KR20220052138A - New compound, curable composition containing the same, and cured product thereof - Google Patents

Abstract

The present invention relates to a thiol generator compound, which is a novel compound for improving storage stability and adhesive strength, and uses thereof. According to the present invention, a curing process can be initiated by causing a cyclization reaction with a very small amount of light with high reaction efficiency, and the compound has excellent light curing and thermal curing properties, so that it is possible to select and carry out photo curing, thermal curing, or double curing in parallel according to the use environment or purpose, and thus it is possible to be usefully applied as an adhesive layer between components such as mobile or vehicle camera modules since the adhesive strength per unit area is high.

Description

New compound, curable composition containing same, and cured product thereof {New compound, curable composition containing the same, and cured product thereof}

The present invention relates to novel thiol generator compounds and uses thereof. Specifically, the present invention relates to a novel thiol generator compound for improving storage stability and adhesive strength under low temperature fast curing conditions, a curable composition comprising the same, and a cured product thereof.

With the development of portable devices and autonomous vehicles, camera modules mounted inside and outside the vehicle are also getting smaller, and the required reliability specifications are also increasing. In addition, as a camera module is expected to be mounted in a wearable device, the demand for miniaturization and thinness is increasing. And since the site|part which adhesively fixes between each structural member of a camera module is also becoming fine with downsizing of a camera module, the impact resistance of the camera module with respect to a fall or vibration becomes a very important subject. That is, even if the camera module receives an impact or external vibration due to a drop, the adhesion between the constituent members must be maintained. In addition, when the bonding area is small, the bonding and fixing portions between the constituent members are easily peeled off. Therefore, it is more important to improve the bonding strength per unit area of the adhesive.

On the other hand, the adhesive used for assembling the camera module is required to have low-temperature curing properties in order to avoid thermal damage caused by high-temperature treatment with an image sensor or the like. In addition, from the viewpoint of improving production efficiency, fast curable property is also required at the same time. From this point of view, as a low-temperature fast-curing adhesive, a photocurable or thermosetting adhesive is widely used (Patent Document 1). However, while the light-curable adhesive can be cured quickly, it has disadvantages such as curing deformation due to curing shrinkage or being unable to be used for bonding parts that do not reach light. The thermosetting adhesive may be a low-temperature, fast-setting adhesive, but during bonding, the bonding member must be fixed with a jig or device in order to maintain the bonding posture. In addition, the viscosity was lowered by the temperature rise, causing problems such as sagging just before curing or flowing out of a desired portion, which was not always satisfactory.

In order to solve the above problems, in order to arrange each member constituting the camera module with high precision, it is temporarily fixed by pre-curing by light (eg, ultraviolet, visible light) irradiation, and main curing is performed by heat. It has been proposed (Patent Document 2 and Patent Document 3).

JP 2013-088525 A JP 2009-051954 A JP 2001-133794 A

An object of the present invention is to provide a thiol generator compound, which is a novel compound for improving storage stability and adhesive strength, and uses thereof.

In detail, a thiol generator compound that has excellent storage stability at room temperature, can perform a rapid photo-curing process with high reaction efficiency when used as a photo-curing material, and does not generate gas due to thiol generation, and photothiol generation containing the same to provide a composition.

Specifically, to provide a curable composition and a cured product thereof having a low-temperature fast-curing adhesive having excellent photo-curing properties and heat-curing properties.

Specifically, to provide a curable composition for providing a cured product having sufficient adhesive strength and retention required for a camera module.

In order to solve the above problems, the present invention provides a compound represented by the following formula (1), that is, a thiol generator compound.

[Formula 1]

[In Formula 1,

R ₁ is a monovalent organic group, and may include one or more selected from N, O, S, Si, and C(=O);

R ₂ to R ₅ are each independently hydrogen, halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are linked to each other to form a substituted or unsubstituted ring can be formed.]

The compound represented by Formula 1 according to an embodiment of the present invention may be derived from a trifunctional or higher thiol compound.

In the compound represented by Formula 1 according to an embodiment of the present invention, R ₁ may include a unit structure represented by Formula 1-1 below.

[Formula 1-1]

[In Formula 1-1,

L ₁ to L ₃ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

In the compound represented by Formula 1 according to an embodiment of the present invention, R ₁ may include a unit structure represented by Formula 1-2 or Formula 1-3 below.

[Formula 1-2]

[Formula 1-3]

[In Formula 1-2 or Formula 1-3,

Y ₁ is Si or C;

X ₁ to X ₄ are each independently a divalent linking group including an amide group, an ester group, or a silane group;

L ₁ to L ₈ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

In the compound represented by Formula 1 according to an embodiment of the present invention, R ₁ may include a unit structure represented by Formula 1-4 or Formula 1-5.

[Formula 1-4]

[Formula 1-5]

[In Formulas 1-4 and 1-5,

X ₁ to X ₄ are each independently a divalent linking group including an amide group or an ester group;

L ₁ to L ₇ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

In the compound represented by Formula 1 according to an embodiment of the present invention, R ₁ includes one unit structure selected from the unit structures represented by Formulas 1-1 to 1-5, and the unit -* of the structure may each independently satisfy hydrogen or a structure represented by the following Chemical Formula 1-6.

[Formula 1-6]

[In Formula 1-6,

R ₆ to R ₉ are each independently hydrogen, halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are linked to each other to form a substituted or unsubstituted ring can be formed.]

In the present invention, there is provided a photothiol generator composition comprising one or two or more selected from the compounds represented by Formula 1 above.

In the present invention, there is provided a curable composition comprising a compound represented by Formula 1, an epoxy compound, a polyfunctional acrylic compound, a thermosetting agent and a photoinitiator, that is, a low temperature fast curing adhesive composition.

The curable composition according to an embodiment of the present invention has thermal curing properties, and thermal curing may be performed under a temperature condition of 70 °C to 120 °C.

The curable composition according to an embodiment of the present invention has photocurability, and photocuring may be performed under irradiation conditions of 2.0 J/cm 2 to 6.0 J/cm 2 .

The curable composition according to an embodiment of the present invention has heat and photocurability, thermal curing is performed under a temperature condition of 70 to 120° C., and photocuring is performed under irradiation conditions of 2.0 J/cm 2 to 6.0 J/cm 2 it could be

The curable composition according to an embodiment of the present invention may further include an additive selected from a photoacid generator and an inorganic filler.

