TW202122442A - Curable composition having excellent photo-curing property and excellent thermosetting property - Google Patents

Abstract

The object of the present invention is to provide a curable composition having excellent photo-curing property and excellent thermosetting property. The solution of the present invention is a curable composition, which includes (1) a compound having (meth) acryloyl groups; (2) an epoxy compound having two or more epoxy groups in one molecule and being solid at 25 DEG C; (3) a polythiol compound having two or more mercapto groups in one molecule; (4) a photoradical generator; and (5) a latent curing agent, wherein the amount of the component (3) is 15% by weight or more and 50% by weight or less with respect to the total curable composition.

Description

Hardening composition

The present invention relates to a curable composition.

In recent years, as portable devices such as smartphones have become thinner, camera modules mounted on portable devices such as smartphones have also been gradually reduced in size. In addition, it is expected that camera modules will also be mounted in wearable devices, and the requirements for miniaturization and thinning are increasing. Moreover, with the miniaturization of camera modules, the parts where the components of the camera module are subsequently fixed have become more and more minute. Therefore, the impact resistance of the camera module to the drop becomes very important. Therefore, even if the camera module is impacted by falling, the bonding area between the constituent parts must be maintained even if the bonding area is small. Once the bonding area becomes smaller, the bonding part of the constituent parts will easily peel off. Therefore, each unit of the adhesive The improvement of the area's bonding strength is even more valued.

On the one hand, the adhesive used in the assembly of camera modules, etc., requires low-temperature curability in order to avoid thermal damage to the image sensor, etc. due to high-temperature processing. Also, from the viewpoint of improving production efficiency, it is also required The ability to harden at low temperature and in a short time (low temperature-short time hardening). From such a viewpoint, as a low-temperature-short-time curable adhesive, an ultraviolet curable adhesive or a thermosetting epoxy resin-based adhesive is often used (for example, Patent Documents 1 and 2). However, although ultraviolet curable adhesives can be cured quickly, they have disadvantages such as curing deformation due to curing shrinkage, low bonding strength, and inability to bond parts that cannot be irradiated with light. On the other hand, although thermosetting epoxy resin adhesives can be said to be low-temperature-short-time curing adhesives, in order to maintain the bonding posture during bonding, the subsequent components (parts) must be fixed with a jig or device. In addition, the viscosity decreases due to the increase in heating temperature, sagging occurs before hardening, or problems such as flowing out of the desired part occur, which may not be satisfactory.

Therefore, in order to solve the above-mentioned problems, in order to arrange the components constituting the camera module with high precision, the curing (preliminary curing) caused by light (ultraviolet, visible light) irradiation is used for temporary fixation, and then by heat Several kinds of adhesives of this type that cause hardening (formal hardening) for bonding (formal fixing) have been proposed (for example, Patent Documents 3 and 4). [Prior Technical Literature] [Patent Literature]

[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

[The problem to be solved by the invention]

As described in Patent Documents 3 and 4, even if a light and thermosetting adhesive is used, if the bonding strength is low, and its temporary fixability is low, there will be a problem of loose parts during the manufacturing process. In addition, in the structure of the camera module, there are places where light cannot reach the inside of the module. In such places, light curing cannot be carried out sufficiently. In fact, it becomes only heat curing. As a result, sufficient bonding strength cannot be ensured. Subject.

The present invention was developed focusing on the above-mentioned matters, and its object is to provide a curable composition that has both excellent photocuring properties and excellent thermosetting properties, and excellent adhesive strength. [Means to solve the problem]

The present invention that can achieve the above-mentioned object is as follows. [1] A curable composition containing the following components (1)~(5): (1) Compounds having (meth)acryloyl groups; (2) Epoxy compounds that have more than 2 epoxy groups in one molecule and are solid at 25°C; (3) A polythiol compound having more than two mercapto groups in one molecule; (4) Light free radical generator; and (5) Latent hardener; Here, the amount of the component (3) is 15% by weight or more and 50% by weight or less with respect to the entire curable composition. [2] The curable composition as described in [1] above, wherein the component (2) contains: from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and dicyclopentadiene type epoxy resin At least one selected from the group consisting of resin and biphenyl type epoxy resin. [3] The curable composition as described in [1] or [2], wherein the component (3) contains: a polythiol compound having 2 to 6 mercapto groups in one molecule. [4] The curable composition as described in any one of [1] to [3] above, wherein the acryl group and methacryl group in the component (1) and the epoxy group in the component (2) The total of the groups and the molar ratio of the mercapto groups in the component (3) (the total of the acryl and methacryl groups in the component (1) and the epoxy groups in the component (2)/the total of the epoxy groups in the component (3) Sulfhydryl), which is 0.5~2.0. [5] The curable composition as described in any one of [1] to [4], wherein the component (5) contains an amine-epoxy adduct compound and/or an amine-isocyanate adduct Department of compounds. [6] An adhesive containing the curable composition described in any one of [1] to [5] above. [7] The adhesive as described in [6] above, which is used for bonding between constituent parts of a camera module. [8] A sealant containing the curable composition described in any one of [1] to [5] above. [9] A coating agent containing the curable composition described in any one of [1] to [5] above. [10] A method of manufacturing a camera module, including The following steps (I)~(III): (I) Perform a step of positioning the first bonding part and the second bonding part that have been coated with the curable composition described in any one of [1] to [5]; (II) A step of temporarily fixing the first bonding part and the second bonding part by curing the aforementioned curable composition by light irradiation; and (III) A step of formally fixing the first bonding part and the second bonding part by heating to harden the curable composition. [Effects of the invention]

According to the present invention, a curable composition having both excellent photocuring properties and excellent thermosetting properties can be obtained.

＜Curable composition＞

The curable composition of the present invention is characterized by containing the following components (1) to (5): (1) Compounds having (meth)acryloyl groups; (2) Epoxy compounds that have 2 or more epoxy groups in one molecule and are solid at 25°C (hereinafter sometimes referred to as "solid epoxy compounds"); (3) A polythiol compound having two or more sulfhydryl groups (-SH) in one molecule (hereinafter sometimes referred to as "polythiol compound"); (4) Light free radical generator; and (5) Latent hardener; Here, the amount of the component (3) is 15% by weight or more and 50% by weight or less with respect to the entire curable composition.

The components (1) to (5) can be used individually by one type, or two or more types can be used at the same time. When the curable composition of the present invention contains components other than the components (1) to (5), the components may be used alone or in combination of two or more. The ingredients are explained in order below.

<(1) Compounds having (meth)acryloyl groups> The compound having a (meth)acryloyl group used as the component (1) in the present invention is a component that mainly plays a role of improving the adhesive strength. In addition, the "(meth)acryloyl group" in the present invention means one or both of an acryloyl group and a methacryloyl group.

