KR20230049245A - Double Curable Epoxy Adhesive Composition and cured product thereof - Google Patents

Abstract

The present invention relates to a dual curable epoxy adhesive composition. According to the present invention, it is possible to provide a cured product that has excellent curability and excellent adhesive strength and water resistance. Accordingly, according to the present invention, the present invention can be usefully applied as a material for forming various optical members and optical devices, and in particular, it can be usefully applied as an adhesive layer between structural members such as camera modules that require high adhesive strength and water resistance per unit area.

Description

Double curable epoxy adhesive composition and cured product thereof {Double Curable Epoxy Adhesive Composition and cured product thereof}

The present invention relates to a dual-curing type epoxy adhesive composition and a cured product thereof, and specifically, to a dual-curing type epoxy adhesive composition having excellent adhesion and adhesion and high reliability, and a cured product thereof.

With the development of portable devices and self-driving cars, camera modules mounted inside and outside vehicles are also being miniaturized, and the required reliability specifications are also increasing. In addition, as a camera module is expected to be mounted in a wearable device, a demand for miniaturization and thinning is increasing. Further, as the size of the camera module is reduced, the portion where each constituent member of the camera module is adhered and fixed is also becoming smaller, so the impact resistance of the camera module against falling and vibration has become a very important issue. That is, even when the camera module receives an impact or external vibration due to a fall, adhesion between constituent members must be maintained. In addition, when the bonding area is reduced, the adhesively fixed portion between the constituent members is easily peeled off, so it is more important to improve the bonding strength per unit area of the adhesive, and the moisture resistance must also be excellent.

An adhesive used for assembling a camera module requires low-temperature curability in order to avoid thermal damage caused by high-temperature processing to 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 light-curing or heat-curing adhesive is widely used (Patent Document 1).

However, light-curable adhesives, while capable of rapid curing, have disadvantages such as causing curing deformation due to curing shrinkage or being unable to be used for bonding parts where light does not reach. The heat-curing adhesive may be a low-temperature, fast-curing adhesive, but during bonding, a member to be bonded must be fixed with a jig or device to maintain the bonding posture. In addition, the viscosity is lowered by the temperature rise, causing problems such as sagging immediately before curing or flowing out of a desired portion, which is not always satisfactory.

In order to solve the above problems, in order to arrange each member constituting the camera module with high precision, a type of adhesive that is temporarily fixed by pre-curing by light (eg, ultraviolet, visible light) irradiation and final curing by heat is provided. is being proposed

JP 2013-088525 A

An object of the present invention is to provide a dual curing type epoxy adhesive composition and a cured product thereof having high reliability while realizing remarkably improved adhesive strength due to the bonding between a photocurable matrix and a thermosetting matrix.

Specifically, to provide a dual-curing epoxy adhesive composition that can be used as a low-temperature fast-curing adhesive, maintains its shape without flow by fluidity after photocuring, and can realize high curing degree and adhesive strength by thermal curing and a cured product thereof will be.

In order to solve the above problems, the present invention provides a dual curing type epoxy adhesive composition. Specifically, the dual curing type epoxy adhesive composition includes a cyanate ester having at least three acrylate groups and one cyanate group in one molecule - a photocurable component including a multifunctional acrylate compound and a photoinitiator; and a heat curable component including an epoxy-containing compound and a heat curing agent.

In the dual curing type epoxy adhesive composition according to an embodiment, the cyanate ester-multifunctional acrylate compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

또는

이고;L ¹ , L ² and L ³ are each independently a single bond;

or

ego;

L ^A , L ^B and L ^C are C1-C20 alkylene;

a is an integer from 1 to 10;

b and c are each independently an integer from 0 to 10;

)은 산소 원자에 연결되는 부위를 나타내고; wave(

) represents a site connected to an oxygen atom;

)는 탄소 원자에 연결되는 부위를 나타낸다.asterisk(

) represents a site connected to a carbon atom.

이며; L^A는 C1-C5알킬렌이고; a는 1 내지 5의 정수일 수 있다.In the dual curing type epoxy adhesive composition according to an embodiment, the L ¹ , L ² and L ³ are a single bond or

is; L ^A is C1-C5 alkylene; a may be an integer from 1 to 5.

이고, 나머지는 단일결합 또는

이며, L^A, L^B 및 L^C는 C1-C5알킬렌이고; a는 1 내지 5의 정수이고; b 및 c는 각각 독립적으로 0 내지 5의 정수일 수 있다.In the dual curing epoxy adhesive composition according to an embodiment, at least one of L ¹ , L ² and L ³ is

And the remainder is a single bond or

, and L ^A , L ^B and L ^C are C1-C5 alkylene; a is an integer from 1 to 5; b and c may each independently be an integer from 0 to 5.

