JP6699145B2 - Light and thermosetting resin composition - Google Patents

Description

  The present invention relates to a light and thermosetting resin composition.

  In recent years, as mobile devices such as smartphones have become thinner, camera modules mounted in mobile devices such as smartphones have become smaller. In addition, a camera module is expected to be mounted on a wearable device, and there is an increasing demand for downsizing and thinning. Due to the miniaturization of the camera module, the parts for adhering and fixing the constituent members of each constituent member of the camera module are becoming finer, so that the impact resistance of the camera module against a drop becomes a very important issue. There is. That is, even if the camera module receives an impact due to a drop, the adhesion must be maintained even if the bonding area between the constituent members is small, and if the bonding area is small, the bonding site of the constituent member is easily peeled off. Greater emphasis is placed on improving the adhesive strength per unit area of the agent.

  On the other hand, the adhesive used for assembling the camera module is required to have low-temperature curability in order to avoid thermal damage to the image sensor due to high-temperature treatment. Also, from the viewpoint of improving production efficiency, short-time curability is also required. Required. From such a viewpoint, an ultraviolet curable adhesive or a thermosetting epoxy resin adhesive is often used as a low temperature short time curable adhesive (for example, Patent Documents 1 and 2). However, the ultraviolet curable adhesive has a demerit that it can be rapidly cured, but on the other hand, it causes curing strain due to curing contraction and cannot be used for bonding a portion not exposed to light. On the other hand, thermosetting epoxy resin-based adhesives, even though they are low-temperature and short-time curable adhesives, require that the members (parts) to be bonded must be fixed with a jig or device in order to maintain the bonding posture during bonding. In addition, the viscosity decreases due to the temperature rise due to heating, causing problems such as sagging immediately before curing and flowing to a portion other than the desired portion, which is not always satisfactory.

  Therefore, in order to solve the problems described above, in order to arrange each member (part) that constitutes the camera module with high accuracy, temporarily fixing by curing (pre-curing) by irradiation with light (ultraviolet rays, visible light), Several types of adhesives have been proposed in which main curing is performed by heat to perform main bonding (main fixing) (for example, Patent Documents 3 and 4). However, even if such an adhesive is used, due to the structure of the camera module, there is a place where it is difficult for light to reach inside the module. In such a place, the photo-curing component does not cure, and in fact, the heat-curing does not occur. Since it does not completely cure, it cannot secure sufficient adhesive strength, or because sufficient adhesive strength cannot be secured, members (parts) may be displaced from the intended placement position, or However, there is a problem that the uncured component in the cured product becomes a factor of generating outgas, and it is not always satisfactory. In addition, storage stability is not always good, and improvement in storage stability is also a problem to be solved.

JP, 2004-140497, A JP, 2013-88525, A JP, 2009-51954, A JP, 2009-79216, A

  The present invention has been made by paying attention to the above-mentioned circumstances, and its purpose is to have excellent photocurability and excellent thermosetting property, and under the condition that light irradiation produces an unirradiated portion. In the case of the above, by heating thereafter, the entire composition including the non-irradiated portion can be completely cured to form a cured product having high adhesive strength, and storage stability is also good, It is to provide a light and thermosetting resin composition.

  In addition, temporary fixing can be performed by pre-curing by light irradiation, and even if a light non-irradiated portion is generated during the light irradiation, further heating causes the entire composition including the light non-irradiated portion to be completely cured. To provide a photo- and thermosetting resin composition capable of performing main adhesion (main fixation) having sufficient adhesive strength, and particularly useful as an adhesive used for adhesion between constituent members of a camera module. It is in.

  In order to solve the above problems, the present inventor has conducted extensive studies, and as a result, (1) a compound having a (meth)acryloyl group, (2) a polyene having two or more vinyl groups or allyl groups in one molecule. A resin composition containing a compound, (3) a polythiol compound having two or more thiol groups in one molecule, (4) a photo radical generator, (5) a heat radical generator, and (6) a thermal anionic polymerization initiator Not only does it have excellent photo-curability that can produce a cured product with high adhesive strength only by light irradiation, but even if light irradiation is performed under conditions that produce unirradiated parts, by heating after that, It has been found that the entire composition including the non-irradiated portion has excellent thermosetting property that can be completely cured. The present invention based on such findings is as follows.

[1] (1) A compound having a (meth)acryloyl group,
(2) A polyene compound having two or more vinyl groups or allyl groups in one molecule,
(3) Polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
A resin composition comprising (5) a thermal radical generator and (6) a thermal anionic polymerization initiator.
[2] The functional group equivalent ratio of component (1) and component (3) (equivalent of (meth)acryloyl group of component (1)/equivalent of thiol group of component (3)) is 0.1 or more and less than 5.0. And
The functional group equivalent ratio of component (2) and component (3) (equivalent of vinyl group or allyl group of component (2)/equivalent of thiol group of component (3)) is 0.1 or more and less than 5.0,
Functional group equivalent ratio of component (1) and component (2) to component (3) ((equivalent of (meth)acryloyl group of component (1)+equivalent of vinyl group or allyl group of component (2))/component The resin composition according to the above [1], wherein the equivalent weight of the thiol group of (3) is 0.2 or more.
[3] The resin composition according to the above [1] or [2], which further comprises (7) a polymerization reaction inhibitor.
[4] The resin composition according to any one of the above [1] to [3], which is used for light and heat curing.
[5] An adhesive containing the resin composition according to any one of [1] to [4].
[6] The adhesive according to the above [5], which is for bonding between constituent members of a camera module.
[7] A sealant containing the resin composition according to any one of [1] to [4].
[8] A coating agent containing the resin composition according to any one of the above [1] to [4].
[9] A positioning step of performing positioning between an adhesive component coated with the resin composition according to any one of the above [1] to [4] and an adhered component,
Curing the curable resin composition by light irradiation to temporarily fix the adhesive component and the adhered component, and heating the curable resin composition to cure the adhesive component and the adhered component. A method for manufacturing a camera module, the method including a step of permanently fixing a camera module.

