Curable composition

Abstract

To provide a curable composition that has both of excellent photocurability and excellent thermosetting properties, and has a small viscosity and a low curing shrinkage rate.SOLUTION: A curable composition contains following components (1)-(4): (1) a compound having a (meth)acryloyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, (3) a photoradical generating agent, and (4) a latent curing agent. The component (1) contains component (1-1): a compound that has a poly(oxyalkylene) chain and has a (meth)acryloyl group equivalent of 300 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition. [Background technology]

[0002] In recent years, as mobile devices such as smartphones have become more sophisticated, the camera modules installed in such devices have become more pixelated. As camera modules become smaller and more sophisticated, the positional accuracy of the lens and image sensor, for example, has become extremely important.

[0003] On the other hand, adhesives used in assembling camera modules are required to have low-temperature curing properties in order to avoid thermal damage to image sensors and the like due to high-temperature processing, and are also required to have the ability to cure at low temperatures and in a short time (low-temperature-short-time curing properties) from the viewpoint of improving production efficiency. From this viewpoint, ultraviolet-curing adhesives and thermosetting epoxy resin adhesives are often used as low-temperature-low-temperature-short-time curing adhesives (for example, Patent Documents 1 and 2). However, while ultraviolet-curing adhesives can cure quickly, they have a large cure shrinkage, which causes parts to become misaligned after curing. On the other hand, even though thermosetting epoxy resin adhesives are low-temperature-short-time curing adhesives, they require the parts to be bonded with a jig or device to maintain the bonding position during bonding, and the viscosity decreases due to a temperature increase caused by heating, which may cause parts to become misaligned, and therefore they are not necessarily satisfactory.

[0004] In order to solve the problems described above, several types of adhesives have been proposed that temporarily fix the components that make up the camera module by hardening (preliminary hardening) through exposure to light (ultraviolet light, visible light) in order to position the components with high precision, and then bond (mainly fix) the components by the effect of heat (mainly hardening) (e.g., Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-140497 A [Patent Document 2] JP 2013-88525 A [Patent Document 3] JP 2009-51954 A [Patent Document 4] JP 2009-79216 A Summary of the Invention [Problem to be solved by the invention]

[0006] Even when a photo- or thermosetting adhesive is used as described in Patent Documents 3 and 4, if the adhesive has a large cure shrinkage rate, there is a problem that the shrinkage can cause component position displacement. Also, if the viscosity of the adhesive is high, the workability of the adhesive (ease of application, etc.) decreases.

[0007] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a curable composition which has both excellent photocurability and excellent thermocurability, a low viscosity, and a small cure shrinkage rate. [Means for solving the problem]

[0008] The present invention capable of achieving the above object is as follows. [1] The following ingredients (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 photoradical generator, and (4) Latent hardener A curable composition comprising: 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 1. A curable composition comprising: [2] The curable composition according to [1] above, wherein the poly(oxyalkylene) chain contains at least one unit selected from the group consisting of an oxyethylene unit, an oxypropylene unit and an oxybutylene unit. [3] The curable composition according to the above [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). [4] The curable composition according to any one of the above [1] to [3], wherein the component (2) comprises a polythiol compound having 2 to 6 mercapto groups in one molecule. [5] The curable composition according to any one of the above [1] to [4], wherein the molar ratio of the total of the acryloyl groups and methacryloyl groups in component (1) to the mercapto groups in component (2) (the total of the acryloyl groups and methacryloyl groups in component (1) / mercapto groups in component (2)) is 0.5 to 2.0. [6] The curable composition according to any one of the above [1] to [5], wherein the component (4) contains an amine-epoxy adduct compound and / or an amine-isocyanate adduct compound. [7] An adhesive comprising the curable composition according to any one of [1] to [6] above. [8] The adhesive according to [7] above, which is for bonding components of a camera module. [9] A sealant comprising the curable composition according to any one of the above [1] to [6].

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

[11] The following steps (I) to (III): (I) a step of positioning a first adhesive part coated with the curable composition according to any one of the above [1] to [6] and a second adhesive part; (II) curing the curable composition by light irradiation to temporarily fix the first adhesive part and the second adhesive part together; and (III) A step of curing the curable composition by heating to completely fix the first adhesive part and the second adhesive part together. A method for manufacturing a camera module, comprising: Effect of the Invention

[0009] According to the present invention, it is possible to obtain a curable composition which has both excellent photocurability and excellent thermocurability, a low viscosity, and a small cure shrinkage rate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Curable composition> The curable composition of the present invention 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 (hereinafter sometimes abbreviated as "polythiol compound"). (3) a photoradical generator, and (4) Latent hardener Includes.

[0011] The present invention relates to a compound (1) comprising the following compound (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 By using the component (1-1), it is possible to obtain a curable composition that has both excellent photocurability and excellent thermocurability and has a small cure shrinkage rate.

[0012] The curable composition of the present invention is characterized by having a low viscosity. From the viewpoint of workability, the viscosity of the curable composition of the present invention is preferably less than 10 Pa·s, more preferably less than 8 Pa·s. 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, more preferably 0.1 Pa·s or more. 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.

[0013] Components (1) to (4) and component (1-1) may each 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 components may each be used alone or in combination of two or more. Each component will be described below in order.

[0014] <(1) Compound Having a (Meth)acryloyl Group> The compound having a (meth)acryloyl group used as component (1) in the present invention mainly plays a role of increasing adhesive strength. In addition, in the present invention, the "(meth)acryloyl group" means either or both of an acryloyl group and a methacryloyl group.