In the dual curing type epoxy adhesive composition according to an embodiment, the epoxy-containing compound is a novolac 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 triphenyl Methane-type epoxy resins, phenolaralkyl-type epoxy resins, halogenated epoxy resins, alicyclic epoxy resins, rubber-modified epoxy resins, aliphatic polyglycidyl-type epoxy resins, glycidyl amine-type epoxy resins, polyglycol epoxy resins, and cardanol epoxy resins It may be one or a mixture of two or more selected from.

In the dual curing type epoxy adhesive composition according to one embodiment, the thermal curing agent may be a latent thermal curing agent.

In the dual curing type epoxy adhesive composition according to an embodiment, the heat curing agent may be one or a mixture of two or more selected from an imidazole type heat curing agent, a dihydrazide type heat curing agent, and a polyamine type heat curing agent.

In the dual curing epoxy adhesive composition according to an embodiment, one or more selected from inorganic fillers, adhesion promoters, retarders, and stabilizers may be further included.

In the dual curing epoxy adhesive composition according to an embodiment, the inorganic filler is fumed 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, fused silica, quartz powder, sericite, talcite, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia, and can be one or a mixture of two or more selected from ferrite. there is.

In the dual curing type epoxy adhesive composition according to an embodiment, the adhesion promoter may be one or two or more selected from epoxy-containing silane, amine-containing silane, and mercapto-containing silane.

In addition, in the present invention, a cured product of the dual curing type epoxy adhesive composition is provided.

In addition, the present invention provides a camera module attached by the dual curing type epoxy adhesive composition.

According to the present invention, due to the photocuring composition including the cyanate ester-multifunctional acrylate compound, sufficient crosslinking between the photocuring composition and the thermal curing composition through light/thermal dual curing, that is, the cyanate functional group remaining after photocuring is achieved. During thermal curing, it reacts with an amine-based thermal curing agent to combine a photocurable matrix and a thermosetting matrix to realize remarkably improved adhesive strength and provide a highly reliable cured product with improved moisture resistance. With the implementation of such physical properties, the cured product according to the present invention can be usefully applied as a material for forming various optical members and optical devices, especially between constituent members such as camera modules that require high adhesive strength and water resistance per unit area. It is expected that it can be usefully applied as an adhesive layer of

In addition, according to the present invention, it is possible to implement more improved adhesive strength through double curing, so it can be usefully used as a higher quality adhesive for camera modules.

Hereinafter, a dual curing type epoxy resin composition and a cured product thereof according to the present invention will be described in detail.

At this time, if there is no other definition in the technical terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and will unnecessarily obscure the gist of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

The singular form used herein may be intended to include the plural form as well, unless the context dictates otherwise.

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

Further, as used herein, numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically 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.

The term "comprising" in this specification is an open description having the same meaning as "comprises", "includes", "has" or "characterized by", and elements not additionally listed, No materials or processes are excluded.

In addition, the term "substantially" in this specification means that other elements, materials, or processes not listed together with a specified element, material, or process are unacceptable to at least one basic and novel technical idea of the invention. It means that it can be present in an amount or degree that does not have a significant effect.

In addition, as used herein, the term "cured product" may be a cured product of a curable composition or a cured product of an epoxy adhesive composition as a general meaning. In addition, the cured product may include a semi-cured product.

In addition, the term "structural adhesives" used herein refers to materials used for adhesive bonding of at least two structural components constituting a structure to each other.

As reviewed in the background description above, when the conventional epoxy resin adhesive is double-cured in the order of photocuring and thermal curing, the fluidity after photocuring is lowered and the curing degree is lowered during thermal curing, so that the adhesive layer, which is a cured product, has sufficient adhesive strength It was often not indicated. In addition, conventional adhesives have poor storage stability or void formation due to gas generated during the curing process, making it difficult to achieve sufficient adhesive strength.

In order to solve this problem, the present inventors have repeatedly studied adhesives of various compositions using epoxy resins. As a result, by including a cyanate ester-multifunctional acrylate compound having at least three acrylate groups and one cyanate group in one molecule as a photocurable component in the dual curing type epoxy adhesive composition, the adhesive form against external impact after photocuring It was confirmed that not only can realize adhesive strength that is not deformed, but also significantly improved adhesive strength and water/moisture resistance after heat curing.