  The resin composition of the present invention has both excellent photocurability and excellent thermosetting property. Therefore, depending on the use environment, curing by light irradiation, curing by heating, or a combination of both can be performed. Moreover, in any case, a cured product that has been sufficiently cured can be obtained, so that it can be applied to various uses such as an adhesive, a sealant, and a coating agent. Further, although it is a one-pack type curable resin composition, it has good storage stability without necessarily incorporating a polymerization reaction inhibitor.

  Further, since the resin composition of the present invention has both excellent photocurability and excellent thermosetting property, even when the composition is irradiated with light, unirradiated portions are generated in the composition. By heating thereafter, the entire composition including the non-irradiated portion can be completely cured, and a cured product having high adhesive strength is produced. Therefore, the resin composition of the present invention can be used, for example, as an adhesive between the constituent members of a camera module, and can be temporarily fixed by preliminary curing by light irradiation, and then can be main cured by heating to perform main fixing. The temporary fixing can be performed in a short time due to the rapid curing property by photo-curing, and the main fixing can be performed with a sufficiently high adhesive strength. Therefore, when assembling precision parts such as a camera module, the constituent members (parts) can be positioned efficiently and with high precision, and the constituent members (parts) can be bonded with high adhesive strength, resulting in a high quality camera. The module can be manufactured efficiently.

The resin composition of the present invention (hereinafter, also abbreviated as “light and thermosetting resin composition” or simply “curable resin composition”), as an essential component,
(1) a compound having a (meth)acryloyl group,
(2) A polyene compound having two or more vinyl groups or allyl groups in one molecule,
(3) Polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
The main characteristics are that (5) a thermal radical generator and (6) a thermal anionic polymerization initiator are included.

<Compound having (1) (meth)acryloyl group>
In the curable resin composition of the present invention, the “(meth)acryloyl group-containing compound” of the component (1) is a component mainly responsible for enhancing the adhesive strength.

  The compound having a (meth)acryloyl group is not particularly limited as long as it is a compound having an acryloyl group and/or a methacryloyl group in the molecule. The number of (meth)acryloyl groups in one molecule in the compound having a (meth)acryloyl group may be 1 or more, and a monofunctional compound (a compound in which the number of (meth)acryloyl groups in one molecule is 1), A bifunctional compound (a compound in which the number of (meth)acryloyl groups in one molecule is 2), a polyfunctional compound (a compound in which the number of (meth)acryloyl groups in one molecule exceeds 2) and the like can be used. .

  The "number of (meth)acryloyl groups in one molecule" as used herein is a mixture of molecules in which a compound having a (meth)acryloyl group has different numbers of (meth)acryloyl groups in one molecule. In the case, it is the average number per molecule.

  The compound having a (meth)acryloyl group preferably has a molecular weight of 50 to 5,000, more preferably a molecular weight of 70 to 4,000, and particularly preferably a molecular weight of 100 to 2,000. When the molecular weight is less than 50, the volatility is high, which is not preferable in terms of odor and handleability. When the molecular weight is more than 5000, the viscosity of the composition tends to be high and the coating property of the composition tends to decrease. The molecular weight of 1,000 or more means the weight average molecular weight and can be measured by gel permeation chromatography (GPC). A molecular weight of less than 1000 can be measured by a gravimetric analyzer (for example, ESI-MS).

  The compound having a (meth)acryloyl group is preferably a compound having an acryloyl group, and a bifunctional compound and/or a polyfunctional compound is preferable. Further, the polyfunctional compound is preferably one in which the number of (meth)acryloyl groups in one molecule is more than 2 and 3 or less.

  Specific examples of the compound having a (meth)acryloyl group include the following.

(Monofunctional)
β-carboxyethyl acrylate Isobornyl acrylate Octyl/decyl acrylate Ethoxylated phenyl acrylate Phenol EO modified acrylate
o-Phenylphenol EO modified acrylate Paracylphenol EO modified acrylate Nonylphenol EO modified acrylate Nonylphenol PO modified acrylate N-acryloyloxyethyl hexahydrophthalimide ω-carboxy-polycaprolactone monoacrylate Phthalic acid monohydroxyethyl acrylate 2-hydroxy-3-phenoxy Propyl acrylate

(Bifunctional)
Dipropylene glycol di(meth)acrylate 1,6-hexanediol di(meth)acrylate Tripropylene glycol di(meth)acrylate PO modified neopentyl glycol di(meth)acrylate tricyclodecane dimethanol di(meth)acrylate Bisphenol FEO modified Di(meth)acrylate Bisphenol AEO modified di(meth)acrylate Isocyanuric acid EO modified di(meth)acrylate Polypropylene glycol di(meth)acrylate Polyethylene glycol di(meth)acrylate Neopentyl glycol hydroxypivalic acid ester di(meth)acrylate Urethane (meth ) Acrylate Polyester (meth)acrylate Epoxy (meth)acrylate

(Multifunctional)
Trimethylolpropane tri(meth)acrylate Trimethylolpropane PO modified tri(meth)acrylate Trimethylolpropane EO modified tri(meth)acrylate Isocyanuric acid EO modified (di/tri)(meth)acrylate pentaerythritol (tri/tetra) (meth) ) Acrylate Glycerin propoxytri(meth)acrylate Pentaerythritol ethoxytetra(meth)acrylate Ditrimethylolpropane tetra(meth)acrylate Dipentaerythritol (penta/hexa)(meth)acrylate Dipentaerythritol hexa(meth)acrylate Dichryserine EO modified (meth) ) Acrylate Polyester (meth)acrylate

  Here, the isocyanuric acid EO-modified (di/tri)(meth)acrylate is a mixture of isocyanuric acid EO-modified di(meth)acrylate and isocyanuric acid EO-modified tri(meth)acrylate, and the mixing ratio (di(meth)acrylate /Tri(meth)acrylate is preferably 1/99 to 99/1 in weight ratio, more preferably 10/90 to 90/10, and particularly preferably 40/60 to 60/40.

