JP2017101112A - Photocurable and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable and thermosetting resin composition which has both excellent photocurability and excellent thermosetting property, when the composition is irradiated with light under such a condition that a portion not irradiated with light occurs, the composition is heated to completely cure the whole composition containing the portion not irradiated with light and to produce a cured product having a high adhesive strength, and has good storage stability.SOLUTION: A resin composition contains (1) a compound having a (meth)acryloyl group, (2) a polyene compound having two or more vinyl groups and aryl groups in one molecule, (3) a polythiol compound having two or more thiol groups in one molecule, (4) a photoradical generator, (5) a thermal radical generator, and (6) a thermal anionic polymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to light and thermosetting resin compositions.

  In recent years, with the thinning of portable devices such as smartphones, camera modules mounted on portable devices such as smartphones have been downsized. In addition, wearable devices are expected to be equipped with camera modules, and demands for miniaturization and thinning are increasing. Since the size of the camera module has been reduced, the parts where the components of the camera module are bonded and fixed have also become finer, so the impact resistance of the camera module against dropping has become a very important issue. Yes. That is, even if the camera module receives an impact caused by dropping, the adhesion must be maintained even if the adhesion area between the constituent members is small. If the adhesion area is small, the adhesion part of the constituent members is easily peeled off. The improvement of the adhesive strength per unit area of the agent is regarded as more important.

  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 due to high temperature processing on the image sensor, etc. Required. From such a point of view, ultraviolet curable adhesives and thermosetting epoxy resin adhesives are often used as low temperature and short time curable adhesives (for example, Patent Documents 1 and 2). However, the ultraviolet curable adhesive is capable of rapid curing, but has disadvantages such as causing curing strain due to curing shrinkage and being unable to be used for bonding a portion that is not exposed to light. On the other hand, a thermosetting epoxy resin adhesive is a low-temperature, short-time-curing adhesive, but the member (parts) to be bonded must be fixed with a jig or device to maintain the bonding posture during bonding. In addition, the viscosity is lowered due to the temperature rise due to heating, causing problems such as sagging immediately before curing or flowing to a portion other than the desired portion, which is not always satisfactory.

  Therefore, in order to solve the problems as described above, each member (component) constituting the camera module is temporarily fixed by curing (pre-curing) by irradiation with light (ultraviolet rays and visible light) in order to arrange with high accuracy, Several types of adhesives that are permanently cured by heat and perform main bonding (main fixing) have been proposed (for example, Patent Documents 3 and 4). However, even if such an adhesive is used, there are places where the light cannot reach inside the module due to the structure of the camera module. In such a place, the photocuring component does not cure, and in fact it is heat cured. It will not be cured completely, so that sufficient adhesive strength cannot be secured, and sufficient adhesive strength cannot be secured, causing problems such as displacement of the member (parts) from the intended placement position. The uncured component in the cured product has a problem of causing outgassing, and is not always satisfactory. Moreover, it cannot be said that the storage stability is always good, and improvement of the 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 paying attention to the circumstances as described above, and its purpose is to have both excellent photocurability and excellent thermosetting, and the conditions under which light irradiation generates a non-light-irradiated portion. In the case of the above, by heating after that, the entire composition including the non-light-irradiated part can be completely cured to produce a cured product with high adhesive strength, and the storage stability is also good. The object is to provide a light and thermosetting resin composition.

  Moreover, temporary fixing can be performed by preliminary curing by light irradiation, and even if a non-light-irradiated part occurs during the light irradiation, the entire composition including the non-light-irradiated part is completely cured by further heating. Providing a light and thermosetting resin composition that can be used for main bonding (main fixing) with sufficient adhesive strength, and that is particularly useful as an adhesive used for bonding between components of a camera module. It is in.