The number of (meth)acryloyl groups in one molecule of the compound having (meth)acryloyl groups may be 1 or more. When the compound having a (meth)acryloyl group is a mixture, the number system represents an average value per molecule. In addition, when there are both acryloyl groups and methacryloyl groups in one molecule, the number means the total number of acryloyl groups and methacryloyl groups in one molecule. The number of (meth)acryloyl groups in a molecule of compounds having (meth)acryloyl groups (except for the phosphoric acid denatured (meth)acrylates described later) is preferably 1 to 6, and 2~ 6 is better, and 2 to 4 are even better.

The molecular weight of the compound having a (meth)acryloyl group (except for the phosphoric acid denatured (meth)acrylate described later) is preferably 50 to 5,000, preferably 70 to 4,000, and more preferably 100 to 2,000. When the molecular weight is less than 50, the volatility is high, and it is not good from the viewpoint of odor and handleability; when the molecular weight is more than 5,000, the viscosity of the composition becomes high, and the coating property of the composition There will be a tendency to decrease. In addition, a molecular weight above 1000 means a weight average molecular weight, which can be measured by gel permeation chromatography (GPC). The molecular weight of less than 1,000 can be determined by a gravimetric analyzer (such as ESI-MS).

Examples of the compound having a (meth)acryloyl group include the following compounds. In addition, all of the following compounds can be used singly, or two or more of them can be used at the same time.

(Compounds with one acryloyl or methacryloyl group in one molecule) β-carboxyethyl (meth)acrylate (Meth) isobornyl acrylate Octyl/decyl (meth)acrylate Ethoxylated phenyl (meth)acrylate EO denatured phenol (meth)acrylate EO denatured o-phenylphenol (meth)acrylate EO modified p-formylphenol (meth)acrylate EO denatured nonylphenol (meth)acrylate PO denatured nonylphenol (meth)acrylate N-(meth)acryloyloxyethyl hexahydrophthalimide ω-carboxy-polycaprolactone mono(meth)acrylate Monohydroxyethyl phthalate (meth)acrylate 2-hydroxy-3-phenoxypropyl (meth)acrylate

In addition, the "(meth)acrylate" in the present invention means one or both of acrylate and methacrylate. In addition, the so-called "EO denaturation" means denaturation by adding ethylene oxide (EO). In addition, the so-called "PO denaturation" means denaturation by adding propylene oxide (PO).

(Compounds with 2 (meth)acryloyl groups in 1 molecule) Dipropylene glycol ``di(meth)acrylate 1,6-Hexanediol 　di(meth)acrylate Tripropylene glycol ``di(meth)acrylate PO denatured neopentyl glycol 　 di (meth) acrylate Tricyclodecane dimethanol 　 bis (meth) acrylate EO denatured bisphenol F　di(meth)acrylate EO denatured 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 with 2 (meth)acrylic groups in 1 molecule Polyester with 2 (meth)acrylic groups in 1 molecule

(Compounds with 3 or more (meth)acryloyl groups in 1 molecule) Trimethylolpropane 　 tris (meth) acrylate PO denatured trimethylolpropane 　 tri (meth) acrylate EO denatured trimethylolpropane 　 tri (meth) acrylate EO denatured isocyanuric acid (three) (meth)acrylate Pentaerythritol (tri/tetra) (meth)acrylate Glycerin 　 propoxy tri (meth) acrylate Pentaerythritol ``ethoxy'' tetra(meth)acrylate Ditrimethylolpropane 　 tetra (meth) acrylate Dipentaerythritol (5/6) (meth)acrylate Dipentaerythritol hexa(meth)acrylate EO denatured diglycerin 　 tetra (meth) acrylate Polyurethane with 3 (meth)acrylic groups in 1 molecule A polyester with 3 (meth)acrylic groups in one molecule

In addition, the so-called pentaerythritol"(tri/tetra)(meth)acrylate is a mixture of pentaerythritol"tri(meth)acrylate and pentaerythritol"tetra(meth)acrylate. The mixing ratio (pentaerythritol tri(meth)acrylate/pentaerythritol tetra(meth)acrylate) is a weight ratio, and is preferably 5/95~95/5, preferably 30/70~70/30 .

In addition, the so-called dipentaerythritol"(5/6)(meth)acrylate is a mixture of dipentaerythritol"penta(meth)acrylate and dipentaerythritol"hexa(meth)acrylate. The mixing ratio (dipentaerythritol penta(meth)acrylate/dipentaerythritol hexa(meth)acrylate) is the weight ratio, and 5/95~95/5 is better, and 30/70~70/30 is Better.

In addition, as a compound having a (meth)acryloyl group, EO denatured isocyanuric acid "(di/tri)(meth)acrylate" can be used. Here, the so-called EO denatured isocyanuric acid (di/tri) (meth)acrylate refers to EO denatured isocyanuric acid di(meth)acrylate and EO denatured isocyanuric acid tris(meth) A mixture of acrylates. The mixing ratio (EO denatured isocyanurate di(meth)acrylate/EO denatured isocyanurate tri(meth)acrylate) is a weight ratio, and preferably 1/99~99/1, 10/90~90/10 is preferable, and 40/60~60/40 is more preferable.

From the viewpoint of storage stability and adhesion, it is preferable that the component (1) contains phosphoric acid denatured (meth)acrylate. Here, "phosphoric acid denaturation" means denaturation by ester bonding with phosphoric acid. Phosphoric acid denatured (meth)acrylate type may be used individually by 1 type, and may use 2 or more types together. Phosphoric acid denatured (meth)acrylate is preferably phosphoric acid denatured methacrylate.

The phosphoric acid denatured (meth)acrylate system can be produced by the following method (i), for example, but the present invention is not limited to this. (i) A method of reacting a compound having a (meth)acryloyl group and a hydroxyl group with phosphoric acid.

The compound having a (meth)acryloyl group and a hydroxyl group in one molecule that can be used in the above method (i) can be produced by, for example, the following method (ii) or (iii), but the present invention is not limited to this . (ii) A method of reacting (meth)acrylic acid or (meth)acrylic acid ester and polyol (for example, alkylene glycol, glycerin, etc.) at a ratio such that the hydroxyl group of the polyol remains. (iii) A method of adding alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) to (meth)acrylic acid.

Phosphoric acid denatured (meth)acrylate can also use commercially available products. Examples of the commercially available products include "EBECRYL168" manufactured by Allnex Co., Ltd., "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., and manufactured by Kyoeisha Chemical Co., Ltd. "LIGHT ESTER P-1M", "LIGHT ESTER P-2M", "LIGHT ESTER ACRYLATE P-1A(N)", and "JPA-514" manufactured by Chengbei Chemical Industry Co., Ltd.