In the present invention, a cured product of the above-described curable composition is provided.

In the present invention, there is provided a structure comprising a first adherend, a second adherend, and an adhesive layer provided between the first adherend and the second adherend, wherein the adhesive layer is a cured product of the above-described curable composition.

The structure according to an embodiment of the present invention may be a camera module.

The compound according to the present invention has excellent storage stability under room temperature conditions. In addition, by initiating the curing process by causing a cyclization reaction with a very small amount of light with high reaction efficiency, not only can the curing process be performed quickly, but also gas generation due to thiol generation is not accompanied. Accordingly, according to the present invention, it is possible to provide a curable composition capable of exhibiting low-temperature fast-curable property.

In addition, according to the present invention, it is possible to provide a one-component curable composition having excellent photo-curing properties and thermal curing properties and capable of performing dual curing at the same time. The cured product prepared therefrom can implement improved adhesive strength, and can maintain it stably.

In addition, according to the present invention, it is possible to provide a curable composition that has little change in appearance, viscosity, or other physical properties under room temperature conditions, and satisfies improved storage stability.

Therefore, according to the present invention, it is possible to provide a cured product capable of stably maintaining improved adhesive strength, that is, an adhesive layer, which is usefully utilized in a mobile or vehicle camera module to provide a highly reliable structure.

1 is a schematic diagram of a method of manufacturing a cell for measuring adhesive strength according to the present invention.

Hereinafter, the thiol generator compound according to the present invention and its use will be described in detail. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and in the following description, it may unnecessarily obscure the subject matter of the present invention. A description of possible known functions and configurations will be omitted.

As used herein, the singular form may also be intended to include the plural form unless the context dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and the weight % means any one component of the entire composition unless otherwise defined. It means the weight % occupied in the composition.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, the term "comprises" is an open-ended description having an equivalent meaning to expressions such as "comprises", "contains", "has" or "characterized by", and is an element not listed further; Materials or processes are not excluded.

As used herein, the term "alkyl", "alkoxy" or a substituent comprising alkyl includes both straight-chain and branched-chain forms.

As used herein, the term “halogen” refers to a fluorine, chlorine, bromine or iodine atom.

As used herein, the term "aminoalkyl" refers to an alkyl group including an amino group (*-NR'R"), wherein R' and R" are each independently hydrogen or C _1-20 alkyl.

As used herein, the term “substituted” means that one or more hydrogen atoms bonded to a carbon atom are replaced with a halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl, C _1-20 aminoalkyl, or a combination thereof. it has become

As salpin in the background description above, the adhesive layer, which is a cured product obtained by photo-curing, thermal curing, or light and thermal curing of a conventional adhesive, often did not exhibit sufficient adhesive strength. In addition, it was difficult to realize sufficient adhesive strength due to poor storage stability or void formation due to gas generated during the curing process in conventional adhesives.

Under this background, the present inventors have confirmed the thiol generator compound and according to the prior patent (JP 2013-237750 A). The thiol generator compound disclosed in the prior patent blocks the thiol functional group with ortho-hydroxy cinnamate to inhibit the initiation of the thiol functional group until light is irradiated. According to the prior patent, the thiol generator compound has a characteristic that the alpha-position substituent of the carbonyl group does not contain a hydrogen atom as the difference in the effect depending on the alpha-position substituent of the carbonyl group is evident. This is because the E/Z selectivity of the double bond produced by hydrogen during the Wittig reaction is lowered due to the lowering of the hindrance effect. That is, when the partially generated (Z) form of the compound becomes a final thioester form, thiol is generated even if light is not irradiated, and storage stability is remarkably deteriorated. On the other hand, the thiol generator compound disclosed in the prior patent was able to secure storage stability by increasing the selectivity of the form (E) during the Wittig reaction as the alpha-position substituent of the carbonyl group had a substituent other than a hydrogen atom. However, it was judged that the reagents required for the Wittig reaction are very expensive and difficult to apply to mass production.

With such a tank, the present inventors have devised a thiol generator compound that has excellent storage stability and can be applied to a one-component adhesive capable of double curing at a low cost. The thiol generator compound according to the present invention is a compound in which a thiol functional group is blocked with ortho-amino cinnamate or the like, and does not react with the curable compound before light irradiation. In particular, the thiol generator compound of the present invention is distinguished from the technical features disclosed in the prior patents in that it does not show a difference in effect depending on the alpha-position substituent of the carbonyl group.

Hereinafter, the thiol generator compound of the present invention and use thereof will be described in detail.

In the present invention, a compound represented by the following formula (1), that is, a thiol generator compound is provided.

[Formula 1]

[In Formula 1,

R ₁ is a monovalent organic group, and may include one or more selected from N, O, S, Si, and C(=O);

R ₂ to R ₅ are each independently hydrogen, halogen, amino, cyano, hydroxy, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are connected to each other to be substituted or unsubstituted It can form a fixed ring.]

For example, the ring may be an alicyclic or aromatic ring, and the ring may be a monocyclic or polycyclic ring.

For example, when two substituents selected from R ₂ to R ₅ are connected to each other, the two substituents are R ₂ and R ₃ ; R ₃ and R ₄ ; or R ₄ and R ₅ ; may be, and these may form a ring through a linking group such as C _4-8 alkylene or C _4-8 alkenylene.

The compound represented by Chemical Formula 1 according to an embodiment of the present invention may be derived from a trifunctional or higher functional thiol compound, and specific embodiments of the unit structure derived from the thiol compound include the following Chemical Formulas 1-1 to 1-5 may be displayed as

For example, the thiol compound may be a 3 to 10 functional thiol compound.

For example, the thiol compound may be a 3 to 6 functional thiol compound.

The compound represented by Formula 1 according to an embodiment of the present invention may include a unit structure derived from a trifunctional thiol compound, and specifically, R ₁ of Formula 1 is represented by Formula 1-1 It may include a unit structure.

[Formula 1-1]

[In Formula 1-1,

L ₁ to L ₃ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

For example, L ₁ to L ₃ in Formula 1-1 may be each independently C _1-7 alkylene.