  In order to solve the above-mentioned 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 comprising a compound, (3) a polythiol compound having two or more thiol groups in one molecule, (4) a photoradical generator, (5) a thermal radical generator, and (6) a thermal anion polymerization initiator In addition to having excellent photocurability that can produce a cured product with high adhesive strength only by light irradiation, even if light irradiation is performed under conditions that produce an unirradiated part, by heating after that, It has been found that the entire composition including the non-irradiated part has excellent thermosetting properties that can be completely cured. The present invention based on such knowledge 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) a polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
(5) A thermal radical generator, and (6) a thermal anionic polymerization initiator.
[2] Functional group equivalent ratio of component (1) to 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 (3) The resin composition according to the above [1], wherein the equivalent of the thiol group) is 0.2 or more.
[3] The resin composition according to [1] or [2], further including (7) a polymerization reaction inhibitor.
[4] The resin composition according to any one of [1] to [3], which is used for light and thermosetting.
[5] An adhesive comprising the resin composition according to any one of [1] to [4].
[6] The adhesive according to [5], which is used for bonding between constituent members of the camera module.
[7] A sealant comprising the resin composition according to any one of [1] to [4].
[8] A coating agent comprising the resin composition according to any one of [1] to [4].
[9] A positioning step for positioning between an adhesive part to which the resin composition according to any one of [1] to [4] is applied and an adhesive part.
A step of curing the curable resin composition by light irradiation to temporarily fix the adhesive component and the adherend component; and a step of curing the curable resin composition by heating to cure the adhesive component and the adherend component. The manufacturing method of a camera module including the process of carrying out this fixing.

  The resin composition of the present invention has both excellent photocurability and excellent thermosetting properties. For this reason, it can implement by hardening by light irradiation, hardening by heating, or combining both according to a use environment. In addition, a cured product that is sufficiently cured can be obtained in any case, and can be applied to various uses such as an adhesive, a sealant, and a coating agent. Moreover, although it is a one-pack type curable resin composition, it has good storage stability without necessarily incorporating a polymerization reaction inhibitor.

  In addition, since the resin composition of the present invention has both excellent photocurability and excellent thermosetting properties, even if light irradiation to the composition is performed under such a condition that a light non-irradiated part is generated in the composition. Then, by heating, the entire composition including the non-light-irradiated part can be completely cured, and a cured product with high adhesive strength is generated. Therefore, the resin composition of the present invention is used as an adhesive between the constituent members of the camera module, for example, temporarily fixed by preliminary curing by light irradiation, and then finally cured by heating to perform final fixing. Temporary fixing can be performed in a short time due to fast curing by photocuring, and the main fixing can be performed with sufficiently high adhesive strength. For this reason, in the assembly of precision parts such as camera modules, the structural members (parts) can be positioned efficiently and with high precision, and the structural members (parts) can be bonded with high adhesive strength. Modules 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”) is 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) a polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
The main feature is that it includes (5) a thermal radical generator, and (6) a thermal anionic polymerization initiator.

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

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

  As used herein, “the number of (meth) acryloyl groups in one molecule” refers to a mixture of molecules in which a compound having a (meth) acryloyl group differs in the number 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 5000, more preferably a molecular weight of 70 to 4000, and particularly preferably a molecular weight of 100 to 2000. 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 exceeds 5000, the viscosity of the composition becomes high and the applicability of the composition tends to decrease. In addition, the molecular weight of 1000 or more means a weight average molecular weight, and can be measured by gel permeation chromatography (GPC). Molecular weights less than 1000 can be measured with a gravimetric analyzer (eg 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. The polyfunctional compound preferably has a number of (meth) acryloyl groups in one molecule of 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 (meta ) 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) (meta) ) Acrylate Glycerin propoxytri (meth) acrylate Pentaerythritol ethoxytetra (meth) acrylate Ditrimethylolpropane tetra (meth) acrylate Dipentaerythritol (penta / hexa) (meth) acrylate Dipentaerythritol hexa (meth) acrylate Diglycerin EO modified (meta Acrylate Polyester (meth) acrylate

  Here, 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, more preferably 10/90 to 90/10, and particularly preferably 40/60 to 60/40.