Hereinafter, the present invention will be described in detail.

The present invention provides a dual-curing epoxy adhesive composition of a novel composition for providing a cured product having excellent curability, adhesive strength, and water/moisture resistance. Specifically, the dual curing type epoxy adhesive composition according to an embodiment of the present invention comprises a cyanate ester-multifunctional acrylate compound having at least three acrylate groups and one cyanate group in one molecule and a photocurable component including a photoinitiator ; and a heat curable component including an epoxy-containing compound and a heat curing agent.

The dual curing type epoxy adhesive composition according to an embodiment includes a cyanate ester-multifunctional acrylate compound having at least three acrylate groups and one cyanate group in one molecule as a photocuring agent included in the photocurable component, Compared to the conventional dual-curing type epoxy adhesive composition containing a multifunctional acrylic compound as a photocuring agent, storage stability is high, and there are advantages in terms of curing degree, adhesion, and reliability.

In the dual curing type epoxy adhesive composition according to an embodiment, the cyanate ester-multifunctional acrylate compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

또는

이고;L ¹ , L ² and L ³ are each independently a single bond;

or

ego;

L ^A , L ^B and L ^C are C1-C20 alkylene;

a is an integer from 1 to 10;

b and c are each independently an integer from 0 to 10;

)은 산소 원자에 연결되는 부위를 나타내고; wave(

) represents a site connected to an oxygen atom;

)는 탄소 원자에 연결되는 부위를 나타낸다.asterisk(

) represents a site connected to a carbon atom.

또는

이고; L^A, L^B 및 L^C는 C1-C10알킬렌이고; a는 1 내지 5의 정수이고; b 및 c는 각각 독립적으로 0 내지 5의 정수일 수 있다.Specifically, in Formula 1, the L ¹ , L ² and L ³ are each independently a single bond;

or

ego; L ^A , L ^B and L ^C are C1-C10 alkylene; a is an integer from 1 to 5; b and c may each independently be an integer from 0 to 5.

일 수 있으며; L^A는 C1-C5알킬렌이고; a는 1 내지 5의 정수일 수 있다.For example, in Formula 1, L ¹ , L ² and L ³ may be a single bond or

can be; L ^A is C1-C5 alkylene; a may be an integer from 1 to 5.

For example, in Chemical Formula 1, all of L ¹ , L ² and L ³ may be single bonds.

일 수 있으며; L^A는 C1-C5알킬렌이고; a는 1 내지 5의 정수일 수 있다.For example, in Formula 1, L ¹ , L ² and L ³ are all

can be; L ^A is C1-C5 alkylene; a may be an integer from 1 to 5.

일 수 있다.For example, in Formula 1, L ¹ , L ² and L ³ may be a single bond or

can be

일 수 있으며; a는 1 내지 5의 정수일 수 있다.For example, in Formula 1, L ¹ , L ² and L ³ are all

can be; a may be an integer from 1 to 5.

이고, 나머지는 단일결합 또는

일 수 있으며, L^A, L^B 및 L^C는 C1-C5알킬렌이고; a는 1 내지 5의 정수이고; b 및 c는 각각 독립적으로 0 내지 5의 정수일 수 있다.For example, in Formula 1, at least one of L ¹ , L ² and L ³

And the remainder is a single bond or

, L ^A , L ^B and L ^C are C1-C5 alkylene; a is an integer from 1 to 5; b and c may each independently be an integer from 0 to 5.

이고, 나머지는 단일결합 또는

일 수 있다.For example, in Formula 1, at least one of L ¹ , L ² and L ³

And the remainder is a single bond or

can be

For example, the cyanate ester-multifunctional acrylate compound may be included in an amount of 10 to 40% by weight, or 15 to 30% by weight, or 20 to 30% by weight based on the total weight of the dual curing type epoxy adhesive composition.

The dual curing type epoxy adhesive composition according to an embodiment is sufficient crosslinking between the light curing composition and the heat curing composition through light/thermal double curing due to the light curing composition including the cyanate ester-multifunctional acrylate compound, that is, after light curing Remaining cyanate functional group reacts with a heat curing agent, especially an amine-based heat curing agent during heat curing, thereby combining a light curable matrix and a heat curable matrix to realize remarkably improved adhesive strength and significantly improved water/moisture resistance. A high cured product can be provided. Adhesion retention time can also be further improved.