For example, L ₁ to L ₃ in Formula 1-1 may be each independently C _1-4 alkylene.

For example, in Formula 1-1, L ₁ to L ₃ may be each independently linear C _1-4 alkylene, and preferably, L ₁ to L ₃ may be the same straight-chain C _1-4 alkylene. there is.

The compound represented by Formula 1 according to an embodiment of the present invention may include a unit structure derived from a tetrafunctional thiol compound, and specifically, R ₁ of Formula 1 is Formula 1-2 or Formula 1 It may include a unit structure represented by -3.

[Formula 1-2]

[Formula 1-3]

[In Formula 1-2 or Formula 1-3,

Y ₁ is Si or C;

X ₁ to X ₄ are each independently a divalent linking group including an amide group, an ester group, or a silane group;

L ₁ to L ₈ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

, 상기 R 및 R'은 서로 독립적으로 수소 또는 C_1-7 알킬이다)이고, 상기 L₁ 내지 L₈은 서로 독립적으로 C_1-7 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is Si, X ₁ to X ₄ are silane groups (

, wherein R and R' are each independently hydrogen or C _1-7 alkyl), and L ₁ to L ₈ may be each independently C _1-7 alkylene.

, 상기 R 및 R'은 서로 독립적으로 수소 또는 C_1-4 알킬이다)이고, 상기 L₁ 내지 L₈은 서로 독립적으로 C_1-4 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is Si, X ₁ to X ₄ are silane groups (

, wherein R and R' are each independently hydrogen or C _1-4 alkyl), and L ₁ to L ₈ may be each independently C _1-4 alkylene.

, 상기 R 및 R'은 서로 독립적으로 C_1-4 알킬이다)이고, 상기 L₁ 내지 L₈은 서로 독립적으로 직쇄의 C_1-4 알킬렌일 수 있으며, 좋게는 상기 L₁ 내지 L₈이 동일하게 직쇄의 C_1-4 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is Si, X ₁ to X ₄ are silane groups (

, wherein R and R' are each independently C _1-4 alkyl), and L ₁ to L ₈ may independently be linear C _1-4 alkylene, preferably L ₁ to L ₈ are the same It may be a straight-chain C _1-4 alkylene.

) 또는 에스테르기(

)를 포함하는 2가의 연결기이고, 상기 L₁ 내지 L₈은 서로 독립적으로 C_1-7 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is C (carbon atom), X ₁ to X ₄ are amide groups (

) or an ester group (

) is a divalent linking group including, and L ₁ to L ₈ may be each independently C _1-7 alkylene.

) 또는 에스테르기(

)이고, 상기 L₁ 내지 L₈은 서로 독립적으로 C_1-4 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is C, X ₁ to X ₄ are amide groups (

) or an ester group (

), and L ₁ to L ₈ may be each independently C _1-4 alkylene.

)이고, 상기 L₁ 내지 L₈은 서로 독립적으로 직쇄의 C_1-4 알킬렌일 수 있으며, 좋게는 상기 L₁ 내지 L₈이 동일하게 직쇄의 C_1-4 알킬렌일 수 있다.For example, when Y ₁ of Formula 1-2 is C, X ₁ to X ₄ are an ester group (

), and L ₁ to L ₈ may be each independently linear C _1-4 alkylene, and preferably, L ₁ to L ₈ may be the same straight-chain C _1-4 alkylene.

For example, L ₁ to L ₄ in Formula 1-3 may be each independently C _1-7 alkylene.

For example, L ₁ to L ₄ in Formula 1-3 may be each independently C _1-4 alkylene.

For example, in Formula 1-3, L ₁ to L ₄ may be each independently linear C _1-4 alkylene, and preferably, L ₁ to L ₃ may be the same straight-chain C _1-4 alkylene. there is.

The compound represented by Formula 1 according to an embodiment of the present invention may include a unit structure derived from a hexafunctional thiol compound, and specifically, R ₁ of Formula 1 is Formula 1-4 or Formula 1 It may include a unit structure represented by -5.

[Formula 1-4]

[Formula 1-5]

[In Formulas 1-4 and 1-5,

X ₁ to X ₄ are each independently a divalent linking group including an amide group or an ester group;

L ₁ to L ₇ are each independently C _1-20 alkylene;

은 상기 화학식1의 S와 결합하는 위치이다.]

is a position bonded to S in Formula 1 above.]

) 또는 에스테르기(

)를 포함하는 2가의 연결기이고; 상기 L₁ 내지 L₆은 서로 독립적으로 C_1-7 알킬렌일 수 있다.For example, in Formula 1-4, X ₁ to X ₄ are each independently an amide group (

) or an ester group (

) is a divalent linking group comprising; The L ₁ to L ₆ may be each independently C _1-7 alkylene.

) 또는 에스테르기(

)이고, 상기 L₁ 내지 L₆은 서로 독립적으로 C_1-4 알킬렌일 수 있다.For example, in Formula 1-4, X ₁ to X ₄ are each independently an amide group (

) or an ester group (

), and L ₁ to L ₆ may be each independently C _1-4 alkylene.

)이고, 상기 L₁ 내지 L₆은 서로 독립적으로 직쇄의 C_1-4 알킬렌일 수 있으며, 좋게는 상기 L₁ 내지 L₃이 동일하게 직쇄의 C_1-4 알킬렌일 수 있다.For example, in Formula 1-4, X ₁ to X ₄ are an ester group (

), and L ₁ to L ₆ may each independently be a straight-chain C _1-4 alkylene, and preferably, L ₁ to L ₃ may be the same straight-chain C _1-4 alkylene.

For example, L ₁ to L ₇ in Formula 1-5 may be each independently C _1-7 alkylene.

For example, L ₁ to L ₇ in Formula 1-5 may be each independently C _1-4 alkylene.

For example, in Formula 1-5, L ₁ to L ₇ may be each independently linear C _1-4 alkylene, and preferably, L ₁ to L ₇ may be the same straight-chain C _1-4 alkylene. there is.

R ₁ of the compound represented by Formula 1 according to an embodiment of the present invention includes one unit structure selected from the unit structures represented by Formulas 1-1 to 1-5, and -* may each independently satisfy hydrogen or a structure represented by the following Chemical Formula 1-6.

