane bis (3-mercaptobutyrate), and trimethyl Olethane bis(4-mercaptobutylate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutylate), trimethyl Allpropane bis (4-mercaptobutyrate), pentaerythritol tris (mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tris ( 4-mercaptobutylate), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipenta And erythritol tetrakis (4-mercaptobutylate).

Specific examples of the complete ester of a polyol and a mercapto organic acid include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptobutylate), and ethylene glycol bis ( 4-mercaptobutylate), trimethylolethane tris (mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolethane tris ( 4-mercaptobutylate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris ( 4-mercaptobutylate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis ( 4-mercaptobutylate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), dipenta Erythritol hexakis (4-mercaptobutyrate), etc. are mentioned.

From the viewpoint of storage stability, the partial ester and the complete ester preferably have as little as possible the amount of basic impurities, and more preferably do not require the use of a basic substance for production.

Further, as the component (2), an alkane polythiol compound such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; Terminal mercapto group-containing polyether; Terminal mercapto group-containing polythioether; A polythiol compound obtained by reaction of an epoxy compound and hydrogen sulfide; A polythiol compound prepared using a basic substance may also be used as a reaction catalyst in the production process, such as a polythiol compound having a terminal mercapto group obtained by reaction of a polythiol compound with an epoxy compound. It is preferable to use the polythiol compound produced by using a basic substance after subjecting the alkali metal ion to an alkali metal ion concentration of 50 ppm by weight or less.

Dealkali treatment of a polythiol compound prepared using a basic substance includes, for example, dissolving a polythiol compound in an organic solvent such as acetone and methanol, neutralizing it by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then extracting A method of desalting by washing or the like; Adsorption method using an ion exchange resin; Although a method of purifying by distillation may be mentioned, it is not limited to these.

In addition, as component (2), for example, tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1, 3,5-triazine-2,4,6(1H,3H,5H)-trione, tris(3-mercaptopropyl)isocyanurate, bis(3-mercaptopropyl)isocyanurate, 1 ,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 4,4'-isopropylidenediphenyl bis(3-mercaptopropyl) ether, and the like can be used.

Component (2) is preferably a polythiol compound having 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, particularly preferably 3 or 4 mercapto groups per molecule. Includes.

In one aspect of the present invention, the component (2) is preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) and tris (3-mercapto). Propyl) contains at least one selected from the group consisting of isocyanurate, more preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) and It is at least one selected from the group consisting of tris(3-mercaptopropyl)isocyanurate.

In another aspect of the present invention, the component (2) is preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) or tris (3-mer). Captopropyl) isocyanurate, more preferably, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutylate) or tris (3-mercaptopropyl) ) Isocyanurate, more preferably pentaerythritol tetrakis (3-mercaptopropionate).

From the viewpoint of curability, the sum of the acryloyl groups and methacryloyl groups in the component (1) and the molar ratio of the mercapto groups in the component (2) (the sum of the acryloyl groups and methacryloyl groups in the component (1) / component The mercapto group in (2)) is preferably 0.5 to 2.0, more preferably 0.6 to 1.6, still more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3.

From the viewpoint of curability, viscosity and cure shrinkage of the curable composition, the amount of component (2) per the total curable composition, preferably 10% by weight or more, more preferably 15% by weight or more, even more preferably 20% by weight or more , Preferably 50% by weight or less, more preferably 45% by weight or less, and still more preferably 40% by weight or less.

<(3) Photo radical generator>

There is no particular limitation on the photo radical generator used as the component (3) in the present invention. Examples of the photo-radical generator include an alkylphenone-based photo-radical generator, an acylphosphine oxide-based photo-radical generator, an oxime ester-based photo-radical generator, and an α-hydroxyketone-based photo-radical generator. have. The photo radical generator is preferably an alkylphenone-based photo radical generator.

Examples of the alkylphenone-based photo radical generator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethyl Thioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzo Phenone, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy Oligomers of 2-methyl-1-propan-1-one and 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, etc. are mentioned.

Examples of the acylphosphine oxide-based photo radical generator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, etc. Can be lifted.