In the dual curing epoxy adhesive composition according to an embodiment, the photoinitiator included in the photocurable component may be used without limitation as long as it is conventional, and non-limiting examples thereof include benzoin, benzoin methyl ether, and benzoin ethyl Ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, dimethoxy-2-phenylacetophenone, 3-methylacetophenone , 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4-chlorocetophenone, 4,4-dimethoxyacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 4-hydroxycyclophenylketone, 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-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, 2-methyl Thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, diphenylketonebenzyldimethylketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, fluorene, triphenylamine, carbazole, benzyldiphenyl sulfide and tetramethylthiuram monosulfide; and the like. , One or a mixture of two or more selected from these may be used. In addition, commercially available products such as Darocur 1173, Irgacure 184, and Igacure 907 (Ciba) may also be used. These can be used individually or in combination of 2 or more types.

For example, the photoinitiator may be included in 0.01 to 5% by weight, or 0.05 to 3% by weight, or 0.1 to 2% by weight, or 0.1 to 2% by weight based on the total weight of the dual-curing type epoxy adhesive composition.

In the dual curing epoxy adhesive composition according to an embodiment, the epoxy-containing compound included in the heat-curable component is a bifunctional or higher-functional epoxy-containing compound, and may be used without limitation as long as it is conventional, and one non-limiting example thereof is Novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin, halogenated epoxy resin, alicyclic epoxy It may be one or a mixture of two or more selected from resins, rubber-modified epoxy resins, aliphatic polyglycidyl-type epoxy resins, glycidyl amine-type epoxy resins, polyglycol epoxy resins, and cardanol epoxy resins. Also, a mixture of triglycidyl isocyanurate, diglycidyl terephthalate and triglycidyl trimellitate, glycidyl ester of versatic acid, 3,4-epoxycyclohexylmethyl 3', 4'-epoxy Epoxy compounds selected from cyclohexane carboxylate, ethylhexyl glycidyl ether, butyl glycidyl ether, and pentaerythrityl tetraglycidyl ether; It may further include one or a mixture of two or more selected from or an epoxy resin derived therefrom, but is not limited thereto.

For example, the epoxy-containing compound may be included in an amount of 10 to 60% by weight, or 20 to 50% by weight, or 30 to 50% by weight based on the total weight of the dual curing type epoxy adhesive composition.

In the dual curing type epoxy adhesive composition according to an embodiment, the thermal curing agent included in the thermal curing component is a latent thermal curing agent that acts not to initiate thermal curing below a desired temperature (room temperature, 25 ° C.), Anything can be used without limitation. It is preferable to use a latent amine-based heat curing agent containing at least one selected from alicyclic amines, aromatic amines, aliphatic amines, polyamines, and dihydrazides in terms of curing time, storage stability, and adhesive strength improvement. Non-limiting examples thereof include imidazole-type, polyamine-type, dihydrazide-type heat curing agents, and the like, and one or a mixture of two or more selected from these may be used. In addition, as commercially available products, Ancamine 2014AS (Evonik), PN-23J (Ajinomoto Co., Ltd.), EH-5057PK (ADEKA), EH-4357S (ADEKA), Fujicure FXR-1081, etc. can be used.

For example, the heat curing agent may be included in 1 to 30% by weight, or 5 to 25% by weight, or 10 to 25% by weight, or 15 to 25% by weight based on the total weight of the dual-curing type epoxy adhesive composition.

The dual curing type epoxy adhesive composition according to an embodiment is a cyanate ester-multifunctional acrylate compound having at least three acrylate groups and one cyanate group in one molecule, based on the total weight of the dual curing type epoxy adhesive composition 10 to 40% by weight, 0.01 to 5% by weight of a photoinitiator, 10 to 60% by weight of an epoxy-containing compound, and 1 to 30% by weight of a thermal curing agent, specifically, 15 to 30% by weight of the cyanate ester-multifunctional acrylate compound %, 0.05 to 3% by weight of a photoinitiator, 20 to 50% by weight of an epoxy-containing compound, and 5 to 25% by weight of a heat curing agent.

More specifically, the dual curing epoxy adhesive composition according to one embodiment is a cyanate ester having at least three acrylate groups and one cyanate group in one molecule, based on the total weight of the dual curing epoxy adhesive composition. 20 to 30% by weight of a late compound, 0.1 to 2% by weight of a photoinitiator, 30 to 50% by weight of an epoxy-containing compound, and 10 to 25% by weight of a heat curing agent.

The dual curing type epoxy adhesive composition according to an embodiment may further include additives as needed, and examples of the additives include inorganic fillers, adhesion promoters, retarders, stabilizers, and the like, and one or more selected from these. You may use more than one.