[Formula 1-6]

[In Formula 1-6,

R ₆ to R ₉ are each independently hydrogen, halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are linked to each other to form a substituted or unsubstituted ring can be formed.]

The compound represented by Formula 1 according to an embodiment of the present invention may satisfy a molecular weight range of 500 to 3,000, specifically 600 to 2,500, and more specifically 700 to 2,000.

The compound represented by Formula 1 according to an embodiment of the present invention, that is, the thiol generator compound may be selected from the following structure, but is not limited thereto.

[Structure 1]

[Structure 2]

[Structure 3]

[Structure 4]

[Structure 5]

[Structure 6]

[Structure 7]

The present invention provides a photothiol generator composition comprising one or two or more selected from the compounds represented by Formula 1 above.

As an example, the photothiol generator composition may further include a thiol compound, a binder resin that can be commonly used, or a combination thereof.

In addition, the present invention provides a curable composition comprising a compound represented by Formula 1, an epoxy compound, a polyfunctional acrylic compound, a thermosetting agent, a photoinitiator, and the like.

Since the curable composition according to an embodiment of the present invention includes the compound represented by Formula 1, it is excellent in photocurability and heat curability, and thus a cured product having sufficient adhesive strength even under mild curing conditions can be provided. That is, the curable composition according to the present invention is useful as an adhesive capable of fast curing at a low temperature.

For example, the curable composition has thermosetting properties, and the thermal curing may be carried out at a temperature condition of 70 to 120 °C, preferably 80 to 100 °C, more preferably 80 to 90 °C. can

For example, the curable composition has photocurability, and photocuring may be performed under irradiation conditions of 2.0 to 6.0 J/cm 2 , preferably 2.0 to 4.0 J/cm 2 , more preferably 2.0 to 2.5 J/cm 2 It may be carried out under irradiation conditions.

As an example, the curable composition may have thermal and photocuring properties, and thermal and photocuring may satisfy the above-described conditions.

The epoxy compound is selected from a novolak-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol E-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, and a phenol aralkyl-type epoxy resin. epoxy resin; and a mixture of triglycidyl isocyanurate, diglycidyl terephthalate and triglycidyl trimellitate, glycidyl ester of versatic acid, 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclo an epoxy compound selected from hexanecarboxylate (ECC), ethylhexyl glycidyl ether, butyl glycidyl ether and pentaerythrityl tetraglycidyl ether; and the like, and may be used as one or a mixture of two or more selected from these. Specifically, the epoxy-based compound may include the above-described epoxy resin.

The polyfunctional acrylic compound is dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylpropane tri (meth) acrylate, glycerol Tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, di-trimethylpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and penta and erythritol tetra (meth) acrylate, and may be used as one or a mixture of two or more selected from these.

The thermosetting agent may be a latent thermosetting agent that acts not to initiate thermal curing below a desired temperature (room temperature, 25° C.). As a non-limiting example thereof, an imidazole type thermosetting agent, a dihydrazide type thermosetting agent or an amine type thermosetting agent may be used, but it is preferable to use an amine type curing agent in terms of curing time, storage stability, and adhesive strength improvement.

The photoinitiator may be used without limitation as long as it is a conventional one, and non-limiting examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin iso Butyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-die oxy-2-phenylacetophenone, 4-chronolocetophenone, 4,4-dimethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-hydroxycyclophenyl ketone; 1-Hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2 -(hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diaminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2-methyl Anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, diphenyl ketone benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyl and diphenylphosphine oxide, fluorene, triphenylamine, carbazole, benzyldiphenylsulfide and tetramethylthiuram monosulfide, and one or a mixture of two or more selected from these may be used. In addition, as commercially available products, brand names Darocur 1173, Igacure 184, Igacure 907 (Ciba) and the like can also be used. These can be used individually or in combination of 2 or more types.

The curable composition according to an embodiment of the present invention is based on 100 parts by weight of the epoxy compound, 1 to 30 parts by weight of the compound represented by Formula 1, 1 to 10 parts by weight of the polyfunctional acrylic compound, 5 to 10 parts by weight of the thermosetting agent 50 parts by weight and 0.1 to 5 parts by weight of the photoinitiator may be included.

For example, the curable composition may include 3 to 20 parts by weight of the compound represented by Chemical Formula 1, 3 to 10 parts by weight of the polyfunctional acrylic compound, 10 to 40 parts by weight of the thermosetting agent, and the above based on 100 parts by weight of the epoxy compound. It may include 0.5 to 3 parts by weight of the photoinitiator.

For example, the curable composition may include, based on 100 parts by weight of the epoxy compound, 5 to 15 parts by weight of the compound represented by Formula 1, 5 to 10 parts by weight of the polyfunctional acrylic compound, 15 to 30 parts by weight of the thermosetting agent, and the It may include 0.5 to 2 parts by weight of the photoinitiator.

The curable composition according to an embodiment of the present invention may further include an additive selected from a photoacid generator and an inorganic filler.

The photo-acid generator may be a photocation initiator containing an iodonium salt or a sulfonium salt. Non-limiting examples of photoacid generators containing iodonium salts include (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate Phenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecyl) Phenyl) iodonium hexafluoro antimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1 -Methylethyl)phenyliodoniumhexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodoniumhexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetra Fluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc. are mentioned. In addition, as a non-limiting example of a photoacid generator containing a sulfonium salt, diphenyl (4-phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl (4-phenylthio) phenylsulfonium hexafluorophosphate , (phenyl) [4- (2-methylpropyl) phenyl] -iodonium hexafluorophosphate, (thiodi-4,1-phenylene) bis (diphenylsulfonium) dihexafluoroantimonate and ( and thiodi-4,1-phenylene)bis(diphenylsulfonium)dihexafluorophosphate. In this case, the photoacid release agent may be included in an amount of 0.01 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.5 to 2 parts by weight, based on 100 parts by weight of the epoxy-based compound.

The inorganic filler may be used without limitation as long as it is a conventional one, and non-limiting examples thereof include silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite, talc, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia and ferrite, and one or two or more selected from these It can be used as a mixture. In this case, the inorganic filler may be included in an amount of 1 to 20 parts by weight, 1 to 15 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the epoxy-based compound.