  Pentaerythritol (tri / tetra) (meth) acrylate is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, and the 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.

  Dipentaerythritol (penta / hexa) (meth) acrylate is a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the mixing ratio (penta (meth) acrylate / hexa (meta) ) Acrylate) is preferably 5/95 to 95/5 in weight ratio, more preferably 30/70 to 70/30.

  Among the above exemplified compounds, urethane acrylate, epoxy acrylate, isocyanuric acid EO-modified (di / tri) acrylate, tricyclodecane dimethanol diacrylate, pentaerythritol (tri / tetra) (meth) acrylate from the viewpoint of improving adhesive strength. , 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 tricyclodecane dimethanol diacrylate is particularly preferable.

  In the present invention, the component (1) can 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 component (2) “polyene compound having two or more vinyl groups or allyl groups in one molecule” is a component mainly responsible for increasing 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 component (1) are excluded.

  A 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 (a vinyl group in one molecule). Or a compound having 3 allyl groups) is preferred. 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 exceeds 5000, the viscosity of the composition becomes high and the applicability of the composition tends to decrease. In addition, the molecular weight of 1000 or more means a weight average molecular weight, and can be measured by gel permeation chromatography (GPC). Molecular weights less than 1000 can be measured with a gravimetric analyzer (eg 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, cyclohexane dimethanol divinyl ether, 1,4-butanediol divinyl ether, and the like. Polyene compounds having two or more allyl groups in one molecule are triallyl isocyanurate, trimethallyl isocyanurate, tris (2,3-dibromopropyl) isocyanurate, allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol. Triallyl ether, glycerin monoallyl ether, diallyldimethylammonium chloride, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, allyl derivative of cyanurate (“LDAIC, DD-1” manufactured by Shikoku Kasei Co., Ltd.), triallyl isocyanurate, 1, 3,4,6-tetraallylglycoluril (manufactured by Shikoku Kasei Co., Ltd., TA-G) and the like.

  Among the above-exemplified compounds, cyclohexane dimethanol divinyl ether, triallyl isocyanurate and 1,3,4,6-tetraallyl glycoluril are preferable, more preferably cyclohexane dimethanol divinyl ether, Allyl isocyanurate.

  In this invention, a component (2) can use 1 type (s) or 2 or more types.

<(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 plays the role of an agent or a curing agent that cures 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. Is a compound in which 3 is a compound) or a tetrafunctional compound (a compound in which the number of thiol groups in one molecule is 4).

  Specific examples of such polythiol compounds include partial esters and complete esters of polyols and mercapto organic acids. Here, the partial ester is an ester of a polyol and a carboxylic acid, in which a part of the polyol hydroxy group forms an ester bond, and the complete ester is an all ester hydroxy bond of the polyol. It means what is forming. Examples of the polyol include ethylene glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (eg, 3-mercaptopropionic acid), mercaptobutyric acid (eg, 3-mercaptobutyric acid, 4-mercaptobutyric acid); Ester containing thiol group and carboxy group obtained by esterification reaction of acid and mercapto organic acid; mercaptoaliphatic dicarboxylic acid 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); The number of carbon atoms of the mercaptoaliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among the mercapto organic acids, mercaptoaliphatic 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-mercaptopropionate is preferable. Acid is more preferred.

Specific examples of partial esters of polyols and mercapto organic acids include trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane bis (3-mercaptobutyrate), trimethylolpropane Methylolpropane bis (4-mercaptobutyrate), pentaerythritol tris (mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tris (4-mercaptobutyrate) Rat), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol Rakisu (3-mercapto butyrate), dipentaerythritol tetrakis (4-mercapto butyrate), and the like.
Specific examples of complete esters of polyols and mercapto organic acids include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), ethylene glycol bis ( 4-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate) Ratato), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3- Lucaptobutyrate), 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, the partial ester and the complete ester preferably have as little basic impurity content as possible, and more preferably those that do not require the use of a basic substance in production.