[0015] Component (1) includes a compound having a poly(oxyalkylene) chain and a (meth)acryloyl group equivalent of 300 or more (hereinafter, sometimes abbreviated as "POA-(meth)acryloyl compound", component (1-1)). In the present invention, the "poly(oxyalkylene) chain" refers to a compound 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. In addition, n, which is the number of oxyalkylene units represented by the formula: -(OR)-, may be a decimal number. Note that compounds having only oxyalkylene units with n being 1 and no poly(oxyalkylene) chain (e.g., ethylene glycol di(meth)acrylate) are not included in the POA-(meth)acryloyl compounds.

[0016] The (meth)acryloyl group equivalent of a POA-(meth)acryloyl compound means the 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 / number of (meth)acryloyl groups in one molecule).

[0017] Since POA-(meth)acryloyl compounds are compounds having a poly(oxyalkylene) chain composed of oxyalkylene units, the weight-average molecular weight is used as the molecular weight for calculating the (meth)acryloyl group equivalent. This weight-average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, the measurement apparatus is LC-9A / RID-6A manufactured by Shimadzu Corporation, the column is Shodex K-800P / K-804L / K-804L manufactured by Showa Denko K.K., and the mobile phase is 1000 g / l. The weight average molecular weight can be calculated using a calibration curve of standard polystyrene by measuring the weight average molecular weight at a column temperature of 40° C. using chloroform or the like.

[0018] The weight average molecular weight of the POA-(meth)acryloyl compound is preferably 500 or more, more preferably 600 or more, from the viewpoints of the curability, viscosity and cure shrinkage rate of the curable composition. It is more preferably 700 or more, and is preferably 4,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.

[0019] When the POA-(meth)acryloyl compound is a mixture, the number of (meth)acryloyl groups in one molecule of the compound represents the average value per molecule. When both acryloyl groups and methacryloyl groups are present in one molecule of the compound, this number means the total number of acryloyl groups and methacryloyl groups in one molecule.

[0020] The number of (meth)acryloyl groups in one molecule of the POA-(meth)acryloyl compound can be calculated, for example, from the weight average molecular weight and the iodine value measured by the method specified in JIS K0070.

[0021] The number of (meth)acryloyl groups in one molecule of the POA-(meth)acryloyl compound is preferably 1 to 6, more preferably 2 to 5, and further preferably 2 to 4, from the viewpoints of the curability, viscosity, and cure shrinkage rate of the curable composition.

[0022] The (meth)acryloyl group equivalent of the POA-(meth)acryloyl compound must be 300 or more. From the viewpoints of curability, viscosity, and cure shrinkage rate of the curable composition, this (meth)acryloyl group equivalent is preferably 320 or more, more preferably 350 or more. On the other hand, from the viewpoints of curability and viscosity, this (meth)acryloyl group equivalent is preferably 1,000 or less, more preferably 800 or less.

[0023] The poly(oxyalkylene) chain of the POA-(meth)acryloyl compound preferably contains at least one selected from the group consisting of oxyethylene units, oxypropylene units, and oxybutylene units, and more preferably at least one selected from the group consisting of oxyethylene units, oxypropylene units, and oxybutylene units. Here, the oxypropylene unit may be a straight chain (i.e., -O-(CH2)3-) or a branched chain (e.g., -O-CH2-CH(CH3)-). Also, the oxybutylene unit may be a straight chain (i.e., -O-(CH2)4-) or a branched chain (e.g., -O-CH2-CH(CH2CH3)-).

[0024] Examples of the POA-(meth)acryloyl compound include the following compounds: Each of the following compounds may be used alone or in combination of two or more.

[0025] (POA-(meth)acryloyl compound having one acryloyl or methacryloyl group per molecule) Methoxypolyethyleneglycol (meth)acrylate Methoxypolypropyleneglycol (meth)acrylate Methoxypolytetramethylene glycol (meth)acrylate Phenoxypolyethylene glycol (meth)acrylate Nonylphenoxy polyethylene glycol (meth)acrylate In the present invention, "(meth)acrylate" means either or both of acrylate and methacrylate.

[0026] (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 the present invention, "EO-modified" means modified by the addition of ethylene oxide (EO), and "PO-modified" means modified by the addition of propylene oxide (PO).

[0027] (Compounds having three or more (meth)acryloyl groups in one molecule) Ethoxylated pentaerythritol tetra(meth)acrylate Here, ethoxylated pentaerythritol tetra(meth)acrylate refers to a compound having a structure obtained by ester bonding pentaerythritol having a poly(oxyethylene) chain with four (meth)acrylates.

[0028] Component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate, and more preferably at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0029] The amount of component (1-1) is preferably 15 to 100 parts by weight, more preferably 19.5 to 100 parts by weight, and even more preferably 19.5 to 99.5 parts by weight, per 100 parts by weight of component (1), from the viewpoints of the curability, viscosity, and cure shrinkage rate of the curable composition.

[0030] 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, this number represents the average value per molecule. When both acryloyl groups and methacryloyl groups are present in one molecule, this 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 (excluding the phosphoric acid-modified (meth)acrylate described later) is preferably 1 to 6, more preferably 2 to 6, and even more preferably 2 to 4.