The number of (meth)acrylic groups in one molecule of the phosphoric acid denatured (meth)acrylate is preferably 0.5 to 3, preferably 1 to 2, and more preferably 1 to 1.5. In addition, when phosphoric acid denatured (meth)acrylate is a mixture, this number system shows the average value per 1 molecule.

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

In the case of using phosphoric acid-denatured (meth)acrylate, from the standpoint of storage stability and curability, the amount is preferably 0.001 to 5 parts by weight relative to 100 parts by weight of component (1) , 0.01~3 weight score is better, 0.05~2 weight score is better.

In one aspect of the present invention, the component (1) contains: from tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate, dipentaerythritol hexa(methyl) ) At least one selected from the group consisting of acrylate and phosphoric acid denatured (meth)acrylate is preferred; from tricyclodecane dimethanol bis(meth)acrylate, EO denatured bisphenol A 　 two ( At least one selected from the group consisting of meth)acrylate, dipentaerythritol hexa(meth)acrylate and phosphoric acid denatured (meth)acrylate is preferred.

In another aspect of the present invention, the component (1) contains: from tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A" di(meth)acrylate and dipentaerythritol hexa(meth)acrylate At least one selected from the group consisting of acrylate, preferably a mixture with phosphoric acid denatured (meth)acrylate; from tricyclodecane dimethanol bis(meth)acrylate, EO denatured double A mixture of at least one selected from the group consisting of phenol A" di(meth)acrylate and dipentaerythritol hexa(meth)acrylate, and phosphoric acid denatured (meth)acrylate is preferable.

In another aspect of the present invention, component (1) contains tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate or dipentaerythritol hexa(meth)acrylate" Acrylate, a mixture with phosphoric acid denatured (meth)acrylate is preferred; tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A　di(meth)acrylate or dipentaerythritol hexa(meth)acrylate ) A mixture of acrylate and phosphoric acid denatured (meth)acrylate is preferred.

From the perspective of curability and adhesiveness, the amount of component (1) is preferably 5 wt% or more, preferably 10 wt% or more, and more preferably 15 wt% or more, relative to the entire curable composition. Good; 60% by weight or less is preferable, 55% by weight or less is preferable, and 50% by weight or less is more preferable.

＜(2) Solid epoxy compound＞ The component (2) used in the present invention is not particularly limited as long as it is a compound that has two or more epoxy groups in one molecule and is solid at 25°C.

Examples of the solid epoxy compound system include epoxy resins that have two or more epoxy groups in one molecule and are solid at 25°C. In addition, epoxy resins that are monomers (ie monomeric epoxy resins) can be regarded as the present invention as long as they have two or more epoxy groups in one molecule and are solid at 25°C. Ingredient (2) to use.

Examples of epoxy resins include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and dicyclopentadiene epoxy resins. Oxygen resin, biphenyl type epoxy resin, biphenyl arylene type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, aromatic glycidyl amine type epoxy resin, alicyclic Formula epoxy resin, oxazolidone cyclic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, etc. The epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The epoxy equivalent of component (2) (ie solid epoxy compound), from the standpoint of reactivity, etc., is preferably 50~5,000 g/eq, preferably 100~3,000 g/eq, 150~1,000 g/eq is better. The epoxy equivalent here means the number of grams (unit: g/eq) of the compound containing 1 gram equivalent of epoxy group. In other words, the so-called epoxy equivalent means the value obtained by dividing the molecular weight of an epoxy group-containing compound by the number of epoxy groups the compound has, that is, the molecular weight per epoxy group. The epoxy equivalent can be measured in accordance with the method specified in JIS K 7236.

In one aspect of the present invention, component (2) contains: from bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin At least one selected from the group consisting of is preferably; from bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin At least one selected from the formed group is preferred. In this aspect, bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin are all having two or more in one molecule. Epoxy, and solid at 25°C.

In another aspect of the present invention, the component (2) contains: bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, or biphenyl type epoxy resin Preferably; bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, or biphenyl type epoxy resin is preferable. In this aspect, bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin are all having two or more in one molecule. Epoxy, and solid at 25°C.

In another aspect of the present invention, the component (2) is preferably a bisphenol A epoxy resin that contains two or more epoxy groups in one molecule and is solid at 25°C; Bisphenol A type epoxy resin which has 2 or more epoxy groups and is solid at 25°C is preferred.

The curable composition system of the present invention may also contain a compound that has two or more epoxy groups in one molecule and is liquid at 25°C (hereinafter sometimes referred to as "liquid epoxy compound"). However, from the viewpoint of the effects of the present invention (that is, excellent light curability and excellent thermal curability), the curable composition of the present invention does not contain a liquid epoxy compound or is relative to the component ( 2) (ie, solid epoxy compound) 100 parts by weight, and preferably contains a liquid epoxy compound in an amount of 20 parts by weight or less. The amount of the liquid epoxy compound is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the component (2). It is particularly preferable that the curable composition of the present invention does not contain a liquid epoxy compound.

From the standpoint of the curability and workability of the curable composition, the amount of component (2) is preferably 5% by weight or more, preferably 10% by weight or more, relative to the entire curable composition. The weight% or more is more preferable; 70 weight% or less is preferable, 60 weight% or less is preferable, and 55% weight or less is more preferable.

＜(3) Polythiol compound＞ The "polythiol compound having two or more sulfhydryl groups in one molecule" used as the component (3) in the present invention mainly serves as a composition that reacts with the component (1) when irradiated with light such as ultraviolet rays. The role of hardening hardener. The number of mercapto groups in a molecule of the polythiol compound is preferably 2-6, preferably 3-6, more preferably 3-5, and particularly preferably 3 or 4.

As the polythiol compound, commercially available products can be used, or compounds produced by a known method (for example, the method described in JP 2012-153794 or International Publication No. 2001/00698) can be used.

Examples of polythiol compounds include partial esters of polyhydric alcohols and mercapto organic acids, and complete esters of polyhydric alcohols and mercapto organic acids. Here, the so-called partial ester refers to the ester of a polyhydric alcohol and a carboxylic acid, and a part of the hydroxyl group of the polyhydric alcohol is one that forms an ester bond; the so-called complete ester refers to all the hydroxyl groups of the polyhydric alcohol forming an ester bond Ender.