Examples of the oxime ester photo radical generator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[6-(2-methylbenzoyl) )-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyloxime, and the like.

Examples of the α-hydroxyketone-based photo radical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexylphenyl ketone, and 1-phenyl-2-hydroxy-2-methyl Propan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned.

As commercially available products of the photo radical generator, for example, BASF's "Irgacure 1173" (2-hydroxy-2-methyl-1-phenylpropan-1-one), "Irgacure OXE01" (1-[4-( Phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime)), "Irgacure OXE02" (1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3- Yl]ethanone O-acetyloxime), "Esacure KTO 46" manufactured by IGM Resins BV (2,4,6-trimethylbenzoyldiphenylphosphine oxide and oligo[2-hydroxy-2-methyl1-[4-) (1-methylvinyl)phenyl]propane] and a mixture of methylbenzophenone derivatives), "Esacure KIP 150" (2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one) Oligomer) and the like.

The amount of component (3) is, from the viewpoint of obtaining a curable composition that can be efficiently photocured upon irradiation with light, per the total curable composition, preferably 0.001% by weight or more, more preferably 0.01% by weight or more, even more preferably It is 0.1% by weight or more. On the other hand, from the viewpoint of suppressing outgassing due to the photoradical generator remaining in the cured product or its decomposition product, per the total curable composition, 10% by weight or less is preferable, more preferably 5% by weight or less, even more preferably It is 2% by weight or less.

<(4) Latent curing agent>

In the present invention, the latent curing agent used as the component (4) is a well-known additive in the field of epoxy resins, etc., and does not cure the epoxy resin at room temperature (25°C), but the epoxy resin can be cured by heating. It means an additive that is present. In the present invention, the latent curing agent serves to accelerate the reaction of component (1) (a compound having a (meth)acryloyl group) and component (2) (a polythiol compound having two or more mercapto groups in one molecule). In charge of

Examples of the latent curing agent include imidazole compounds that are solid at room temperature, amine-epoxy adduct compounds (reaction products of amine compounds and epoxy compounds), amine-isocyanate adduct compounds (reaction of amine compounds and isocyanate compounds). Product) and the like.

Examples of imidazole compounds that are solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 2-phenyl-4 -Methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imida Zolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine/iso Cyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-methylimidazole-trimelitate, 1-cyanoethyl-2-phenylimidazole-trimelitate, N-(2-methylimidazolyl-1-ethyl)-urea, and the like.

Examples of the epoxy compound used as the raw material of the amine-epoxy adduct-based compound include polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin or polyethylene glycol, and epichlorohydrin. Polyglycidyl ether obtained by reacting; glycidyl ether ester obtained by reacting epichlorohydrin with hydroxy acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; Polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; A glycidylamine compound obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; In addition, polyfunctional epoxy compounds such as epoxidized phenol novolak resin, epoxidized cresol novolak resin, and epoxidized polyolefin, monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate, etc. Can be mentioned.

As the amine compound used as a raw material for the amine-epoxy adduct-based compound or the amine-isocyanate adduct-based compound, an active hydrogen atom capable of addition reaction with an epoxy group or an isocyanate group (another name: isocyanato group) is 1 per molecule. It is good to have at least one amino group (at least one of a primary amino group, a secondary amino group, and a tertiary amino group) in one molecule. Examples of such amine compounds include aliphatic compounds such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane. Amine compounds; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; And heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. have.

In addition, when a compound having a tertiary amino group is used, an excellent latent curing agent can be prepared. As a compound having a tertiary amino group, for example, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpipe Amines having a tertiary amino group such as ragine, 2-methylimidazole, 2-ethylimidal, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-( 2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2- Hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy -3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4, 6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2-mer Captobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethyl Alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group such as propionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

When an epoxy compound and an amine compound are subjected to an addition reaction to prepare an amine-epoxy adduct-based compound, an active hydrogen compound having two or more active hydrogens per molecule may be further added. Examples of such active hydrogen compounds include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolak resin, and polyhydric alcohols such as trimethylolpropane, Polyhydric carboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid. I can.

