Sclerotic composition

Abstract

To provide a curable composition that is small in curing shrinkage rate and ensures good compatibility of used components.SOLUTION: A curable composition comprises (1) a compound having a methacryloyl group, (2) a polythiol compound, (3) at least one selected from the group consisting of crystalline bisphenol type epoxy resin and crystalline phenyl sulfide epoxy resin, (4) a photoradical generator, and (5) a latent curing agent.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 mounted on 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-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 fixed with a jig or device to maintain the adhesive 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 to 5). [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 [Patent Document 5] Patent Publication No. 2021-75698 Summary of the Invention [Problem to be solved by the invention]

[0006] Even when a photo- or thermosetting adhesive is used, if the adhesive has a large cure shrinkage rate, there is a problem that the parts may become misaligned due to shrinkage. In addition, if the compatibility between a compound having a (meth)acryloyl group and a solid epoxy compound is low, precipitation of the solid epoxy compound may occur when preparing a curable composition, or phase separation may occur in the cured product obtained from the curable composition.

[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 having a small cure shrinkage rate and excellent compatibility of the components used (in detail, compatibility of component (3) described below with component (1) described below). [Means for solving the problem]

[0008] The present invention capable of achieving the above object is as follows. [1] The following ingredients (1) to (5): (1) A compound having a (meth)acryloyl group, (2) a polythiol compound, (3) at least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins; (4) a photoradical generator, and (5) Latent hardener 1. A curable composition comprising: [2] The curable composition according to the above [1], wherein the component (2) contains a polythiol compound having 2 to 6 mercapto groups in one molecule. [3] The curable composition according to the above [1] or [2], wherein the molar ratio of the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition to the mercapto groups in component (2) (the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition / mercapto groups in component (2)) is 0.5 to 2.0. [4] The component (3) has the formula (3a):

[0009] [ka]

[0010] [In formula (3a), n is a number of 0 or more.] Epoxy resins represented by formula (3b):

[0011] [ka]

[0012] [In formula (3b), Me represents a methyl group, and t-Bu represents a tert-butyl group.] Epoxy resins represented by the formula:

[0013] [ka]

[0014] [In formula (3c), Me represents a methyl group.] The curable composition according to any one of the above [1] to [3], comprising at least one selected from the group consisting of epoxy resins represented by the following formula: [5] The curable composition according to any one of the above [1] to [4], wherein the component (5) comprises at least one selected from the group consisting of an amine-epoxy adduct compound and an amine-isocyanate adduct compound. [6] An adhesive comprising the curable composition according to any one of [1] to [5] above. [7] The adhesive according to [6] above, which is for bonding components of a camera module. [8] A sealant comprising the curable composition according to any one of [1] to [5] above. [9] A coating agent comprising the curable composition according to any one of [1] to [5] above.

[10] 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 [1] to [5] above 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

[0015] According to the present invention, it is possible to obtain a curable composition which has a small cure shrinkage rate and excellent compatibility of the components used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] <Curable composition> The curable composition of the present invention comprises the following components (1) to (5): (1) A compound having a (meth)acryloyl group, (2) a polythiol compound, (3) at least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins; (4) a photoradical generator, and (5) Latent hardener The present invention is characterized by comprising:

[0017] The curable composition of the present invention is liquid at 25° C. Here, "the curable composition is liquid at 25° C." means that the curable composition is a fluid having fluidity at 25° C. The curable composition of the present invention may contain a solid component such as an inorganic filler, and even if the curable composition contains both a liquid component and a solid component, it is included in the liquid composition of the present invention as long as it is a fluid having fluidity at 25° C.

[0018] When the viscosity of the curable composition is high, the workability (ease of application, etc.) of the curable composition tends to decrease. For example, the curable composition described in Patent Document 5 contains a compound having a (meth)acryloyl group and an epoxy compound having two or more epoxy groups in one molecule and being solid at 25°C, but the viscosity of the curable composition containing a solid epoxy compound tends to increase. For example, in terms of dischargeability when applied with a dispenser and stable discharge in a place with a small application area, it is desired that the viscosity of the curable composition is lower. The viscosity of the curable composition of the present invention at 25°C is preferably 0.1 to 100 Pa·s, more preferably 0.1 to 10 Pa·s, and even more preferably 0.1 to 1.2 Pa·s. The viscosity is a value measured using an E-type viscometer under conditions of 25°C and 20 rpm. An example of an E-type viscometer is "RE-25U" manufactured by Toki Sangyo Co., Ltd.