In terms of improving the degree of curing through the improvement of thermal conductivity during thermal curing, an inorganic filler may be further included. The inorganic filler is fumed 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 It may be one or a mixture of two or more selected from beads, fused silica, quartz powder, sericite, talc clay, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia, and ferrite, but is not limited thereto. does not

For example, the amount of the inorganic filler used is not particularly limited, but may be included in an amount of 5 to 25% by weight, or 10 to 20% by weight, or 10 to 15% by weight based on the total weight of the dual curing type epoxy adhesive composition.

For example, the inorganic filler is one or more first inorganic fillers selected from fumed silica, diatomaceous earth, and alumina, and fused silica, quartz powder, sericite, talc clay, and bentonite to secure viscosity performance and increase impact resistance. It may be a mixture in which one or two or more second inorganic fillers selected from are mixed. Here, in the mixture, the second inorganic filler may be used in excess compared to the first inorganic filler, and specifically, the weight ratio (first inorganic filler: second inorganic filler) of the first inorganic filler and the second inorganic filler is 1:2. to 10, or 1:2 to 5, or 1:2 to 4.

The "adhesion" promoter is a material added to improve the "adhesion" initial adhesion between objects or to improve the "adhesion" durability after curing, and "adhesion" promoter or adhesion promoter known in the art can be used without limitation.

As the adhesion promoter, epoxy-containing silane, amine-containing silane, or mercapto-containing silane may be used, and epoxy-containing 2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycy Doxytrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane containing an amine group , N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysily-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, containing mercapto, 3-mercaptopropylmethyl Dimethoxysilane and 3-mercaptopropyltriethoxysilane can be exemplified. The above components may be used alone or in combination of two or more. As the adhesion promoter, it is preferable to use an epoxy-containing silane.

For example, the amount of the adhesion promoter is not particularly limited, but may be included in an amount of 0.01 to 10% by weight, or 0.1 to 5% by weight, or 0.5 to 3% by weight based on the total weight of the dual curing type epoxy adhesive composition.

The "retardant" is a material added to control the curing speed, and a "retardant" known in the art may be used without limitation. Boric acid, salicylic acid, hydrochloric acid, sulfuric acid, oxalic acid, terephthalic acid, isophthalic acid, phosphoric acid, lactic acid, acetic acid, phenylboric acid, toluenesulfonic acid, etc. may be used as the retardant, and the amount used is not particularly limited, but the dual curing type epoxy adhesive composition Based on the total weight, 0.0001 to 0.001% by weight, or 0.0001 to 0.0005% by weight.

The stabilizer may be further included in order to provide a dual curing epoxy adhesive composition having excellent thermal stability under high temperature conditions and excellent curability.

The stabilizer may include at least one stabilizer selected from phenolic stabilizers, hindered amine stabilizers, phosphorus stabilizers, boric acid ester stabilizers, and alkoxy amine radical stabilizers, and specifically, among phenolic stabilizers and boric acid ester stabilizers It may include one or more selected stabilizers, but is not limited thereto.

As an example of the stabilizer, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, tri Octylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris(2-ethylhexoxy)borane, bis(1,4,7,10)-tetraoxa undecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri- m-tolyl borate, triethanolamine borate, tri-2-ethylhexyl borate, trimethylene borate, tris (trimethylsilyl) borate, tri-sec-butyl borate, tri-tert-butyl borate, methoxyethoxide boron, hydro quinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butyl hydroquinone, pyrogallol, p-benzoquinone, 2,5-di-t-butyl-p-benzoquinone, It may be picric acid, tri-p-nitrophenyl methyl, butylated hydroxytoluene, cyclohexanone oxime cresol, guayacol, o-isopropyl phenol, etc. Specifically, trimethyl borate, triethyl borate, tri-n-propyl borate , triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, but may be any one or more selected from, but is not limited thereto.

For example, the amount of the stabilizer is not particularly limited, but may be included in an amount of 0.05 to 1% by weight, or 0.1 to 0.5% by weight, or 0.1 to 0.3% by weight based on the total weight of the dual curing type epoxy adhesive composition.

The dual curing type epoxy adhesive composition according to an embodiment of the present invention may be a one-component type. Accordingly, it is possible to stably form a primary cured product by photocuring, which is the first step, and form a cured product having improved adhesive strength by thermal curing, which is the second step. Furthermore, according to the present invention, it is possible to provide a cured product with improved adhesion reliability, especially reliability even under a high temperature and high humidity environment, and may not exhibit a decrease in adhesion strength.