Examples of polyhydric alcohols include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

Examples of mercapto organic acid systems include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g. 3-mercaptopropionic acid), mercaptobutyric acid (e.g. 3-mercaptobutyric acid and 4-mercaptobutyric acid). Acids; esters containing mercapto and carboxyl groups obtained by the esterification reaction of hydroxy acids and mercapto organic acids; mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (example: 2,3-dimercaptosuccinic acid) Acid; mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid (e.g. 4-mercaptobenzoic acid); etc. The number of carbon atoms of the aforementioned mercapto aliphatic monocarboxylic acid is preferably 2 to 8, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among the aforementioned mercapto organic acids, mercapto aliphatic monocarboxylic acids with 2 to 8 carbon atoms are preferred, and mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are preferred. 3-mercaptopropionic acid is more preferable.

Specific examples of partial esters of polyhydric alcohols and mercapto organic acids include: trimethylolethane bis(mercaptoacetate), trimethylolethane bis(3-mercaptopropionate), trimethylolethane Ethylene bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3 -Mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol ginseng (mercaptoacetate), pentaerythritol ginseng (3 -Mercaptopropionate), pentaerythritol ginseng (3-mercaptobutyrate), pentaerythritol ginseng (4-mercaptobutyrate), dipentaerythritol 4 (mercaptoacetate), dipentaerythritol 4 (3-mercaptopropionate) , Dipentaerythritol 4 (3-mercaptobutyrate), dipentaerythritol 4 (4-mercaptobutyrate) and so on.

Specific examples of complete esters of polyhydric alcohols and mercapto organic acids include: ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyric acid) Ester), ethylene glycol bis(4-mercaptobutyrate), trimethylolethane ginseng (thioglycolate), trimethylolethane ginseng (3-mercaptopropionate), trimethylol Ethane ginseng (3-mercaptobutyrate), trimethylol ethane ginseng (4-mercaptobutyrate), trimethylolpropane ginseng (mercaptoacetate), trimethylolpropane ginseng (3- Mercaptopropionate), trimethylolpropane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (4-mercaptobutyrate), pentaerythritol four (mercaptoacetate), pentaerythritol four (3- Mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate), pentaerythritol 4 (4-mercaptobutyrate), dipentaerythritol (mercaptoacetate), dipentaerythritol (3-mercaptopropionate), Dipentaerythritol land (3-mercaptobutyrate), dipentaerythritol land (4-mercaptobutyrate) and so on.

From the standpoint of storage stability, it is preferable that the aforementioned partial esters and complete esters have a very low content of alkaline impurities, and those that do not require the use of alkaline substances for production are preferable.

In addition, as component (3), alkane polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc. can also be used; the terminal contains a mercapto group Polyethers; polythioethers with mercapto groups at the ends; polythiol compounds obtained by the reaction of epoxy compounds and hydrogen sulfide; polythiols with mercapto groups obtained by the reaction of polythiol compounds and epoxy compounds Compounds; etc., these are polythiol compounds produced by using alkaline substances as reaction catalysts in their production process. The polythiol compound produced by using an alkaline substance is preferably subjected to a dealkalization treatment, and the alkali metal ion concentration is adjusted to 50 wt ppm or less before use.

An example of a dealkalization treatment system for polythiol compounds produced using alkaline substances can include, for example, dissolving the polythiol compound in organic solvents such as acetone, methanol, and adding acids such as dilute hydrochloric acid and dilute sulfuric acid. After mixing, a method of desalting by extraction/washing, etc.; a method of using ion exchange resin adsorption; a method of purifying by distillation; etc., but not limited to this.

In addition, as component (3), for example, ginseng [(3-mercaptopropoxy)ethyl] isocyanurate, 1,4-bis(3-mercaptobutoxy)butane, 1, 3,5-ginseng (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione, ginseng (3-mercaptopropyl) Isocyanurate, bis(3-mercaptopropyl) isocyanurate, 1,3,4,6-four (2-mercaptoethyl) glycoluril, and 4,4'-isopropylidene bis Phenyl bis(3-mercaptopropyl) ether and the like.

Component (3) preferably contains a polythiol compound having 2-6 mercapto groups in one molecule, preferably 3-6, more preferably 3-5, particularly preferably 3 or 4.

In one aspect of the present invention, component (3) contains: from pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate), ginseng (3-mercaptopropyl) isocyanurate Acid ester, trimethylolpropane ginseng (3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate), ginseng [(3-mercaptopropionoxy) ethyl] isocyanurate, Ethylene glycol bis (thioglycolate), trimethylolpropane (thioglycolate), pentaerythritol 4 (thioglycolate), 1,4-bis(3-mercaptobutanoyloxy)butane, 1,3,5-ginseng (3-mercaptobutyroxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane (3-mercaptobutyrate), trimethylolethane ginseng (3-mercaptobutyrate), 1,3,4,6-four (2-mercaptoethyl) glycoluril, and 4,4'- At least one selected from the group consisting of isopropylidene diphenyl bis (3-mercaptopropyl) ether is preferably; from pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-mercapto At least one selected from the group consisting of butyrate) and ginseng (3-mercaptopropyl) isocyanurate is preferred.

In another aspect of the present invention, component (3) contains: pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate) or ginseng (3-mercaptopropyl) isocyanurea Esters are better; pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate) or ginseng (3-mercaptopropyl) isocyanurate is better; pentaerythritol 4 (3-mercapto Propionate) is more preferred.

From the standpoint of curability, the sum of the acryl group, methacryl group in component (1) and the epoxy group in component (2) and the molar ratio of the mercapto group in component (3) (component ( The total of the acryl group, the methacryl group and the epoxy group in the component (2)/the mercapto group in the component (3)) in 1) is preferably 0.5 to 2.0, preferably 0.6 to 1.6, 0.7~1.5 is more preferable, 0.8~1.3 is particularly preferable.

From the viewpoint of curability and adhesiveness, the amount of component (3) must be 15% by weight or more and 50% by weight or less with respect to the entire curable composition. The amount of the component (3) is preferably 20% by weight or more, preferably 25% by weight or more, preferably 45% by weight or less, and preferably 40% by weight or less, relative to the entire curable composition.

From the viewpoint of the workability of the curable composition, the total amount of the components (1) and (3) is preferably 50 parts by weight or more, and 60 parts by weight or more with respect to 100 parts by weight of the component (2) Preferably, it is more preferably 70 parts by weight or more. On the other hand, from the point of view of adhesion, the total amount of components (1) and (3) is relative to 100 parts by weight of component (2), preferably 2,000 parts by weight or less, and 1,500 parts by weight or less. Preferably, 1,000 parts by weight or less is more preferable.

＜(4) Light radical generator＞ The photo radical generator used as the component (4) in the present invention is not particularly limited. Examples of photo-radical generators include alkyl phenone-based photo-radical generators, acetoxy phosphine oxide-based photo-radical generators, oxime ester-based photo-radical generators, and α-hydroxy ketone-based photo-radicals. Producer, etc. The photo-radical generator is preferably an alkylphenone-based photo-radical generator.

