KR20190130013A - Curable Compositions and Structures - Google Patents

Abstract

The present invention includes (1) a compound having a (meth) acryloyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, (3) an optical radical generator, and (4) a latent curing agent It provides a curable composition.

Description

Curable Compositions and Structures

The present invention relates to a structure comprising a curable composition and a cured product of the curable composition as an adhesive layer between a first adherend and a second adherend.

In recent years, with the thinning of portable devices, such as a smart phone, the camera module mounted in portable devices, such as a smart phone, is miniaturizing. Due to the miniaturization of the camera module, the sites for joining the constituent members of the camera module are also finer, and therefore, a high adhesive strength is required for the adhesive layer formed of an adhesive for joining them.

In addition, the adhesive used for assembly of a camera module or the like is required to have low temperature curability in order to avoid thermal damage to an image sensor or the like due to a high temperature treatment, and also requires a short time curability at the same time from the viewpoint of improving production efficiency. From such a viewpoint, as a low temperature short time hardening-type adhesive agent, an ultraviolet curable adhesive agent and a thermosetting epoxy resin adhesive are used a lot. However, UV curable adhesives have disadvantages such as rapid curing, which cannot cause curing deformation due to cure shrinkage, or cannot be used for bonding to parts not exposed to light. On the other hand, the thermosetting epoxy resin adhesive, even if it is a low-temperature short-time curing type adhesive, during bonding, in order to maintain the bonding posture, the member (part) to be bonded must be fixed with a jig or a device, and the temperature rises by heating. As a result, the viscosity was lowered, causing a sag immediately before curing or flowing out of the desired portion, which was not always satisfactory.

Therefore, in order to solve the above-mentioned problem, in order to arrange | position the members which comprise a camera module with high precision, it is temporarily fixed by hardening (preliminary hardening) by light (ultraviolet and visible light) irradiation, and it sees by heat. Some adhesives of the type which harden | cure and perform main bonding (bone fixation) are proposed (for example, patent document 1 and 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 2009-51954 Patent Document 2: Japanese Patent Application Laid-Open No. 2009-79216

The adhesive layer which is a hardened | cured material obtained by photocuring, thermosetting, or light and thermosetting a conventional adhesive agent may not show sufficient adhesive strength. Moreover, the conventional adhesive agent may be inadequate storage stability. In addition, in the case where one of the adherends is a polycarbonate member (for example, a lens), when a conventional adhesive agent is used, the adhesive strength may be lowered by decomposing the polycarbonate and generating voids in the member.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cured product (adhesive layer) having excellent photocurability and thermosetting properties, having sufficient adhesive strength, excellent storage stability, and a polycarbonate product. It is providing the curable composition which can suppress the decomposition in the case of adhering the member of.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, (1) the compound which has a (meth) acryloyl group, (2) the polythiol compound which has two or more mercapto groups in 1 molecule, (3) an optical radical generator, and ( 4) It has been found that curable compositions comprising latent curing agents can achieve the above object. This invention based on this knowledge is as follows.

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

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

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

    (3) an optical radical generator, and

    (4) latent curing agents

    It comprises a curable composition.

[2] The component (1) is the following component (1-1):

    (1-1) A compound having a (meth) acryloyl group and an epoxy group

    Curable composition as described in said [1] containing.

[3] The component (1) is the following component (1-2):

    (1-2) Phosphoric Acid Modified (meth) acrylate

    Curable composition as described in said [1] or [2] containing.

[4] The component (1) is the following components (1-1) to (1-3):

    (1-1) a compound having a (meth) acryloyl group and an epoxy group,

    (1-2) phosphoric acid modified (meth) acrylate, and

    (1-3) Compound which has a (meth) acryloyl group which does not correspond to any of component (1-1) and component (1-2)

    Curable composition in any one of said [1]-[3] containing.

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

[6] Component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, trimethyl All propane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, ethylene glycol bis (Mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mercaptobutyrate), trimethylol Ethanetris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-isopropylidenediphenylbis (3-mercaptopropyl) Comprising at least one member selected from the group consisting of a hotel, the (1) to (5) of the curable composition according to any one.

[7] The component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and The curable composition as described in any one of said [1] to [5] containing at least 1 chosen from the group which consists of dipentaerythritol hexakis (3-mercaptopropionate).

[8] Molar ratio of acryloyl group, methacryloyl group and epoxy group in component (1) with mercapto group in component (2) (total acryloyl group, methacryloyl group and epoxy group in component (1)) Curable composition in any one of said [1]-[7] whose mercapto group in / component (2)) is 0.5-2.0.

[9] The curable composition according to any one of the above [1] to [8], wherein the component (4) contains at least one selected from the group consisting of an amine-epoxy adduct-based compound and an amine-isocyanate adduct-based compound. .

[10] The curable composition according to any one of the above [1] to [9], further comprising a thermal radical generator as component (5).

[11] A structure comprising a first adherend, a second adherend, and an adhesive layer thereof.

    The first adherend is a member made of polycarbonate,

    The structure whose adhesive layer is hardened | cured material of the curable composition in any one of said [1]-[10].

[12] The structure according to the above [11], which is a camera module.

The curable composition of the present invention is excellent in photocurability and thermosetting, can form a cured product (adhesive layer) having sufficient adhesive strength, is excellent in storage stability, and decomposes when bonding a polycarbonate member. It can be suppressed.

Curable composition of the present invention

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

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

(3) an optical radical generator, and

(4) latent curing agents

Characterized in that it comprises a. Hereinafter, each component is demonstrated in order.

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

In this invention, the "compound which has a (meth) acryloyl group" of component (1) is a component which plays a role which mainly raises adhesive strength. In the present invention, "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group". The component (1) may be one kind or two or more kinds.

The number of (meth) acryloyl groups in 1 molecule of the compound which has a (meth) acryloyl group should just be 1 or more. When the compound which has a (meth) acryloyl group is a mixture, this number shows the average value per molecule. In addition, when both of acryloyl group and methacryloyl group exist in 1 molecule, this number means the total number of the acryloyl group and methacryloyl group in 1 molecule. The number of (meth) acryloyl groups in one molecule of the compound having a (meth) acryloyl group is preferably 1 to 4, more preferably 1 to 2.

The molecular weight of the compound which has a (meth) acryloyl group becomes like this. Preferably it is 50-5,000, More preferably, it is 70-4,000, More preferably, it is 100-2,000. When this molecular weight is less than 50, volatility is high and it is unpreferable in terms of odor and handleability, and when this molecular weight exceeds 5,000, the viscosity of a composition becomes high and there exists a tendency for the applicability | paintability of a composition to fall. In addition, a molecular weight of 1,000 or more means a weight average molecular weight and can be measured by gel permeation chromatography (GPC). Molecular weight less than 1,000 can be measured by gravimetric apparatus (for example ESI-MS).