  In addition, the polythiol compound of the component (3) includes 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol and other alkyl polythiol compounds; terminal thiol group-containing polyethers; 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 using a sex substance can also be used. The polythiol compound produced using a basic substance is preferably used after subjecting it to a dealkalization treatment and setting the alkali metal ion concentration to 50 ppm by weight or less.

  As a dealkalizing 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, 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 and washing, a method of adsorption using an ion exchange resin, a method of purification by distillation, and the like.

  Examples of the polythiol compound of the component (3) include 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 of a complete ester of ethylene glycol, trimethylolpropane, pentaerythritol or dipentaerythritol and a mercaptoaliphatic 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 Lakis (4-mercaptobutyrate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), and dipentaerythritol hexakis (4 -At least one selected from 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 (Pionate).

  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 hydroxyl 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-me Lucatopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol pentakis (mercaptoacetate), dipentaerythritol pentakis (3-mercaptopropio) NATO), dipentaerythritol pentakis (3-mercaptobutyrate), dipentaerythritol pentakis (4-mercaptobutyrate), and the like.

  In the present invention, the component (3) can be used alone or in combination of two or more.

  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) to component (3) (equivalent of (meth) acryloyl group of component (1) / equivalent of thiol group of component (3)), that is, component (1) The number of (meth) acryloyl groups contained / number of thiol groups contained in component (3) particularly affects the curability of the curable resin composition with light and heat, 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, in 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, preferably 0.1 or more. 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, [number of (meth) acryloyl groups contained in component (1) + number of vinyl groups or allyl groups contained in component (2)] / The number of thiol groups contained in component (3) particularly affects the curability of the curable resin composition with light and heat, and is preferably 0.2 or more, and more preferably 0.8 or more. In addition, since there exists a possibility that it may become uncured when this functional group equivalent ratio is too large, this functional group equivalent ratio is preferably 10 or less, and 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 100% by weight when the nonvolatile component in the resin composition is 100% by weight. Is 50% by weight or more, 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, and examples thereof include alkylphenone photoradical generators, acylphosphine oxide photoradical generators, and oxime ester photopolymers. Examples include radical generators and α-ketone photo radical generators.

  Examples of the alkylphenone 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, benzoyl ethyl 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, -Hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- Propan-1-one etc. are mentioned.

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

  Examples of the oxime ester photo radical 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 photo radical 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 commercially available product of a photoradical generator, “OXE-02” (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1, 1 manufactured by BASF Japan Ltd. -(O-acetyloxime)), "OXE-01" (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), "Esacure KTO 46 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. .

  Among them, the photoradical generator preferably includes an α-hydroxyketone photoradical generator and an oxime ester photoradical generator because of its high sensitivity.

  In this invention, a component (4) can use 1 type (s) or 2 or more types.

  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 during light irradiation. More preferably, it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more. On the other hand, from the viewpoint of suppressing outgassing caused by the photoradical generator remaining in the cured product or a decomposition product thereof, when the nonvolatile component in the resin composition is 100% by weight, it is preferably 10% by weight or less, more preferably 5%. % By weight or less, more preferably 2% by weight or less.

<(5) Thermal radical generator>
In the curable resin composition of the present invention, the thermal radical generator of component (5) is not particularly limited, and examples thereof include azo compounds and organic peroxides.

  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-me Carboxymethyl-2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate), and the like.

  Organic peroxides include benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, 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-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, di- (2 -T-butylperoxyisopropyl) benzene, dicumylperoxa 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 Oxide, dibenzoyl peroxide, di-n-propyl peroxycarbonate, di-isopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxycarbonate, di (2-ethylhexyl) peroxycarbonate, di-sec -Butylperoxycarbonate, cumylperoxyneode Canoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t- Butyl peroxypivalate, 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-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl -Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate And t-butyl peroxybenzoate, t-butyl peroxybenzoate, t-butyl peroxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbol) benzophenone, etc. It is 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 this invention, a component (5) can use 1 type (s) or 2 or more types.