[0031] The molecular weight of the (meth)acryloyl compound (excluding the 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. If the molecular weight is less than 50, the volatility is high, which is undesirable in terms of odor and handling, and if the molecular weight exceeds 5,000, the viscosity of the composition increases, and the coating property of the composition tends to decrease. Note that a molecular weight of 1,000 or more means a weight average molecular weight, which can be measured by gel permeation chromatography (GPC). A molecular weight of less than 1,000 can be measured by a gravimetric analyzer (for example, ESI-MS).

[0032] Examples of the (meth)acryloyl compound include the following compounds. Note that, each of the following compounds may be used alone or in combination of two or more kinds.

[0033] ((Meth)acryloyl compounds having one acryloyl 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

[0034] ((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 Tricyclodecane dimethanol di(meth)acrylate Neopentyl glycol hydroxypivalate di(meth)acrylate Polyurethane containing two (meth)acryloyl groups per molecule Polyester containing two (meth)acryloyl groups in one molecule Bisphenol A type epoxy (meth)acrylate Caprolactone modified epoxy (meth)acrylate Here, the caprolactone-modified epoxy (meth)acrylate having two (meth)acryloyl groups in one molecule (sometimes abbreviated as "caprolactone-modified epoxy (meth)acrylate" in this specification) means a compound that can be produced by reacting (meth)acrylic acid with ε-caprolactone to produce a carboxylic acid compound, and then reacting this carboxylic acid compound with a bifunctional epoxy compound.

[0035] ((Meth)acryloyl compound having three 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 containing three or more (meth)acryloyl groups in one molecule Polyester containing three or more (meth)acryloyl groups in one molecule

[0036] Pentaerythritol (tri / tetra)(meth)acrylate is a mixture of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate. The mixture ratio (pentaerythritol tri(meth)acrylate / pentaerythritol tetra(meth)acrylate) is preferably 5 / 95 to 95 / 5, more preferably 30 / 70 to 70 / 30, by weight.

[0037] Dipentaerythritol (penta / hexa)(meth)acrylate is a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. The mixture ratio (dipentaerythritol penta(meth)acrylate / dipentaerythritol hexa(meth)acrylate) is preferably 5 / 95 to 95 / 5, more preferably 30 / 70 to 70 / 30, by weight.

[0038] Among the above-mentioned (meth)acryloyl compounds, tricyclodecane dimethanol di(meth)acrylate, bisphenol A type epoxy (meth)acrylate, caprolactone derivative, Among these, preferred are bisphenol A type epoxy (meth)acrylate and dipentaerythritol hexa(meth)acrylate, and more preferred is bisphenol A type epoxy (meth)acrylate.

[0039] From the viewpoint of storage stability, the component (1) preferably contains a phosphoric acid-modified (meth)acrylate. Here, "phosphoric acid-modified" means modified by an ester bond with phosphoric acid. The phosphoric acid-modified (meth)acrylate may be used alone or in combination of two or more kinds. The phosphoric acid-modified (meth)acrylate is preferably a phosphoric acid-modified methacrylate.

[0040] The phosphoric acid-modified (meth)acrylate can be produced, for example, by the following method (i), although 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.

[0041] The compound having a (meth)acryloyl group and a hydroxy group in one molecule that can be used in the above method (i) can be produced, for example, by the following method (ii) or (iii), although the present invention is not limited thereto. (ii) A method of reacting (meth)acrylic acid or a (meth)acrylate with a polyhydric alcohol (for example, alkylene glycol, glycerin, etc.) in such an amount ratio that hydroxy groups of the polyhydric alcohol remain. (iii) A method in which an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) is added to (meth)acrylic acid.

[0042] The phosphoric acid-modified (meth)acrylate may be a commercially available product, such as "EBECRYL168" manufactured by Allnex Co., Ltd., "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "Light Ester P-1M", "Light Ester P-2M", and "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd., and "JPA-514" manufactured by Johoku Chemical Industry Co., Ltd.

[0043] 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 even more preferably 1 to 1.5. When the phosphoric acid-modified (meth)acrylate is a mixture, this number represents the average value per molecule.

[0044] The molecular weight of the phosphoric acid-modified (meth)acrylate is preferably 100-1,000, more preferably 150-800, and further preferably 200-600.

[0045] When a phosphoric acid-modified (meth)acrylate is used, from the viewpoint of storage stability, the amount thereof is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, and even more preferably 0.05 to 2 parts by weight, per 100 parts by weight of component (1).

[0046] From the viewpoint of the curability of the curable composition, it is preferable that the component (1) contains a compound having two or more (meth)acryloyl groups in one molecule. The compound having two or more (meth)acryloyl groups in one molecule may be the above-mentioned POA-(meth)acryloyl compound, or may be other than the above (i.e., the above-mentioned (meth)acryloyl compound). When using a compound having two or more (meth)acryloyl groups in one molecule, from the viewpoint of the curability of the curable composition, the amount is preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight, and even more preferably 30 to 99.5 parts by weight per 100 parts by weight of the component (1).