For example, the light curing may be performed by irradiating light such as infrared light, visible light, ultraviolet light, electron beam, etc. having a wavelength of 800 nm or more, and the light is 100 to 2,000 mW/cm 2 , or 300 to 1,500 mW/cm 2 , or 500 to 1,500 mW/cm 2 , or In the range of 1,000 mW/cm 2 , it may be performed for 1 to 30 seconds, or for 1 to 10 seconds, or for 3 to 5 seconds. Or it may be performed under irradiation conditions of 2.0 to 10.0 J/cm 2 , preferably 2.0 to 4.0 J/cm 2 , more preferably 2.0 to 2.5 J/cm 2 .

For example, the light irradiation unit 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 SPOT type UV irradiator , a xenon lamp or a DEEP UV lamp, but is not limited thereto.

For example, the light may be ultraviolet light, and the peak wavelength of the ultraviolet light may be specifically in the range of 300 to 500 nm.

For example, the thermal curing may be performed at a temperature of 70 to 120 °C, preferably at 80 to 100 °C, and more preferably at 80 to 90 °C.

In addition, the present invention provides a cured product of the dual curing type epoxy adhesive composition according to the present invention. Specifically, the cured product through double curing may realize an adhesive strength of 120 kgf or more, specifically in the range of 120 to 200 kgf.

In addition, as well as such excellent adhesive strength, excellent moisture resistance can be exhibited even under high temperature and high humidity conditions of 85 ° C. or higher and 85% RH or higher. Thus, the cured product according to an embodiment of the present invention can be usefully used as an adhesive, a sealant, a coating agent, and the like. Specifically, it can be usefully applied as an adhesive layer between constituent members such as camera modules that require high adhesive strength and water resistance per unit area, and can be used for structural purposes in assembling vehicles such as automobiles, aircrafts, ships, etc. as well as structures such as civil engineering buildings. Of course, it can also be used as an adhesive. It can be used in various industries throughout the industry by realizing excellent adhesion performance between the same or different materials such as metal and metal, metal and glass, and metal and carbon fiber.

In addition, the present invention provides a structure comprising the cured product. Specifically, 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 include the hard adhesive layer. It can be cargo.

For example, the first adherend and the second adherend may be members 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 high-quality structure may be formed by partially or entirely adhered to each other with high adhesive strength by the above-described adhesive layer. .

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

For example, the structure may include a camera module mounted on a mobile device such as a smartphone; Alternatively, it may be a vehicle camera module.

The present invention will be described in more detail through the following examples. However, the following examples are only one reference for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms. Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, terms used in description in the present invention are only for effectively describing specific embodiments, and are not intended to limit the present invention.

[Preparation Examples 1 to 3] Preparation of cyanate ester-multifunctional acrylate compounds

After dissolving monohydroxy-polyfunctional acrylate compound 2 (1.0 mmol) and cyanogen bromide (CNBr) (1.0 mmol) in methyl ethyl ketone, triethylamine (1.0 mmol) was added and stirred for 3 hours. After that, in order to remove the remaining organic matter of the product, it was extracted using water and 100ml of EA (Ethyl Acetate), washed three times with water (10ml), and the remaining organic layer was removed under reduced pressure to obtain cyanate ester-acrylate. compound was obtained. The structure of the prepared cyanate ester-acrylate compound was identified through ¹ H NMR and FT-IR.

The monohydroxy-polyfunctional acrylate compound 2 used and the structures of the prepared cyanate ester-multifunctional acrylate compound 1 are shown in Table 1 below.

[Table 1]

[Comparative Preparation Examples 1 to 4] Preparation of cyanate ester-acrylate compound

A cyanate ester-acrylate compound was prepared by reacting in the same manner as in Preparation Examples 1 to 3, except that the hydroxy acrylate compound shown in Table 2 was used as a starting material. The structure of the prepared cyanate ester-acrylate compound was identified through ¹ H NMR.

[Table 2]

[Examples 1 to 6 and Comparative Examples 1 to 9] Preparation of dual curing type epoxy adhesive composition

After mixing at room temperature (25 ℃) with the composition shown in Table 3, and then stirred using a paste mixer to prepare a dual curing type epoxy adhesive composition, respectively. The content unit of each component is weight% (wt%).