The present invention also provides a cured product of the above-mentioned curable composition.

As the light irradiated when photocuring the curable composition according to an embodiment of the present invention, infrared rays having a wavelength of 800 nm or more, visible light, ultraviolet rays, electron beams, etc. may be used, but ultraviolet rays are preferable.

For example, the peak wavelength of the ultraviolet rays is specifically in the range of 300 to 500 nm.

For example, the illuminance of the ultraviolet rays is specifically 3,000 to 4,000 mW/cm 2 , more specifically 2,000 to 3,000 mW/cm 2 .

For example, the exposure amount of the ultraviolet rays is specifically 500 to 4,000 mJ/cm 2 , more specifically 1,000 to 3,000 mJ/cm 2 .

For example, the light irradiation means is 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, an LED type SPOT type UV irradiator , a xenon lamp, or a DEEP UV lamp.

The heating temperature when thermally curing the curable composition according to an embodiment of the present invention is not limited, but is specifically in the range of 70 to 120 °C, specifically 80 to 100 °C, and more specifically 80 to 90 °C.

Since the cured product according to an embodiment of the present invention can implement improved adhesive strength, it can be usefully used as an adhesive, a sealing agent, a coating agent, and the like.

In addition, the present invention provides a structure including the cured product.

The structure according to an embodiment of the present invention may include a first adherend, a second adherend, and an adhesive layer provided between the first adherend and the second adherend, and the adhesive layer may be the cured product. there is.

For example, the first adherend and the second adherend may be a member made of aluminum, brass, or polycarbonate. Specifically, the first adherend and the second adherend may be selected from a lens, a lens holder, a housing, and the like, and a part or the whole part is adhered with high adhesive strength by the above-described adhesive layer to form a high-quality structure. .

The structure according to an embodiment of the present invention may be a camera module.

For example, the structure is a camera module mounted on a mobile device such as a smartphone.

For example, the structure is a vehicle camera module.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples. In the present invention, unless otherwise stated, temperature means a unit of °C, and unless otherwise stated, the amount of the composition used means a unit of weight %.

(Assessment Methods)

1)Measurement of adhesive strength

As shown in FIG. 1, the curable compositions of Examples and Comparative Examples were dispensed at the interface of one aluminum first adherend in the form of an inner diameter of 13.5 mm and an outer diameter of 16.5 mm, followed by bonding with the second adherend to prepare a cell. At this time, the distance between the first adherend and the second adherend was set to 500 μm. Thereafter, the prepared cell was cured through the following curing conditions.

[Cure condition 1]

Using 6 light sources in the horizontal direction of the cell to the LED 365nm wavelength UV light (exposure dose for each irradiated light source = 2.0 J/cm 2 )

[Cure condition 2]

It was heated in a heat cycle oven at 80° C. for 30 minutes.

[Cure condition 3]

Using 6 light sources in the horizontal direction of the cell to the cell above the LED 365nm wavelength UV light. Then, it was heated in a thermal cycle oven at 80° C. for 30 minutes.

The adhesive strength of each cured cell was measured using UTM. At this time, the tensile speed was set to 50 mm/min, and the results are shown in Table 2 below.

2) Storage stability

The curable compositions of the following Examples and Comparative Examples were stored at 25° C. in a plastic sealed container, and the number of days until the initial viscosity increased by 50% or more was checked, and the results are shown in Table 2 below.

(Example 1)

Synthesis of compound 1c :

Dichloromethane (DCM, 50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 ° C. Then, polyfunctional thiol compound 1b (10 g, 0.026 mol), compound 1a (22.2 g, 0.115 mol) was added and dissolved while stirring for 10 minutes. . After dissolution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 22.0 g, 0.115 mol) and 4-dimethylaminopyridine (DMAP, 1.3g, 0.010 mol) were added in that order, and 0 It was stirred at ℃ condition for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporation of all solvents under reduced pressure, compound 1c was separated using column chromatography (20% EtOAc in hexane) to obtain 22.6-24.1 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.18 (dd, J = 7.5, 1.3 Hz, 4H), 7.88 (d, J = 15.0 Hz, 4H), 7.78 (dtd, J = 8.8, 7.5, 1.6 Hz, 8H), 7.63 (td, J = 7.2, 1.9 Hz, 4H), 6.93 (s, 2H), 6.89 (d, J = 15.2 Hz, 4H), 3.69 - 3.58 (m, 8H), 3.55 (ddd , J = 8.8, 2.6, 1.7 Hz, 8H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.25, 157.68, 147.46, 133.23, 131.55, 130.44, 130.37, 128.51, 125.10, 84.78, 38.82, 28.05.

Synthesis of compound 1d :

Acetic acid (AcOH, 57 mL) and 66% ethanol (EtOH, 84 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 1c (10g, 9.232 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (3.6 g, 64.626 mol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, and iron powder was filtered using a Celite filter and washed with EtOH (10mL X 3).

After evaporation of all solvents under reduced pressure, ethyl acetate (EtOAc, 100 mL), ? (30 mL) was dissolved in a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 1d (8.4-8.8 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.74 (d, J = 15.2 Hz, 4H), 7.34 (dd, J = 7.4, 1.5 Hz, 4H), 7.18 (td, J = 7.4, 1.5 Hz, 4H), 6.92 (s, 2H), 6.86 (td, J = 7.5, 1.4 Hz, 4H), 6.73 (dd, J = 7.5, 1.4 Hz, 4H), 6.57 (d, J = 15.0 Hz, 4H), 4.05 (s, 8H), 3.69 - 3.58 (m, 8H), 3.36 - 3.27 (m, 8H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.26, 157.68, 148.43, 129.91, 128.29, 127.70, 125.45, 122.08, 117.36, 116.32, 84.79, 38.82, 28.02.