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

  Further, dipentaerythritol (penta/hexa)(meth)acrylate is a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate, and has a mixing ratio (penta(meth)acrylate/hexa(meth)acrylate). 5/95 to 95/5 is preferable, and 30/70 to 70/30 is more preferable.

  Among the compounds exemplified above, from the viewpoint of improving the adhesive strength, urethane acrylate, epoxy acrylate, isocyanuric acid EO-modified (di/tri)acrylate, tricyclodecanedimethanol diacrylate, pentaerythritol (tri/tetra)(meth)acrylate. , Polyester (meth) acrylate, urethane acrylate, epoxy acrylate, isocyanuric acid EO-modified (di/tri) acrylate, tricyclodecane dimethanol diacrylate, urethane acrylate, epoxy acrylate, isocyanuric acid EO-modified (di/tri) acrylate , Tricyclodecane dimethanol diacrylate is particularly preferred. Further, an embodiment using urethane acrylate and/or epoxy acrylate and isocyanuric acid EO-modified (di/tri)acrylate and/or tricyclodecanedimethanol diacrylate is particularly preferable.

  In the present invention, the component (1) may be used alone or in combination of two or more.

<(2) Polyene compound having two or more vinyl groups or allyl groups in one molecule>
In the curable resin composition of the present invention, the “polyene compound having two or more vinyl groups or allyl groups in one molecule” of the component (2) is a component mainly responsible for enhancing the adhesive strength.

  The polyene compound having two or more vinyl groups or allyl groups in one molecule is not particularly limited as long as it is a compound having two or more vinyl groups or allyl groups in one molecule. However, those corresponding to the component (1) are excluded.

  The polyene compound having two or more vinyl groups or allyl groups in one molecule is a bifunctional compound (a compound having two vinyl groups or allyl groups in one molecule) or a trifunctional compound (vinyl group in one molecule). Alternatively, a compound in which the number of allyl groups is 3) is preferable. Further, from the viewpoint of storage stability, a polyene compound having two or more allyl groups in one molecule is preferable.

  The polyene compound having two or more vinyl groups or allyl groups in one molecule preferably has a molecular weight of 50 to 5,000, more preferably a molecular weight of 100 to 2,000. When the molecular weight is less than 50, the volatility is high, which is not preferable in terms of odor and handleability. When the molecular weight is more than 5000, the viscosity of the composition tends to be high and the coating property of the composition tends to decrease. The molecular weight of 1,000 or more means the weight average molecular weight and can be measured by gel permeation chromatography (GPC). A molecular weight of less than 1000 can be measured by a gravimetric analyzer (for example, ESI-MS).

Specific examples include the following.
Examples of the polyene compound having two or more vinyl groups in one molecule include triethylene glycol divinyl ether, diethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, and 1,4-butanediol divinyl ether. Further, as a polyene compound having two or more allyl groups in one molecule, triallyl isocyanurate, trimetallyl isocyanurate, tris(2,3-dibromopropyl) isocyanurate, allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol. Triallyl ether, glycerin monoallyl ether, diallyl dimethyl ammonium chloride, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, allyl cyanurate derivative (“LDAIC, DD-1” manufactured by Shikoku Kasei), triallyl isocyanurate, 1, 3,4,6-tetraallylglycoluril (TA-G manufactured by Shikoku Kasei Co., Ltd.) and the like can be mentioned.

  Among the compounds exemplified above, from the viewpoint of improving the adhesive strength, cyclohexanedimethanol divinyl ether, triallyl isocyanurate, and 1,3,4,6-tetraallylglycoluril are preferable, and cyclohexanedimethanol divinyl ether and triaryl are more preferable. It is allyl isocyanurate.

  In the present invention, the component (2) may be used alone or in combination of two or more.

<(3) Polythiol compound having two or more thiol groups (-SH) in one molecule>
In the curable resin composition of the present invention, the "polythiol compound having two or more thiol groups in one molecule" of the component (3) is a curing that cures the component (1) mainly by irradiation with light such as ultraviolet rays or heat. It acts as a curing agent or a curing agent for curing the component (2) by irradiation with light such as ultraviolet rays.

  The polythiol compound having two or more thiol groups in one molecule is not particularly limited as long as it is a compound having two or more thiol groups in one molecule and is not particularly limited, but it is a trifunctional compound (the number of thiol groups in one molecule. Is 3) or a tetrafunctional compound (a compound in which the number of thiol groups in one molecule is 4) is preferable.

  Specific examples of such polythiol compounds include partial esters and complete esters of polyol and mercapto organic acid. Here, the partial ester is an ester of a polyol and a carboxylic acid, in which a part of the hydroxyl group of the polyol forms an ester bond, and the complete ester means that all the hydroxyl groups of the polyol form an ester bond. It means what is formed. Examples of the polyol include ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. As the mercapto organic acid, for example, mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid (eg: 3-mercaptopropionic acid), mercaptobutyric acid (eg: 3-mercaptobutyric acid, 4-mercaptobutyric acid); hydroxy An ester containing a thiol group and a carboxy group obtained by an esterification reaction of an acid with a mercapto organic acid; mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (eg, 2,3-dimercaptosuccinic acid) A mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid); and the like. The mercapto aliphatic monocarboxylic acid preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Among the mercapto organic acids, mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms are preferable, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferable, and 3-mercaptopropione. Acids are more preferred.

Specific examples of the partial ester of a polyol and a mercapto organic acid include trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane bis (3-mercaptobutyrate), and trimethylolpropane bis (3-mercaptobutyrate). Methylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), pentaerythritol tris(4-mercaptobutyrate). Lato), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (4-mercaptobutyrate), etc. Can be mentioned.
Specific examples of the complete ester of a polyol and a mercapto organic acid include ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis( 4-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate) Lat), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol hexakis ( Mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (4-mercaptobutyrate) and the like.

  From the viewpoint of storage stability, it is preferable that the partial ester and the complete ester have a content of basic impurities as small as possible, and it is more preferable that the use of a basic substance is not required for production.