  The content of the component (5) in the resin composition is preferably from the viewpoint of obtaining a resin composition that can be efficiently thermally cured by heating, when the non-volatile component in the resin composition is 100% by weight. 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 the outgas caused by the thermal radical generator remaining in the cured product or its decomposition product, when the nonvolatile component in the resin composition is 100% by weight, it is preferably 10% by weight or less, more preferably 5%. % By weight or less, more preferably 2% by weight or less.

<(6) Thermal anionic polymerization initiator>
In the curable resin composition of the present invention, the thermal anionic polymerization initiator of component (6) means a basic compound that is dissolved by heat or a compound that is dissociated by heat and becomes a basic compound. Thermal anionic polymerization initiators include imidazole compounds that are solid at room temperature, amine-epoxy adduct compounds (reaction products of amine compounds and epoxy compounds), amine-isocyanate compounds (reaction products of amine compounds and isocyanate compounds) ) And the like.

  Examples of the imidazole compound that is solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-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, - cyanoethyl-2-phenylimidazole - trimellitate, N-(2-methylimidazolyl-1-ethyl) - but urea and the like, but 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 epithelial compounds. 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 with 4,4′-diaminodiphenylmethane, m-aminophenol, etc. and epichlorohydrin Furthermore, polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; However, 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 in the molecule capable of undergoing an addition reaction with an epoxy group or an isocyanate group (also known as an isocyanate group), and an amino group (1 Any one having at least one of a secondary amino group, a secondary amino group, and a tertiary amino group in the molecule may be used. Examples of such amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4′-diamino-dicyclohexylmethane; -Aromatic amine compounds such as 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.

  Moreover, if the compound which has a tertiary amino group in a molecule | numerator is used especially in the above-mentioned raw material, the thermal anion polymerization initiator of the outstanding anion polymerization initiating ability can be manufactured. 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-ethylimidar, 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-methylimi Sol, 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 hydrazide, nicotinic acid Examples thereof include alcohols having a tertiary amino group in the molecule such as hydrazide and isonicotinic acid hydrazide, phenols, thiols, carboxylic acids and hydrazides.

  When an amine-epoxy adduct compound is produced by addition reaction of the epoxy compound and the amine compound, an active hydrogen compound having two or more active hydrogens in the molecule can be further added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins, polyhydric alcohols such as trimethylolpropane, and adipic acid. Polycarboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid, etc. 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 Polyfunctional isocyanate compounds such as triisocyanate and bicycloheptane triisocyanate; Obtained by reaction of an isocyanate compound with an active hydrogen compound, terminal isocyanate group-containing compound; and the like. As such a terminal isocyanate group-containing compound, for example, an addition compound having a terminal isocyanate group obtained by reaction of tolylene diisocyanate and trimethylolpropane, a terminal isocyanate group obtained by reaction of tolylene diisocyanate and pentaerythritol, However, the present invention is not limited thereto.

  The thermal anionic polymerization initiator of component (6) can be prepared, for example, by appropriately mixing the above-mentioned production raw materials and reacting at room temperature to 200 ° C., then cooling and solidifying, or pulverizing, or methyl ethyl ketone, dioxane, tetrahydrofuran It can obtain easily by making said manufacturing raw material react in solvents, such as etc., and grind | pulverizing solid content after solvent removal.

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

  As the component (6), one type or two or more types can be used.

  The content of the component (6) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more when the nonvolatile component in the resin composition is 100% by weight from the viewpoint of curability by heat. More preferably, it is 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, and further preferably 5% by weight or less.

<(7) Polymerization reaction inhibitor>
In addition to the above components (1) to (6), the curable resin composition of the present invention can contain a polymerization reaction inhibitor as necessary. The polymerization reaction inhibitor of component (7) is used to further improve the storage stability of the resin composition, and is a reaction (so-called darkness) that does not depend on light irradiation or heat at the working environment temperature at which the resin composition is used. Demonstrate the 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 (particularly an anion reaction).