[0019] The curable composition of the present invention may contain each of the components either alone or in combination of two or more. Each component will be described below in order.

[0020] <(1) Compound Having a (Meth)acryloyl Group> One of the features of the present invention is the use of a compound having a (meth)acryloyl group as component (1). This component (1) is a component that mainly plays a role in increasing adhesive strength. Here, the "(meth)acryloyl group" means either or both of an acryloyl group and a methacryloyl group.

[0021] The number of (meth)acryloyl groups in one molecule of a compound having a (meth)acryloyl group may be 1 or more. When the compound having a (meth)acryloyl group 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 a compound having a (meth)acryloyl group (excluding phosphoric acid-modified (meth)acrylate described later) is preferably 1 to 6, more preferably 2 to 6, and even more preferably 2 to 4.

[0022] The molecular weight of the compound having a (meth)acryloyl group is preferably 50 to 5,000, more preferably 70 to 4,000, and even more preferably 100 to 2,000, in consideration of ease of handling, low volatility, and low viscosity. Note that a molecular weight of 1,000 or more means a weight average molecular weight, and can be measured by gel permeation chromatography (GPC). A molecular weight of less than 1,000 can be measured by a gravimetric analyzer (e.g., ESI-MS).

[0023] Examples of the compound having a (meth)acryloyl group include the following compounds. Note that, each of the following compounds may be used alone or in combination of two or more kinds.

[0024] (Compounds containing one acryloyl or methacryloyl group per molecule) β-Carboxyethyl (meth)acrylate Isobornyl (meth)acrylate Octyl / Decyl (meth)acrylate Ethoxylated phenyl (meth)acrylate EO modified phenol (meth)acrylate EO modified o-phenylphenol (meth)acrylate EO modified paracumylphenol (meth)acrylate EO modified nonylphenol (meth)acrylate PO modified nonylphenol (meth)acrylate N-(meth)acryloyloxyethylhexahydrophthalimide ω-Carboxy-polycaprolactone mono(meth)acrylate Monohydroxyethyl phthalate (meth)acrylate 2-Hydroxy-3-phenoxypropyl (meth)acrylate

[0025] In the present invention, "(meth)acrylate" means either or both of acrylate and methacrylate. "EO-modified" means modified by the addition of ethylene oxide (EO). "PO-modified" means modified by the addition of propylene oxide (PO).

[0026] (Compound having two (meth)acryloyl groups in one molecule) Dipropylene glycol di(meth)acrylate 1,6-Hexanediol di(meth)acrylate Tripropylene glycol di(meth)acrylate PO modified neopentyl glycol di(meth)acrylate Tricyclodecane dimethanol di(meth)acrylate EO modified bisphenol F di(meth)acrylate EO modified bisphenol A di(meth)acrylate EO modified isocyanuric acid di(meth)acrylate Polypropylene glycol di(meth)acrylate Polyethylene glycol 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

[0027] (Compounds having three or more (meth)acryloyl groups in one molecule) Trimethylolpropane tri(meth)acrylate PO modified trimethylolpropane tri(meth)acrylate EO modified trimethylolpropane tri(meth)acrylate EO modified isocyanuric acid (tri)(meth)acrylate Pentaerythritol (tri / tetra)(meth)acrylate Glycerin Propoxytri(meth)acrylate Pentaerythritol ethoxy tetra(meth)acrylate Ditrimethylolpropane tetra(meth)acrylate Dipentaerythritol (penta / hexa)(meth)acrylate Dipentaerythritol hexa(meth)acrylate EO modified diglycerin tetra(meth)acrylate Polyurethane containing three or more (meth)acryloyl groups in one molecule Polyester containing three or more (meth)acryloyl groups in one molecule

[0028] 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.

[0029] 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.

[0030] As a compound having a (meth)acryloyl group, EO modified isocyanuric acid (di / tri)(meth)acrylate can be used. Here, EO modified isocyanuric acid (di / tri)(meth)acrylate is a mixture of EO modified isocyanuric acid di(meth)acrylate and EO modified isocyanuric acid tri(meth)acrylate. The mixture ratio (EO modified isocyanuric acid di(meth)acrylate / EO modified isocyanuric acid tri(meth)acrylate) is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and even more preferably 40 / 60 to 60 / 40 by weight.