(Example 2)

Synthesis of compound 2c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 ° C. Polyfunctional thiol compound 2b (10 g, 0.020 mol) and compound 1a (17.4 g, 0.090 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (17.3 g, 0.090 mol) and DMAP (1.0 g, 0.008 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporating all solvents under reduced pressure, compound 2c was separated using column chromatography (20% EtOAc in hexane) to obtain 19.5-20.7 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.29 (dd, J = 7.5, 1.4 Hz, 4H), 7.95 (d, J = 15.0 Hz, 4H), 7.78 (td, J = 7.5, 1.6 Hz, 4H), 7.75 (dd, J = 7.5, 1.6 Hz, 4H), 7.67 (td, J = 7.4, 1.6 Hz, 4H), 6.73 (d, J = 15.2 Hz, 4H), 4.25 (s, 8H), 3.47 - 3.34 (m, 8H), 2.99 - 2.87 (m, 8H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.26, 172.40, 147.44, 133.24, 131.56, 130.42, 130.38, 128.51, 125.09, 66.77, 40.13, 35.40, 22.29.

Compound 2d synthesis:

AcOH (56 mL) and 66% EtOH (82 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 2c (10g, 8.409 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (3.287 g, 58.862 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, the iron powder was filtered using a Celite filter, and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and water (30 mL), added to a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 2d (8.5-8.9 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.73 (d, J = 15.0 Hz, 4H), 7.35 (dd, J = 7.5, 1.4 Hz, 4H), 7.19 (td, J = 7.5, 1.4 Hz, 4H), 6.86 (td, J = 7.5, 1.4 Hz, 4H), 6.70 (dd, J = 7.5, 1.4 Hz, 4H), 6.58 (d, J = 15.0 Hz, 4H), 4.21 (s, 8H), 4.10 (s, 8H), 3.42 - 3.32 (m, 8H), 2.89 - 2.76 (m, 8H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.24, 172.41, 148.41, 129.95, 128.28, 127.68, 125.45, 122.09, 117.34, 116.36, 66.76, 40.11, 35.40, 22.29.

(Example 3)

Synthesis of compound 3c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 ° C. Then, polyfunctional thiol compound 3b (10 g, 0.025 mol) and compound 1a (16.0 g, 0.083 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (15.9 g, 0.083 mol) and DMAP (0.90 g, 0.008 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporation of all solvents under reduced pressure, compound 3c was separated using column chromatography (20% EtOAc in hexane) to obtain 18.5-19.7 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.28 - 8.19 (m, 3H), 8.12 (d, J = 15.0 Hz, 3H), 7.79 (t, J = 6.5 Hz, 6H), 7.70 - 7.62 ( m, 3H), 6.83 (d, J = 15.2 Hz, 3H), 4.21 (s, 6H), 3.46 - 3.29 (m, 6H), 2.99 - 2.84 (m, 6H), 1.36 (q, J = 6.6 Hz) , 2H), 0.98 (t, J = 6.7 Hz, 3H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.25, 172.41, 147.47, 133.24, 131.55, 130.44, 130.39, 128.50, 125.10, 69.20, 40.16, 35.40, 22.28, 21.54, 8.78.

Compound 3d synthesis:

AcOH (60 mL) and 66% EtOH (88 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 3c (10g, 10.823 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (4.231 g, 75.759 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, filtered iron powder using a Celite filter, and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and H ₂ O (30 mL), added to a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 3d (8.6-8.9 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.69 (d, J = 15.2 Hz, 3H), 7.33 (dd, J = 7.5, 1.5 Hz, 3H), 7.19 (td, J = 7.5, 1.4 Hz, 3H), 6.85 (td, J = 7.5, 1.4 Hz, 3H), 6.72 (dd, J = 7.5, 1.4 Hz, 3H), 6.55 (d, J = 15.0 Hz, 3H), 4.29 (s, 6H), 4.16 (s, 6H), 3.60 - 3.44 (m, 6H), 2.98 - 2.82 (m, 6H), 1.52 (q, J = 6.7 Hz, 2H), 1.03 (t, J = 6.7 Hz, 3H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.25, 172.41, 148.42, 129.94, 128.28, 127.68, 125.45, 122.10, 117.38, 116.36, 69.22, 40.15, 35.41, 22.28, 21.55, 8.79.

(Example 4)

Synthesis of compound 4c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 °C, and then polyfunctional thiol compound 4b (10 g, 0.013 mol) and compound 1a (16.3 g, 0.084 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (16.2 g, 0.084 mol) and DMAP (0.9 g, 0.008 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporation of all solvents under reduced pressure, compound 4c was separated using column chromatography (20% EtOAc in hexane) to obtain 18.7-19.9 g of pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.27 - 8.16 (m, 6H), 8.03 (d, J = 15.0 Hz, 6H), 7.83 - 7.74 (m, 12H), 7.65 (ddd, J = 7.5) , 5.9, 3.1 Hz, 6H), 6.70 (d, J = 15.2 Hz, 6H), 4.21 (dd, J = 4.6, 2.7 Hz, 12H), 4.05 (dd, J = 4.6, 2.8 Hz, 12H), 3.43 (d, J = 7.6 Hz, 4H), 3.36 - 3.29 (m, 12H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.26, 172.42, 147.47, 133.24, 131.56, 130.42, 130.38, 128.52, 125.09, 72.91, 66.75, 40.05, 35.40, 22.27.

Synthesis of compound 4d :

AcOH (51 mL) and 66% EtOH (75 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 4c (10g, 5.453 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (2.132 g, 38.170 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, and iron powder was filtered using a Celite filter and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and water (30 mL), introduced into a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 4d (8.6-8.9 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.76 (d, J = 15.2 Hz, 6H), 7.38 (dd, J = 7.5, 1.4 Hz, 6H), 7.21 (td, J = 7.5, 1.4 Hz, 6H), 6.87 (td, J = 7.4, 1.5 Hz, 6H), 6.73 (dd, J = 7.5, 1.4 Hz, 6H), 6.64 (d, J = 15.0 Hz, 6H), 4.85 (s, 12H), 4.21 (dd, J = 4.6, 2.7 Hz, 6H), 3.82 (dd, J = 4.5, 2.7 Hz, 6H), 3.35 (t, J = 8.2 Hz, 12H), 3.16 (d, J = 7.7 Hz, 4H) ) 2.91 (t, J = 8.1 Hz, 12H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.24, 172.43, 148.42, 129.98, 128.28, 127.65, 125.45, 122.12, 117.36, 116.35, 72.91, 66.78, 40.05, 35.41, 22.25.