  Further, the polythiol compound of the component (3) includes alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; terminal thiol group-containing polyether; terminal thiol group-containing Polythioether; polythiol compound obtained by reaction of epoxy compound and hydrogen sulfide; polythiol compound having terminal thiol group obtained by reaction of polythiol compound and epoxy compound; A polythiol compound produced by using a volatile substance can also be used. The polythiol compound produced using a basic substance is preferably subjected to dealkalization treatment so that the alkali metal ion concentration is 50 ppm by weight or less before use.

  As the dealkalizing treatment of the polythiol compound produced using a basic substance, for example, the polythiol compound is dissolved in an organic solvent such as acetone or methanol, and neutralized by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, Examples include, but are not limited to, a method of desalting by extraction/washing, a method of adsorbing using an ion exchange resin, a method of purifying by distillation, and the like.

  Examples of the polythiol compound as the component (3) include, for example, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3. , 5-triazine-2,4,6(1H,3H,5H)-trione, tris(3-mercaptopropyl)isocyanurate, bis(3-mercaptopropyl)isocyanurate and the like can be used.

Component (3) is preferably one or more complete ester of ethylene glycol, trimethylolpropane, pentaerythritol or dipentaerythritol and a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms;
More preferably, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolpropane tris. (Mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), pentaerythritol tetrakis(mercaptoacetate), Pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol hexakis(mercaptoacetate), dipentaerythritol hexakis(3-). Mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), and dipentaerythritol hexakis(4-mercaptobutyrate).
More preferably, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and dipentaerythritol hexakis(3-mercaptopropionate). At least one selected from (Pionato).

  The above-mentioned compounds are compounds having no hydroxy group in the molecule, but compounds having a hydroxy group together with two or more thiol groups in the molecule can also be used as the component (3). Examples of the compound having a hydroxy group together with two or more thiol groups in the molecule include trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3- Mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol bis(mercaptoacetate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercaptobutyrate), pentaerythritol. Bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), pentaerythritol tris(4-mercaptobutyrate). , Dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropionate), dipentaerythritol bis(3-mercaptobutyrate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol Tris (mercaptoacetate), dipentaerythritol tris (3-mercaptopropionate), dipentaerythritol tris (3-mercaptobutyrate), dipentaerythritol tris (4-mercaptobutyrate), dipentaerythritol tetrakis (mercaptoacetate) ), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol pentakis (mercaptoacetate), dipenta Erythritol pentakis (3-mercaptopropionate), dipentaerythritol pentakis (3-mercaptobutyrate), dipentaerythritol pentakis (4-mercaptobutyrate) and the like can be mentioned.

  In the present invention, the component (3) may be one type or two or more types.

  In the curable resin composition of the present invention, the components (1) to (3) are preferably blended so as to satisfy the following functional group equivalent ratios of [A] to [C] from the viewpoint of curability. preferable.

  [A]: Functional group equivalent ratio of component (1) and component (3) (equivalent of (meth)acryloyl group of component (1)/equivalent of thiol group of component (3)), that is, to component (1) The number of (meth)acryloyl groups contained/the number of thiol groups contained in the component (3) particularly affects the curability of the curable resin composition with light and heat, and is preferably 0.1 or more, It is less than 5.0, more preferably 0.5 or more and 3.0 or less. When the functional group equivalent ratio is less than 0.1, the curability with light and heat tends to deteriorate, and when it is 5.0 or more, the curability with heat tends to deteriorate.

  [B]: Functional group equivalent ratio of component (2) and component (3) (equivalent of vinyl group or allyl group of component (2)/equivalent of thiol group of component (3)), that is, to component (2) The number of vinyl groups or allyl groups contained/the number of thiol groups contained in the component (3) particularly affects the curability of the curable resin composition with light, and is preferably 0.1 or more and 5. It is less than 0, more preferably 0.3 or more and 3.0 or less. When the functional group equivalent ratio is less than 0.1, the curability with light tends to deteriorate, and when it is 5.0 or more, the adhesive strength tends to decrease.

  [C]: Functional group equivalent ratio of component (1) and component (2) to component (3) ((equivalent of (meth)acryloyl group of component (1) + vinyl group or allyl group of component (2)) Equivalent)/equivalent of all groups of component (3)), that is, [the number of (meth)acryloyl groups contained in component (1) + the number of vinyl groups or allyl groups contained in component (2)]/ The number of thiol groups contained in the component (3) particularly affects the curability of the curable resin composition with light and heat and is preferably 0.2 or more, more preferably 0.8 or more. If the functional group equivalent ratio is too large, uncured may occur. Therefore, the functional group equivalent ratio is preferably 10 or less, more preferably 5 or less.

  The total content of the components (1) to (3) in the curable resin composition of the present invention is preferably 30% by weight or more, more preferably 30% by weight, when the nonvolatile component in the resin composition is 100% by weight. Is 50% by weight or more, and more preferably 70% by weight or more.

<(4) Photoradical generator>
In the curable resin composition of the present invention, the photoradical generator of component (4) is not particularly limited, but examples thereof include an alkylphenone photoradical generator, an acylphosphine oxide photoradical generator, and an oxime ester photopolymer. Examples thereof include radical generators and α-ketone-based photoradical generators.

  Examples of the alkylphenone-based photoradical generator include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and 2-(dimethylamino)-2-[(4-methylphenyl). Methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoyl Benzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenyl Phosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy) )-Phenyl]-2-hydroxy-2-methyl-1-propan-1-one and the like.

  Examples of the acylphosphine oxide-based photoradical generator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

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

  Examples of the α-hydroxyketone photoradical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl Examples include ketones.

  As a commercial product of a photo radical generator, "OXE-02" manufactured by BASF Japan Ltd. (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1, 1 -(O-acetyloxime)), "OXE-01" (1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)]), "Esacure KTO 46" manufactured by DKSH. (A mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo[2-hydroxy-2-methyl 1-[4-(1-methylvinyl)phenyl]propane], and a methylbenzophenone derivative) and the like. ..

  Since the photoradical generator has high sensitivity among them, it is preferable to include an α-hydroxyketone photoradical generator and an oxime ester photoradical generator.

  In the present invention, the component (4) may be used alone or in combination of two or more.