Examples of the isocyanate compound used as the raw material of the amine-isocyanate adduct-based compound include monofunctional isocyanate compounds such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; Hexamethylene diisocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone Polyfunctional isocyanate compounds such as diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; Moreover, the terminal isocyanate group-containing compound etc. obtained by reaction of these polyfunctional isocyanate compounds and an active hydrogen compound are mentioned. As such a terminal isocyanate group-containing compound, for example, an addition compound having a terminal isocyanate group obtained by reaction of tolylene diisocyanate and trimethylolpropane, an addition compound having a terminal isocyanate group obtained by reaction of tolylene diisocyanate and pentaerythritol, etc. Can be lifted.

The latent curing agent is, for example, appropriately mixed with the raw materials for production, reacted at a temperature of 20°C to 200°C, cooled and solidified, and then pulverized, or a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc. It can be easily obtained by reacting the raw materials for production in the above, removing the solvent, and pulverizing the solid content.

As the latent curing agent, a commercial item may be used. As commercially available products of amine-epoxy adduct-based compounds, for example, ``Amicure PN-23'', ``Amicure PN-40'', ``Amicure PN-50'', ``Amicure PN-'' manufactured by Ajinomoto Fine Techno Co., Ltd. H", "Hardner X-3661S" by ACR, "Hardner X-3670S", "Novacure HX-3742" by Asahi Kasei, and "Novacure HX-3721" are mentioned. In addition, as commercially available products of amine-isocyanate adduct compounds, for example, ``Fujicure FXR-1000'', ``Fujicure FXR-1030'', ``Fujicure FXR-1020'', ``Fujicure FXR'' manufactured by T&K TOKA. -1030", "Fujicure FXR-1081", and "Fujicure FXR-1121".

Component (4) preferably contains an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound, and more preferably, an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct The compound is more preferably an amine-epoxy adduct-based compound or an amine-isocyanate adduct-based compound, and particularly preferably an amine-epoxy adduct-based compound.

From the viewpoint of curability, the amount of the component (4) per the entire curable composition is preferably 1% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more. In addition, from the viewpoint of storage stability, the amount of component (4) per the entire curable composition is preferably 20% by weight or less, more preferably 15% by weight or less, and still more preferably 10% by weight or less.

<(5) Epoxy resin>

The curable composition of the present invention may contain an epoxy resin as component (5). Examples of the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin. , Phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (e.g., tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, Diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, butadiene structure epoxy resin, bisphenol di Glycidyl ether products, diglycidyl ether products of naphthalenediol, diglycidyl ether products of phenols, diglycidyl ether products of alcohols, and alkyl substituents, halides and hydrogenated products of these epoxy resins And the like. Epoxy resins may be used alone or in combination of two or more. The epoxy resin may be liquid at 25°C or solid at 25°C. The epoxy resin may be a monomer (ie, a monomer type epoxy resin).

Epoxy resins have two or more epoxy groups in one molecule and are more solid at 25°C from the viewpoint of temporary fixability and adhesion to relatively difficult members such as liquid crystal polymers (LCPs). desirable. The epoxy resin may contain a liquid epoxy resin that is liquid at 25°C, but from the viewpoint of the above effect, the epoxy resin does not contain a liquid epoxy resin, or in an amount of 20 parts by weight or less per 100 parts by weight of the epoxy resin. It is preferable to contain a liquid epoxy resin. The amount of the liquid epoxy resin is per 100 parts by weight of the epoxy resin, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less. It is particularly preferable that the epoxy resin does not contain a liquid epoxy resin.

The epoxy equivalent of the epoxy resin, from the viewpoint of reactivity and the like, is preferably 50 to 5,000, more preferably 100 to 3,000, and still more preferably 150 to 1,000. Here, the epoxy equivalent means the number of grams of a compound containing 1 gram equivalent of an epoxy group (unit: g/eq). In other words, the epoxy equivalent means a value obtained by dividing the molecular weight of a compound containing an epoxy group by the number of epoxy groups that the compound has, that is, a molecular weight per epoxy group. Epoxy equivalent is measured according to the method specified in JIS K 7236.