[0047] In one embodiment of the present invention, component (1) is preferably component (1-1) and a phosphoric acid modified (meth)acrylate, more preferably a mixture of component (1-1) and phosphoric acid-modified (meth)acrylate. In this embodiment, component (1-1) preferably comprises at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0048] In another embodiment of the present invention, component (1) preferably contains at least one selected from the group consisting of tricyclodecanedimethanol di(meth)acrylate, bisphenol A type epoxy (meth)acrylate, caprolactone-modified epoxy (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, component (1-1), and a phosphoric acid-modified (meth)acrylate, and is more preferably a mixture of at least one selected from the group consisting of tricyclodecanedimethanol di(meth)acrylate, bisphenol A type epoxy (meth)acrylate, caprolactone-modified epoxy (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, component (1-1), and a phosphoric acid-modified (meth)acrylate. In this embodiment, component (1-1) preferably comprises at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate, and more preferably at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0049] In another embodiment of the present invention, component (1) preferably contains component (1-1), bisphenol A type epoxy (meth)acrylate, and phosphoric acid modified (meth)acrylate, and is more preferably a mixture of component (1-1), bisphenol A type epoxy (meth)acrylate, and phosphoric acid modified (meth)acrylate. In this embodiment, component (1-1) preferably contains at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate, and is more preferably at least one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0050] From the viewpoints of the curability, viscosity and cure shrinkage rate of the curable composition, the amount of component (1) is preferably 10 wt % or more, more preferably 15 wt % or more, even more preferably 20 wt % or more, and is preferably 80 wt % or less, more preferably 75 wt % or less, even more preferably 70 wt % or less, based on the total amount of the curable composition.

[0051] <(2) Polythiol compounds> The "polythiol compound having two or more mercapto groups in one molecule" used as component (2) in the present invention mainly plays the role of a curing agent that reacts with component (1) by irradiation with light such as ultraviolet light to cure the composition. The number of mercapto groups in one molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, even more preferably 3 to 5, and particularly preferably 3 or 4.

[0052] The polythiol compound to be used may be a commercially available product, or may be produced by a known method (for example, the method described in JP-A-2012-153794 or WO 2001 / 00698).

[0053] Examples of the polythiol compound include partial esters of polyols and mercapto organic acids, and complete esters of polyols and mercapto organic acids. Here, the partial ester refers to an ester of a polyol and a carboxylic acid in which some of the hydroxyl groups of the polyol form ester bonds, and the complete ester refers to an ester of a polyol and a carboxylic acid in which all of the hydroxyl groups of the polyol form ester bonds.

[0054] Examples of polyols include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0055] Examples of mercapto organic acids include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g., 3-mercaptopropionic acid), and mercaptobutyric acid (e.g., 3-mercaptobutyric acid and 4-mercaptobutyric acid); esters containing a mercapto group and a carboxy group obtained by esterification of a hydroxy acid with a mercapto organic acid; mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (e.g., 2,3-dimercaptosuccinic acid); and mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (e.g., 4-mercaptobenzoic acid). The number of carbon atoms in the mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 3. Among the above mercapto organic acids, mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms are preferred, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferred, and 3-mercaptopropionic acid is even more preferred.

[0056] Specific examples of partial esters of polyols and mercapto organic acids include trimethylolethane bis(mercaptoacetate), trimethylolethane bis(3-mercaptopropionate), trimethylolethane bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), and pentaerythritol. Examples of such mercaptoglycerides include tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), and dipentaerythritol tetrakis(4-mercaptobutyrate).

[0057] Specific examples of complete esters of polyols and mercapto organic acids include ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolethane tris(mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolethane tris(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane ... Examples of the mercaptobutyrate include pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol hexakis(mercaptoacetate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), and dipentaerythritol hexakis(4-mercaptobutyrate).

[0058] From the viewpoint of storage stability, the partial ester and complete ester preferably contain as little basic impurities as possible, and more preferably do not require the use of a basic substance in the production.

[0059] Also usable as component (2) are polythiol compounds produced using a basic substance as a reaction catalyst in the production process, such as alkane polythiol compounds such as 1,4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol; terminal mercapto group-containing polyethers; terminal mercapto group-containing polythioethers; polythiol compounds obtained by the reaction of an epoxy compound with hydrogen sulfide; polythiol compounds having terminal mercapto groups obtained by the reaction of a polythiol compound with an epoxy compound; etc. It is preferable that polythiol compounds produced using a basic substance are subjected to a dealkalization treatment to reduce the alkali metal ion concentration to 50 ppm by weight or less before use.

[0060] Examples of the dealkalization treatment of a polythiol compound produced using a basic substance include, but are not limited to, a method in which the polythiol compound is dissolved in an organic solvent such as acetone or methanol, neutralized by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then desalted by extraction, washing, or the like; a method in which the compound is adsorbed using an ion exchange resin; and a method in which the compound is purified by distillation.

[0061] Furthermore, examples of component (2) that can be used include 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.

[0062] Component (2) contains a polythiol compound having preferably 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, and particularly preferably 3 or 4 mercapto groups in one molecule.

[0063] In one embodiment of the present invention, component (2) preferably contains at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate, and more preferably contains at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0064] In another embodiment of the present invention, component (2) is preferably pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) or tris(3-mercaptopropyl)isocyanurate, more preferably pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) or tris(3-mercaptopropyl)isocyanurate, and even more preferably pentaerythritol Tetrakis(3-mercaptopropionate).

[0065] From the viewpoint of curability, the molar ratio of the total of acryloyl groups and methacryloyl groups in component (1) to the mercapto groups in component (2) (the total of acryloyl groups and methacryloyl groups in component (1) / mercapto groups in component (2)) is preferably 0.5 to 2.0, more preferably 0.6 to 1.6, even more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3.