[0031] The compound having a (meth)acryloyl group may be a commercially available product, such as "IRR-214K" or "EBECRYL TMPTMA" manufactured by Daicel-Allnex Corporation.

[0032] The viscosity of component (1) at 25°C is preferably 1 to 2,000 mPa·s, more preferably 10 to 1,000 mPa·s, even more preferably 30 to 500 mPa·s, and particularly preferably 50 to 200 mPa·s. The viscosity is measured using an E-type viscometer at 25°C and 20 rpm. An example of an E-type viscometer is the "RE-25U" manufactured by Toki Sangyo Co., Ltd. When two or more types of component (1) are used, the viscosity of component (1) refers to the viscosity of the entire mixture of two or more types of component (1). Similarly, when two or more types of components different from component (1) are used, the viscosity of the component refers to the viscosity of the entire mixture of two or more types of the component.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] The phosphoric acid-modified (meth)acrylate may be a commercially available product, such as "EBECRYL168" manufactured by Allnex, "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Nippon Kayaku, "Light Ester P-1M", "Light Ester P-2M", and "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical, and "JPA-514" manufactured by Johoku Chemical Industry.

[0037] 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.

[0038] When a phosphoric acid-modified (meth)acrylate is used, from the viewpoints of storage stability and curability, 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).

[0039] In another embodiment of the present invention, component (1) preferably comprises a mixture of at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate and trimethylolpropane tri(meth)acrylate with a phosphoric acid-modified (meth)acrylate, and is more preferably a mixture of at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate and trimethylolpropane tri(meth)acrylate with a phosphoric acid-modified (meth)acrylate.

[0040] In another embodiment of the present invention, component (1) preferably comprises a mixture of tricyclodecane dimethanol di(meth)acrylate or trimethylolpropane tri(meth)acrylate and a phosphoric acid modified (meth)acrylate, more preferably a mixture of tricyclodecane dimethanol di(meth)acrylate or trimethylolpropane tri(meth)acrylate and a phosphoric acid modified (meth)acrylate.

[0041] From the viewpoints of low viscosity, cure shrinkage rate, etc. of the curable composition, the amount of component (1) is preferably 20 to 60 mass %, more preferably 20 to 50 mass %, and even more preferably 30 to 40 mass %, based on the total mass of the curable composition.

[0042] <(2) Polythiol compounds> One of the features of the present invention is the use of a polythiol compound as component (2). Here, "polythiol compound" means a compound having two or more mercapto groups in one molecule. Component (2) mainly plays a role of reacting with component (1) by irradiation with light such as ultraviolet light to cure the composition.

[0043] In one embodiment of the present invention, component (2) contains a polythiol compound having preferably 2 to 6, more preferably 3 to 6, even more preferably 3 to 5, and particularly preferably 3 or 4 mercapto groups in one molecule.

[0044] In another embodiment of the present invention, component (2) is 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.

[0045] 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).

[0046] 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 in which all of the hydroxyl groups of the polyol form ester bonds.

[0047] Examples of polyols include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0048] 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.

[0049] 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).

[0050] 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 tris(4-mercaptobutyrate), and pentaerythritol. Examples of the mercaptoacetate include 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).

[0051] 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.

[0052] 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.

[0053] 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.

[0054] Examples of component (2) that can be used include tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,4-bis(3-mercaptobutyryloxy)butane, 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.

[0055] From the viewpoint of curability, the molar ratio of the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition to the mercapto groups in component (2) (the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition / 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.

[0056] The viscosity of component (2) at 25°C is preferably 1 to 10,000 mPa·s, more preferably 50 to 3,000 mPa·s, and even more preferably 100 to 1,500 mPa·s. The viscosity is measured using an E-type viscometer at 25°C and 20 rpm. An example of an E-type viscometer is the "RE-25U" manufactured by Toki Sangyo Co., Ltd.

[0057] In one embodiment of the present invention, component (2) preferably comprises 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-mercaptobutyrate).

[0058] From the viewpoints of low viscosity, curability, and adhesion of the curable composition, the amount of component (2) is preferably 20 to 60 mass %, more preferably 30 to 50 mass %, and even more preferably 40 to 50 mass %, based on the total mass of the curable composition.

[0059] <(3) At least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins> One of the features of the present invention is that at least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins is used as component (3). By using component (3), which is a crystalline epoxy resin, the viscosity of the curable composition can be reduced compared to the case of using an amorphous epoxy resin. In addition, by using component (3), the cure shrinkage rate of the curable composition can be reduced.