  The content of the component (4) is preferably 0.001% by weight or more, when the nonvolatile component in the resin composition is 100% by weight, from the viewpoint of obtaining a resin composition that can be efficiently photocured when irradiated with light. It is more preferably 0.01% by weight or more, and even more preferably 0.1% by weight or more. On the other hand, from the viewpoint of suppressing outgas due to the photoradical generator remaining in the cured product or its decomposed product, when the nonvolatile component in the resin composition is 100% by weight, it is preferably 10% by weight or less, and more preferably 5%. It is not more than 2% by weight, more preferably not more than 2% by weight.

<(5) Thermal radical generator>
In the curable resin composition of the present invention, the heat radical generator as the component (5) is not particularly limited, but examples thereof include an azo compound and an organic peroxide.

  Examples of the azo compound include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile) and 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), dimethyl-2,2'-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) and the like.

  Examples of the organic peroxide include benzoyl peroxide, tert-butylhydroperoxide, cumene hydroperoxide, di-tert-butylperoxide, methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)cyclohexane, 2 ,2-di(t-butylperoxy)butane, n-butyl 4,4-di-(t-butylperoxy)valate, 2,2-di(4,4-di-(t-butylperoxy)) Cyclohexyl)propane, p-menthane hydroperoxide, diisopropoxylbenzene peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, t-butylhydroperoxide, di-(2 -T-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-Dimethyl-2,5-di(t-butylperoxy)hexane-3, diisobutyryl peroxide, di(3,5,5-t-methylhexanoyl)peroxide, dilauroyl peroxide, disuccinic Acid peroxide, di-(3-methylbenzoyl) peroxide, dibenzoyl peroxide, di-n-propylperoxycarbonate, di-isopropylperoxydicarbonate, di(4-t-butylcyclohexyl)peroxycarbonate, Di(2-ethylhexyl) peroxycarbonate, di-sec-butylperoxycarbonate, cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, t-hexylperoxy Neodecanoate, t-butylperoxy neodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate , 2,5-dimethyl-2,5-di(t-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t -Hexyl peroxyisopropyl monocarbonate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl Ruperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate And t-butylperoxybenzoate, t-butylperoxybenzoate, t-butylperoxyallyl monocarbonate, 3,3′,4,4′-tetra(t-butylperoxycarbol)benzophenone and the like. Be done.

  From the viewpoint of low-temperature curability, the thermal radical generator preferably has a 10-hour half-life temperature of 40°C or higher and lower than 100°C, more preferably 50°C or higher and 90°C or lower.

  In the present invention, the component (5) may be used alone or in combination of two or more.

  The content of the component (5) in the resin composition is preferably 0.1% when the nonvolatile component in the resin composition is 100% by weight, from the viewpoint of obtaining a resin composition that can be efficiently thermoset by heating. It is 001% by weight or more, more preferably 0.01% by weight or more, and further preferably 0.1% by weight or more. On the other hand, from the viewpoint of suppressing outgas due to the thermal radical generator remaining in the cured product or its decomposed product, when the nonvolatile component in the resin composition is 100% by weight, preferably 10% by weight or less, more preferably 5% by weight or less. It is not more than 2% by weight, more preferably not more than 2% by weight.

<(6) Thermal anionic polymerization initiator>
In the curable resin composition of the present invention, the thermal anionic polymerization initiator of the component (6) means a basic compound which is dissolved by heat or a compound which is dissociated by heat to become a basic compound. As the thermal anionic polymerization initiator, an imidazole compound that is solid at room temperature, an amine-epoxy adduct compound (a reaction product of an amine compound and an epoxy compound), an amine-isocyanate compound (a reaction product of an amine compound and an isocyanate compound) ) And the like.

  Examples of the imidazole compound that is solid at room temperature include 2-heptadecyl imidazole, 2-phenyl-4,5-dihydroxymethyl imidazole, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-Phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'. -Methylimidazolyl-(1)')-ethyl-S-triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -Cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea and the like can be mentioned, but the present invention is not limited thereto.

  Examples of the epoxy compound used as one of the raw materials for producing the amine-epoxy adduct compound include polyhydric phenols such as bisphenol A, bisphenol F, catechol and resorcinol, and polyhydric alcohols such as glycerin and polyethylene glycol and epi Polyglycidyl ether obtained by reacting with chlorohydrin; glycidyl ether ester obtained by reacting hydroxy acid such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; phthalic acid, terephthalic acid A polyglycidyl ester obtained by reacting a polycarboxylic acid such as epichlorohydrin; a glycidylamine compound obtained by reacting 4,4′-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; Furthermore, epoxidized phenol novolac resin, epoxidized cresol novolac resin, polyfunctional epoxy compounds such as epoxidized polyolefin and butyl glycidyl ether, phenyl glycidyl ether, monofunctional epoxy compounds such as glycidyl methacrylate; It is not limited to these.

  The amine compound used as a raw material for producing the amine-epoxy adduct compound has at least one active hydrogen atom capable of undergoing an addition reaction with an epoxy group or an isocyanate group (also known as an isocyanato group) in the molecule, and has an amino group (1 At least one of a primary amino group, a secondary amino group and a tertiary amino group) may be contained in the molecule. Examples of such amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine and 4,4′-diamino-dicyclohexylmethane; 4,4′ -Aromatic amine compounds such as diaminodiphenylmethane and 2-methylaniline; nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine are contained. Heterocyclic compounds; and the like. However, the present invention is not limited to these.

  In addition, when a compound having a tertiary amino group in the molecule is used among the above-mentioned raw materials, a thermal anionic polymerization initiator having excellent anionic polymerization initiation ability can be produced. Examples of the compound having a tertiary amino group in the molecule include dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methyl. Amines having a tertiary amino group in the molecule such as imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol , 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2 -Hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2 -Ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl) ) Phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2- Mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid Examples thereof include alcohols having a tertiary amino group in the molecule such as hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide, phenols, thiols, carboxylic acids and hydrazides; and the like.