In one aspect of the present invention, the component (5) is preferably at least one selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin. And more preferably, at least one selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin. In this aspect, the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the dicyclopentadiene type epoxy resin, and the biphenyl type epoxy resin all have two or more epoxy groups per molecule, and are solid at 25°C.

In another aspect of the present invention, component (5) preferably contains a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin or a biphenyl type epoxy resin, and more preferably Is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene type epoxy resin, or a biphenyl type epoxy resin. In this aspect, the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the dicyclopentadiene type epoxy resin, and the biphenyl type epoxy resin all have two or more epoxy groups per molecule, and are solid at 25°C.

In another aspect of the present invention, the component (5) preferably contains a bisphenol A type epoxy resin having two or more epoxy groups in one molecule and solid at 25°C, more preferably 1 It is a bisphenol A type epoxy resin which has two or more epoxy groups in a molecule|numerator, and is solid at 25 degreeC.

When an epoxy resin is used as the component (5), the amount thereof is, from the viewpoint of curability, per the entire curable composition, preferably 1% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more. , Preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 55% by weight or less.

<Other ingredients>

To the extent that the effects of the present invention are not impaired, the curable composition of the present invention may contain other components other than those described above. Examples of other components include polymerization inhibitors (eg, dibutylhydroxytoluene, barbituric acid); Antioxidants; Inorganic fillers (e.g., calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, quartz Minutes, etc.); An organic filler made of a copolymer of polymethyl methacrylate and/or polystyrene and a monomer constituting them and a copolymerizable monomer; Thixotropic agents; Antifoam; Leveling agents; Coupling agents; Flame retardant; Pigment; dyes; Fluorescent agents, etc. are mentioned. All other ingredients may be used alone or in combination of two or more.

<Preparation and curing of curable composition>

The curable composition of the present invention can be prepared as a one-component curable composition by uniformly mixing each component using, for example, a kneader, a stirring mixer, a three roll mill, or the like. The temperature of the curable composition at the time of mixing is usually 10 to 50°C, preferably 20 to 40°C.

As the light to be irradiated when photocuring the curable composition of the present invention, ultraviolet rays are preferable. The peak wavelength of the irradiated light is preferably 300 to 500 nm. The illuminance of the irradiated light is preferably 100 to 5,000 mW/cm ² , more preferably 300 to 4,000 mW/cm ² . The exposure amount is preferably 500 to 3,000 mJ/cm ² , more preferably 1,000 to 3,000 mJ/cm ² .

Examples of light irradiation means include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave excitation mercury lamps, metal halide lamps, sodium lamps, fluorescent lamps, LED type SPOT UV An irradiator, a xenon lamp, a DEEP UV lamp, etc. are mentioned.

The heating temperature when thermosetting the curable composition of the present invention is not particularly limited, but is, for example, 50 to 150°C, preferably 60 to 100°C. The heating time when thermosetting the curable composition of the present invention is not particularly limited, but is, for example, 10 to 120 minutes, preferably 30 to 60 minutes.

<Use of the curable composition>

The curable composition of the present invention has excellent photocurability and excellent thermosetting properties, and can form a cured product having high adhesive strength, and is therefore useful for adhesives, sealants, coating agents, and the like. Accordingly, the present invention also provides an adhesive, a sealant and a coating agent, including the curable composition. The adhesive is preferably used for bonding between constituent parts of the camera module.

<Method of manufacturing camera module>

The present invention, the following steps (I) to (III):

(I) a step of positioning the first adhesive component and the second adhesive component to which the curable composition of the present invention has been applied,

(II) a step of curing the curable composition by light irradiation to temporarily fix the first adhesive component and the second adhesive component, and

(III) Step of curing the curable composition by heating to fix the first adhesive component and the second adhesive component

It provides a method of manufacturing a camera module comprising a. Here, the first adhesive component means a component to which the curable composition of the present invention is applied, and the second adhesive component means another component to be bonded to the first adhesive component. The second adhesive component may or may not be coated with the curable composition of the present invention.

According to the manufacturing method of the present invention, each component is positioned with high precision, and it is possible to bond between the first adhesive component and the second adhesive component with high adhesive strength, and as a result, a high-quality camera module can be efficiently manufactured. I can.