[0060] In this specification, "crystalline epoxy resin" means an epoxy resin that is solid at 25°C and has a melting point (in other words, an epoxy resin that has a melting point higher than 25°C), and "amorphous epoxy resin" means an epoxy resin that is solid at 25°C and does not have a melting point (in other words, an epoxy resin that does not have a melting point and has a softening point higher than 25°C). Therefore, neither the concept of "crystalline epoxy resin" nor the concept of "amorphous epoxy resin" includes an epoxy resin that is liquid at 25°C (in other words, an epoxy resin that has a melting point or softening point of 25°C or lower). Whether an epoxy resin has a melting point can be determined by whether or not there is a clear endothermic peak indicating a melting point in a DSC chart obtained by differential scanning calorimetry (DSC) of the epoxy resin.

[0061] In the present specification, the term "bisphenol type epoxy resin" refers to an epoxy resin having a structure in which bisphenol and epichlorohydrin are condensed. Examples of the bisphenol include bisphenol A, bisphenol AD, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z.

[0062] In this specification, the term "phenyl sulfide type epoxy resin" refers to an epoxy resin having a structure in which bis(4-hydroxyphenyl) sulfide and epichlorohydrin are condensed.

[0063] The crystalline bisphenol type epoxy resin and the crystalline phenyl sulfide type epoxy resin may each have one or more repeating units. In addition, the hydrogen atoms of the benzene ring in the crystalline bisphenol type epoxy resin and the crystalline phenyl sulfide type epoxy resin may each be substituted with a substituent. Examples of the substituent include halogen atoms, C 1-6 Alkyl group, C 1-6 Examples include haloalkyl groups.

[0064] The melting point of each epoxy resin, component (3), is preferably 60 to 150°C, more preferably 70 to 150°C, further preferably 70 to 140°C, and particularly preferably 70 to 130°C.

[0065] The endothermic heat of the endothermic peak at the melting point in the DSC chart of each epoxy resin, which is component (3), is preferably 100 μW / mg or more, more preferably 300 μW / mg or more, and even more preferably 500 μW / mg or more.

[0066] The molecular weight of each epoxy resin, which is component (3), is preferably 200 to 700, more preferably 300 to 700, and even more preferably 300 to 600, from the viewpoint of reactivity.

[0067] From the viewpoint of reactivity, the epoxy equivalent of each epoxy resin, which is component (3), is preferably 100 to 350 g / eq, more preferably 150 to 350 g / eq, and even more preferably 150 to 300 g / eq. Here, "epoxy equivalent" means the number of grams of a resin containing 1 gram equivalent of epoxy groups (unit: g / eq). The epoxy equivalent can be measured according to the method specified in JIS K 7236. Theoretically, the epoxy equivalent can be calculated by dividing the molecular weight of a resin by the number of epoxy groups that the resin has.

[0068] Component (3) preferably has the formula (3a):

[0069] [ka]

[0070] [In formula (3a), n is a number of 0 or more.] Epoxy resin represented by formula (3b):

[0071] [ka]

[0072] [In formula (3b), Me represents a methyl group, and t-Bu represents a tert-butyl group.] (hereinafter, may be referred to as "epoxy resin (3b)") represented by the formula:

[0073] [ka]

[0074] [In formula (3c), Me represents a methyl group.] The epoxy resin (3c) includes at least one selected from the group consisting of epoxy resins represented by the following formula (hereinafter, may be referred to as "epoxy resin (3c)").

[0075] In the formula (3a), n may be a decimal number (for example, 0.5). n is preferably 0 to 1, and more preferably 0.

[0076] Commercially available products may be used for the epoxy resins (3a) to (3c). An example of a commercially available product of the epoxy resin (3a) in which n is 0 is "YX-7760" manufactured by Mitsubishi Chemical Corporation. An example of a commercially available product of the epoxy resin (3b) is "YSLV-120TE" manufactured by Nippon Steel Chemical & Material Corporation. An example of a commercially available product of the epoxy resin (3c) is "YSLV-80XY" manufactured by Nippon Steel Chemical & Material Corporation.

[0077] The component (3) is more preferably at least one selected from the group consisting of epoxy resin (3a), epoxy resin (3b) and epoxy resin (3c), and even more preferably epoxy resin (3a), epoxy resin (3b) or epoxy resin (3c).