[0066] From the viewpoints of the curability, viscosity and cure shrinkage rate of the curable composition, the amount of component (2) is preferably 10 wt % or more, more preferably 15 wt % or more, even more preferably 20 wt % or more, and is preferably 50 wt % or less, more preferably 45 wt % or less, even more preferably 40 wt % or less, based on the total weight of the curable composition.

[0067] <(3) Photoradical generator> The photoradical generator used as component (3) in the present invention is not particularly limited. Examples of the photoradical generator include alkylphenone-based photoradical generators, acylphosphine oxide-based photoradical generators, oxime ester-based photoradical generators, and α-hydroxyketone-based photoradical generators. The photoradical generator is preferably an alkylphenone-based photoradical generator.

[0068] Examples of alkylphenone-based photoradical generators 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, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4 -diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one.

[0069] Examples of the acylphosphine oxide photoradical generator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, and the like.

[0070] Examples of oxime ester-based photoradical generators 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.

[0071] Examples of the α-hydroxyketone-based photoradical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i- propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

[0072] Commercially available photoradical generators include, 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)), and "Irgacure OXE02" (1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone). O-acetyloxime), IGM Resins BV's "Esacure KTO 46" (a mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane], and a methylbenzophenone derivative), and "Esacure KIP 150" (oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one).

[0073] The amount of component (3) is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and even more preferably 0.1% by weight or more, based on the total curable composition, from the viewpoint of obtaining a curable composition that can be efficiently photocured upon irradiation with light. On the other hand, from the viewpoint of suppressing outgassing due to the photoradical generator remaining in the cured product or its decomposition product, the amount is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 2% by weight or less, based on the total curable composition.

[0074] <(4) Latent hardener> The latent curing agent used as component (4) in the present invention refers to an additive well known in the field of epoxy resins and the like, which does not cure epoxy resins at room temperature (25°C) but can cure epoxy resins by heating. In the present invention, the latent curing agent plays a role in promoting 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).

[0075] Examples of the latent curing agent include imidazole compounds that are solid at room temperature, amine-epoxy adduct compounds (reaction products of an amine compound and an epoxy compound), and amine-isocyanate adduct compounds (reaction products of an amine compound and an isocyanate compound).

[0076] Examples of imidazole compounds that are solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2 -(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine·isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, etc.

[0077] Examples of epoxy compounds that can be used as raw materials for amine-epoxy adduct compounds include polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol. Examples of such glycidyl ethers include polyglycidyl ethers obtained by reacting epichlorohydrin with phenol, or polyhydric alcohols such as glycerin or polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxy acids such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid or terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0078] The amine compound used as the raw material for the amine-epoxy adduct compound or the amine-isocyanate adduct compound may have at least one active hydrogen atom capable of addition reaction with an epoxy group or an isocyanate group (also known as an isocyanato group) in one molecule, and 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 amine compounds such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; and the like.

[0079] In addition, by using a compound having a tertiary amino group, an excellent latent curing agent can be produced. Examples of the compound having a tertiary amino group include amines having a tertiary amino group such as dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 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-benzimidazole, 2 1-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, and other alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group;

[0080] When an epoxy compound and an amine compound are subjected to an addition reaction to produce an amine-epoxy adduct compound, an active hydrogen compound having two or more active hydrogens in one molecule can be added. Examples of such active hydrogen compounds include bisphenol A, bisphenol B, and bisphenol C. Examples of the polyhydric phenols include phenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin; polyhydric alcohols include trimethylolpropane; polycarboxylic acids include adipic acid and phthalic acid; 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0081] Examples of isocyanate compounds used as raw materials for amine-isocyanate adduct compounds include monofunctional isocyanate compounds such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by reacting tolylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting tolylene diisocyanate with pentaerythritol.

[0082] The latent curing agent can be easily obtained, for example, by appropriately mixing the above-mentioned production raw materials, reacting them at a temperature of 20°C to 200°C, cooling to solidify, and then pulverizing them, or by reacting the above-mentioned production raw materials in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0083] The latent curing agent may be a commercially available product. Examples of commercially available amine-epoxy adduct compounds include "Amicure PN-23", "Amicure PN-40", "Amicure PN-50", and "Amicure PN-H" manufactured by Ajinomoto Fine Techno Co., Ltd., "Hardener X-3661S" and "Hardener X-3670S" manufactured by ACR Co., Ltd., and "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Co., Ltd. In addition, examples of commercially available amine-isocyanate adduct compounds include "Fujicure FXR-1000", "Fujicure FXR-1030", "Fujicure FXR-1020", "Fujicure FXR-1030", "Fujicure FXR-1081", and "Fujicure FXR-1121" manufactured by T&K TOKA Co., Ltd.

[0084] Component (4) preferably contains an amine-epoxy adduct compound and / or an amine-isocyanate adduct compound, more preferably an amine-epoxy adduct compound and / or an amine-isocyanate adduct compound, still more preferably an amine-epoxy adduct compound or an amine-isocyanate adduct compound, and particularly preferably an amine-epoxy adduct compound.

[0085] From the viewpoint of curability, the amount of component (4) is preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more based on the total curable composition. Also, from the viewpoint of storage stability, the amount of component (4) is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less based on the total curable composition.