As a compound which has a (meth) acryloyl group, the following compounds are mentioned, for example. In addition, all of the following compounds may use only 1 type, or may use 2 or more types together.

(Compound having one acryloyl group or methacryloyl group in one molecule)

β-carboxyethyl (meth) acrylate

Isobornyl (meth) acrylate

Octyl / decyl (meth) acrylate

Ethoxylated phenyl (meth) acrylate

(Meth) acrylate having an epoxy group

Phosphoric Acid Modified (Meta) 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

Phthalate Monohydroxyethyl (meth) acrylate

2-hydroxy-3-phenoxypropyl (meth) acrylate

In addition, in this invention, "(meth) acrylate" means "acrylic acid ester and / or methacrylic acid ester." In addition, "EO modification" means what was modified by the addition of ethylene oxide (EO). In addition, "PO modification" means what was modified by the addition of propylene oxide (PO). In addition, "phosphoric acid modification" means what was modified | denatured by ester bond with phosphoric acid.

(Compound having two (meth) acryloyl groups in one molecule)

Dipropylene glycol di (meth) acrylate

1,6-hexanedioldi (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 (meth) acrylate

Polypropylene Glycol Di (meth) acrylate

Polyethylene Glycol Di (meth) acrylate

Neopentylglycol hydroxy pivalic acid ester di (meth) acrylate

Polyurethane having two (meth) acryloyl groups in one molecule

Polyester having two (meth) acryloyl groups in one molecule

(Compound having 3 or more (meth) acryloyl groups in 1 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

Trimethylolpropane tetra (meth) acrylate

Dipentaerythritol (penta / hexa) (meth) acrylate

Dipentaerythritol hexa (meth) acrylate

EO modified diglycerin tetra (meth) acrylate

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

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

In addition, pentaerythritol (tri / tetra) (meth) acrylate is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. This mixing ratio (pentaerythritol tri (meth) acrylate / pentaerythritol tetra (meth) acrylate) is weight ratio, Preferably it is 5/95-95/5, More preferably, it is 30/70-70/30 to be.

In addition, dipentaerythritol (penta / hexa) (meth) acrylate is a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. This mixing ratio (Dipentaerythritol penta (meth) acrylate / dipentaerythritol hexa (meth) acrylate) is in weight ratio, Preferably it is 5/95-95/5, More preferably, it is 30/70-70 / 30.

Moreover, EO modified isocyanuric acid (di / tri) (meth) acrylate can be used as a compound which has a (meth) acryloyl group. 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. This mixing ratio (EO modified isocyanuric acid di (meth) acrylate / EO modified isocyanuric acid tri (meth) acrylate) is weight ratio, Preferably it is 1/99 to 99/1, More preferably, it is 10 / 90 to 90/10, more preferably 40/60 to 60/40.

From the viewpoint of thermosetting and adhesiveness, the component (1) preferably includes a compound having a (meth) acryloyl group and an epoxy group (hereinafter sometimes referred to as "component (1-1)"). 1 type may be sufficient as component (1-1), and 2 or more types may be sufficient as it.

Component (1-1) can be manufactured by the following method (i), for example, but this invention is not limited to this.

(i) A method in which an epoxy compound having two or more epoxy groups in one molecule and (meth) acrylic acid are reacted in an amount ratio in which the epoxy group of the epoxy compound remains.

In addition, in this invention, "(meth) acrylate" means "acrylic acid and / or methacrylic acid."

There is no restriction | limiting in particular in the epoxy compound which can be used by the said method (i), For example, a bisphenol-A epoxy resin, a hydrogenated bisphenol-A epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol type Epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin , A cresol novolac epoxy resin, a bisphenol A novolac epoxy resin, and the like. Among these, bisphenol A type epoxy resin is preferable and bisphenol A diglycidyl ether is more preferable.

You may use a commercial item for component (1-1). As the commercial item, for example, "UVACURE 1561" by Daicel Orunex Co., Ltd., "EA-1010N" by Shin-Nakamura Kagaku Kogyo Co., Ltd., and "4HBAGE" by Nippon Kasei Co., Ltd. Can be mentioned.

Component (1-1), Preferably, it is a compound which has frame | skeleton of bisphenol-A epoxy resin, and has a (meth) acryloyl group and an epoxy group.

The number of (meth) acryloyl groups in one molecule of the compound having a (meth) acryloyl group and an epoxy group is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably To be one. In addition, when the compound which has a (meth) acryloyl group and an epoxy group is a mixture, this number shows the average value per molecule.

The number of epoxy groups in one molecule of the compound having a (meth) acryloyl group and an epoxy group is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1. In addition, when the compound which has a (meth) acryloyl group and an epoxy group is a mixture, this number shows the average value per molecule.

The epoxy equivalent of the compound which has a (meth) acryloyl group and an epoxy group becomes like this. Preferably it is 100-2,000, More preferably, it is 200-1,000, More preferably, it is 300-500. In addition, "epoxy equivalent" is the number of grams (g / eq) of resin containing an epoxy group of 1 gram equivalent, and is measured according to the method prescribed | regulated to JISK7236.

The molecular weight of the compound which has a (meth) acryloyl group and an epoxy group becomes like this. Preferably it is 100-2,000, More preferably, it is 200-1,000, More preferably, it is 300-500.

When using component (1-1), from the viewpoint of the viscosity of the whole composition and curability, the amount is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts per 100 parts by weight in total of the component (1). Parts by weight, more preferably 30 to 70 parts by weight.

From the viewpoint of storage stability, the component (1) preferably includes phosphoric acid modified (meth) acrylate (hereinafter sometimes abbreviated as "component (1-2)"). 1 type may be sufficient as a component (1-2), and 2 or more types may be sufficient as it. Component (1-2) is preferably phosphoric acid modified methacrylate.

Component (1-2) can be manufactured by the following method (ii), for example, but this invention is not limited to this.

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

The compound which has a (meth) acryloyl group and a hydroxyl group in 1 molecule which can be used for the said method (ii) can be manufactured by the following method (iii) or (iv), for example, It is not limited to these.

(iii) A method in which (meth) acrylic acid or (meth) acrylate and a polyhydric alcohol (for example, alkylene glycol, glycerin, etc.) are reacted in an amount ratio in which the hydroxyl group of the polyhydric alcohol remains.

(iv) A method of adding an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) to (meth) acrylic acid.