[0078] From the viewpoints of compatibility with component (1), cure shrinkage rate, etc., the amount of component (3) is preferably 1 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 10 to 30 mass %, based on the total mass of the curable composition.

[0079] <(4) Photoradical generator> The photoradical generator used as component (4) 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] Examples of α-hydroxyketone photoradical generators 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, and 1-hydroxycyclohexyl phenyl ketone.

[0084] Commercially available photoradical generators include, for example, "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-carbazol-3-yl]ethanone O-acetyloxime), "Esacure KTO 46" (mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane] and methylbenzophenone derivatives) and "Esacure KIP 150" (oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one).

[0085] The amount of component (4) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, based on the total amount of the 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 products, the amount of component (4) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, based on the total amount of the curable composition.

[0086] <(5) Latent hardener> In the present invention, a latent curing agent is used as component (5). The term "latent curing agent" used herein means an additive well known in the field of epoxy resins that does not cure epoxy resins at room temperature (25°C) but can cure epoxy resins by heating.

[0087] 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).

[0088] 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.

[0089] Examples of epoxy compounds used as raw materials for amine-epoxy adduct compounds include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxy acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and 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.

[0090] 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.

[0091] 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;

[0092] When an amine-epoxy adduct compound is produced by addition reaction of an epoxy compound with an amine compound, an active hydrogen compound having two or more active hydrogens in one molecule can be added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin, polyhydric alcohols such as trimethylolpropane, polycarboxylic 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] Component (5) preferably contains at least one selected from the group consisting of an amine-epoxy adduct compound and an amine-isocyanate adduct compound, more preferably at least one selected from the group consisting of an amine-epoxy adduct compound and 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.

[0097] From the viewpoint of thermosetting property, the amount of component (5) is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 3 mass% or more based on the total curable composition. Also, from the viewpoint of storage stability, the amount of component (5) is preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less based on the total curable composition.

[0098] <Other ingredients> The curable composition of the present invention may contain components other than the above-mentioned components (1) to (5) (sometimes referred to as "other components" in this specification) as long as the effects of the present invention are not impaired.

[0099] For example, the curable composition of the present invention may contain an epoxy resin other than component (3) within a range that does not impair the effects of the present invention. Examples of epoxy resins other than component (3) include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, phosphorus-containing epoxy resins, aromatic glycidylamine type epoxy resins, alicyclic epoxy resins, oxazolidone ring type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and bisphenol A novolac type epoxy resins. The epoxy resins other than component (3) may be used alone or in combination of two or more.

[0100] From the viewpoint of fully exerting the effects of the present invention, it is preferable that the curable composition of the present invention does not contain any epoxy resin other than component (3) or contains it in an amount of 30 mass% or less based on the entire curable composition. The amount of epoxy resin other than component (3) is more preferably 20 mass% or less, and further preferably 10 mass% or less. It is most preferable that the curable composition of the present invention does not contain any epoxy resin other than component (3).

[0101] Other components include, for example, polymerization inhibitors; 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 consisting of copolymers obtained by copolymerizing polymethyl methacrylate and / or polystyrene with monomers that constitute these and monomers that are copolymerizable therewith; thixotropic agents; defoamers; leveling agents; coupling agents; flame retardants; pigments; dyes; fluorescent agents, etc.

[0102] As another component, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include tert-butylhydroquinone, dibutylhydroxytoluene, barbituric acid, etc. When a polymerization inhibitor is used, the amount thereof is preferably 0.001 to 1 mass %, more preferably 0.001 to 0.5 mass %, and even more preferably 0.001 to 0.1 mass % or less based on the total amount of the curable composition.

[0103] The curable composition of the present invention may contain a stabilizer as another component from the viewpoint of storage stability, etc. Examples of the stabilizer include borate ester compounds, titanate ester compounds, aluminate compounds, zirconate compounds, and isocyanate compounds.

[0104] As described above, the phosphoric acid-modified (meth)acrylate, which is one of the components (1), has a function of improving the storage stability of the curable composition. Therefore, from the viewpoint of storage stability, the curable composition of the present invention preferably contains a phosphoric acid-modified (meth)acrylate as the component (1) and / or a stabilizer.

[0105] Examples of borate ester compounds include trimethyl borate, triethyl borate, Examples of the borate include tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0106] Examples of titanate compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0107] Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

[0108] Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0109] Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, toluylene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, and bicycloheptane triisocyanate.