[0086] <(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 and hydrogenated bisphenol A. Epoxy resins include, for example, 1,2-dimethylphenyl-2,3-dimethylphenyl-2,4-dimethylphenyl-2,5-dimethylphenyl-2,6-dimethylphenyl-2,7-dimethylphenyl-2,8-dimethylphenyl-2,9-dimethylphenyl-2,10-dimethylphenyl-2,11-dimethylphenyl-2,12-dimethylphenyl-2,13-dimethylphenyl-2,14-dimethylphenyl-2,15-dimethylphenyl-2,16-dimethylphenyl-2,17-dimethylphenyl-2,18-dimethylphenyl-2,19-dimethylphenyl-2,20-dimethylphenyl-2,21-dimethylphenyl-2,22-dimethylphenyl-2,30-dimethylphenyl-2,15-dimethylphenyl-2,16-dimethylphenyl-2,17-dimethylphenyl-2,18-dimethylphenyl-2,19-dimethylphenyl-2,19-dimethylphenyl-2,22-dimethylphenyl-2,19 ... The epoxy resin may be liquid at 25° C. or solid at 25° C. The epoxy resin may be a monomer (i.e., a monomer-type epoxy resin).

[0087] From the viewpoint of temporary fixation and adhesion to members that are relatively difficult to adhere to, such as liquid crystal polymers (LCPs), the epoxy resin is more preferably an epoxy resin having two or more epoxy groups in one molecule and being solid at 25°C. The epoxy resin may contain a liquid epoxy resin that is liquid at 25°C, but from the viewpoint of the above effects, it is preferable that the epoxy resin does not contain a liquid epoxy resin or contains a liquid epoxy resin in an amount of 20 parts by weight or less per 100 parts by weight of the epoxy resin. The amount of the liquid epoxy resin is more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, per 100 parts by weight of the epoxy resin. It is particularly preferable that the epoxy resin does not contain a liquid epoxy resin.

[0088] From the viewpoint of reactivity, the epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 100 to 3,000, and even 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 the value obtained by dividing the molecular weight of a compound containing an epoxy group by the number of epoxy groups contained in the compound, that is, the molecular weight per epoxy group. The epoxy equivalent is measured according to the method specified in JIS K 7236.

[0089] In one embodiment of the present invention, component (5) preferably contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin, and more preferably at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin. In this embodiment, the bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin all have two or more epoxy groups in one molecule and are solid at 25°C.

[0090] In another embodiment 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 embodiment, 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 in one molecule and are solid at 25°C.

[0091] In another embodiment of the present invention, the component (5) preferably has two epoxy groups in one molecule. The epoxy resin includes a bisphenol A type epoxy resin having two or more epoxy groups in one molecule and being a solid at 25°C, and more preferably a bisphenol A type epoxy resin having two or more epoxy groups in one molecule and being a solid at 25°C.

[0092] When an epoxy resin is used as component (5), the amount thereof is, from the viewpoint of curability, preferably 1 wt % or more, more preferably 3 wt % or more, even more preferably 5 wt % or more, and preferably 70 wt % or less, more preferably 60 wt % or less, even more preferably 55 wt % or less, based on the entire curable composition.

[0093] <Other ingredients> The curable composition of the present invention may contain other components different from the above-mentioned components, as long as the effect of the present invention is not impaired. Examples of the other components include polymerization inhibitors (e.g., 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 powder, etc.); organic fillers made of copolymers obtained by copolymerizing polymethyl methacrylate and / or polystyrene with monomers constituting these and monomers copolymerizable therewith; thixotropic agents; defoamers; leveling agents; coupling agents; flame retardants; pigments; dyes; fluorescent agents, etc. The other components may be used alone or in combination of two or more.

[0094] <Production and curing of curable composition> The curable composition of the present invention can be prepared as a one-liquid type curable composition by uniformly mixing each component using, for example, a kneader, a stirring mixer, a three-roll mill, etc. The temperature of the curable composition during mixing is usually 10 to 50°C, preferably 20 to 40°C.

[0095] The light to be irradiated when photocuring the curable composition of the present invention is preferably ultraviolet light. 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 dose is preferably 500 to 3,000 mJ / cm. 2 , more preferably 1,000 to 3,000 mJ / cm 2 It is.

[0096] 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 excited mercury lamps, metal halide lamps, sodium lamps, fluorescent lamps, LED type SPOT type UV irradiators, xenon lamps, and DEEP UV lamps.

[0097] The heating temperature when the curable composition of the present invention is thermally cured is not particularly limited, but is, for example, 50 to 150° C., and preferably 60 to 100° C. The heating time when the curable composition of the present invention is thermally cured is not particularly limited, but is, for example, 10 to 120 minutes, and preferably 30 to 60 minutes.

[0098] <Uses of the curable composition> The curable composition of the present invention has both excellent photocurability and excellent thermosetting property, and can form a cured product having high adhesive strength, and is therefore useful for adhesives, sealants, coating agents, etc. Therefore, the present invention also provides adhesives, sealants, and coating agents containing the curable composition. The adhesive is preferably one for bonding between components of a camera module.

[0099] <Camera module manufacturing method> The present invention relates to a method for producing a semiconductor device comprising the steps of: (I) a step of positioning a first adhesive part to which the curable composition of the present invention has been applied and a second adhesive part; (II) curing the curable composition by light irradiation to temporarily fix the first adhesive part and the second adhesive part together; and (III) A step of curing the curable composition by heating to completely fix the first adhesive part and the second adhesive part together. The present invention provides a method for manufacturing a camera module, comprising: a first adhesive part means a part to which the curable composition of the present invention is applied, and a second adhesive part means the other part to be adhered to the first adhesive part. The second adhesive part may or may not be coated with the curable composition of the present invention.