Examples of alkylphenone-based photoradical generators include 2-hydroxy-2-methyl-1-phenylpropane-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-morpholinoprop-1-one, benzophenone, methylbenzophenone, o- Benzoic acid, benzyl ethyl ether, 2,2-diethoxy, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzyl) Phosphine oxide, ethyl-(2,4,6-trimethylbenzyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexylbenzene Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl The oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, etc.

Examples of phosphine oxide-based photo-radical generators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl) (Actyl)-phenyl-phosphine oxide and the like.

Examples of oxime ester-based photoradical generators include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzyloxime), 1-[ 6-(2-Methylbenzyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetoxime and the like.

Examples of α-hydroxyketone-based photoradical generators include: benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2- Methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2- Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and the like.

Examples of commercially available products as photoradical generators include: "Irgacure 1173" (2-hydroxy-2-methyl-1-phenylpropane-1-one) manufactured by BASF, "Irgacure OXE01" (1- [4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzyloxime)), "Irgacure OXE02" (1-[6-(2-methylbenzamide Yl)-9-ethyl-9H-carbazol-3-yl) ethyl ketone (O-acetoxime), "Esacure KTO 46" manufactured by IGM Resins BV (2,4,6-trimethylbenzyl) Diphenylphosphine oxide and oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane] and a mixture of methylbenzophenone derivatives), " Esacure KIP 150" (2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one oligomer), etc.

The amount of component (4) is based on the viewpoint of obtaining a curable composition that can be efficiently photocured when exposed to light. Relative to the entire curable composition, it is preferably 0.001% by weight or more, and 0.01% by weight or more. It is preferable, and 0.1% by weight or more is more preferable. In addition, from the viewpoint of suppressing the exhaust gas caused by the photo radical generator or its decomposition products remaining in the cured product, relative to the entire curable composition, 10% by weight or less is preferable, and 5% by weight or less is more preferable. Preferably, 2% by weight or less is more preferable.

＜(5) Latent hardener＞ The so-called latent curing agent used as component (5) in the present invention means an additive well-known in the field of epoxy resins. It does not harden the epoxy resin at room temperature (25°C), but does not harden the epoxy resin at room temperature (25°C). Additives that harden epoxy resins etc. by heating.

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

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 Cyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-Methylimidazole-trimellitic acid ester, 1-cyanoethyl-2-phenylimidazole-trimellitic acid ester, N-(2-methylimidazolyl-1-ethyl)-urea and the like.

As the epoxy compound used as the raw material of the amine-epoxy adduct compound, for example, polyphenols such as bisphenol A, bisphenol F, catechol, resorcinol, or glycerin or Polyglycidyl ether derived from the reaction of polyols such as polyethylene glycol and epichlorohydrin; glycidyl ether ester derived from the reaction of hydroxy acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; phthalic acid Polyglycidyl ester obtained by the reaction of polycarboxylic acids such as formic acid and terephthalic acid with epichlorohydrin; Glycidylamine obtained by reaction of 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin Compounds; in addition, epoxidized phenol novolak resin, epoxidized cresol phenol resin, epoxidized polyolefin and other multifunctional epoxy compounds or single butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc. Functional epoxy compounds; etc.

The amine compound used as the raw material of the amine-epoxy adduct compound or the amine-isocyanate adduct compound can be combined with an epoxy group or an isocyanate group (also known as an isocyanate group) as long as it is used as the raw material for the amine-epoxy adduct compound or amine-isocyanate adduct compound. The active hydrogen atom undergoing the addition reaction has one or more in one molecule, and the amino group (at least one of the primary, secondary, and tertiary amino group) has one or more in one molecule Who can. Examples of such amine compound systems include diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexyl, etc. Aliphatic amine compounds; 4,4'-diaminodiphenylmethane, 2-methylaniline and other aromatic amine compounds; 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-Dimethylimidazoline, piperidine, piperazine and other heterocyclic compounds containing nitrogen atoms; etc.

In addition, if a compound having a tertiary amine group is used, an excellent latent hardener can be produced. Examples of the compound system having a tertiary amino group include: dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N- Amines with tertiary amines such as methylpiperazine, 2-methylimidazole, 2-ethylimino, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.; 2-dimethylamino Ethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-di Methylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methyl Imidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methyl Imidazole, 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-mercapto Pyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, niacin, Alcohols with tertiary amines such as isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazine, N,N-dimethylpropionate hydrazine, nicotinic acid hydrazine, isonicotinic acid hydrazine, etc. Phenols, mercaptans, carboxylic acids and hydrazines; etc.

When an epoxy compound and an amine compound are subjected to an addition reaction to produce an amine-epoxy adduct-based compound, an active hydrogen compound having two or more active hydrogens per molecule may also be added. Examples of such active hydrogen compound systems include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolak resin, etc. , Polyols such as trimethylolpropane, polycarboxylic acids such as adipic acid, phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy -2-propanol, thioglycolic acid, anthranilic acid, lactic acid, etc.

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; hexamethylene Diisocyanate, toluene diisocyanate (example: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophor Polyfunctional isocyanate compounds such as ketone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; in addition, there are many A compound containing an isocyanate group at the end obtained by the reaction of a functional isocyanate compound and an active hydrogen compound; etc. Examples of such compounds having an isocyanate group at the end include: an addition compound having an isocyanate group at the end obtained by the reaction of toluene diisocyanate and trimethylolpropane, and an end obtained by the reaction of toluene diisocyanate and pentaerythritol Addition compounds with isocyanate groups, etc.

Latent hardener, for example, the above-mentioned manufacturing raw materials are appropriately mixed, reacted at a temperature from 20°C to 200°C, cooled and solidified, then ground, or mixed with methyl ethyl ketone, dioxane, or tetrahydrofuran It can be easily obtained by pulverizing the solid content by reacting the above-mentioned manufacturing raw materials in a solvent such as a solvent, and removing the solvent.

Latent hardeners can also use commercially available products. Examples of commercially available products of amine-epoxy adduct compounds include "Amicure PN-23", "Amicure PN-40", "Amicure PN-50", and "Amicure PN-23" manufactured by Ajinomoto FINE-TECHNO. "Amicure PN-H", "Hardener X-3661S" and "Hardener X-3670S" manufactured by ACR, "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Corporation. In addition, examples of commercially available products of the amine-isocyanate adduct compound include: "Fujicure FXR-1000", "Fujicure FXR-1030", "Fujicure FXR-1020", and "Fujicure FXR-1000" manufactured by T&K TOKA. 1030", "Fujicure FXR-1081", "Fujicure FXR-1121".