[0110] As the stabilizer, from the viewpoints of versatility of the stabilizer and storage stability of the curable composition, borate ester compounds are preferred, triethyl borate, tri-n-propyl borate, triisopropyl borate and tri-n-butyl borate are more preferred, and triethyl borate is even more preferred.

[0111] When a stabilizer is used, the amount thereof is not particularly limited, but from the viewpoint of storage stability, the amount thereof is preferably 0.001 mass % or more, more preferably 0.01 mass % or more, even more preferably 0.1 mass % or more, and is preferably 5 mass % or less, more preferably 3 mass % or less, even more preferably 2 mass % or less, based on the total amount of the curable composition.

[0112] <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.

[0113] 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.

[0114] 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, UV-LED irradiation devices, xenon lamps, and DEEP UV lamps.

[0115] 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.

[0116] <Uses of the curable composition> The curable composition of the present invention is useful for adhesives, sealants, coating agents, etc., and the present invention also provides adhesives, sealants, and coating agents containing the curable composition. The adhesive is preferably used for adhesion between components of a camera module.

[0117] <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.

[0118] 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.

[0119] In step (II), depending on the positional relationship between the first adhesive part and the second adhesive part, there may be an unirradiated portion of the applied curable composition that is not irradiated with light. This unirradiated portion also undergoes sufficient curing by the thermal curing in step (III) to reach full curing, and a cured product having high adhesive strength can be formed from the entire applied curable composition.

[0120] 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

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" refers to "parts by weight."

[0122] 1.Raw materials [Component (1): Compound having a (meth)acryloyl group] (1A) IRR-214K: Tricyclodecane dimethanol diacrylate manufactured by Daicel Allnex Corporation, molecular weight: 300, number of acryloyl groups in one molecule: 2, viscosity (25°C): 140 mPa s (1B) EBECRYL TMPTMA: Trimethylolpropane trimethacrylate manufactured by Daicel Allnex Co., Ltd., molecular weight: 338, number of methacryloyl groups in one molecule: 3, viscosity (25°C): 60 mPa s (1C) EBECRYL168: Daicel-Allnex Corporation, phosphoric acid modified methacrylate, molecular weight: 270, number of methacryloyl groups per molecule: 1.5, viscosity (25°C): 1,700 mPa s

[0123] [Component (2): Polythiol compound] PE1: Showa Denko "Karenz MT" pentaerythritol tetrakis(3-mercaptobutyrate), molecular weight: 544, number of mercapto groups per molecule: 4, viscosity (25°C): 1,100 mPa·s

[0124] [Component (3): at least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins] (3A) YX-7760: Mitsubishi Chemical Corporation, crystalline bisphenol AF type epoxy resin, epoxy equivalent: 236 g / eq, melting point: 72°C (endothermic heat of melting point peak in DSC chart: 701 mW / mg), number of epoxy groups per molecule: 2 (3B) YSLV-120TE: Crystalline bisphenol sulfide type epoxy resin manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 246g / eq, melting point: 120℃ (endothermic heat of melting point peak in DSC chart: 893mW / mg), number of epoxy groups in one molecule: 2 (3C) YSLV-80XY: crystalline tetramethylbisphenol F type epoxy resin manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 192 g / eq, melting point: 70°C (endothermic heat of melting point peak in DSC chart: 602 mW / mg), number of epoxy groups in one molecule: 2

[0125] The melting point of component (3) was measured using a differential scanning calorimeter (Hitachi DSC7000X). Specifically, the melting point of component (3) was determined from a DSC chart obtained by measuring in the range of -10°C to 250°C at a rate of 10°C / min. When there were multiple endothermic peaks, the temperature of the endothermic peak with the maximum amount of endotherm was taken as the melting point.