[Table 3]

[Assessment Methods]

Room temperature stability evaluation

The dual curing type epoxy adhesive compositions of Examples and Comparative Examples were filled in a syringe capable of blocking UV, and DSC calorific value and viscosity analysis were performed at the beginning and after 1, 6, 12, 24, 48, and 72 hours at room temperature (25 ° C.). Room temperature stability evaluation using DSC analysis means the time point (time) at which the heating value reduction rate compared to the initial heating value (HV0) exceeds 10%. Room temperature stability evaluation using viscosity analysis means the time point (time) exceeding 25% compared to the initial viscosity of each composition using the HBDV2T viscometer (SC4-14 spindle). In addition, the evaluation results were evaluated at the time of analysis when both calorific value and viscosity criteria were satisfied as the final mountain stability time.

Specimen fabrication and adhesion measurement

After dispensing the dual curing type epoxy adhesive compositions of Examples and Comparative Examples on the aluminum lower interface in the form of an inner diameter of 17.3 mm and an outer diameter of 19.1 mm, a cell was prepared by bonding to the upper interface (see Table 4 below). At this time, the gap between the lower part and the upper part was set to 300 μm, and the applied dual curing type epoxy adhesive composition was maintained at a level of 85-90 μm. Thereafter, the manufactured cell was cured through the following curing conditions or reliability conditions.

Then, the adhesive strength of each cured cell was measured using UTM. At this time, the tensile speed was set to 30 mm/min.

(curing conditions)

UV light of 365 nm wavelength was applied to the cell by using four light sources (1,000 mW, 5 s) while maintaining a distance of 25 mm between the dual curing type epoxy adhesive composition and the light source in the horizontal direction of the cell. Second curing was performed by heating in a heat circulation oven for 30 minutes. After leaving the second cured specimen at room temperature for 24 hours, the adhesive force was measured.

(reliability condition)

After the above curing conditions were completed, the specimen was exposed to an environment maintained at 85 ° C and 85% RH for 250 hours using a constant temperature / humidity machine, and then left at room temperature for 24 hours, and then the adhesive force was measured.

[Table 4]

[Evaluation results]

The physical property results through the evaluation method are shown in Table 5 below.

[Table 5]

As shown in Table 5, the dual curing type epoxy adhesive composition according to the present invention exhibited an adhesive strength of 9 kgf or more after UV curing, and a very good adhesive strength of 120 kgf or more after both UV/heat curing. That is, after UV/thermal curing, both the cyanate functional group of the cyanate ester-multifunctional acrylate and the epoxy functional group of the epoxy resin were crosslinked by the amine-based thermal curing agent, thereby realizing very high adhesive strength. In addition, even when polyamine-based as well as imidazole-based thermal curing agents were used as amine-based thermal curing agents, excellent adhesive strength was still achieved. In particular, when a mixture of polyamine-based C-1 and imidazole-based thermal curing agents of C-2 was used, significantly improved adhesive strength. and reliability were implemented. In addition, the dual curing type epoxy adhesive composition according to the present invention not only exhibits excellent adhesive strength even under reliability conditions, but also has further increased adhesive strength due to additional curing under 85/85 reliability conditions. That is, the cured product according to the present invention not only has excellent moisture resistance because the adhesive strength is not reduced under the conditions of constant temperature / constant humidity (85 ℃), but also has further improved adhesive strength due to additional curing. The adhesive composition exhibited excellent storage stability at room temperature as little change in viscosity before/after storage was observed despite the absence of a stabilizer.

From these results, according to the present invention, crosslinking between the photocuring composition and the heat curing composition through UV/thermal curing, that is, the cyanate functional group of the photocuring composition and the epoxy functional group of the thermal curing composition through UV/thermal curing are amine-based thermal It was confirmed that a cured product having excellent moisture resistance as well as implementing a remarkably improved level of high adhesive strength while being crosslinked by the curing agent could be provided. Further, according to the present invention, curing deformation due to curing shrinkage was not caused. In addition, according to the present invention, not only room temperature storage stability, but also freezer storage stability under -20 ° C. or less was excellent.

On the other hand, Comparative Examples 1 to 4 use cyanate ester-monoacrylate having only one acrylate functional group instead of the cyanate ester-multifunctional acrylate of the present invention, and Comparative Example 5 uses cyanate ester monoacrylate. Functional acrylates are used, and Comparative Examples 6 to 9 are mixtures of cyanate ester-monoacrylates and multifunctional acrylates, and all have low adhesive strength after UV/heat curing, as well as adhesive strength under 85/85 reliability conditions This was reduced or implemented with a marginal rise.