[0100] According to the manufacturing method of the present invention, each component can be positioned with high precision, and the first adhesive component and the second adhesive component can be bonded together with high adhesive strength, resulting in efficient production of high-quality camera modules.

[0101] In step (II), due to the positional relationship between the first adhesive part and the second adhesive part, there may be some unirradiated parts of the applied curable composition that are not irradiated with light. However, since the curable composition of the present invention has good thermosetting properties, the unirradiated parts are sufficiently cured by the thermal curing in step (III) to reach the main curing, and a cured product having high adhesive strength can be formed from the entire applied curable composition.

[0102] The light irradiation conditions in step (II) and the heating conditions in step (III) in the method for producing a camera module of the present invention are as described above. EXAMPLES

[0103] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with appropriate modifications within the scope of the above and below spirit, all of which are included in the technical scope of the present invention.

[0104] 1. Raw materials <Component (1): Compound having a (meth)acryloyl group> (I) Component (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. (1A) APG-700: Polypropylene glycol #700 diacrylate manufactured by Shin-Nakamura Chemical 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 Shin-Nakamura Chemical 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 Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 1892, number of acryloyl groups in one molecule: 4, (meth)acryloyl group equivalent: 473 (1D) A-1000: polyethylene glycol #1000 diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 1108, number of acryloyl groups in one molecule: 2, (meth)acryloyl group equivalent: 554

[0105] (II) Component (1-1'): A compound having an oxyalkylene unit and a (meth)acryloyl group, and having a (meth)acryloyl group equivalent of less than 300 (1E) "M-313": Toagosei Co., Ltd., mixture of isocyanuric acid EO-modified diacrylate 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

[0106] (III) Compounds having a (meth)acryloyl group other than components (1-1) and (1-1') (1F) EBECRYL600: bisphenol A type epoxy acrylate manufactured by Daicel Allnex Corporation, molecular weight: 500, number of acryloyl groups in one molecule: 2 (1G)IRR-214K: Tricyclodecanedimethanol manufactured by Daicel-Allnex Corporation Diacrylate, molecular weight: 300, number of acryloyl groups in one molecule: 2 (1H)DPHA: Dipentaerythritol hexaacrylate manufactured by Daicel Allnex Co., Ltd., molecular weight: 524, number of acryloyl groups in one molecule: 6 (1I) EBECRYL3708: Caprolactone-modified epoxy acrylate manufactured by Daicel-Allnex Corporation, molecular weight: 1,500, number of acryloyl groups in one molecule: 2 (1J) EBECRYL168: Daicel-Allnex Corporation, phosphoric acid modified methacrylate, molecular weight: 270, number of methacryloyl groups per molecule: 1.5

[0107] <Component (2): Polythiol compound> (2A) PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), manufactured by SC Organic Chemicals, molecular weight: 489, number of mercapto groups in one molecule: 4 (2B) PE1: Showa Denko "Karenzu MT" 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

[0108] <Component (3): Photoradical generator> (3A) Irgacure 1173: BASF, 2-hydroxy-2-methyl-1-phenylpropan-1-one (3B) Esacure KIP 150: manufactured by IGM Resins BV, oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one

[0109] <Component (4): Latent hardener> (4A)PN-23: Amine-epoxy adduct compound manufactured by Ajinomoto Fine-Techno Co., Ltd. (4B) FXR1081: Amine-isocyanate adduct compound manufactured by T&K TOKA

[0110] <Component (5): Epoxy resin> (5A) jER1001: Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent (EPW): 475g / eq, softening point: 64°C, number of epoxy groups in one molecule: 2 (5B) jER4005P: Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent (EPW): 538g / eq, softening point: 87℃, number of epoxy groups in one molecule: 2 (5C) HP-7200: DIC Corporation, dicyclopentadiene type epoxy resin, epoxy equivalent (EPW): 258g / eq, softening point: 56-66℃, number of epoxy groups in one molecule: 2-3 (5D) YX4000H: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent (EPW): 192g / eq, melting point: 105℃, number of epoxy groups in one molecule: 2

[0111] 2.Evaluation Test <Evaluation of Viscosity> The viscosity of the curable composition was measured using an E-type viscometer RE-80 manufactured by Toki Sangyo Co., Ltd. under conditions of temperature: 25° C., rotation speed: 20 rpm, and rotor: 3°×R9.7, and evaluated according to the following criteria. (Evaluation Criteria) ○: Viscosity is less than 10 Pa s ×: Viscosity is 10 Pa s or more

[0112] <Evaluation of curability> (1) Evaluation of photocuring properties The curable composition was spread to a thickness of about 50 μm on a glass epoxy resin laminate (manufactured by Risho Kogyo, FR-4.0) having dimensions of 2.5 mm wide x 8.0 mm long x 0.8 mm thick, using a spacer and a glass rod having a thickness of about 50 μm, to form a coating film of the curable composition, which was then photocured under the conditions described below. The appearance of the coating film was observed by touching with a finger, and the photocurability was evaluated according to the following criteria. (Curing conditions) The UV-LED irradiation device UniField NF150 manufactured by Ushio Electric Co., Ltd. was used, and the illuminance was 10mW / cm.2 The coating was irradiated with ultraviolet light (peak wavelength: 365 nm) for 100 seconds (exposure dose 1000 mJ / cm 2 ). (Evaluation Criteria) ○: There are no uncured areas on the coating ×: There are uncured areas on the coating