Component (5) contains amine-epoxy adduct compound and/or amine-isocyanate adduct compound, preferably amine-epoxy adduct compound and/or amine-isocyanate adduct compound Preferably, an amine-epoxy adduct compound or an amine-isocyanate adduct compound is more preferable, and an amine-epoxy adduct compound is particularly preferable.

From the viewpoint of heat-induced curability, the amount of component (5) relative to the entire curable composition is preferably 1% by weight or more, preferably 2% by weight or more, and more preferably 3% by weight or more. good. In addition, from the standpoint of storage stability, the weight of component (5) is preferably 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less relative to the entire curable composition. .

＜(6) Stabilizer＞ The curable composition of the present invention may further contain a stabilizer as the component (6) from the viewpoint of storage stability and the like. Examples of stabilizer systems include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, and isocyanate compounds.

As described above, the phosphoric acid-denatured (meth)acrylate, which is one of the component (1), has the 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 phosphoric acid denatured (meth)acrylate as component (1) and/or contains a stabilizer as component (6).

Examples of the borate compound system include: trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, and tripentyl borate. Boronate, Triallyl Borate, Trihexyl Borate, Tricyclohexyl Borate, Tricyclooctyl Borate, Trinonyl Borate, Tridecyl Borate, Trilaurin Borate, trihexadecyl borate, trioctadecyl borate, ginseng (2-ethylhexyloxy) borane, tribenzyl borate, triphenyl borate Esters, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, etc.

Examples of the titanate compound system include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

Examples of the aluminate compound system include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

Examples of the zirconate compound system include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

Examples of isocyanate compound systems include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethyl Phenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4, 4'-diisocyanate, toluidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, bicycloheptane triisocyanate, etc.

As a stabilizer, from the viewpoint of the versatility of the stabilizer and the storage stability of the curable composition, borate compounds are preferred, such as triethyl borate, tri-n-propyl borate, and triisopropyl Borate and tri-n-butyl borate are preferred, and triethyl borate is more preferred.

In the case of using component (6), its amount is not particularly limited, but from the standpoint of storage stability, its amount is preferably 0.001% by weight or more, and 0.01% by weight or more with respect to the entire curable composition Preferably, 0.1% by weight or more is more preferable; 5% by weight or less is preferable, 3% by weight or less is preferable, and 2% by weight or less is more preferable.

In a preferred aspect of the present invention, the curable composition of the present invention is composed of tricyclodecane dimethanol di(meth)acrylate, EO modified bisphenol A 　 di(meth) acrylate and dipentaerythritol six At least one selected from the group consisting of (meth)acrylates is used as component (1), and the curable composition of the present invention contains phosphoric acid-denatured (meth)acrylate as component (1) , And/or contain stabilizers as ingredient (6). In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

In another preferred aspect of the present invention, the component (1) is from tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate and dipentaerythritol six A mixture of at least one selected from the group consisting of (meth)acrylate and phosphoric acid denatured (meth)acrylate.

In another preferred aspect of the present invention, the component (1) is from tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate and dipentaerythritol six At least one selected from the group consisting of (meth)acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

In another preferred aspect of the present invention, the component (1) is from tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate and dipentaerythritol six A mixture of at least one selected from the group consisting of (meth)acrylate and phosphoric acid denatured (meth)acrylate, and the curable composition of the present invention contains a stabilizer as a component (6) . In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

In another preferred aspect of the present invention, the curable composition of the present invention contains tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A "di(meth)acrylate or dipentaerythritol Hexa(meth)acrylate is used as component (1), and the curable composition of the present invention contains phosphoric acid-denatured (meth)acrylate as component (1), and/or contains stabilizer as component (6) ). In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

In another preferred aspect of the present invention, the component (1) is tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A 　di(meth)acrylate or dipentaerythritol hexa( A mixture of meth)acrylate and phosphoric acid denatured (meth)acrylate.

In another preferred aspect of the present invention, the component (1) is tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A 　di(meth)acrylate or dipentaerythritol hexa( Meth) acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

In another preferred aspect of the present invention, the component (1) is tricyclodecane dimethanol di(meth)acrylate, EO denatured bisphenol A 　di(meth)acrylate or dipentaerythritol hexa( A mixture of meth)acrylate and phosphoric acid denatured (meth)acrylate, and the curable composition of the present invention contains a stabilizer as the component (6). In this aspect, the stabilizer is preferably a borate compound, from triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate At least one selected from the group formed is preferable, and triethyl borate is more preferable.

＜Other ingredients＞ The curable composition of the present invention may contain other components different from the above-mentioned components within a range that does not impair the effects of the present invention. Examples of other components include: polymerization inhibitors (such as dibutylhydroxytoluene, barbituric acid); antioxidants; inorganic fillers (such as calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, silicon Zirconium oxide, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, quartz powder, etc.); the composition can be combined with polymethylmethacrylate and/or polymethylmethacrylate Organic fillers made of copolymers made by polymerizing monomers such as styrene; thixotropic agents; defoamers; leveling agents; coupling agents; flame retardants; pigments; dyes; Fluorescent and so on. For the other component systems, only one type may be used alone, or two or more types may be used simultaneously.

＜Manufacturing and curing of curable composition＞ The curable composition of the present invention uses, for example, a kneader, agitating mixer, a three-roll mill, etc., and by uniformly mixing the components, it can be adjusted to a single-liquid curable composition. The temperature of the curable composition during mixing is usually 10 to 50°C, preferably 20 to 40°C.

The light irradiated when the curable composition of the present invention is photocured is preferably ultraviolet light. The peak wavelength of the irradiated light is preferably 300~500nm. The illumination light is irradiated, based in 100 ~ 5,000mW / cm ² preferably, 300 ~ 4,000mW / cm ² is preferred. In exposure system 500 ~ 3,000mJ / cm ² preferably, 1,000 ~ 3,000mJ / cm ² is preferred.

Examples of light irradiation methods 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, DEEP UV lamps, etc.

The heating temperature when thermally hardening the curable composition of the present invention is not particularly limited, but it is, for example, 50 to 150°C, and preferably 60 to 100°C. The curable composition system of the present invention has excellent low-temperature curability, and can exhibit excellent thermal curability even at a relatively low curing temperature of 100°C or less. The heating time when heat-curing the curable composition of the present invention is not particularly limited, but it is, for example, 10 to 120 minutes, and preferably 30 to 60 minutes.

＜Use of curable composition＞ The curable composition of the present invention has both excellent light curability and excellent thermal curability, and can form a cured product with high bonding strength, so it is useful as an adhesive, sealant, coating agent, etc. of. Therefore, the present invention also provides adhesives, sealants, and coating agents containing the aforementioned curable composition. As an adhesive, it is better to bond between the constituent parts of the camera module.

