KR20240056091A - Novel Acrylic Compound and Composition of Low Dielectric Coating Solution Containing the Same - Google Patents

Abstract

The present invention relates to an acrylic compound containing both an aromatic substituent and an aliphatic substituent and a coating composition containing the same. More specifically, it has a low dielectric constant and has strong resistance to plasma used in the OLED device encapsulation process. It relates to a coating liquid composition that can provide an organic coating film that has a low cure shrinkage rate.

Description

Novel Acrylic Compound and Composition of Low Dielectric Coating Solution Containing the Same}

The present invention relates to a novel aliphatic acrylic monomer and a low-dielectric coating liquid composition containing the same. More specifically, it has a low dielectric constant, has strong resistance to plasma used in the OLED device encapsulation process, and has a low cure shrinkage rate. It relates to a coating liquid composition that can provide an organic coating film representing.

Acrylates or methacrylates are useful monomer components that are polymerized alone or copolymerized with other monomers to provide polymers with excellent performance. Polymers manufactured using them are generally characterized by excellent weather resistance and transparency. Depending on the type of ester substituent, polymers with various performances can be produced, and in particular, they can be applied as coating compositions for sealing or display purposes.

However, in the case of (meth)acrylate monomers with an alicyclic hydrocarbon skeleton previously proposed for coating solutions for touch panels, TFT-LCDs, or organic light emitting devices (OLEDs) according to the prior art, their use in the process is limited due to their low boiling point. In addition, it has a limitation of having a relatively high curing shrinkage rate, low touch sensitivity, and insufficient physical properties of the manufactured coating film. In addition, even if these conditions are relatively satisfied, multifunctional monomer monomers are needed to produce thinner displays and improve TSP sensitivity. There is a need to lower the dielectric constant.

As a prior art regarding such a coating composition for sealing or display purposes, Korean Patent Publication No. 10-2016-0030077 (2016.03.16) describes a resin composition for sealing organic EL devices and its cured product. In Korea Patent Publication No. 10-2019-0065896 (2019.06.26), the relevant technology is described in the composition for encapsulating organic light-emitting devices and the organic light-emitting device display device manufactured therefrom, and in Korean Patent Publication No. 10- No. 2016-0053751 (2016.05.13) presents technology regarding a composition for display sealing material, an organic protective layer containing the same, and a display device containing the same.

However, despite the prior art including the above prior art, as a coating composition for sealing or display purposes, it is suitable for the process of forming a resin layer on a continuously running substrate and has a low dielectric constant, Since it has high dry etching resistance, it is possible to suppress plasma damage during the encapsulation process of the coating composition, and the need to develop a new coating composition that can improve the process reliability of the coating film during the coating process or curing is continuously required. there is.

Korean Patent Publication No. 10-2016-0030077 (2016.03.16) Korean Patent Publication No. 10-2019-0065896 (2019.06.26) Korean Patent Publication No. 10-2016-0053751 (2016.05.13)

In order to solve the problems caused by the prior art described above, the present invention has a low dielectric constant and is excellent in adhesion, curability, and processability, and in particular, the insulating layer between the two electrodes of the touch panel, OCR (Optically Clear Resin) , overcoat, a novel acrylic that has strong resistance to plasma used in the OLED device encapsulation process, has a low dielectric constant, and exhibits low curing shrinkage, thereby ensuring process reliability of the coating film during the coating process or curing. The purpose of the invention is to provide a rate monomer and a coating liquid composition containing the same, and in particular, a coating liquid suitable for the process of forming a resin layer on a continuously running substrate for use such as an organic light emitting device (OLED) encapsulation process. The purpose of the invention is to provide a novel acrylate monomer for a composition and a coating solution containing the same.

In order to solve the above problems, the present invention provides a cured product obtained by photo-curing or heat-curing a coating liquid composition containing a monofunctional acrylic compound (A) represented by the following [Chemical Formula 1], which has low dielectric constant and shrinkage, high plasma resistance and adhesion. It was discovered that it was possible to implement and at the same time solve the problems of the prior art described above, leading to the present invention.

More specifically, the present invention provides an acrylic compound simultaneously containing an aromatic substituent and an aliphatic substituent, represented by the following [Chemical Formula 1].