A commercial item may be used for component (1-2). As the commercial item, for example, "EBECRYL168" by Orunex Corporation, "KAYAMER PM-2" by Nippon Kayaku Co., Ltd., "KAYAMER PM-21", and Kyoeisha Kagaku Co., Ltd. "Light ester P-1M", "light ester P-2M", and "light acrylate P-1A (N)" The "JPA-514" made by Johoku Kagaku Kogyo Co., Ltd. is mentioned.

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

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

In the case of using the component (1-2), the amount is preferably from 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the component (1) from the viewpoint of storage stability and curability. More preferably, it is 0.05-2 weight part.

Component (1), Preferably it is (meth) acryloyl group which does not correspond to any of component (1-1), component (1-2), and component (1-1) and component (1-2). The compound which has a (it may abbreviate as "component (1-3)" hereafter) is included. In this embodiment, any of the components (1-1) to (1-3) may be one kind or two or more kinds.

When component (1) contains components (1-1) to (1-3), the amount of component (1-1) per 100 parts by weight of the total of component (1) is determined from the viewpoint of the viscosity and curability of the whole composition. , Preferably it is 10-90 weight part, More preferably, it is 20-80 weight part, More preferably, it is 30-70 weight part, The quantity of component (1-2), Preferably it is from a viewpoint of storage stability and curability. Is 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 2 parts by weight, and the amount of component (1-3) is remainder.

<(2) Polythiol compound having two or more mercapto groups in one molecule>

In the curable composition of the present invention, the "polythiol compound having two or more mercapto groups in one molecule" of the component (2) mainly serves as a curing agent for curing the component (1) by light irradiation such as ultraviolet rays. In charge. 1 type of components (2) may be sufficient, and 2 or more types may be sufficient as it. The number of mercapto groups in one molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, still more preferably 3 to 5, particularly preferably 3 or 4.

A commercial product may be used for a polythiol compound, and what was manufactured by a well-known method (for example, the method of Unexamined-Japanese-Patent No. 2012-153794 or international publication 2001/00698) may be used.

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

As a polyol, ethylene glycol, trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, etc. are mentioned, for example.

Examples of mercapto organic acids include mercapto aliphatic monos such as mercaptoacetic acid, mercaptopropionic acid (such as 3-mercaptopropionic acid), and mercaptobutyric acid (such as 3-mercaptobutyric acid and 4-mercaptobutyric acid). Carboxylic acid; Esters containing a mercapto group and a carboxyl group obtained by esterification of a hydroxy acid with a mercapto organic acid; Mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (for example, 2,3-dimercaptosuccinic acid); Mercapto aromatic monocarboxylic acids, such as mercaptobenzoic acid (for example, 4-mercaptobenzoic acid), etc. are mentioned. Carbon number of the said mercapto aliphatic monocarboxylic acid becomes like this. Preferably it is 2-8, More preferably, it is 2-6, More preferably, it is 2-4, Especially preferably, it is 3. Among the 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-mer Captopropionic acid is more preferred.

Specific examples of partial esters of polyols and mercapto organic acids include trimethylolethane bis (mercaptoacetate), trimethylolethanebis (3-mercaptopropionate), trimethylolethanebis (3-mercaptobutyrate), and trimethylol Ethanebis (4-mercaptobutyrate), trimethylolpropanebis (mercaptoacetate), trimethylolpropanebis (3-mercaptopropionate), trimethylolpropanebis (3-mercaptobutyrate), trimethylolpropanebis (4-mercaptobutyrate), pentaerythritol tris (mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tris (4 Mercaptobutyrate), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobu) Acrylate), dipentaerythritol tetrakis (4-mercapto butyrate), and the like.

Specific examples of the complete ester of the polyol and the mercapto organic acid include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), and ethylene glycol bis ( 4-mercaptobutyrate), trimethylol ethane tris (mercaptoacetate), trimethylol ethane tris (3-mercapto propionate), trimethylol ethane tris (3- mercapto butyrate), trimethylol ethane tris (4- Mercaptobutyrate), trimethylolpropanetris (mercaptoacetate), trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetris (3-mercaptobutyrate), trimethylolpropanetris (4-mercapto Butyrate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrei) ), Pentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis ( 3-mercaptobutyrate), dipentaerythritol hexakis (4-mercaptobutyrate), etc. are mentioned.

From the standpoint of storage stability, the partial esters and complete esters are preferably extremely low in basic impurity content, and more preferably do not require the use of basic substances in production.

Moreover, as a component (2), Alkan polythiol compounds, such as 1, 4- butanedithiol, 1, 6- hexanedithiol, 1, 10- decandithiol; Terminal mercapto group-containing polyethers; Terminal mercapto group-containing polythioethers; Polythiol compound obtained by reaction of an epoxy compound and hydrogen sulfide; Like the polythiol compound having a terminal mercapto group obtained by the reaction between the polythiol compound and the epoxy compound, a polythiol compound produced by using a basic substance as a reaction catalyst in the production process can also be used. It is preferable to use the polythiol compound manufactured using a basic substance after dealkali process to make alkali metal ion concentration 50 weight ppm or less.

As dealkali treatment of a polythiol compound produced using a basic substance, for example, 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 extracted and washed. Desalting by, or the like; Adsorption using an ion exchange resin; Although the method of refine | purifying by distillation, etc. are mentioned, It is not limited to these.

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

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

In a preferable embodiment of the present invention, component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) iso Cyanurate, trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanu Ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), 1,4-bis (3-mercaptobutyryloxy) butane, 1, 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mercapto Butyrate), trimethylolethanetris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-isopropyl At least one selected from the group consisting of dendiphenylbis (3-mercaptopropyl) ether. In this aspect, it is more preferable that component (2) consists of at least one selected from the group.

In a more preferable aspect of the present invention, component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) Isocyanurate, and at least one selected from the group consisting of dipentaerythritol hexakis (3-mercaptopropionate). In this aspect, it is particularly preferred that component (2) consists of at least one selected from the group above.

From the viewpoint of curability, the molar ratio of the sum of the acryloyl group, the methacryloyl group and the epoxy group in the component (1) and the mercapto group in the component (2) (the acryloyl group, the methacryloyl group and the epoxy group in the component (1)) Mercapto group in the sum / component (2)) is preferably 0.5 to 2.0, more preferably 0.6 to 1.6, still more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3. In addition, when the component (1) does not have an epoxy group (that is, when the component (1) does not include the component (1-1)), the "acryloyl group, methacryloyl group and epoxy group of the component (1) A total "is" the sum of the acryloyl group and methacryloyl group in component (1) ". For example, when component (1) has acryloyl group and does not have a methacryloyl group, "the sum of the acryloyl group, the methacryloyl group, and the epoxy group in component (1)" means "component (1). The sum of the acryloyl group and the epoxy group in the &quot;

From the viewpoint of curability and adhesiveness, the amount of component (1) is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more per curable composition. Similarly, from the viewpoint of curability and adhesiveness, the amount of component (1) is preferably 85% by weight or less, more preferably 80% by weight or less, still more preferably 75% by weight or less per curable composition.