[0126] [Ingredient (4): Photoradical generator] Esacure KTO 46: DKSH, mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane] and methylbenzophenone derivatives

[0127] [Component (5): Latent hardener] PN-23: Amicure PN-23 (amine-epoxy adduct compound) manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0128] [Component (6): Epoxy resin other than component (3)] (6A) jER1001: Amorphous bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 475g / eq, softening point: 64°C, number of epoxy groups in one molecule: 2 (6B) jER828EL: Amorphous bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190g / eq, liquid at 25℃, number of epoxy groups per molecule: 2 (6C)HP-6000L: DIC amorphous naphthylene ether type epoxy resin, epoxy equivalent: 213g / eq, softening point: 59℃ (6D)HP-7200: Amorphous dicyclopentadiene type epoxy resin manufactured by DIC Corporation, epoxy equivalent: 258g / eq, softening point: 56-66℃, number of epoxy groups in one molecule: 2-3 (6E) YX-4000H: Mitsubishi Chemical Corporation, crystalline biphenyl type epoxy resin, epoxy equivalent: 192g / eq, melting point: 105℃, number of epoxy groups per molecule: 2

[0129] [Other ingredients] TBHQ: tert-butylhydroquinone (polymerization inhibitor) manufactured by Fujifilm Wako Co., Ltd.

[0130] 2. Examples and Comparative Examples The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were prepared by mixing the components in the amounts shown in Tables 1 to 3 below. In Examples 1 to 5, the components (1) and (3) were mixed and dissolved at 110°C, cooled sufficiently to room temperature, and then the component (5) was added thereto and thoroughly dispersed, and then the components (2) and (4) were added thereto and mixed, and then the mixture was left to stand and degassed to prepare the curable compositions. In Comparative Examples 1 to 6, the components (1) and (6) were mixed, then the component (5) was added thereto and thoroughly dispersed, and then the components (2) and (4) were added thereto and mixed, and then the mixture was left to stand and degassed to prepare the curable compositions. The preparation operations other than the mixing and dissolving of the components (1) and (3) were carried out at 25°C. In the column "((meth)acryloyl group + epoxy group) / mercapto group" in Tables 1 to 3 below, the "molar ratio of the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition to the mercapto groups in component (2)" is shown.

[0131] 3.Evaluation Test [Uniformity of the cured product] 4 mL of the curable composition obtained as described above was poured into a 10 mL disposable syringe (manufactured by Tomsic), vacuum degassed, and then heated at 80°C for 1 hour to obtain a cured product. The obtained cured product was visually observed and evaluated according to the following criteria. The results are shown in Tables 4 to 6 below. (Evaluation Criteria) ◯: A uniform cured product was obtained, and no phase separation was observed. ×: Phase separation was observed in the cured product.

[0132] [Storage stability of resin solution] In order to evaluate the storage stability of a solution of a compound having a (meth)acryloyl group and an epoxy resin (referred to as "resin solution" in the Examples column), in Examples 1 to 5, components (1) and (3) were mixed in the amounts shown in Table 1, the resulting mixture was heated and dissolved at 110°C, and cooled to 25°C to obtain a resin solution. Similarly, in Comparative Examples 1 to 6, components (1) and (6) were mixed in the amounts shown in Tables 2 and 3, the resulting mixture was heated and dissolved at 110°C, and cooled to 25°C to obtain a resin solution. The resulting resin solution was left to stand at 25°C, and the presence or absence of crystal precipitation was confirmed, and evaluated according to the following criteria. The results are shown in Tables 4 to 6 below. (Evaluation Criteria) ○: No crystal precipitation was observed within three days. ×: Crystal precipitation was observed within three days.

[0133] [Cure shrinkage rate] (1) Preparation of hardened material 4 mL of the curable composition obtained as described above was poured into a 10 mL disposable syringe (manufactured by Tomsic), and the mixture was degassed under vacuum and then heated at 80° C. for 1 hour to obtain a cured product.

[0134] (2) Measurement of cure shrinkage rate The density of the cured product obtained as described above was measured using a pycnometer (Shimadzu Corporation's "Accupyk II"). Similarly, the density of the curable composition obtained as described above was measured. Using the density obtained, the following formula: Curing shrinkage rate (%) = 100 × [(density of cured product) - (density of curable composition)] / (density of cured product) The cure shrinkage was calculated based on the following criteria and evaluated. The results are shown in Tables 4 to 6 below. (Evaluation Criteria) Good: Curing shrinkage rate is less than 5.5% ×: Curing shrinkage rate is 5.5% or more

[0135] [viscosity] The viscosity of the curable composition obtained as described above was measured using an E-type viscometer "RE-85U" manufactured by Toki Sangyo Co., Ltd. under the conditions of temperature: 25°C, rotation speed: 20 rpm, and rotor: 1.34° × R24. The results are shown in Tables 4 to 6 below.