(Example 5)

Synthesis of compound 5c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 ° C. Then, polyfunctional thiol compound 5b (10 g, 0.018 mol) and compound 1a (23.3 g, 0.121 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (23.1 g, 0.121 mol) and DMAP (1.3 g, 0.011 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporation of all solvents under reduced pressure, compound 5c was separated using column chromatography (20% EtOAc in hexane) to obtain 23.4-24.8 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.18 (dd, J = 7.5, 1.4 Hz, 6H), 7.96 (d, J = 15.2 Hz, 6H), 7.76 (td, J = 7.4, 1.4 Hz, 6H), 7.70 (dd, J = 7.5, 1.7 Hz, 6H), 7.62 (td, J = 7.4, 1.7 Hz, 6H), 6.76 (d, J = 15.0 Hz, 6H), 4.32 (t, J = 7.4) Hz, 12H), 3.34 (t, J = 7.4 Hz, 12H), 0.57(s, 4H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.25, 147.46, 133.26, 131.56, 130.42, 130.38, 128.52, 125.09, 60.16, 29.31, 6.68.

Synthesis of compound 5d :

AcOH (52 mL) and 66% EtOH (77 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 5c (10g, 6.259 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (2.447 g, 43.810 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, filtered iron powder using a Celite filter, and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and water (30 mL), introduced into a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 5d (8.4-8.8 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.75 (d, J = 15.0 Hz, 6H), 7.38 (dd, J = 7.5, 1.6 Hz, 6H), 7.21 (td, J = 7.5, 1.4 Hz, 6H), 6.87 (td, J = 7.5, 1.4 Hz, 6H), 6.75 (dd, J = 7.4, 1.5 Hz, 6H), 6.53 (d, J = 15.0 Hz, 6H), 4.44 - 4.34 (m, 12H) ), 3.61 (s, 12H), 3.23 - 3.07 (m, 12H), 0.60 (s, 4H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.24, 148.43, 129.95, 128.25, 127.69, 125.44, 122.09, 117.38, 116.38, 60.16, 29.24, 6.69.

(Example 6)

Synthesis of compound 6c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0°C. Then, polyfunctional thiol compound 6b (10 g, 0.016 mol) and compound 1a (13.8 g, 00.071 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (13.7 g, 0.071 mol) and DMAP (0.8 g, 0.006 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporation of all solvents under reduced pressure, compound 6c was isolated using column chromatography (20% EtOAc in hexane) to obtain 17.1-18.1 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.23 (dd, J = 7.5, 1.4 Hz, 4H), 7.87 (d, J = 15.0 Hz, 4H), 7.82 (td, J = 7.4, 1.4 Hz, 4H), 7.77 (dd, J = 7.5, 1.6 Hz, 4H), 7.66 (td, J = 7.4, 1.6 Hz, 4H), 6.78 (d, J = 15.0 Hz, 4H), 2.98 (t, J = 8.7) Hz, 8H), 0.86 (t, J = 8.6 Hz, 8H), 0.64 (dd, J = 5.1, 4.3 Hz, 16H), 0.18 (s, 24H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.26, 147.44, 133.23, 131.56, 130.42, 130.38, 128.49, 125.09, 28.55, 11.23, 5.37, -3.63, -3.91

Synthesis of compound 6d :

AcOH (54 mL) and 66% EtOH (80 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 6c (10g, 7.587 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (2.966 g, 53.112 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, and iron powder was filtered using a Celite filter and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and water (30 mL), introduced into a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 6d (8.6-9.0 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.74 (d, J = 15.2 Hz, 4H), 7.31 (dd, J = 7.5, 1.4 Hz, 4H), 7.16 (td, J = 7.5, 1.4 Hz, 4H), 6.87 (td, J = 7.5, 1.4 Hz, 4H), 6.68 (dd, J = 7.4, 1.5 Hz, 4H), 6.51 (d, J = 15.0 Hz, 4H), 4.49 (s, 8H), 3.03 (t, J = 8.5 Hz, 8H), 1.00 (t, J = 8.5 Hz, 8H), 0.80 - 0.71 (m, 8H), 0.71 - 0.60 (m, 8H), 0.25 (s, 24H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.27, 148.45, 129.98, 128.25, 127.66, 125.41, 122.09, 117.37, 116.36, 28.55, 11.23, 5.37, -3.60, -3.95.

(Example 7)

Synthesis of compound 7c :

DCM (50ml) was put into a 100ml eggplant flask, and the condition was maintained at 0 ° C. Then, polyfunctional thiol compound 7b (10 g, 0.032 mol) and compound 1a (20.6 g, 0.107 mol) were added and dissolved while stirring for 10 minutes. After dissolution, EDCI (20.4 g, 0.107 mol) and DMAP (1.2 g, 0.010 mol) were added in order and stirred at 0 °C for 1 hour. After slowly warming to room temperature at 25 °C, the reaction was carried out at 25 °C for 3 hours.

By using FT-IR, it was confirmed that all of the thiol peaks (2570 cm ^-1 ) disappeared and the reaction was terminated. After the reaction was completed, a saturated aqueous NaHCO ₃ solution (20 ml) was added to the mixture. After separating the organic layer using a separatory funnel, anhydrous MgSO ₄ (2.0 g) was added to remove a small amount of water remaining. After evaporating all solvents under reduced pressure, compound 7c was separated using column chromatography (20% EtOAc in hexane) to obtain 21.6-22.9 g of a pale yellow oil, and the yield was 80-85%.

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.19 (dd, J = 7.5, 1.2 Hz, 3H), 7.84 - 7.74 (m, 6H), 7.72 (s, 3H), 7.63 (td, J = 7.2) , 2.0 Hz, 3H), 6.95 (d, J = 15.0 Hz, 3H), 4.37 - 4.27 (m, 6H), 3.36 - 3.26 (m, 6H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.25, 150.44, 147.45, 133.28, 131.56, 130.46, 130.38, 128.52, 125.09, 39.08, 27.21.