In the step (II), there is a case where an unirradiated portion to which light is not irradiated remains in the applied curable composition due to the relationship between the arrangement positions of the first adhesive component and the second adhesive component. However, since the curable composition of the present invention has good thermosetting properties, even the unirradiated portion of light is sufficiently cured by the thermal curing in step (III) to achieve main curing, and high adhesive strength is achieved in the entire applied curable composition. It is possible to form a cured product having.

The conditions for light irradiation in step (II) and heating conditions in step (III) in the method for manufacturing a camera module of the present invention are as described above.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, but it is also possible to implement it with appropriate changes within the range suitable for the above and the following purposes. , These are all included in the technical scope of the present invention.

1. Raw material

<Component (1): Compound having (meth)acryloyl group>

(I) Component (1-1): A compound having a poly(oxyalkylene) chain and a (meth)acryloyl group, and having an equivalent (meth)acryloyl group of 300 or more

(1A) APG-700: Polypropylene glycol #700 diacrylate manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., weight average molecular weight: 808, number of acryloyl groups in one molecule: 2, (meth)acryloyl group equivalent: 404

(1B) A-PTMG-65: Polytetramethylene glycol #650 diacrylate manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., weight average molecular weight: 758, number of acryloyl groups in one molecule: 2, (meth)acryloyl group equivalent : 379

(1C) ATM-35E: Ethoxylated pentaerythritol tetraacrylate manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., weight average molecular weight: 1,892, number of acryloyl groups in one molecule: 4, (meth)acryloyl group equivalent: 473

(1D) A-1000: Polyethylene glycol #1000 diacrylate manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., weight average molecular weight: 1,108, number of acryloyl groups in one molecule: 2, (meth)acryloyl group equivalent: 554

(II) Component (1-1'): A compound having an oxyalkylene unit and a (meth)acryloyl group, and having an equivalent (meth)acryloyl group of less than 300

(1E) "M-313": A mixture of isocyanuric acid EO-modified diacrylate manufactured by Toa Kosei Co., Ltd. and isocyanuric acid EO-modified triacrylate (diacrylate content: 35% by weight, triacrylate) Content: 65% by weight), weight average molecular weight: 404, number of acryloyl groups in one molecule: 2.65, (meth)acryloyl group equivalent: 158

(III) Compounds having a (meth)acryloyl group other than component (1-1) and component (1-1')

(1F) EBECRYL600: Bisphenol A type epoxy acrylate manufactured by Daicel Allnex, molecular weight: 500, number of acryloyl groups in one molecule: 2

(1G) IRR-214K: tricyclodecanedimethanol diacrylate manufactured by Daicel-Allnex, molecular weight: 300, number of acryloyl groups in one molecule: 2

(1H) DPHA: Dipentaerythritol hexaacrylate manufactured by Daicel Allnex, molecular weight: 524, number of acryloyl groups in one molecule: 6

(1I) EBECRYL3708: Caprolactone-modified epoxy acrylate manufactured by Daicel Allnex, molecular weight: 1,500, number of acryloyl groups in one molecule: 2

(1J) EBECRYL168: manufactured by Daicel Allnex, phosphoric acid-modified methacrylate, molecular weight: 270, number of methacryloyl groups in one molecule: 1.5

<Component (2): Polythiol compound>

(2A) PEMP: SC Yuki Chemical Co., Ltd. pentaerythritol tetrakis (3-mercaptopropionate), molecular weight: 489, number of mercapto groups in one molecule: 4

(2B) PE1: "Carens MT" manufactured by Showa Denko Co., Ltd. pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight: 544, number of mercapto groups in one molecule: 4

(2C) TMPIC: tris(3-mercaptopropyl)isocyanurate, molecular weight: 351, number of mercapto groups in one molecule: 3

<Component (3): Photo radical generator>

(3A) Irgacure 1173: manufactured by BASF, 2-hydroxy-2-methyl-1-phenylpropan-1-one

(3B) Esacure KIP 150: manufactured by IGM Resins B.V., an oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one