＜Manufacturing method of camera module＞ The present invention provides a method for manufacturing a camera module, which includes the following steps (I) to (III): (I) Perform a step of positioning the first bonding part and the second bonding part that have been coated with the curable composition of the present invention; (II) A step of temporarily fixing the first bonding part and the second bonding part by curing the aforementioned curable composition by light irradiation; and (III) A step of formally fixing the first bonding part and the second bonding part by heating to harden the curable composition. The first bonding part here means a part coated with the curable composition of the present invention, and the so-called second bonding part means the other part to be bonded to the first bonding part. The second adhesive part may have been coated with the curable composition of the present invention, or may not be coated.

According to the manufacturing method of the present invention, each part can be positioned with high precision, and the first bonding part and the second bonding part can be bonded with high bonding strength. As a result, a high-quality camera can be manufactured efficiently Module.

In the step (II), due to the relationship between the arrangement positions of the first bonding part and the second bonding part, the coated curable composition still has many unirradiated parts that are not irradiated with light. However, because the curable composition of the present invention has good thermosetting properties, even the part that is not irradiated with light can be cured sufficiently by the thermal curing of the process (III) to achieve full curing. The entire sexual composition forms a cured product with high adhesive strength.

The light irradiation conditions of the process (II) and the heating conditions of the process (III) in the manufacturing method of the camera module of the present invention are the same as described above. [Example]

Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

1. Raw materials <Component (1): Compound having (meth)acryloyl group> (1A) IRR-214K: "Tricyclodecane dimethanol" diacrylate manufactured by DAICEL-ALLNEX, molecular weight: 300, number of propylene groups per molecule: 2 (1B) EBECRYL150: "EO denatured bisphenol A" diacrylate manufactured by DAICEL-ALLNEX, molecular weight: 512, number of acryl groups per molecule: 2 (1C) DPHA: "Dipentaerythritol" hexaacrylate manufactured by DAICEL-ALLNEX, molecular weight 524, number of propylene groups per molecule: 6 (1D) EBECRYL168: manufactured by DAICEL-ALLNEX, phosphoric acid denatured methacrylate, molecular weight: 270, the number of methacrylic groups per molecule: 1.5

<Component (2): solid epoxy compound> (2A) jER1001: Bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent (EPW): 475g/eq, softening point: 64°C, number of epoxy groups per molecule: 2 (2B) jER4005P: Bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent (EPW): 538g/eq, softening point: 87°C, number of epoxy groups per molecule: 2 (2C) HP-7200: Dicyclopentadiene epoxy resin manufactured by DIC Company, epoxy equivalent (EPW): 258g/eq, softening point: 56~66°C, number of epoxy groups per molecule: 2~3 (2D) YX4000H: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent (EPW): 192g/eq, melting point: 105°C, number of epoxy groups per molecule: 2

<Component (2'): Liquid epoxy compound> (2'A)EX-211: Neopentyl glycol diglycidyl ether manufactured by Nagase ChemteX, epoxy equivalent (EPW): 138g/eq, liquid at 25°C, epoxy group in 1 molecule Number of: 2 (2'B) jER828EL: Bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent (EPW): 190g/eq, liquid at 25°C, number of epoxy groups per molecule: 2 (2'C) EXA-4816: Aliphatic modified bisphenol A epoxy resin manufactured by DIC Corporation, epoxy equivalent (EPW) 403g/eq, liquid at 25°C, one of epoxy groups in 1 molecule Number: 2 (2'D) BF-1000: Epoxidized 1,2-polybutadiene manufactured by ADEKA Co., Ltd., epoxy equivalent (EPW): 210g/eq, liquid at 25°C, epoxy group in 1 molecule Number of: 5

<Component (3): Polythiol compound> (3A) PEMP: "Pentaerythritol" (3-mercaptopropionate) manufactured by SC Organic Chemical Company, molecular weight: 489, number of mercapto groups per molecule: 4 (3B) PE1: "Karenz MT" made by Showa Denko Corporation "pentaerythritol" (3-mercaptobutyrate), molecular weight: 544, number of mercapto groups per molecule: 4 (3C) TMPIC: ginseng (3-mercaptopropyl) isocyanurate, molecular weight: 351, number of mercapto groups in 1 molecule: 3

<Component (4): Light Radical Generator> (4A) Irgacure 1173: manufactured by BASF, 2-hydroxy-2-methyl-1-phenylpropane-1-one (4B) Esacure KIP 150: manufactured by IGM Resins B.V., oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropane-1-one

＜Component (5): Latent hardener＞ (5A) PN-23: "Amine-epoxy adduct compound" manufactured by Ajinomoto Fine-Techno (5B) FXR1081: "Amine-isocyanate adduct compound" manufactured by T&K TOKA

＜Ingredient (6): Stabilizer＞ (6A) Triethyl borate: manufactured by Tokyo Chemical Industry Co., Ltd.

2. Evaluation test ＜Determination of Adhesion Strength＞ (1) Measurement of adhesive strength 1 after light curing A 100mm×25mm×2mm thick liquid crystal polymer (LCP) board (CM-301B manufactured by JX Nippon Oil & Energy Co., Ltd.) is coated with a curable composition in an amount of 1 to 3 mg, and chip capacitors are placed on it (JIS nominal 2012 size), light curing was carried out under the following conditions, the adhesive strength 1 of the cured product was measured, and the evaluation was performed based on the following criteria.

(2) Measurement of adhesive strength 2 after light and heat hardening In the same manner as above, the LCP plate was coated with the curable composition and mounted on the chip capacitor, then light and thermally cured under the following conditions, and the adhesive strength 2 of the cured product was measured and evaluated based on the following criteria.

(3) Measurement of adhesive strength 3 after thermal hardening In the same manner as above, the LCP board was coated with the curable composition and mounted on the chip capacitor, and then thermally cured under the following conditions, the adhesive strength of the cured product was measured 3, and the evaluation was performed based on the following criteria.

Next, for the strength, the chip capacitor was destroyed in the lateral direction with a Bond tester (series 4000 manufactured by Dega), and the adhesive strength (N/mm ² ) was measured. The measurement was performed 3 times, and the average value was obtained.

＜Evaluation of thermosetting properties＞ A 5mm diameter hole was made in a 30mm×50mm×2mm thick silicon film (manufactured by AS ONE), and the curable composition was buried in an amount of 1 to 3 mg, and thermally cured under the following conditions. According to the touch test of the cured product, the thermosetting properties were evaluated based on the following criteria.