  When the above-mentioned epoxy compound and amine compound are subjected to an addition reaction to produce an amine-epoxy adduct compound, an active hydrogen compound having two or more active hydrogen atoms in the molecule can be added. Examples of such active hydrogen compounds include bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, polyhydric phenols such as phenol novolac resin, polyhydric alcohols such as trimethylolpropane, and adipic acid. Examples thereof include polycarboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid. It is not limited.

  Examples of the isocyanate compound used as a raw material for producing the amine-isocyanate compound include monofunctional isocyanate compounds such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate, tolylene diisocyanate (Example: 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene Examples thereof include polyfunctional isocyanate compounds such as triisocyanate and bicycloheptane triisocyanate; and further, terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds and active hydrogen compounds. As such a terminal isocyanate group-containing compound, for example, an addition compound having a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and trimethylolpropane, a terminal isocyanate group obtained by the reaction of tolylene diisocyanate and pentaerythritol Examples thereof include addition compounds and the like, but are not limited thereto.

  The thermal anionic polymerization initiator of the component (6) is, for example, appropriately mixed with the above-mentioned production raw materials, reacted at a temperature from room temperature to 200° C., cooled and solidified and then pulverized, or methyl ethyl ketone, dioxane or tetrahydrofuran. It can be easily obtained by reacting the above-mentioned production raw materials in a solvent such as the above, desolvating and then pulverizing the solid content.

  A commercially available product may be used as the thermal anionic polymerization initiator of the component (6). Examples of the amine-epoxy adduct thermal anionic polymerization initiator include “Amicure PN-23”, “Amicure PN-40”, Amicure PN-50”, and “Amicure PN-H” (all are products of Ajinomoto Fine-Techno Co., Inc. Name), "HARDNER X-3661S" (trade name of AC R Co., Ltd.), "HARDNER X-3670S" (trade name of AC R Co., Ltd.), "NOVACURE HX-3742" (product of Asahi Kasei Corporation) Name), "Novacure HX-3721" (trade name of Asahi Kasei Co., Ltd.), and the thermal base generator comprising an amine-isocyanate compound is, for example, "Fujicure FXE-1000" (Fuji Kasei Co., Ltd.). Trade name), "Fujicure FXR-1030" (trade name of Fuji Kasei), and the like.

  The component (6) can use 1 type(s) or 2 or more types.

  From the viewpoint of curability by heat, the content of the component (6) is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, when the nonvolatile component in the resin composition is 100% by weight. , And more preferably 0.5% by weight or more. On the other hand, from the viewpoint of storage stability, when the nonvolatile component in the resin composition is 100% by weight, it is preferably 15% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less.

<(7) Polymerization reaction inhibitor>
The curable resin composition of the present invention may contain a polymerization reaction inhibitor, if necessary, in addition to the components (1) to (6) described above. The polymerization inhibitor as the component (7) is used to further improve the storage stability of the resin composition, and does not depend on light irradiation or heat (so-called dark) at the working environment temperature in which the resin composition is used. Exerts the effect of suppressing (reaction). The working environment temperature here is generally in the range of about 15°C to about 30°C. The reaction is a radical reaction or an ionic reaction (in particular, an anion reaction).

  The polymerization reaction inhibitor that suppresses the radical reaction is not particularly limited, and examples thereof include quinone-based, hydroquinone-based, and nitrosamine-based agents. Specific examples thereof include hydroquinone, t-butylhydroquinone, p-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum and the like. The amount of the polymerization reaction inhibitor that suppresses the radical reaction is 0.0001 to 2.0% by weight, more preferably 0.001 to 1.0% by weight, when the nonvolatile component in the resin composition is 100% by weight. %. If it is less than 0.00001% by weight, a sufficient effect cannot be obtained, and if it exceeds 2.0% by weight, the polymerization reaction during light irradiation or heating may be affected.

  Examples of the polymerization reaction inhibitor that suppresses ionic reaction (particularly anionic reaction) include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids.

  Examples of the borate compound include trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, trione borate. Decyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10, 13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate and the like. Be done.

  Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisoproplytitanate, tetrabutyl titanate, tetraoctyl titanate, and the like.

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

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

  Examples of the isocyanate compound include butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, and tri-ethyl phenyl isocyanate. Diisocyanate (eg, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene Examples thereof include diisocyanate and bicycloheptane triisocyanate.

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

  Examples of the acid anhydride include succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and aliphatic polybasic anhydride such as methyltetrahydrophthalic anhydride. And aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrolimellitic anhydride.

  As the mercapto organic acid, for example, mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid (eg: 3-mercaptopropionic acid), mercaptobutyric acid (eg: 3-mercaptobutyric acid, 4-mercaptobutyric acid); hydroxy An ester containing a thiol group and a carboxy group obtained by an esterification reaction of an acid with a mercapto organic acid; mercapto aliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (eg, 2,3-dimercaptosuccinic acid) A mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid); and the like.

  As the component (7), a borate compound is preferable, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate are more preferable, and triethyl borate is further preferable, from the viewpoints of high versatility and safety, and improving storage stability. preferable.

  The amount of the polymerization reaction inhibitor that suppresses the ionic reaction is 0.0001 to 2.0% by weight, more preferably 0.001 to 1.0% by weight, when the nonvolatile component in the resin composition is 100% by weight. %. If it is less than 0.00001% by weight, a sufficient effect cannot be obtained, and if it exceeds 2.0% by weight, the polymerization reaction upon heating is affected, which is not preferable.

  In the present invention, either one of the polymerization reaction inhibitor that suppresses the radical reaction and the polymerization reaction inhibitor that suppresses the ionic reaction may be used, or both may be used as necessary.

<(8) Other ingredients>
The curable resin composition of the present invention, if necessary, within a range that does not impair the effects of the present invention, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, Inorganic fillers such as aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, and quartz powder; polymethylmethacrylate and/or polystyrene are used together with a monomer constituting them and a copolymerizable monomer. Organic fillers such as polymerized copolymers, thixotropic agents, defoaming agents, leveling agents, coupling agents, flame retardants, pigments, dyes, fluorescent agents, and other conventional components may be contained.