  Although it does not specifically limit as a polymerization reaction inhibitor which suppresses a radical reaction, A quinone type, a hydroquinone type, a nitrosamine type etc. are mentioned. Specific examples include hydroquinone, t-butyl hydroquinone, p-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum and the like. The addition 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 the amount is less than 0.00001% by weight, a sufficient effect cannot be obtained. If the amount exceeds 2.0% by weight, the polymerization reaction during light irradiation or heating may be affected.

  Examples of polymerization reaction inhibitors that suppress ionic reactions (particularly anionic reactions) 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, trinonyl borate, and the like. 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, triethanol Minboreto, and the like.

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

  Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate, 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, Range isocyanate (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 acids. Halogenated fatty acids such as acetic acid and dichloroacetic acid, monobasic hydroxy acids such as glycolic acid, lactic acid, and glucose, aliphatic aldehyde acids such as glyoxylic acid and ketone acids, oxalic acid, malonic acid, succinic acid, maleic acid, etc. Examples include aliphatic polybasic acids, benzoic acids, halogenated benzoic acids, toluic acid, aromatic monobasic acids such as phenylacetic acid, cinnamic acid, and mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid. .

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

  Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (eg, 3-mercaptopropionic acid), mercaptobutyric acid (eg, 3-mercaptobutyric acid, 4-mercaptobutyric acid); Ester containing thiol group and carboxy group obtained by esterification reaction of acid and mercapto organic acid; mercaptoaliphatic dicarboxylic acid 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);

  Component (7) is preferably a borate compound from the viewpoint of high versatility and safety and improving storage stability, more preferably triethyl borate, tripropyl borate, triisopropyl borate, and tributyl borate, and further triethyl borate. preferable.

  The addition amount of the polymerization reaction inhibitor for suppressing 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 during heating is affected, which is not preferable.

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

<(8) Other ingredients>
In the curable resin composition of the present invention, if necessary, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, as long as the effects of the present invention are not impaired. Inorganic fillers such as aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, and quartz powder; polymethyl methacrylate and / or polystyrene are copolymerized with monomers composing these monomers Organic fillers composed of polymerized copolymers and the like; thixotropic agents; antifoaming agents; leveling agents; coupling agents; flame retardants; pigments; dyes;

  Moreover, you may contain an epoxy compound (namely, epoxy group containing compound) in the quantity in the range which does not impair the objective of this invention in the curable resin composition of this invention.

  There is no particular difficulty in producing the curable resin composition of the present invention. For example, it can be prepared as a one-pack type curable resin composition by uniformly mixing each component using a kneader, a stirring mixer, a three-roll mill, or the like. The temperature of the resin composition at the time of 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 at the time of photocuring the curable resin composition of the present invention can use infrared rays having a wavelength of 800 nm or more, visible light, ultraviolet rays, electron beams, etc., but ultraviolet rays are preferred. Moreover, it is preferable that the peak wavelength of an ultraviolet-ray exists in the range of 300-500 nm. Examples of the light irradiation means include low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave excitation mercury lamp, metal halide lamp, sodium lamp, fluorescent lamp, LED system SPOT type A UV irradiator, a xenon lamp, a DEEP UV lamp, sunlight, etc. are mentioned.

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

  The curable resin composition of the present invention has both excellent photocurability and excellent thermosetting properties, and can form a cured product with high adhesive strength. Accordingly, examples of the use of the curable resin composition of the present invention include an adhesive, a sealant, and a coating agent. Especially, it is useful especially as an adhesive agent used for the assembly of the camera module mounted in portable apparatuses, such as a smart phone.