<Component (4): Latent curing agent>

(4A) PN-23: Ajinomoto Fine Techno Co., Ltd. amine-epoxy adduct compound

(4B) FXR1081: An amine-isocyanate adduct-based compound manufactured by T&K TOKA

<Component (5): Epoxy resin>

(5A) jER1001: Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent (EPW): 475 g/eq, softening point: 64°C, number of epoxy groups in one molecule: 2

(5B) jER4005P: Bisphenol F-type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent (EPW): 538 g/eq, softening point: 87°C, number of epoxy groups in one molecule: 2

(5C) HP-7200: dicyclopentadiene type epoxy resin manufactured by DIC, epoxy equivalent (EPW): 258 g/eq, softening point: 56 to 66°C, number of epoxy groups in one molecule: 2 to 3

(5D) YX4000H: Biphenyl-type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent (EPW): 192 g/eq, melting point: 105°C, number of epoxy groups in one molecule: 2

2. Evaluation test

<Evaluation of viscosity>

The viscosity of the curable composition was measured using the Toki Sangyo E-type viscometer RE-80 under the conditions of temperature: 25°C, rotation speed: 20 rpm, and rotor: 3°×R9.7, and evaluated according to the following criteria.

(Evaluation standard)

○: viscosity is less than 10 Pa·s

×: viscosity of 10 Pa·s or more

<Evaluation of hardenability>

(1) Evaluation of photocurability

A curable composition was spread to a thickness of about 50 μm with a spacer and a glass rod having a thickness of about 50 μm on a glass epoxy resin laminate (produced by Risho Kogyo, FR-4.0) having a thickness of 2.5 mm × 8.0 mm × 0.8 mm thick, and a coating film of the curable composition Was formed, photocured under the following conditions, and the appearance of the coating film due to the touch was observed, and photocurability was evaluated based on the following criteria.

(Curing conditions)

With the Ushio Denki UV-LED irradiation apparatus UniField NF150, ^{ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 10 mW/cm 2} were irradiated to the coating film for 100 seconds (exposure amount 1,000 mJ/cm ² ).

(Evaluation standard)

○: There is no uncured part in the coating film

×: There is an uncured portion in the coating

(2) Evaluation of light and thermosetting properties

In the same manner as above, the coating film of the curable composition formed on the glass epoxy resin laminate was subjected to light and thermosetting under the following conditions, and the appearance of the coating film by the touch was observed, and light and thermosetting were evaluated based on the following criteria.

(Curing conditions)

With Ushio Denki's UV-LED irradiation device UniField NF150, ^{ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 10 mW/cm 2} were irradiated to the coating film for 100 seconds (exposure amount 1,000 mJ/cm ² ), and then the light-irradiated coating film was It heated at 100 degreeC for 30 minutes in a hot air circulation oven.

(Evaluation standard)

○: There is no uncured part in the coating film

×: There is an uncured portion in the coating film

(3) Evaluation of thermosetting properties

In the same manner as above, the coating film of the curable composition formed on the glass epoxy resin laminate was subjected to thermosetting under the following conditions, and the appearance of the coating film due to the touch was observed, and thermosetting was evaluated based on the following criteria.

(Curing conditions)

The coating film was heated in a hot air circulation oven at 100°C for 30 minutes.

(Evaluation standard)

○: There is no uncured part in the coating film

×: There is an uncured portion in the coating film

<Evaluation of curing shrinkage rate>

The specific gravity of the curable composition before curing and the cured product thereof was measured with a dry automatic density meter (Acupic II1340) manufactured by Shimadzu Seisakusho, respectively, and the following equation:

Curing shrinkage rate (%) = {(specific gravity of cured product-specific gravity of curable composition before curing) / specific gravity of cured product} × 100

The cure shrinkage ratio was calculated by and evaluated according to the following criteria.

(Evaluation standard)

○: The curing shrinkage rate is less than 5%

×: curing shrinkage of 5% or more

In addition, as for the cured product, a curable composition was applied to the release surface of a release polyethylene terephthalate (PET) film (NS-80A), spread to a thickness of about 50 μm with a glass rod, and a UV-LED lighting device manufactured by Ushio Denki Co., Ltd. With UniField NF150, ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 10 mW/cm ² were irradiated for 100 seconds (exposure amount 1,000 mJ/cm ² ), and then the curable composition irradiated with light was heated in a hot air circulation oven at 100° C. for 30 minutes. Made.