  Further, the curable resin composition of the present invention may contain an epoxy compound (that is, an epoxy group-containing compound) in an amount within a range that does not impair the object of the present invention.

  There is no particular difficulty in producing the curable resin composition of the present invention. For example, a one-pack type curable resin composition can be prepared by uniformly mixing the components using a kneader, a stirring mixer, a three-roll mill, or the like. The temperature of the resin composition during mixing is usually 10 to 50°C, preferably 20 to 40°C, and the mixing time is usually 1 second to 5 minutes, preferably 5 seconds to 3 minutes.

  Irradiation light for photocuring the curable resin composition of the present invention may be infrared rays having a wavelength of 800 nm or more, visible light, ultraviolet rays, electron beams, etc., but ultraviolet rays are preferable. The peak wavelength of ultraviolet rays is preferably in the range of 300 to 500 nm. Examples of the light irradiation means include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a fluorescent lamp, and an LED system SPOT type. A UV irradiator, a xenon lamp, a DEEP UV lamp, sunlight, etc. are mentioned.

  The heating temperature for thermosetting the curable resin composition of the present invention is not particularly limited, but is generally 50 to 150°C, preferably 60 to 100°C.

  The curable resin composition of the present invention has both excellent photocurability and excellent thermosetting property, and can form a cured product having high adhesive strength. Therefore, examples of the use of the curable resin composition of the present invention include adhesives, sealants, coating agents and the like. Among them, it is particularly useful as an adhesive used for assembling a camera module mounted on a mobile device such as a smartphone.

That is, in assembling the camera module, the components (1) to (III) are subjected to the following steps to position each component with high accuracy, and the components to be bonded are bonded to each other with high bonding strength. It is possible to efficiently manufacture high quality camera modules.
(I): The curable resin composition of the present invention is applied to one of two parts to be adhered constituting a camera module, and the part to which the curable resin composition is applied (adhesive part) and the other part The step of positioning the parts (adhered parts).
(II): A step of curing (precuring) the curable resin composition by light irradiation to temporarily fix the adhesive component and the adherend component.
(III): A step of curing (main curing) the curable resin composition by heating to permanently fix the adhesive component and the adhered component.

  In the step (II), due to the positional relationship between the two components to be bonded, a large amount of unirradiated portions where the curable resin composition applied to the bonded components is not irradiated may remain. However, since the curable resin composition of the present invention has an extremely good thermosetting property, even if a non-irradiated portion is generated, only the portion that has been cured by light irradiation (pre-cured portion) is present. Nonetheless, the unirradiated portion of the light is sufficiently cured by thermal curing to reach complete curing, and the entire curable resin composition applied is cured into a cured product capable of providing high adhesive strength.

  Hereinafter, the present invention will be described in detail with reference to representative examples, but the present invention is not limited thereto. The raw materials used in the following examples and the test methods carried out are as follows.

1. raw materials
[Component (1)]
(1A) "EBECRYL8701": manufactured by Daicel Ornex Co., Ltd. Urethane acrylate, weight average molecular weight of about 2000, trifunctional (1B) "EBECRYL3708": manufactured by Daicel Ornex Co., Ltd. epoxy acrylate, weight average molecular weight of about 1500, bifunctional (1C) ) "M-313": manufactured by Toagosei Co., Ltd. isocyanuric acid EO-modified diacrylate/triacrylate (40% by weight/60% by weight), molecular weight about 480, 2.6 functional (1D) "IRR-214K": Daicel- Ornex tricyclodecane dimethanol diacrylate, molecular weight 300, bifunctional

[Component (2)]
(2A) CHDVE: manufactured by Nippon Carbide Co., Ltd. cyclohexanedimethanol divinyl ether, bifunctional (2B) TAIC: manufactured by Nippon Kasei Co., Ltd. triallyl isocyanurate, trifunctional

[Component 3]
(3A) PE1: Showa Denko KK "Karenzu MT" pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight 544, tetrafunctional (3B) PEMP: SC Organic Chemistry pentaerythritol tetrakis (3-mercaptopropio) Nato) Molecular weight 489, tetrafunctional (3C)TMTP: trimethylolpropane tris (3-mercaptopropionate) manufactured by Yodo Chemical Co., Ltd., molecular weight 398, trifunctional

[Component 4]
(4A) Esacure KTO 46: manufactured by DKSH, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo[2-hydroxy-2-methyl 1-[4-(1-methylvinyl)phenyl]propane], and methylbenzophenone derivative Mixture with (4B) Irgacure 184: BASF 1-hydroxy-cyclohexyl-phenyl-ketone (4C) Irgacure OXE 01: BASF Corporation 1,2-octadiene, 1-[4-(phenylthio-2-(O-benzoyloxime )

[Component 5]
(5A) V-601: Wako Pure Chemical Industries, Ltd. dimethyl 2,2′-azobis(2-methylpropionate) 10 hours half-life temperature 66° C.
(5B) Perhexyl O: manufactured by NOF CORPORATION t-hexyl peroxy-2-ethylhexanoate 10 hours half-life temperature 69.9°C

[Component 6]
(6A) PN-40: manufactured by Ajinomoto Fine-Techno Co., Ltd. Amine adduct basic compound (solid)
(6B) PN-50: manufactured by Ajinomoto Fine-Techno Co., Ltd. amine adduct basic compound (solid)
(6C) FXR1081: manufactured by T&K TOKA Co., Ltd. Latent epoxy curing agent solid type

[Component 7]
(7A) Q-1301: manufactured by Wako Pure Chemical Industries, Ltd. N-nitroso-N-phenylhydroxyamine aluminum salt (7B) triethylborate: manufactured by Junsei Chemical Industry Co., Ltd.