[Formula 1]

In [Formula 1] above,

R ₁ is any one selected from hydrogen, deuterium, and a substituted or unsubstituted C1 to C10 alkyl group,

The X is any one selected from oxygen (O), sulfur (S), or -NR'-,

R' and R2 are each the same or different, and are independently hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C1~C30 halogenated alkyl group, or a substituted or unsubstituted C6~ Any one selected from a C24 aryl group, a C4 to C24 heteroaryl group that is substituted or unsubstituted and contains 1 to 2 O, N or S as heteroatoms,

R3 is any one selected from a substituted or unsubstituted C6~C30 alkyl group and a substituted or unsubstituted C6~C30 halogenated alkyl group,

Ar1 is any one selected from a substituted or unsubstituted C6 to C24 aryl group and a substituted or unsubstituted C4 to C24 heteroaryl group containing 1 to 2 heteroatoms O, N or S,

In Formula 1, 'substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C2-C10 alkenyl group, C2-C10 alkynyl group, C1-C10 heteroalkyl group, C6-C18 aryl group, C7-C19 arylalkyl group, C7-C19 alkylaryl group, C1-C10 alkoxy group, Any selected from the group consisting of C1-C10 alkylthionyl group, C1-C10 alkylamino group, C6-C18 arylamino group, C1-C10 alkylsilyl group, C6-C12 arylsilyl group, and C6-C12 aryloxy group. It means being substituted with one substituent.

In addition, the present invention relates to 1 to 80% by weight of the acrylic compound (A); 19 to 80% by weight of a multifunctional acrylic compound (B) polymerizable with the acrylic compound (A); and 0.1 to 20% by weight of a polymerization initiator (D).

In addition, the present invention provides a photo-cured or thermo-cured organic coating film, which is manufactured by thermally or photo-curing the coating liquid composition.

The acrylic compound (A) according to the present invention simultaneously contains a polymerizable substituent such as a (meth)acrylic group, an aliphatic substituent, and an aromatic substituent in one molecule, and includes an aliphatic substituent and an aromatic substituent with a large molecular weight on one carbon atom in the molecule. By having a structure in which electrons are substituted at the same time, electrons are distributed evenly, resulting in low polarity and low dielectric constant. At the same time, it has excellent plasma resistance and can minimize outgassing during the coating process. In particular, the curing shrinkage rate is low, making it possible for LCD A coating liquid composition for OLED displays can be provided.

In addition, the acrylic compound (A) according to the present invention simultaneously contains an aliphatic substituent and an aromatic substituent with a large molecular weight, thereby showing a high boiling point and low vaporization amount compared to the molecular weight, which causes problems in process stability and causes contamination. There is less outgassing that causes problems such as shortening the lifespan of organic light-emitting devices (OLEDs), etc., and the process reliability of the coating film can be secured during the coating process or curing.

In addition, the coating liquid composition containing the acrylic compound (A) and the polymerizable multifunctional acrylic compound (B) according to the present invention has excellent adhesion, especially to inorganic layers, and has a low cure shrinkage rate, making it suitable for use on flexible substrates. It is easy to apply to flexible or foldable displays.

Specific examples of this application will be described in more detail. However, the content described in this application is provided to convey the idea of this application, and the content of this application is not limited thereto.

The present invention provides an acrylic compound simultaneously containing an aromatic substituent and an aliphatic substituent, represented by the following [Chemical Formula 1].

[Formula 1]

In [Formula 1] above,

R ₁ is any one selected from hydrogen, deuterium, and a substituted or unsubstituted C1 to C10 alkyl group,

The X is any one selected from oxygen (O), sulfur (S), or -NR'-,

R' and R ₂ are each the same or different, and are independently hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C1~C30 halogenated alkyl group, or a substituted or unsubstituted C6. Any one selected from ~C24 aryl group, substituted or unsubstituted C4~C24 heteroaryl group containing 1 to 2 O, N or S as heteroatoms,

R ₃ is any one selected from a substituted or unsubstituted C6~C30 alkyl group and a substituted or unsubstituted C6~C30 halogenated alkyl group,

Ar ₁ is any one selected from a substituted or unsubstituted C6 to C24 aryl group and a substituted or unsubstituted C4 to C24 heteroaryl group containing 1 to 2 heteroatoms O, N or S,

In Formula 1, 'substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C2-C10 alkene. Nyl group, C2-C10 alkynyl group, C1-C10 heteroalkyl group, C6-C18 aryl group, C7-C19 arylalkyl group, C7-C19 alkylaryl group, C1-C10 alkoxy group, C1-C10 alkyl group Substituted with any one substituent selected from the group consisting of oneyl group, C1-C10 alkylamino group, C6-C18 arylamino group, C1-C10 alkylsilyl group, C6-C18 arylsilyl group, and C6-C12 aryloxy group. It means becoming.