From the viewpoint of curability and adhesiveness, the amount of component (2) is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 20% by weight or more per curable composition. Similarly, from the viewpoint of curability and adhesiveness, the amount of component (2) is preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 55% by weight or less per curable composition.

From the viewpoint of curability and adhesiveness, the total amount of the component (1) and the component (2) is preferably 30% by weight or more, more preferably 50% by weight or more, even more preferably 70% by weight or more per the curable composition. to be. Similarly, from the viewpoint of curability and adhesiveness, the total amount of the component (1) and the component (2) is preferably 100% by weight or less, more preferably 97% by weight or less, even more preferably 95% by weight, based on the total curable composition. % Or less

<(3) Photoradical Generator>

Although there is no restriction | limiting in particular in an optical radical generating agent in this invention, For example, Alkylphenone type | system | group photoradical generator, Acylphosphine oxide type | system | group photoradical generator, Oxime ester type | system | group photoradical generator, (alpha)-ketone type | system | group photoradical generation | generation Etc. can be mentioned. 1 type may be sufficient as component (3), and 2 or more types may be sufficient as it. The optical radical generator is preferably an alkylphenone-based optical radical generator.

As an alkyl phenone system radical generating agent, 2-hydroxy-2-methyl-1- phenyl propane-1-one and 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl), for example. -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropane-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethyl Thioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) phosphineoxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate, 4,4'-bis (diethylamino) benzo Phenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy And oligomers of 2-methyl-1-propane-1-one and 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one.

As an acylphosphine oxide type | system | group radical photo-acid generator, 2,4,6-trimethyl benzoyl- diphenyl- phosphine oxide, bis (2,4, 6- trimethylbenzoyl) -phenyl- phosphine oxide etc. are mentioned, for example. Can be mentioned.

As an oxime ester photoradical generator, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyl oxime), 1- [6- (2-methylbenzoyl, for example) ) -9-ethyl-9H-carbazol-3-yl] ethanone O-acetyl oxime and the like.

As an (alpha)-hydroxy ketone system photoradical generator, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methyl, for example. Propane-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

As a commercial item of an optical radical generating agent, "IRGACURE 1173" (2-hydroxy-2-methyl-1-phenylpropan-1-one) by BASF Corporation, "IRGACURE OXE-01" (1- [4), for example. -(Phenylthio) phenyl] -1,2-octanedione2- (O-benzoyloxime)), "IRGACURE OXE-02" (1- [6- (2-methylbenzoyl) -9-ethyl-9H-carr Bazol-3-yl] ethanone O-acetyloxime), "Esacure KTO 46" by DKSH (2,4,6-trimethylbenzoyldiphenylphosphine oxide and oligo [2-hydroxy-2-methyl1- [ Mixture of 4- (1-methylvinyl) phenyl] propane] and a methylbenzophenone derivative), "ESACURE KIP 150" by Lamberti SPA (2-hydroxy-1- (4-isopropenylphenyl) -2-methyl Oligomer of propane-1-one).

The amount of component (3) is preferably from 0.001% by weight or more, more preferably from 0.01% by weight or more, more preferably from the viewpoint of obtaining a curable composition that can be photocured efficiently upon light irradiation. 0.1 weight% or more. On the other hand, from a viewpoint of suppressing the outgassing by the photo-radical generator remaining in hardened | cured material or its decomposition product, 10 weight% or less is preferable per whole curable composition, More preferably, it is 5 weight% or less, More preferably, Is 2% by weight or less.

<(4) latent curing agent>

The latent hardener of the component (4) is a well-known additive in the field of epoxy resins, and does not harden an epoxy resin etc. at normal temperature (25 degreeC), but means the hardening agent which can harden an epoxy resin etc. by heating. The component (4) may be one kind or two or more kinds.

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

As a solid imidazole compound at normal temperature, for example, 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-imida Zolyl) ethyl] -1,3,5-triazine, 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine-iso Cyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-methylimidazole- trimellitate, 1-cyanoethyl-2-phenylimidazole-trimelitate, N- (2-methylimidazolyl-1-ethyl) -urea, etc. are mentioned.

As an epoxy compound used as a raw material of an amine-epoxy adduct type compound, For example, polyhydric phenols, such as bisphenol A, bisphenol F, catechol, resorcinol, or polyhydric alcohols, such as glycerin and polyethylene glycol, and epichloro high Polyglycidyl ether obtained by reacting drine; glycidyl ether esters obtained by reacting hydroxy acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; Glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol and epichlorohydrin; Furthermore, polyfunctional epoxy compounds, such as epoxidized phenol novolak resin, epoxidized cresol novolak resin, and epoxidized polyolefin, and monofunctional epoxy compounds, such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate Etc. can be mentioned.

As an amine compound used as a raw material of an amine-epoxy adduct type compound, it has one or more active hydrogen atoms which can react with an epoxy group or an isocyanate group (another name: isocyanato group) in 1 molecule, and also an amino group (primary) What is necessary is just to have 1 or more of an amino group, a secondary amino group, and a tertiary amino group) in 1 molecule. As such an amine compound, For example, aliphatic, such as diethylene triamine, triethylene tetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'- diamino dicyclohexyl methane, Amine compounds; 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. have.

Moreover, when the compound which has a tertiary amino group is used, the outstanding latent hardener can be manufactured. As a compound which has a tertiary amino group, it is dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methyl pipe, for example. Amines having tertiary amino groups such as razin, 2-methylimidazole, 2-ethylimidazole, 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-(-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy Hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy- 3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4,6 -Tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2-mercapto Benzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isnicotinic acid, picolinic acid Alcohols, phenols, thiols, carboxylic acids and hydrazides having tertiary amino groups such as N, N-dimethylglycine hydrazide, N, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide, and the like. Can be mentioned.

When the epoxy compound and the amine compound are added to react to prepare the amine-epoxy adduct-based compound, an active hydrogen compound having two or more active hydrogens in one molecule may 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 novolak resins, trimethylolpropane, and the like. Polyhydric carboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid, and the like. Can be.