That is, in assembling the camera module, the following steps (I) to (III) are performed so that each component is positioned with high accuracy and the components to be bonded are bonded with high adhesive strength. High quality camera modules can be manufactured efficiently.
(I): The curable resin composition of the present invention is applied to one part of two parts to be bonded constituting the camera module, the part (adhered part) to which this curable resin composition is applied, and the other part A step of positioning a component (adhered component).
(II): A step of temporarily fixing between the bonded component and the component to be bonded by curing (precuring) the curable resin composition by light irradiation.
(III): A step of curing (main curing) the curable resin composition by heating to permanently fix the bonded part and the bonded part.

  In the step (II), there may be a large number of unirradiated portions where light is not irradiated to the curable resin composition applied to the bonded part due to the relationship between the arrangement positions of the two parts to be bonded. However, since the curable resin composition of the present invention has a very good thermosetting property, even if an unirradiated part of light is generated, only the part (precured part) where curing has progressed by light irradiation. In addition, the non-irradiated portion of the light is sufficiently cured by thermal curing to reach complete curing, and the entire applied curable resin composition is cured to a cured product that can give high adhesive strength.

  Hereinafter, the present invention will be described in detail by way of typical examples, but the present invention is not limited thereto. The raw materials used in the following examples and the test methods performed are as follows.

1. raw materials
[Ingredient (1)]
(1A) “EBECRYL8701”: urethane acrylate manufactured by Daicel Ornex Co., Ltd., weight average molecular weight of about 2000, trifunctional (1B) “EBECRYL3708”: epoxy acrylate manufactured by Daicel Ornex Co., Ltd., weight average molecular weight of about 1500, bifunctional (1C) ) “M-313”: manufactured by Toa Gosei Co., Ltd. Isocyanuric acid EO-modified diacrylate / triacrylate (40 wt% / 60 wt%), molecular weight of about 480, 2.6 functional (1D) “IRR-214K”: Daicel Ornex-made tricyclodecane dimethanol diacrylate, molecular weight 300, bifunctional

[Ingredient (2)]
(2A) CHDVE: Nippon Carbide Co., Ltd. cyclohexane dimethanol divinyl ether, bifunctional (2B) TAIC: Nippon Kasei Co., Ltd. triallyl isocyanurate, trifunctional

[Component 3]
(3A) PE1: “Karenz MT” manufactured by Showa Denko KK Pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight 544, tetrafunctional (3B) PMP: Pentaerythritol tetrakis (3-mercaptopropio) manufactured by SC Organic Chemical Co., Ltd. (Nato) Molecular weight 489, tetrafunctional (3C) TMTP: Trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional, manufactured by Sakai Chemical Industry Co., Ltd.

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

[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 Nippon Oil & Fats Co., Ltd. t-hexylperoxy-2-ethylhexanoate 10 hours half-life temperature 69.9 ° C

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

[Component 7]
(7A) Q-1301: Wako Pure Chemical Industries, Ltd. N-nitroso-N-phenylhydroxyamine aluminum salt (7B) Triethyl borate: Pure Chemical Industries, Ltd.

[Other ingredients]
(8A) F-351: “Zefiac F351” manufactured by Kaneka Co., Ltd. Core shell type organic filler (8B) SO-C5: Spherical silica filler manufactured by Admatechs Co., Ltd. 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: Epoxy half acrylate, molecular weight of about 450, 1.3 functional, manufactured by Daicel Ornex Co., Ltd.

Evaluation method

2. Evaluation test [Evaluation of thermosetting]
Using a spacer of about 50 μm thickness on a 2.5 mm × 8.0 mm × 0.8 mm thick glass epoxy resin laminate (Risho Kogyo, FR-4.0), the composition is bar coated to apply the composition A film was formed, cured by heating at 80 ° C. for 30 minutes in a hot-air circulating oven, and the curability was evaluated by observing the appearance of the coating film by finger touch.

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

[Measurement of adhesive strength]
(1) Apply 1 to 3 mg of the composition on a 76 mm × 26 mm × 1.0 mm thick glass slide, place a capacitor chip (JIS size 2012 size) on it, and perform photocuring under the following conditions. The adhesive strength (adhesive strength 1) of the cured product was measured.
(2) In the same manner as described above, the composition applied to the slide glass plate and the capacitor chip was placed and subjected to light / thermosetting under the following conditions to obtain the adhesive strength (adhesive strength) of the cured product. 2) was measured.