Meanwhile, considering the range of the alkyl group or aryl group in the “substituted or unsubstituted C ₁ -C ₂₀ alkyl group” and “substituted or unsubstituted C ₆ -C ₅₀ aryl group” in the present invention, , the range of the carbon number of the C ₁ -C ₂₀ alkyl group and the C ₆ -C ₅₀ aryl group is the entire alkyl portion or aryl portion when viewed as unsubstituted without considering the portion on which the substituent is substituted. It means carbon number. For example, a phenyl group substituted with a butyl group at the para position should be viewed as corresponding to an aryl group at C ₆ substituted with a butyl group at C ₄ .

The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and contains a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, Additionally, if the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

Specific examples of the aryl group include phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, terphenyl group (preferably o-terphenyl group, m-terphenyl group, p-terphenyl group), naphthyl group, and aromatic groups such as toryl group, phenanthryl group, pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., and one or more of the aryl groups above. The hydrogen atom is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH2, -NH(R), -N(R')(R''), R' and R" are each other. Independently an alkyl group of C ₁ -C ₁₀ , in this case referred to as “alkylamino group”), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group of C ₁ -C ₂₄ , C ₁ -C ₂₄ halogenated alkyl group, C ₂ -C ₂₄ alkenyl group, C ₂ -C ₂₄ alkynyl group, C ₁ -C ₂₄ heteroalkyl group, C ₆ -C ₂₄ aryl group, C ₇ -C ₂₄ arylalkyl group , may be substituted with a C ₂ -C ₂₄ heteroaryl group or a C ₂ -C ₂₄ heteroarylalkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, contains 1, 2, or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, and Te in the aryl group, and the remaining ring atom is carbon. It refers to an aromatic system with 2 to 50 rings, preferably 2 to 24 rings, and the rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group may be replaced with the same substituent as that of the aryl group.

In addition, the alkyl group, which is a substituent used in the present invention, is a substituent in which one hydrogen is removed from an alkane, and includes all of a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group, and a mixture of the linear alkyl group and the cyclic alkyl group. alkyl group; and an alkyl group that is a mixture of a branched alkyl group and a cyclic alkyl group; specific examples thereof include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso- Amyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopentyl, ethylcyclohexyl, adamantyl, dicyclopentadienyl, decahydronaphthyl, norbornyl, Bornyl, isobornyl, etc. may be mentioned, and at least one hydrogen atom of the alkyl group may be replaced with the same substituent as that of the aryl group.

The alkoxy group, which is a substituent used in the compound of the present invention, is a substituent in which an oxygen atom is bonded to the last carbon position of an alkane, and includes cases where an oxygen atom is bonded to a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group, respectively. In addition, when oxygen atoms are each bonded to the alkyl group that is a mixture of the linear alkyl group and the cyclic alkyl group; and a case where an oxygen atom is bonded to an alkyl group that is a mixture of a branched alkyl group and a cyclic alkyl group; specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, and sec-butyloxy. , pentyloxy, iso-amyloxy, hexyloxy, adamantaneoxy, dicyclopentaneoxy, bornyloxy, etc., and at least one hydrogen atom of the alkoxy group is the same as the substituent as in the case of the aryl group. Substitution is possible.

Specific examples of the arylalkyl group as a substituent used in the compound of the present invention include phenylmethyl (benzyl), phenylethyl, phenylpropyl, naphthylmethyl, and naphthylethyl, and at least one hydrogen atom of the arylalkyl group is as described above. It can be substituted with the same substituent as in the case of an aryl group.

Specific examples of the alkylaryl group as a substituent used in the compound of the present invention include ethylphenyl, propylphenyl, methylnaphthyl, and ethylnaphthyl, and at least one hydrogen atom of the alkylaryl group is in the case of the aryl group. It can be substituted with the same substituent.

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, and methylcyclobutylsilyl. , dimethylfurylsilyl, etc., and one or more hydrogen atoms of the silyl group may be replaced with the same substituent as that of the aryl group.

In addition, in the present invention, an alkenyl group refers to an alkyl substituent containing one carbon-carbon double bond made up of two carbon atoms, and an alkynyl group means one made up of two carbon atoms. It refers to a substituent containing a carbon-carbon triple bond.

In addition, the alkylene group used in the present invention is an organic radical derived by removing two hydrogens in an alkane molecule, which is a straight-chain or branched saturated hydrocarbon. Specific examples of the alkylene group include methylene group. , ethylene group, propylene group, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, iso-amylene group, hexylene group, etc., and hydrogen at least one of the alkylene groups Atoms can be substituted with the same substituents as in the case of the aryl group above.

In addition, “(meth)acryl” in the (meth)acrylic group, (meth)acrylate, (meth)acrylamide, etc. used in the present invention means “acryl and/or methacryl”. .