As an isocyanate compound used as a raw material of an amine-isocyanate adduct type compound, For example, Monofunctional isocyanate compounds, such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate; Hexamethylene diisocyanate, tolylene diisocyanate (eg 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone Polyfunctional isocyanate compounds, such as diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate; Moreover, the terminal isocyanate group containing compound etc. which are obtained by reaction of these polyfunctional isocyanate compounds and an active hydrogen compound are mentioned. As such a terminal isocyanate group containing compound, the addition compound which has a terminal isocyanate group obtained by reaction of tolylene diisocyanate and trimethylol propane, the addition which has terminal isocyanate group obtained by reaction of tolylene isocyanate and pentaerythritol, for example. Compounds and the like.

The latent curing agent of component (4) is, for example, appropriately mixed with the above-mentioned raw materials, reacted at a temperature of 200 ° C. at room temperature, then cooled and solidified and then pulverized or methylethylketone, dioxane, tetra It can be easily obtained by making the above-mentioned raw materials react in a solvent such as hydrofuran and pulverizing the solid content after desolventing.

A latent hardener of component (4) may use a commercial item. As a commercial item of an amine epoxy compound, "Amicure PN-23", "Amicure PN-40", "Amicure PN-50", "Amicure PN-" by Ajinomoto Fine Techno Co., Ltd. H "," HADONA X-3661S "by ACAL Corporation," Hadona X-3670S "," Novacure HX-3742 "and" Novacure HX-3721 "by Asahi Kasei, are mentioned. Moreover, as a commercial item of an amine-isocyanate adduct type compound, "Fuji Cure FXE-1000", "Fuji Cure FXR-1030", "Fuji Cure FXR-1020" by the T & K TOKA company, "Fuji Cure FXR", for example -1030 "," Fujicure FXR-1081 ", and" Fujicure FXR-1121 "are mentioned.

Component (4) at least one selected from the group consisting of latent thermal anionic polymerization initiators, preferably amine-epoxy adduct based compounds and amine-isocyanate adduct based compounds, more preferably selected from said group It consists of at least one, More preferably, it is an amine-epoxy adduct type compound or an amine-isocyanate adduct type compound.

From the viewpoint of curability by heat, the amount of component (4) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and still more preferably 0.5% by weight or more per curable composition. In addition, from the viewpoint of storage stability, the amount of component (4) is preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably 6% by weight or less per curable composition.

((5) thermal radical generator>

The curable composition of this invention may further contain the thermal radical generating agent as a component (5). 1 type of components (5) may be sufficient as it, and 2 or more types may be sufficient as it. As a thermal radical generating agent, an azo compound, an organic peroxide, etc. are mentioned, for example.

As an azo compound, 2,2'- azobis (isobutyronitrile), 2,2'- azobis (2, 4- dimethylvaleronitrile), 2,2'- azobis (2- Methylbutyronitrile), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methyl) dihydrochloride, 1,1'-azobis (1-acetoxy- 1-phenylethane, 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl2,2'-azobis (isobutyrate), 2,2'-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1-[(1-cyano-1 -Methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2,2'- azobis (2-methylpropionate), etc. are mentioned.

As the organic peroxide, for example, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxy) cyclo Hexane, 2,2-di (t-butylperoxy) butane, n-butyl4,4-di (t-butylperoxy) valate, 2,2-di (4,4-di (t-butylperoxy) Oxy) cyclohexyl) propane, p-mentane hydroperoxide, diisopropoxybenzenebenzene, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butylhydroperoxide, di (2-t-butylperoxy isopropyl) benzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylperoxide, di-t-hexylper Oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, diisobutyryl peroxide, di (3,5,5-t-methylhexanoyl) peroxide, dilauro Yl peroxide, disuccinate peroxide, di (3-methylbenzo I) peroxide, dibenzoylperoxide, di-n-propylperoxycarbonate, di-isopropylperoxydicarbonate, di (4-t-butylcyclohexyl) peroxycarbonate, di (2-ethylhexyl) peroxy Carbonate, di-sec-butylperoxycarbonate, cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, t-hexylperoxy neodecanoate, t-butyl Peroxyneodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl- 2,5-di (t-ethylhexanoylperoxy) hexane, t-hexyl peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexyl peroxy isopropyl mono Carbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexyl mono Carbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate and t- A mixture of butyl peroxybenzoate, t-butylperoxybenzoate, t-butylperoxyallyl monocarbonate, 3,3 ', 4,4'-tetra (t-butylperoxycarbor) benzophenone, and the like. Can be.

The 10-hour half-life temperature of the thermal radical generating agent is preferably 40 ° C. or higher and less than 100 ° C. from the viewpoint of low temperature curability, and more preferably 50 ° C. or higher and 90 ° C. or lower.

Component (5) is preferably at least one selected from the group consisting of an azo compound and an organic peroxide, more preferably an azo compound or an organic peroxide.

In the case of using the component (5), the amount thereof is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, even more preferably 0.1% by weight or more per the curable composition from the viewpoint of promoting thermal curing. to be. On the other hand, from the viewpoint of suppressing the outgassing due to the thermal radical generator remaining in the cured product or the decomposition product thereof, the total amount of the curable composition is preferably 5% by weight or less, more preferably 3% by weight or less, even more preferably Is 2% by weight or less.

<(6) other components>

In the range which does not impair the effect of this invention, the curable composition of this invention may contain the other component different from the said components (1)-(5). As another component, For example, a polymerization inhibitor (for example, dibutylhydroxytoluene, barbituric acid); Antioxidants; Inorganic fillers (e.g. calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, quartz Minutes, etc.); An organic filler composed of a copolymer of a polymethyl methacrylate and / or a polystyrene with a monomer copolymerizable with a monomer constituting them; Thixotropic agent; Antifoam; Leveling agents; Coupling agents; Flame retardant; Pigments; dyes; Fluorescent substance; and the like. Any other component may be one type or two or more types.

In order to improve the storage stability of a curable composition, you may use a polymerization inhibitor. A polymerization inhibitor exhibits the effect of suppressing reaction at the working environment temperature using a curable composition, and reaction (so-called dark reaction) which does not depend on light irradiation. As used herein, the working environment temperature is generally in the range of about 15 ° C to 30 ° C. In addition, reaction is a radical reaction or an ionic reaction (especially an anion reaction).