<Curing conditions> (1) Light curing was performed using a UV-LED irradiation device UJ35 manufactured by Panasonic Corporation ^{. Ultraviolet light (peak wavelength: 365nm) with an illuminance of 2500mW/cm 2} was set at an angle of 45° from two directions (light on the surface of the chip capacitor). The incident angle is 45°), and the curable composition is irradiated for 1.0 second (exposure amount 2500mJ/cm ² ).

(2) Light and thermal curing: UV-LED irradiation device UJ35 manufactured by Panasonic Corporation ^{, ultraviolet light (peak wavelength: 365nm) with an illuminance of 2500mW/cm 2} from two directions at an angle of 45° (incidence of light on the surface of the chip capacitor) The angle is 45°), and the curable composition is irradiated for 1.0 second (exposure amount 2500 mJ/cm ² ). Next, the curable composition irradiated with light was heated at 100°C for 30 minutes in a hot-air circulating oven.

(3) Thermal hardening The curable composition was heated in a hot-air circulating oven at 100°C for 30 minutes.

<Evaluation criteria> (1) Evaluation criteria of adhesive strength 1 after photocuring ◎: 10N/mm ² or more ○: 5N/mm ² or more but less than 10N/mm ² ×: less than 5N/mm ²

(2) Evaluation criteria for adhesive strength 2 after light and thermal curing ◎: 30N/mm ² or more ○: 15N/mm ² or more but less than 30N/mm ² ×: less than 15N/mm ²

(3) Evaluation criteria for adhesive strength 3 after thermal curing ◎: 30N/mm ² or more ○: 15N/mm ² or more but less than 30N/mm ² ×: less than 15N/mm ²

(4) Evaluation criteria for thermosetting ⊚: After finger touch, the appearance of the hardened product still does not change. ○: After finger touch, the appearance of the hardened product leaves some traces. ×: Remarkable depressions are seen in the cured product.

3. Examples and Comparative Examples The respective components were blended in the amounts shown in the upper column of the following table to prepare curable compositions of Examples 1 to 14 and Comparative Examples 1 to 7. In addition, the "points" described in the table means "weight points", and "%" means "weight%". In addition, in the following table, "the molar ratio of the total of the acryl group in component (1), methacryl group, and the epoxy group in component (2) to the mercapto group in component (3)" is described. In the column of "((meth)acrylic group + epoxy group)/mercapto", write "the amount of component (3) relative to the whole curable composition" in the "amount of component (3)" "In the field.

In Examples 1 to 13 and Comparative Example 7, the ingredients (1) and (2) were mixed and dissolved at 100°C, cooled sufficiently to room temperature (20-25°C), and then the ingredients (5) were added. ) And fully disperse it, add components (3) and (4) to them and mix them, then stand still to defoam to prepare a curable composition. In addition, the preparation work other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.

In Example 14, the components (1) and (2) were mixed and dissolved at 100°C, and after sufficiently cooled to room temperature (20-25°C), the component (5) was added to it and fully dispersed After adding and mixing components (3) and (4), the components (6) are added and mixed, and then left to stand to defoam to prepare a curable composition. In addition, the preparation work other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.

In Comparative Example 1, the component (5) was added to the component (1) and fully dispersed, the components (3) and (4) were added and mixed, and then left to stand to defoam to prepare a curable composition . In addition, the preparation work is performed at room temperature.

In Comparative Examples 2 to 5, after mixing components (1) and (2'), adding component (5) to it and dispersing it sufficiently, adding components (3) and (4) to it and mixing it, Leave it to defoam and prepare a curable composition. In addition, the preparation work is performed at room temperature.

In Comparative Example 6, the ingredients (1) and (2) were mixed and dissolved at 100°C, and after sufficiently cooled to room temperature (20-25°C), ingredient (5) was added to it and fully dispersed After adding component (4) to it and mixing it, it is allowed to stand for defoaming to prepare a curable composition. In addition, the preparation work other than the mixing and dissolution of the components (1) and (2) was performed at room temperature.

The results of the evaluation test of the curable compositions of Examples 1 to 14 and Comparative Examples 1 to 7 are shown in the following table.

From the results of Examples 1 to 14, it can be seen that the curable composition system of the present invention has both excellent thermosetting properties and excellent photocuring properties. Therefore, depending on the use environment or application, the hardening by heating and the hardening by light irradiation can be selectively implemented, or both can be implemented in combination. In addition, the cured product obtained by curing has high bonding strength per unit area, and is useful as an adhesive for bonding between constituent parts in a camera module. In contrast, the curable composition systems of Comparative Examples 1 to 7 are insufficient in one of the thermosetting properties and the photocuring properties. In particular, the curable composition of Comparative Example 6 which does not contain the component (3) and the curable composition of Comparative Example 7 which has a small amount of the component (3) have insufficient thermosetting properties. [Possibility of Industrial Use]

The curable composition of the present invention is useful as an adhesive, a sealant, a coating agent (especially an adhesive used in the manufacture of camera modules) and the like.

Claims (10)

A curable composition containing the following components (1)~(5): (1) Compounds having (meth)acryloyl groups; (2) Epoxy compounds that have more than 2 epoxy groups in one molecule and are solid at 25°C; (3) A polythiol compound having more than two mercapto groups in one molecule; (4) Light free radical generator; and (5) Latent hardener; Here, the amount of the component (3) is 15% by weight or more and 50% by weight or less with respect to the entire curable composition. The curable composition described in claim 1, wherein the component (2) contains: from bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, and At least one selected from the group consisting of benzene type epoxy resin. The curable composition according to claim 1 or 2, wherein the component (3) contains a polythiol compound having 2 to 6 mercapto groups in one molecule. The curable composition according to claim 1 or 2, wherein the sum of the acryl group, methacryl group in component (1), and the epoxy group in component (2) and the total amount in component (3) The molar ratio of the mercapto group (the total of the acryl group, the methacryl group in the component (1), and the epoxy group in the component (2)/the mercapto group in the component (3)) is 0.5 to 2.0. The curable composition according to claim 1 or 2, wherein the component (5) contains an amine-epoxy adduct-based compound and/or an amine-isocyanate adduct-based compound. An adhesive containing the curable composition described in any one of Claims 1 to 5. The adhesive described in claim 6, which is used for bonding between the constituent parts of the camera module. A sealant containing the curable composition described in any one of Claims 1 to 5. A coating agent containing the curable composition described in any one of Claims 1 to 5. A method for manufacturing a camera module includes the following steps (I)~(III): (I) Perform a step of positioning the first bonding part and the second bonding part that have been coated with the curable composition described in any one of claims 1 to 5; (II) A step of temporarily fixing the first bonding part and the second bonding part by curing the aforementioned curable composition by light irradiation; and (III) A step of formally fixing the first bonding part and the second bonding part by heating to harden the curable composition.