[0136] [Adhesive strength] A 1-3 mg amount of the curable composition was applied onto a liquid crystal polymer (LCP) plate ("CM-529B" manufactured by ENEOS Liquid Crystal Corporation) measuring 100 mm in length, 25 mm in width, and 2 mm in thickness, and a chip capacitor (JIS designation 2012 size) was placed on top of it. Photocuring was performed under the following conditions to form a cured product, and its adhesive strength was measured.

[0137] Adhesive strength (N / mm 2 ) was measured by breaking the chip capacitor from the side using a bond tester (Dega Series 4000). The measurement was performed five times and the average value was calculated. The results are shown in Tables 4 to 6 below. (Curing conditions) The UV-LED irradiation device "UniField NF150" manufactured by Ushio Electric Co., Ltd., has a peak wavelength of 365 nm and an exposure of 3000 mJ / cm 2 The curable compositions were irradiated with light under the above conditions and evaluated according to the following criteria. The results are shown in Tables 4 to 6 below. (Evaluation Criteria) ○: Cured under the above conditions ×: Not cured under the above conditions

[0138] [Table 1]

[0139] [Table 2]

[0140] [Table 3]

[0141] [Table 4]

[0142] [Table 5]

[0143] [Table 6]

[0144] As shown in the above table, curable compositions with small cure shrinkage rates were obtained in Examples 1 to 5. Furthermore, the compatibility of component (3) with component (1) used in Examples 1 to 5 was high, the resin solutions of Examples 1 to 5 had excellent storage stability, and uniform cured products were obtained from the curable compositions of Examples 1 to 5.

[0145] In Comparative Example 1, in which component (6A) (jER1001, amorphous bisphenol A type epoxy resin) was used instead of component (3) of the present invention, the cure shrinkage rate of the curable composition was large.

[0146] In Comparative Example 2, in which component (6B) (JER828EL, amorphous bisphenol A type epoxy resin) was used instead of component (3) of the present invention, the cure shrinkage rate of the curable composition was large.

[0147] In Comparative Example 3, in which component (6C) (HP-6000L, amorphous naphthylene ether type epoxy resin) was used instead of component (3) of the present invention, the cure shrinkage rate of the curable composition was large.

[0148] In Comparative Example 4, in which component (6D) (HP-7200, amorphous dicyclopentadiene-type epoxy resin) was used instead of component (3) of the present invention, the cure shrinkage rate of the curable composition was large.

[0149] In Comparative Example 5, in which component (6E) (YX-4000H, crystalline biphenyl type epoxy resin) was used instead of component (3) of the present invention, the uniformity of the cured product was poor. In Comparative Example 6, in which component (6E) was used instead of component (3) of the present invention, the uniformity of the cured product and the storage stability of the resin solution were poor. [Industrial Applicability]

[0150] 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 (5): (1) A compound having a (meth)acryloyl group, (2) a polythiol compound, (3) at least one selected from the group consisting of crystalline bisphenol type epoxy resins and crystalline phenyl sulfide type epoxy resins; (4) a photoradical generator, and (5) Latent hardener A curable composition comprising: the molar ratio of the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition to the mercapto groups in component (2) (the sum of the acryloyl groups and methacryloyl groups in component (1) and the epoxy groups in the epoxy resin contained in the curable composition / mercapto groups in component (2)) is 0.5 to 2.0, and The amount of component (1) is 20 to 60 mass% and the amount of component (3) is 1 to 50 mass% based on the entire curable composition. Curable composition.

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

3. Component (3) is represented by formula (3a): 【Chemistry 1】 [In formula (3a), n represents a number of 0 or more.] Epoxy resins represented by formula (3b): 【Chemistry 2】 [In formula (3b), Me represents a methyl group, and t-Bu represents a tert-butyl group.] Epoxy resins represented by the formula: 【Chemistry 3】 [In formula (3c), Me represents a methyl group.] The curable composition according to claim 1 or 2, comprising at least one epoxy resin selected from the group consisting of epoxy resins represented by the formula:

4. The curable composition according to any one of claims 1 to 3, wherein the component (5) comprises at least one selected from the group consisting of an amine-epoxy adduct compound and an amine-isocyanate adduct compound.

5. An adhesive comprising the curable composition according to any one of claims 1 to 4.

6. The adhesive of claim 5 for bonding between components of a camera module.

7. A sealant comprising the curable composition according to any one of claims 1 to 4.

8. A coating agent comprising the curable composition according to any one of claims 1 to 4.

9. 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 4 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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