Although it does not specifically limit as a polymerization inhibitor which suppresses a radical reaction, For example, a quinone type polymerization inhibitor, a hydroquinone type polymerization inhibitor, a nitrosoamine type polymerization inhibitor, etc. are mentioned. Specifically, hydroquinone, t-butylhydroquinone, p-methoxyphenol, N-nitroso-N-phenylhydroxyamine aluminum salt, etc. are mentioned, for example. When using the polymerization inhibitor which suppresses a radical reaction, the quantity is preferably 0.0001 to 2.0 weight%, more preferably 0.001 to 1.0 weight% per whole curable composition. If the amount is less than 0.0001% by weight, a sufficient effect may not be obtained. If the amount is more than 2.0% by weight, there is a fear that the polymerization reaction at the time of light irradiation or heating is affected.

As a polymerization inhibitor which suppresses an ionic reaction (especially an anion reaction), a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, a mercapto organic acid, etc. are mentioned, for example. .

As the borate compound, for example, trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, torino Nylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxoundecyl) (1 , 4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxoundecyl) borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m-tolylborate, Triethanol amine borate etc. are mentioned.

As a titanate compound, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, etc. are mentioned, for example.

As an aluminate compound, triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate, etc. are mentioned, for example.

As a zirconate compound, tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, etc. are mentioned, for example.

As an isocyanate compound, for example, butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl Isocyanates, tolylene diisocyanates (eg 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, iso Poron diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, bicyclo heptane triisocyanate, etc. are mentioned.

Examples of the carboxylic acid include unsaturated aliphatic monobasic acids such as saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid and caprylic acid, acrylic acid, methacrylic acid and crotonic acid, monochloroacetic acid and dichloro Halogenated fatty acids such as acetic acid, monobasic hydroxy acids such as glycolic acid, lactic acid, and grape acid, aliphatic aldehyde acids such as glyoxylic acid, and aliphatic polybasic acids such as ketone acid, oxalic acid, malonic acid, succinic acid and maleic acid, benzoic acid, halogenated Aromatic polybasic acids, such as aromatic monobasic acids, such as benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid, phthalic acid, and trimesic acid, etc. are mentioned.

Examples of the acid anhydride include aliphatic polybasic anhydrides such as succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydro phthalic anhydride and methyltetrahydro phthalic anhydride; Aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; Can be mentioned.

Examples of mercapto organic acids include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (such as 3-mercaptopropionic acid), and mercaptobutyric acid (such as 3-mercaptobutyric acid and 4-mercaptobutyric acid); Esters containing a mercapto group and a carboxyl group obtained by esterification of a hydroxy acid with a mercapto organic acid; Mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (for example, 2,3-dimercaptosuccinic acid); Mercapto aromatic monocarboxylic acids, such as mercaptobenzoic acid (for example, 4-mercaptobenzoic acid), etc. are mentioned.

As a polymerization inhibitor which suppresses an ionic reaction, from a viewpoint of high versatility and safety, and improving storage stability, a borate compound is preferable, and triethyl borate, tripropyl borate, triisopropyl borate, and tributyl borate are more preferable. And triethyl borate is more preferable.

The amount of the polymerization inhibitor that suppresses the ionic reaction is preferably 0.0001 to 2.0% by weight, more preferably 0.001 to 1.0% by weight per curable composition. If the amount is less than 0.0001% by weight, a sufficient effect is not obtained. If the amount is more than 2.0% by weight, it is not preferable because it adversely affects the reaction during heating.

In this invention, only the polymerization inhibitor which suppresses a radical reaction and the polymerization inhibitor which suppresses an ionic reaction may use either, and may use both together.

<Preparation and Curing of Curable Composition>

There is no particular difficulty in manufacturing the curable composition of this invention. For example, it can prepare as a one-component curable composition by mixing each component uniformly using a kneader, a stirring mixer, a three roll mill, etc. The temperature of the curable composition at the time of mixing is 10-40 degreeC normally, Preferably it is 20-30 degreeC.

As light irradiated when photocuring the curable composition of this invention, infrared rays, visible light, an ultraviolet-ray, an electron beam, etc. with a wavelength of 800 nm or more can be used, but an ultraviolet-ray is preferable. The peak wavelength of the ultraviolet ray is preferably 300 to 500 nm. The illuminance of the ultraviolet ray 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.

As light irradiation means, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave excitation mercury lamp, metal halide lamp, sodium lamp, fluorescent lamp, LED type SPOT type UV irradiator, xenon lamp, DEEP UV lamp, etc. are mentioned.

Although the heating temperature at the time of thermosetting the curable composition of this invention is not specifically limited, Generally, it is 50-150 degreeC, Preferably it is 60-100 degreeC. Although the heating time at the time of thermosetting the curable composition of this invention is not specifically limited, Generally, it is 10 to 120 minutes, Preferably it is 30 to 60 minutes.

<Use of Curable Composition>

The curable composition of this invention has the outstanding photocurability and the outstanding thermosetting, and can form the hardened | cured material which has high adhesive strength. Therefore, an adhesive agent, a sealing agent, a coating agent, etc. are mentioned as a use of the curable composition of this invention. Among these uses, an adhesive is preferable.

<Structure>

The present invention is a structure comprising a first adherend, a second adherend, and an adhesive layer thereof, wherein the first adherend is a member made of polycarbonate, and the adhesive layer is a cured product of the curable composition of the present invention described above. Provide the structure. In the structure of the present invention, the first adherend and the second adherend are bonded to each other via an adhesive layer. As a polycarbonate member which is a 1st to-be-adhered body, a lens, a lens holder, a housing | casing, etc. are mentioned, for example. The structure of the present invention is preferably a camera module mounted on a portable device such as a smartphone.

In the assembly of the structure of the present invention (for example, a camera module), each component is positioned with high precision by going through the following steps (I) to (III), and the high adhesion strength between the parts to be bonded It is possible to efficiently produce a high quality structure assembled by bonding with.

(I) Process of apply | coating curable composition of this invention to a sensor case, and positioning the sensor case and housing which this curable composition was apply | coated.

(II) A step of curing (preliminary curing) the curing composition by light irradiation to temporarily fix the first adherend and the second adherend.

(III) A step of curing (main curing) the curable composition by heating to form an adhesive layer (that is, a cured product of the curable composition) to fix the first adherend and the second adherend.

In process (II), in the relationship with the arrangement position of a 1st to-be-adhered body and a 2nd to-be-adhered body, many unirradiated parts in which light was not irradiated may remain in the apply | coated curable composition. However, since the curable composition of the present invention has extremely good thermosetting properties, even if an unilluminated portion of light is formed, not only the portion (precured portion) where the curing has been advanced by light irradiation, but also the unirradiated portion of the light is sufficiently formed by heat curing. Curing advances to full curing, whereby the entire applied curable composition forms a cured product having high adhesive strength.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited according to the following Examples, and of course, the present invention is not limited thereto. Possible, these are all included in the technical scope of the present invention.