The adhesive strength was determined by breaking the chip from the lateral direction with a bond tester (dega series 4000) and measuring the adhesive strength (N / mm ² ). The measurement was performed 3 times, and the average value was obtained.

<Curing conditions>
(1) Photo-curing: UV (LED wavelength: 365 nm) with an illuminance of 2500 mW / cm ² was applied from a UV-LED irradiation device UJ35 manufactured by Panasonic Corporation at an angle of 45 ° from two directions (the incident angle of light on the capacitor chip surface was 45 ) For 1.2 seconds (exposure amount 3000 mJ / cm ² ).
(2) Light / thermosetting: UV (LED wavelength: 365 nm) with an illuminance of 2500 mW / cm ² is applied from an UV-LED irradiation device UJ35 manufactured by Panasonic Corporation at an angle of 45 ° from the two directions (the incident angle of light on the surface of the capacitor chip) Was 45 °) for 1.2 seconds (exposure amount 3000 mJ / cm ² ), and subsequently heated at 80 ° C. for 30 minutes.

<Evaluation criteria>
A: 10 N / mm ² or more B: 5-10 N / mm ²
×: Less than 5 N / mm ²

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

3. Examples and Comparative Examples Resin compositions according to Examples 1 to 19 and Comparative Examples 1 to 3 were prepared by mixing each component in the composition shown in the upper column of Table 1 below. The number of each component in a table | surface shows a compounding quantity (weight part). For preparing the resin composition, in Examples 1 to 16, the components (1) to (3) were mixed, the components (4) and (5) were added thereto, and further mixed, and then the components (6 ) Was added and sufficiently dispersed, and then prepared by defoaming by standing. The preparation work was performed at 25 ° C. For Example 17, components (8A) and (8B) were added to and mixed with components (1) to (3). For Example 18, component (8C) was added to and mixed with components (1) to (3). Components (7A) and (7B) in Example 19 and Comparative Examples 1 and 2 were added and mixed after dispersing component (6). Components (8C) and (8D) in Comparative Examples 2 and 3 were added and mixed after components (1) to (3) were mixed.

  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 are shown in the lower column of Table 1.

  As a result of Examples 1-19, it turns out that the resin composition of this invention has the outstanding thermosetting and the outstanding photocurability, and its storage stability is favorable. For this reason, according to 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, it can be seen that the cured product obtained by curing has high adhesive strength per unit area and is useful as an adhesive for bonding between the constituent members in the camera module. On the other hand, it turns out that the resin composition of Comparative Examples 1-3 has not reached the high level like the resin composition of this invention in any of thermosetting and photocurability.

Claims (9)

(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) a polythiol compound having two or more thiol groups in one molecule,
(4) photo radical generator,
(5) A thermal radical generator, and (6) a thermal 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 0.1 or more and less than 5.0,
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 claim 1, wherein the equivalent of the thiol group in (3) is 0.2 or more.   Furthermore, the resin composition of Claim 1 or 2 containing (7) polymerization reaction inhibitor.   The resin composition according to claim 1, which is used for light and thermosetting.   The adhesive agent containing the resin composition of any one of Claims 1-4.   The adhesive according to claim 5, wherein the adhesive is used for bonding between the constituent members of the camera module.   The sealing agent containing the resin composition of any one of Claims 1-4.   The coating agent containing the resin composition of any one of Claims 1-4. A positioning step for positioning between the bonded part to which the resin composition according to any one of claims 1 to 4 is applied and the bonded part;
A step of curing the curable resin composition by light irradiation to temporarily fix the adhesive component and the adherend component; and a step of curing the curable resin composition by heating to cure the adhesive component and the adherend component. The manufacturing method of a camera module including the process of carrying out this fixing.