3. Examples and Comparative Examples

Each component was mixed in the amount shown in the upper column of the following table, and the curable compositions of Examples 1-15 and Comparative Examples 1-4 were prepared. In addition, "parts" described in the table represent "parts by weight". In the following table, "the sum of the acryloyl group and methacryloyl group in component (1) and the molar ratio of the mercapto group in component (2)" is described in the column of "(meth)acryloyl group/mercapto group". do.

In Examples 1 to 11 and Comparative Examples 1, 2 and 4, after sufficiently mixing the components (1) and (4), the components (2) and (3) were added and mixed, followed by static defoaming.置脫泡) to prepare a curable composition. In Comparative Example 3, after sufficiently mixing the components (1) and (4), the component (3) was added thereto and mixed, followed by static defoaming to prepare a curable composition. In Examples 12 to 15, after mixing and dissolving component (1) and component (5) at 100°C, cooling sufficiently to room temperature (20 to 25°C), adding and mixing component (4) thereto, Components (2) and (3) were added to and mixed, followed by static defoaming to prepare a curable composition. In addition, preparation work in Examples 1-15 and Comparative Examples 1-4 was performed at room temperature except mixing and dissolving of component (1) and component (5) in Examples 12-15.

The results of the evaluation tests of the curable compositions of Examples 1 to 15 and Comparative Examples 1 to 4 are shown in the following table.

From the results of Examples 1 to 15, it can be seen that the curable composition of the present invention has a low viscosity and excellent workability. In addition, it is understood that the curable composition of the present invention has a small cure shrinkage ratio and can suppress positional shift due to cure shrinkage. In contrast, all of the curable compositions of Comparative Examples 1 to 4 had high cure shrinkage. Further, the curable compositions of Comparative Examples 2 to 4 had high viscosity, and the curable composition of Comparative Example 3 had insufficient thermosetting properties.

The curable composition of the present invention is useful for adhesives, sealants, coating agents (particularly, adhesives used to manufacture camera modules) and the like.

Claims (11)

The following components (1) to (4):
(1) a compound having a (meth)acryloyl group,
(2) a polythiol compound having two or more mercapto groups in one molecule,
(3) a photo radical generator, and
(4) Latent hardener
As a curable composition comprising a,
Component (1) is the following component (1-1):
(1-1) A compound having a poly(oxyalkylene) chain and a (meth)acryloyl group, and having a (meth)acryloyl group equivalent of 300 or more
Containing, curable composition. The curable composition according to claim 1, wherein the poly(oxyalkylene) chain contains at least one selected from the group consisting of an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. The curable composition according to claim 1 or 2, wherein the amount of component (1-1) is 15 to 100 parts by weight per 100 parts by weight of component (1). The curable composition according to claim 1 or 2, wherein the component (2) contains a polythiol compound having 2 to 6 mercapto groups per molecule. The molar ratio of the sum of acryloyl groups and methacryloyl groups in component (1) and mercapto groups in component (2) according to claim 1 or 2 (acryloyl group and methacrylo group in component (1) The curable composition in which the sum of the diaries/mercapto group in the component (2)) is 0.5 to 2.0. The curable composition according to claim 1 or 2, wherein the component (4) contains an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound. An adhesive comprising the curable composition according to claim 1 or 2. The adhesive according to claim 7, which is for bonding between constituent parts of a camera module. A sealing agent containing the curable composition according to claim 1 or 2. A coating agent containing the curable composition according to claim 1 or 2. The following steps (I) to (III):
(I) A step of positioning the first adhesive component and the second adhesive component to which the curable composition according to claim 1 or 2 is applied,
(II) the step of curing the curable composition by light irradiation to temporarily fix the first adhesive component and the second adhesive component, and
(III) Step of curing the curable composition by heating to fix the first adhesive component and the second adhesive component
Containing, a method of manufacturing a camera module.