1. Raw material

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

(1A) UVACURE 1561: Daicel Ornex Corporation, epoxy resin half acrylate (compound having acryloyl group and epoxy group), epoxy equivalent: 450 g / eq, molecular weight: 450, of acryloyl group in 1 molecule Number: 1, Number of epoxy groups in 1 molecule: 1

(1B) IRR-214K: Daicel Orunex Co., Ltd. make, tricyclodecane dimethanol diacrylate, molecular weight: 300, the number of acryloyl groups in 1 molecule: 2

(1C) EBECRYL150: Daicel Orunex Co., Ltd. make, EO modified bisphenol A diacrylate, molecular weight: 512, the number of acryloyl groups in 1 molecule: 2

(1D) DPHA: manufactured by Daicel Orunex, dipentaerythritol hexaacrylate, molecular weight: 524, number of acryloyl groups in 1 molecule: 6

(1E) EBECRYL810: manufactured by Daicel Orunex, polyester acrylate (polyester having an acrylic group), molecular weight: 1,000, number of acryloyl groups in 1 molecule: 4

(1F) EBECRYL168: Daicel Orunex Co., Ltd. make, phosphoric acid modified methacrylate, the number of methacryloyl groups in 1 molecule: 1.5

(1G) KAYAMER PM-2: Nippon Kayaku Co., Ltd. make, phosphoric acid modified methacrylate, molecular weight: 259, number of methacryloyl groups in 1 molecule: 1.5

(1H) KAYAMER PM-21: Nippon Kayaku Co., Ltd. make, phosphoric acid modified methacrylate, molecular weight: 437, the number of methacryloyl groups in 1 molecule: 1.5

<(2) Polythiol compound having two or more mercapto groups in one molecule>

(2A) PEMP: SC Yuki Kagaku Co., Ltd. make, pentaerythritol tetrakis (3-mercaptopropionate), molecular weight: 489, the number of mercapto groups in 1 molecule: 4

(2B) PE-1: Showa Denko Co., Ltd., "Karenz MT PE-1", pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight: 544, the number of mercapto groups in 1 molecule: 4

(2C) TMPIC: Tris (3-mercaptopropyl) isocyanurate, molecular weight: 351, number of mercapto groups in 1 molecule: 3

(2D) DPMP: manufactured by Yodo Kagaku Kogyo Co., Ltd., dipentaerythritol hexakis (3-mercaptopropionate), molecular weight: 783, number of mercapto groups in one molecule: 6

<(3) Photoradical Generator>

(3A) IRGACURE 1173: The 2-hydroxy-2-methyl-1-phenylpropan-1-one by BASF Corporation

(3B) ESACURE KIP 150: an oligomer of Lamberti SPA, 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one

<(4) latent curing agent>

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

(4B) FXR1081: T & K TOKA Co., Ltd., amine-isocyanate adduct-based compound

((5) thermal radical generator>

(5A) V-601: Wako Pure Chemical Industries, Ltd. make, dimethyl 2,2'- azobis (2-methylpropionate), 10 hours half life temperature: 66 degreeC

(5B) Perocta O: Nichi Oil Co., Ltd., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 10 hours half-life temperature; 65.3 ℃

<(6) other components>

(6A) Q-1301: Wako Pure Chemical Industries, Ltd. make, N-nitroso-N-phenylhydroxyamine aluminum salt

(6B) Triethyl borate: manufactured by Junsei Kagaku Kogyo Co., Ltd.

(6C) barbituric acid: manufactured by Tokyo Kasei Co., Ltd.

2. Evaluation test

[Evaluation of Thermosetting]

A curable composition was applied to a glass epoxy resin laminate (Risko Kogyo Co., Ltd., FR-4.0) having a width of 2.5 mm × length 8.0 mm × thickness 0.8 mm using a spacer having a thickness of about 50 μm using a bar coater to form a curable composition. The coating film of was formed, it was heated and hardened | cured at 80 degreeC for 60 minutes in a hot-air circulation oven, and thermosetting property was evaluated by observing the coating film external appearance by the finger contact of the following references | standards.

<Evaluation Criteria>

○: no uncured components

△: slightly sticky

×: uncured

[Measurement of Adhesive Strength]

(1) Measurement of adhesive strength 1 after photocuring

After drying a polycarbonate plate (Mitsubishi Engineering Plastics Co., Ltd., YUFIRON NF-2000) of width 25mm X length 100mm X thickness 2.0mm in advance at 80 degreeC for 20 minutes, and cooling to room temperature, the curable composition is put on a polycarbonate It apply | coated in the quantity of 1-3 mg, the capacitor | condenser chip (JIS-name: 2012 size) was put on it, photocuring was performed on the following conditions, the adhesive strength 1 of hardened | cured material was measured, and the following reference | standard evaluated.

(2) Measurement of adhesive strength 2 after light and thermosetting

In the same manner as described above, the application of the curable composition to the polycarbonate plate dried in advance and the mounting of the condenser chip were carried out under light and thermal curing under the following conditions, and the adhesive strength 2 of the cured product was measured. Evaluated.

(3) Measurement of adhesive strength 3 after thermosetting

In the same manner as described above, the curing of the curable composition and the mounting of the condenser chip were performed on the polycarbonate plate which had been dried in advance, and the thermosetting was performed under the following conditions, and the adhesive strength 3 of the cured product was measured and evaluated according to the following criteria. .

Adhesive strength (N / mm 2) was measured by breaking the chip in the transverse direction with a bond tester (Series 4000 manufactured by DEGA Co., Ltd.). The measurement was performed 3 times and the average value was calculated | required.

<Cure condition>

(1) photocuring

UV-LED irradiation apparatus UJ35 by Panasonic makes curable composition the ultraviolet-ray (peak wavelength: 365 nm) of illuminance 2,500 mW / cm <2> at an angle of 45 degrees (45 degrees of incident angles of the light to a capacitor chip surface) in two directions. Was irradiated for 1.2 seconds (exposure amount 3,000 mJ / cm 2).

(2) light and heat curing

UV-LED irradiation apparatus UJ35 by Panasonic makes curable composition the ultraviolet-ray (peak wavelength: 365 nm) of illuminance 2,500 mW / cm <2> at an angle of 45 degrees (45 degrees of incident angles of the light to a capacitor chip surface) in two directions. Was irradiated for 1.2 seconds (exposure amount 3,000 mJ / cm 2). Subsequently, the curable composition irradiated with light was heated in a heat cycle oven at 80 ° C. for 60 minutes.