Synthesis of compound 7d :

AcOH (62 mL) and 66% EtOH (91 mL) were added to a 500ml eggplant flask, and then, while stirring at room temperature, compound 7c (10g, 11.978 mmol) was added and dissolved for 10 minutes. After dissolution, iron powder (4.682 g, 83.847 mmol) was added and refluxed for 60 minutes. After refluxing, it was cooled to room temperature, and iron powder was filtered using a Celite filter and washed with EtOH (10mL X 3). After evaporating all solvents under reduced pressure, it was dissolved in EtOAc (100 mL) and water (30 mL), introduced into a separatory funnel, and the compound was extracted. Anhydrous MgSO ₄ (2.0 g) was added to the extracted organic layer to remove a small amount of water remaining. All solvents were evaporated under reduced pressure to obtain compound 7d (8.5-8.8 g, 95-99%).

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.67 (d, J = 15.0 Hz, 3H), 7.31 (dd, J = 7.5, 1.5 Hz, 3H), 7.11 (td, J = 7.5, 1.4 Hz, 3H), 6.82 (td, J = 7.5, 1.4 Hz, 3H), 6.73 (dd, J = 7.5, 1.4 Hz, 3H), 6.55 (d, J = 15.0 Hz, 3H), 4.38 - 4.28 (m, 6H) ), 3.86 (s, 6H), 3.41 - 3.30 (m, 6H).

¹³ C NMR (125 MHz, DMSO-d ₆ ) δ 187.21, 150.45, 148.42, 129.91, 128.29, 127.69, 125.46, 122.09, 117.33, 116.38, 39.12, 27.28.

(Examples 8 to 15 and Comparative Example 1)

After mixing with the composition shown in Table 1 below, each curable composition was prepared by stirring for 30 minutes using a paste mixer. Physical properties of each prepared curable composition and its cured product were measured through the above evaluation method.

As shown in Table 2, the curable composition according to the present invention maintained storage stability of 3 days or more in all cases. In addition, the cured product manufactured using the same could implement excellent adhesive strength under all curing conditions 1 to 3, as well as excellent retention of adhesive strength. In addition, it was confirmed that the adhesive strength could be more stably maintained when the bisphenol A type epoxy resin was used as the epoxy compound, and Example 8 using the compound 1d having the highest Tg value showed superiority in adhesive strength. In addition, in the case of using ECC, it was confirmed that the adhesive strength was somewhat low under curing condition 2 and curing condition 3, but it was also confirmed that the bonding strength could be stably maintained.

On the other hand, the curable composition of Comparative Example 1 showed very poor storage stability because it was cured under room temperature conditions despite the absence of a light source. In addition, the adhesive strength decreased rapidly after curing under all curing conditions.

Therefore, when the curable composition according to the present invention is used, it is possible to select and perform photocuring, thermal curing, or dual curing in parallel therewith depending on the environment or purpose of use, as well as realizing improved adhesive strength through dual curing. Accordingly, since the adhesive strength per unit area is high, it can be usefully applied as an adhesive layer between constituent members such as a camera module.

The present invention is not limited by the above-described embodiments, and it is those of ordinary skill in the art to which the present invention pertains that various substitutions, modifications and changes can be made within the scope without departing from the technical spirit of the present invention. will be clear to

Claims (15)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ is a monovalent organic group, and may include one or more selected from N, O, S, Si, and C(=O);
R ₂ to R ₅ are each independently hydrogen, halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are linked to each other to form a substituted or unsubstituted ring can be formed The method of claim 1,
The compound is
A compound that is derived from a trifunctional or higher thiol compound. The method of claim 1,
R ₁ in Formula 1 is,
A compound comprising a unit structure represented by the following formula 1-1:
[Formula 1-1]

In Formula 1-1,
L ₁ to L ₃ are each independently C _1-20 alkylene;

is a position bonded to S in Formula 1 above. The method of claim 1,
R ₁ in Formula 1 is,
A compound comprising a unit structure represented by the following Chemical Formula 1-2 or Chemical Formula 1-3:
[Formula 1-2]

[Formula 1-3]

In Formula 1-2 or Formula 1-3,
Y ₁ is Si or C;
X ₁ to X ₄ are each independently a divalent linking group including an amide group, an ester group, or a silane group;
L ₁ to L ₈ are each independently C _1-20 alkylene;

is a position bonded to S in Formula 1 above. The method of claim 1,
R ₁ in Formula 1 is,
A compound comprising a unit structure represented by the following Formula 1-4 or Formula 1-5:
[Formula 1-4]

[Formula 1-5]

In Formulas 1-4 and 1-5,
X ₁ to X ₄ are each independently a divalent linking group including an amide group or an ester group;
L ₁ to L ₇ are each independently C _1-20 alkylene;

is a position bonded to S in Formula 1 above. According to any one of claims 3 to 5 selected from,
-* of the unit structures represented by Formulas 1-1 to 1-5 are each independently hydrogen or a structure represented by Formula 1-6, a compound:
[Formula 1-6]

In Formula 1-6,
R ₆ To R ₉ are each independently hydrogen, halogen, amino, cyano, C _1-20 alkoxy, C _1-20 alkyl or C _1-20 aminoalkyl, or adjacent substituents are linked to each other to form a substituted or unsubstituted ring can be formed A photothiol generator composition comprising the compound according to claim 1 . A curable composition comprising the compound of claim 1, an epoxy compound, a polyfunctional acrylic compound, a thermosetting agent, and a photoinitiator. 9. The method of claim 8,
The curable composition has thermosetting properties,
Thermal curing is performed at a temperature condition of 70 to 120 ℃, the curable composition. 9. The method of claim 8,
The curable composition has photocurability,
Light curing is performed under irradiation conditions of 2.0 J/cm 2 to 6.0 J/cm 2 , the curable composition. 9. The method of claim 8,
The curable composition has heat and photocurability,
Thermal curing is performed at a temperature condition of 70 to 120 ° C., and light curing is performed under irradiation conditions of 2.0 J/cm 2 to 6.0 J/cm 2 , the curable composition. 9. The method of claim 8,
A curable composition further comprising an additive selected from a photoacid generator and an inorganic filler. An adhesive comprising the curable composition according to claim 8 . A first adherend, a second adherend, and an adhesive layer provided between the first adherend and the second adherend, wherein the adhesive layer is a curable composition according to any one of claims 8 to 12. A structure that is a cured product. 15. The method of claim 14,
A structure that is a camera module.

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