[Other ingredients]
(8A) F-351: manufactured by Kaneka Co., Ltd. “Zefiac F351” core shell type organic filler (8B) SO-C5: manufactured by Admatex Co., Ltd. spherical silica filler Average particle size=1.6 μm Specific surface area=4.6 m ² /G
(8C) ZX-1059: Nippon Steel & Sumikin Chemical Co., Ltd. high purity bisphenol A, F type epoxy resin epoxy equivalent (EPW) 160-170 g/eq.
(8D) UVACURE 1561: manufactured by Daicel Ornex Co., Ltd. Epoxy half acrylate, molecular weight about 450, 1.3 functional

Evaluation methods

2. Evaluation test [Evaluation of thermosetting]
A glass epoxy resin laminated plate (FR-4.0 manufactured by Risho Kogyo Co., Ltd.) having a thickness of 2.5 mm×8.0 mm×0.8 mm and a spacer having a thickness of about 50 μm was used to bar-coat the composition to apply the composition. A film was formed, heated in a hot air circulation oven at 80° C. for 30 minutes to be cured, and the curability was evaluated by observing the appearance of the coating film with a finger.

<Evaluation criteria>
○: No uncured component △: Some uncured component ×: Uncured

[Measurement of adhesive strength]
(1) 1 to 3 mg of the composition was applied on a 76 mm×26 mm×1.0 mm thick slide glass plate, a capacitor chip (JIS name 2012 size) was placed thereon, and photocuring was performed under the following conditions: The adhesive strength (adhesive strength 1) of the cured product was measured.
(2) In the same manner as above, a composition obtained by applying the composition to a slide glass plate and mounting a capacitor chip was subjected to light/heat curing under the following conditions to obtain the adhesive strength (adhesive strength) of the cured product. 2) was measured.

The adhesive strength was measured by breaking the chip from the lateral direction with a bond tester (Series 4000 manufactured by Dega) and measuring the adhesive strength (N/mm ² ). The measurement was performed 3 times and the average value was calculated.

<Curing conditions>
(1) Photo-curing: UV-LED irradiator UJ35 manufactured by Panasonic Co., Ltd. was used to emit ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 2500 mW/cm ^{2 at} an angle of 45° from two directions (the angle of incidence of light on the surface of the capacitor chip was 45. Irradiation for 1.2 seconds (exposure amount 3000 mJ/cm ² ).
(2) Light/heat curing: UV-LED irradiation device UJ35 manufactured by Panasonic Co., Ltd. was used to emit ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 2500 mW/cm ² from two directions at an angle of 45° (angle of incidence of light on the surface of the condenser chip). At 45°) for 1.2 seconds (exposure amount 3000 mJ/cm ² ) and subsequently heated at 80° C. for 30 minutes.

<Evaluation criteria>
⊚: 10 N/mm ² or more ○: 5 to 10 N/mm ²
X: less than 5 N/mm ²

[Storage stability]
The composition was stored in a plastic closed container at 25° C., and the number of days until gelation was confirmed.
<Evaluation criteria>
○: 4 days or more △: 1-3 days ×: less than 1 day

3. Examples and Comparative Examples The resin compositions according to Examples 1 to 19 and Comparative Examples 1 to 3 were prepared by mixing the components in the formulations shown in the upper column of Table 1 below. The number of each component in the table indicates the blending amount (parts by weight). The resin compositions were prepared by mixing the components (1) to (3) for Examples 1 to 16, adding the components (4) and (5) thereto, and further mixing the components (6). ) Was added and sufficiently dispersed, and then static defoaming was performed. The preparation work was performed at 25°C. In Example 17, the components (8A) and (8B) were added to and mixed with the mixture of the components (1) to (3). As for Example 18, the component (8C) was added to and mixed with the mixture of the components (1) to (3). The components (7A) and (7B) in Example 19 and Comparative Examples 1 and 2 were added and mixed after the component (6) was dispersed. Components (8C) and (8D) in Comparative Examples 2 and 3 were added after mixing components (1) to (3).

  The lower column of Table 1 shows the results of subjecting the prepared resin compositions of Examples 1 to 19 and Comparative Examples 1 to 3 to the above-described evaluation test.

  As can be seen from the results of Examples 1 to 19, the resin composition of the present invention has both excellent thermosetting properties and excellent photocurability, and also has good storage stability. Therefore, the curing by heating and the curing by light irradiation can be selectively performed according to the use environment and the application, or both can be performed in combination. Further, it can be seen that the cured product obtained by curing has a high adhesive strength per unit area and is useful as an adhesive agent for bonding the constituent members in the camera module. On the other hand, it can be seen that the resin compositions of Comparative Examples 1 to 3 have not reached the high level of the resin composition of the present invention in both thermosetting property and photocurability.

Claims (8)

(1) a compound having a (meth)acryloyl group,
(2) A polyene compound having two or more vinyl groups or allyl groups in one molecule,
(3) Polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
(5) viewed contains a heat radical generating agent, and (6) heat anionic polymerization initiator,
The functional group equivalent ratio of component (1) and component (3) (equivalent of (meth)acryloyl group of component (1)/equivalent of thiol group of component (3)) is 0.5 or more and 3.0 or less. ,
The functional group equivalent ratio of component (2) and component (3) (equivalent of vinyl group or allyl group of component (2)/equivalent of thiol group of component (3)) is 0.3 or more and 3.0 or less. , And
Functional group equivalent ratio of component (1) and component (2) to component (3) ((equivalent of (meth)acryloyl group of component (1)+equivalent of vinyl group or allyl group of component (2))/component The resin composition having a (thiol group equivalent of (3)) of 0.8 or more and 5 or less . Furthermore, (7) the polymerization reaction containing inhibitor according to claim 1 Symbol placement of the resin composition. Claim 1 or 2 resin composition according is for light and heat curing. Adhesive comprising the resin composition of any one of claims 1-3. The adhesive according to claim 4 , which is for bonding between constituent members of a camera module. Sealant comprising the resin composition of any one of claims 1-3. Coating agent containing the resin composition of any one of claims 1-3. Positioning step for positioning the adhesion component and the adhesive component coated with the resin composition of any one of claims 1 to 3,
Curing the curable resin composition by light irradiation to temporarily fix the adhesive component and the adhered component, and heating the curable resin composition to cure the adhesive component and the adhered component. A method for manufacturing a camera module, the method including a step of permanently fixing a camera module.