[0113] (2) Evaluation of photo- and thermosetting properties Similarly to the above, a coating film of the curable composition formed on a glass epoxy resin laminate was subjected to photo- and heat-curing under the following conditions, and the appearance of the coating film was observed by touching with a finger, and the photo- and heat-curing properties were evaluated according to the following criteria. (Curing conditions) The UV-LED irradiation device UniField NF150 manufactured by Ushio Electric Co., Ltd. was used, and the illuminance was 10mW / cm. 2 The coating was irradiated with ultraviolet light (peak wavelength: 365 nm) for 100 seconds (exposure dose 1000 mJ / cm 2 ) and then the irradiated coating film was heated in a hot air circulating oven at 100°C for 30 minutes. (Evaluation Criteria) ○: There are no uncured areas on the coating ×: There are uncured areas on the coating

[0114] (3) Evaluation of thermosetting properties Similarly to the above, a coating film of the curable composition formed on a glass epoxy resin laminate was subjected to thermal curing under the following conditions, and the appearance of the coating film was observed by touching with a finger, and the thermosetting property was evaluated according to the following criteria. (Curing conditions) The coating was heated in a hot air circulating oven at 100° C. for 30 minutes. (Evaluation Criteria) ○: There are no uncured areas on the coating ×: There are uncured areas on the coating

[0115] <Evaluation of cure shrinkage rate> The specific gravity of the curable composition before curing and the cured product thereof were measured using a dry automatic density meter (AccuPic II1340) manufactured by Shimadzu Corporation, and calculated using the following formula: Cure shrinkage rate (%) = {(specific gravity of cured product - specific gravity of curable composition before curing) / specific gravity of cured product} x 100 The cure shrinkage was calculated and evaluated according to the following criteria. (Evaluation Criteria) ○: Curing shrinkage rate is less than 5% ×: Curing shrinkage rate is 5% or more

[0116] The cured product was prepared by applying the curable composition to the release surface of a release polyethylene terephthalate (PET) film (NS-80A), spreading it out to a thickness of about 50 μm with a glass rod, and then irradiating it with a UV-LED irradiation device UniField NF150 manufactured by Ushio Inc. at an illumination intensity of 10 mW / cm. 2 of ultraviolet light (peak wavelength: 365 nm) for 100 seconds (exposure dose 1000 mJ / cm 2 ) and then the light-irradiated curable composition was heated in a hot air circulating oven at 100° C. for 30 minutes to prepare a curable film.

[0117] 3. Examples and Comparative Examples The curable compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were prepared by mixing the components in the amounts shown in the upper columns of the following tables. In addition, "parts" in the tables indicate "parts by weight." In addition, in the tables, the "molar ratio of the total of acryloyl groups and methacryloyl groups in component (1) to the mercapto groups in component (2)" is shown in the "(meth)acryloyl groups / mercapto groups" column.

[0118] In Examples 1 to 11 and Comparative Examples 1, 2, and 4, components (1) and (4) were thoroughly mixed, and then components (2) and (3) were added thereto and mixed, and then the mixture was left to stand and defoamed to prepare a curable composition. In Comparative Example 3, components (1) and (4) were thoroughly mixed, and then component (3) was added thereto and mixed, and then the mixture was left to stand and defoamed to prepare a curable composition. In Examples 12 to 15, components (1) and (5) were mixed and dissolved at 100°C, and then cooled sufficiently to room temperature (20 to 25°C), and then component (4) was added thereto and mixed, and then components (2) and (3) were added thereto and mixed, and then the mixture was left to stand and defoamed to prepare a curable composition. The preparation operations in Examples 1 to 15 and Comparative Examples 1 to 4 were carried out at room temperature, except for the mixing and dissolution of components (1) and (5) in Examples 12 to 15.

[0119] 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.

[0120] [Table 1]

[0121] [Table 2]

[0122] [Table 3]

[0123] [Table 4]

[0124] From the results of Examples 1 to 15, it is found that the curable composition of the present invention has a low viscosity and is excellent in workability. It is also found that the curable composition of the present invention has a small cure shrinkage rate and can suppress positional deviation due to cure shrinkage. In contrast, the curable compositions of Comparative Examples 1 to 4 all had a high cure shrinkage rate. Furthermore, the curable compositions of Comparative Examples 2 to 4 had a high viscosity, and the curable composition of Comparative Example 3 had insufficient thermosetting properties. [Industrial Applicability]

[0125] The curable compositions of the present invention are useful for adhesives, sealants, coatings (particularly adhesives used for producing camera modules), and the like.

Claims

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 photoradical generator, and (4) Latent hardener A curable composition comprising: The 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.

1. A curable composition comprising:

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

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

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

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

0.

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

7. An adhesive comprising the curable composition according to any one of claims 1 to 6.

8. The adhesive of claim 7 for bonding between components of a camera module.

9. A sealant comprising the curable composition according to any one of claims 1 to 6.

10. A coating agent comprising the curable composition according to any one of claims 1 to 6.

11. The following steps (I) to (III): (I) a step of positioning a first adhesive part coated with the curable composition according to any one of claims 1 to 6 and a second adhesive part; (II) a step of curing the curable composition by light irradiation to temporarily fix the first adhesive part and the second adhesive part together; and (III) A step of curing the curable composition by heating to completely fix the first adhesive part and the second adhesive part together. A method for manufacturing a camera module, comprising:

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