(3) thermosetting

The curable composition was heated at 80 ° C. for 60 minutes in a heat cycle oven.

<Evaluation Criteria>

(1) Evaluation criteria of adhesive strength 1 after photocuring

○: 5 N / mm 2 or more

Δ: less than 2 to 5 N / mm 2

×: 2N / mm 2 or less

(2) Evaluation criteria of adhesive strength 2 after light and thermosetting

○: 10 N / mm 2 or more

Δ: less than 5 to 10 N / mm 2

×: less than 5N / mm2

(3) Evaluation criteria of adhesive strength 3 after thermosetting

○: 10 N / mm 2 or more

Δ: less than 5 to 10 N / mm 2

×: less than 5N / mm2

[State of polycarbonate]

The state of the polycarbonate of the bonding site after measuring the adhesive strength 3 after the said thermosetting was observed with the digital microscope (VHX-2000 by Kyens Corporation, magnification: 250 times). The ratio (area%) of the void with respect to the whole adhesive site was measured, and the following references | standards evaluated.

<Evaluation Criteria>

○: void amount is less than 5 area%

△: amount of void is less than 5 to 10 area%

X: The amount of voids is 10 area% or more

[Storage Stability]

The curable composition was stored in a plastic sealed container at 25 ° C., and the number of days until gelation was confirmed and evaluated by the following criteria.

<Evaluation Criteria>

○: 7 days or more

△: 3 to 6 days

×: less than 3 days

3. Examples and Comparative Examples

Each component was mixed by the quantity shown to the following Tables 1-3, and the curable composition of Examples 1-15 and Comparative Examples 1-4 was prepared. The number of each component in a table | surface shows a compounding quantity (weight part). In addition, following Tables 1-3, "the molar ratio of the sum of the acryloyl group, the methacryloyl group, and the epoxy group in component (1), and the mercapto group in component (2)" is "((meth) acryloyl group + epoxy group". ) / Mercapto group "column.

In Examples 1 to 15, components (1) and (3) were mixed, then component (4) was added and mixed again, and then component (2) was added and sufficiently dispersed, followed by standing It was defoamed and the curable composition was prepared. In Examples 11 and 12, in the above operation, the component (6) was further added simultaneously with the components (1) and (3), and the component (5) was further added simultaneously with the component (2). In Comparative Examples 1 and 2, the components (1) and (3) were mixed, and then the component (4) was added and sufficiently dispersed, followed by standing defoaming to prepare a curable composition. In Comparative Examples 3 and 4, components (1) and (6) were mixed, then component (4) was added and further mixed, and then component (2) was added to sufficiently disperse and then left still defoaming. To prepare a curable composition. All of these preparation work was performed at 25 degreeC.

The result of the evaluation test of the curable composition of Examples 1-15 and Comparative Examples 1-4 is shown in Tables 1-3.

From the results of Examples 1 to 15, the curable composition that satisfies the requirements of the present invention has excellent thermosetting properties and excellent photocurability, a cured product having a high adhesive strength is obtained, storage stability is good, and polycarbonate It can be seen that decomposition is suppressed. Therefore, when using the curable composition of this invention, according to a use environment and a use, hardening by heating and hardening by light irradiation can be selected and implemented, and it can carry out combining both. Moreover, the hardened | cured material obtained by hardening | curing the curable composition of this invention is high in adhesive strength per unit area, and is useful as an adhesive layer between the structural members in a camera module. On the other hand, from the result of Comparative Examples 1-4, the curable composition which does not satisfy the requirements of this invention is the same level as the curable composition of this invention in any one of thermosetting, adhesive strength, storage stability, and the state of a polycarbonate. It can be seen that it does not reach.

The curable composition of the present invention is useful as an adhesive such as an adhesive, in particular for producing a camera module.

This application is based on Japanese Patent Application No. 2017-066048 for which it applied in Japan, The content is altogether included in this specification.

Claims (12)

Component (1) to (4) below:
(1) a compound having a (meth) acryloyl group,
(2) a polythiol compound having two or more mercapto groups in one molecule,
(3) an optical radical generator, and
(4) latent curing agents
It comprises a curable composition. A component according to claim 1, wherein component (1) comprises the following component (1-1):
(1-1) A compound having a (meth) acryloyl group and an epoxy group
It comprises a curable composition. The component (1) according to claim 1 or 2, wherein the component (1) is:
(1-2) Phosphoric Acid Modified (meth) acrylate
It comprises a curable composition. The component (1) according to any one of claims 1 to 3, wherein the component (1) to (1-3):
(1-1) a compound having a (meth) acryloyl group and an epoxy group,
(1-2) phosphoric acid modified (meth) acrylate, and
(1-3) Compound which has a (meth) acryloyl group which does not correspond to any of component (1-1) and component (1-2)
It comprises a curable composition. The curable composition according to any one of claims 1 to 4, wherein component (2) comprises a polythiol compound having 2 to 6 mercapto groups in one molecule. The component (2) according to any one of claims 1 to 5, wherein the component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), or tris (3). -Mercaptopropyl) isocyanurate, trimethylol propane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy ) Ethyl] isocyanurate, ethylene glycol bis (mercapto acetate), trimethylol propane tris (mercapto acetate), pentaerythritol tetrakis (mercapto acetate), 1, 4-bis (3- mercapto butyryl) Oxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane Tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-iso Ropil Li dendi phenyl-bis (3-mercaptopropyl), the curable composition comprising at least one selected from the group consisting of ether. The component (2) according to any one of claims 1 to 5, wherein the component (2) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), or tris (3). A mercaptopropyl) isocyanurate, and at least one selected from the group consisting of dipentaerythritol hexakis (3-mercaptopropionate). The molar ratio of the sum of the acryloyl group, methacryloyl group, and epoxy group in component (1), and the mercapto group in component (2) (acryl in component (1) in any one of Claims 1-7). Curable composition in which the sum of a loyl group, a methacryloyl group, and an epoxy group / mercapto group in component (2)) is 0.5-2.0. 9. The curable composition according to claim 1, wherein component (4) comprises at least one selected from the group consisting of amine-epoxy adduct based compounds and amine-isocyanate adduct based compounds. 10. Curable composition as described in any one of Claims 1-9 which further contains a thermal radical generating agent as component (5). A structure comprising a first adherend, a second adherend, and an adhesive layer thereof,
The first adherend is a member made of polycarbonate,
The structure whose adhesive layer is hardened | cured material of the curable composition of any one of Claims 1-10. The structure of claim 11 which is a camera module.