Specifically, Comparative Examples 1 to 4 all exhibited an adhesive strength of 1 kgf after UV curing. That is, in Comparative Examples 1 to 4, the curing density after UV curing was too low, and the adhesive strength was not developed at all, and since sufficient curing density was not obtained in the UV curing process, the adhesive strength of 85 kgf or less even after thermal curing, still sufficient. Adhesion was not realized. In addition, a decrease in adhesion was observed even after the 85/85 reliability condition. Comparative Example 5 realized the lowest adhesive strength (58 kgf) after UV/heat curing, and hardly developed adhesive strength even after 85/85 reliability conditions. This low adhesive strength is due to the curing of the acrylate functional group to polyacrylate during UV curing, and the curing of the amine-based thermal curing agent and the epoxy functional group during thermal curing, so that the materials produced in each curing step do not bond to each other and exist in a mixed state. Because of the following, it can be seen that crosslinking between the photocuring composition and the heat curing composition in Comparative Example 5 did not occur or sufficient crosslinking was not achieved. In Comparative Examples 6 to 9, UV curing adhesive strength was expressed, but the adhesive strength was lowered after UV/heat curing, and an increase in adhesive strength was observed after 85/85 reliability, but the degree was insignificant.

Therefore, the dual curing type epoxy adhesive composition according to the present invention is sufficient crosslinking between the light curing composition and the heat curing composition through light/thermal double curing due to the light curing composition including the cyanate ester-multifunctional acrylate compound, that is, light curing After that, the remaining cyanate functional group reacts with the amine-based thermosetting agent during thermal curing to combine the photocurable matrix and the thermosetting matrix to realize significantly improved adhesive strength and to provide a highly reliable cured product with improved moisture resistance. can With the implementation of such physical properties, it is expected that it can be usefully applied as an adhesive layer between constituent members such as camera modules that require high adhesive strength and moisture resistance per unit area.

As described above, the present invention has been described by specific details, limited examples and comparative examples, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (12)

a photocurable component comprising a cyanate ester-multifunctional acrylate compound having at least three acrylate groups and one cyanate group in one molecule and a photoinitiator; and
A dual curing type epoxy adhesive composition comprising a heat curable component including an epoxy-containing compound and a heat curing agent. According to claim 1,
Wherein the cyanate ester-multifunctional acrylate compound is represented by Formula 1 below, a dual curing type epoxy adhesive composition.
[Formula 1]

In Formula 1,
L ¹ , L ² and L ³ are each independently a single bond;

or

ego;
L ^A , L ^B and L ^C are C1-C20 alkylene;
a is an integer from 1 to 10;
b and c are each independently an integer from 0 to 10;
wave(

) represents a site connected to an oxygen atom;
asterisk(

) represents a site connected to a carbon atom. According to claim 2,
Wherein L ¹ , L ² and L ³ are a single bond or

is; L ^A is C1-C5 alkylene; a is an integer from 1 to 5, a dual curing type epoxy adhesive composition. According to claim 2,
At least one of L ¹ , L ² and L ³

And the remainder is a single bond or

, and L ^A , L ^B and L ^C are C1-C5 alkylene; a is an integer from 1 to 5; b and c are each independently an integer of 0 to 5, a dual curing type epoxy adhesive composition. According to claim 1,
The epoxy-containing compound is a novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenolaralkyl type epoxy resin, halogenated epoxy Resin, alicyclic epoxy resin, rubber-modified epoxy resin, aliphatic polyglycidyl type epoxy resin, glycidyl amine type epoxy resin, polyglycol epoxy resin, and cardanol epoxy resin, which is one or a mixture of two or more, a dual curing type epoxy adhesive composition. According to claim 1,
The heat curing agent is a latent heat curing agent, a dual curing type epoxy adhesive composition. According to claim 6,
The heat curing agent is one or a mixture of two or more selected from an imidazole type heat curing agent, a dihydrazide type heat curing agent and a polyamine type heat curing agent, a dual curing type epoxy adhesive composition. According to claim 1,
An inorganic filler, an adhesion promoter, a retardant and a stabilizer that further comprises one or two or more selected from, the dual curing type epoxy adhesive composition. According to claim 8,
The inorganic filler is fumed 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, fused silica , Quartz powder, sericite, talc clay, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia, and one or a mixture of two or more selected from ferrite, dual curing type epoxy adhesive composition. According to claim 8,
The adhesion promoter is one or two or more selected from epoxy-containing silane, amine-containing silane and mercapto-containing silane, dual curing type epoxy adhesive composition. A cured product of the dual curing type epoxy adhesive composition according to claim 1. A camera module attached by the dual curing type epoxy adhesive composition according to claim 1.