Meanwhile, more preferable examples of 'substitution' in 'substituted or unsubstituted' in [Formula 1] include deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-C6 alkyl group, C1-C6 Halogenated alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C1-C6 heteroalkyl group, C6-C12 aryl group, C7-C14 arylalkyl group, C7-C14 alkylaryl group, C1- C6 alkoxy group, C1-C6 alkylthionyl group, C1-C6 alkylamino group, C6-C12 arylamino group, C1-C10 alkylsilyl group, C6-C18 arylsilyl group, C6-C12 aryloxy group. It may mean being substituted with any one substituent selected from the group consisting of

On the other hand, the acrylic compound represented by [Formula 1] according to the present invention has Ar1, an aromatic substituent, bonded to the carbon atom connected to Its technical feature is that R3, which is a chain with 7 or more carbon atoms, is bonded, and through this, it can make the distribution of electrons evenly spread, has a lower dielectric constant than the monomer compound according to the prior art, and has high dry etching resistance. Therefore, plasma damage during the encapsulation process of the coating composition can be suppressed and the reliability of the thin film display device can be improved.

In other words, the 'monofunctional' acrylate compound used as a conventional coating liquid composition has advantages such as low moisture adsorption, low dielectric constant, and excellent adhesion due to the small number of functional groups, whereas the monofunctional acrylate compound in the coating composition has advantages such as low dielectric constant and excellent adhesion. When the specific gravity of the functional acrylate compound increases, problems such as haze occurring in the CVD process stage during inorganic coating occur.

Therefore, from this point of view, the present invention is a monomer compound that can be used in a coating composition, which contains an aliphatic hydrocarbon with a chain length to a certain extent (for example, at least 6) to the carbon atom connected to the The molecular structure is designed to introduce R ₃ , a substituent (chain having at least 7 carbon atoms, preferably at least 7 carbon atoms), and has a low dielectric constant when used as a coating composition compared to existing bifunctional compounds, and has high dry etching properties. It is possible to provide an acrylic compound that can exhibit resistance and has properties that can suppress plasma damage in the encapsulation process of OLED, etc.

That is, the acrylic compound represented by [Formula 1] according to the present invention has a substituent R ₃ It may be a substituent containing at least 6 carbon atoms, and preferably may be a substituent containing 7 or more carbon atoms. As a specific example of the substituent R ₃ , it is a substituted or unsubstituted alkyl group of C6 to C30 and a substituted Alternatively, it may be any one substituent selected from unsubstituted C6~C30 halogenated alkyl groups.

On the other hand, when the number of carbon atoms of the substituent R ₃ is less than 6, the dielectric constant tends to increase and hardening due to the low molecular weight due to the short chain, and adhesive strength may be greatly reduced. Therefore, in order to obtain the desired dielectric constant, the present invention can solve the above problem when the substituent of the R ₃ structure has at least 6 or more carbon chains, preferably 7 or more carbon chains, but has a carbon chain that is too long. In this case, the dielectric constant may be lowered due to an increase in molecular weight, and problems may occur in the CVD process stage due to relative thermal instability, so it must have an appropriate length of 30 or less, preferably 24 or less, and more preferably 20 or less. do.

In addition, as a specific example of the substituent Ar ₁ bonded to the carbon atom bonded to It may be any one substituent selected from C4 to C24 heteroaryl groups containing 1 to 2 O, N, or S.

Therefore, the acrylic compound represented by [Formula 1] can improve dielectric constant and thermal stability by increasing the molecular weight through the introduction of the substituents R ₃ and Ar ₁ , has low polarity due to even distribution of electrons, and has a low polarity compared to the conventional It can exhibit a lower dielectric constant than a difunctional monomer compound containing a (meth)acrylic group according to the technology.

As an example according to the present invention, the substituent R ₁ may preferably be any one selected from hydrogen, deuterium, or an unsubstituted alkyl group of C1 to C5.

In addition, as an embodiment of the present invention, the substituents R' and R ₂ are preferably the same or different from each other, and _are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10. It may be any one selected from an alkyl group, a substituted or unsubstituted C6 to C18 aryl group, and more preferably hydrogen or deuterium.

In addition, the substituent R ₃ according to the present invention may be a substituted or unsubstituted C7 to C20 alkyl group.

Additionally, as a specific example of the linking group X according to the present invention, it may be oxygen (O).

Additionally, as a specific example of the substituent Ar1 according to the present invention, it may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

Meanwhile, as a specific example of the acrylic compound represented by Formula 1 according to the present invention, it may be any one selected from Compound 1 to Compound 46 below, but is not limited thereto.

<Compound 1> <Compound 2> <Compound 3>

<Compound 4> <Compound 5> <Compound 6>

<Compound 7> <Compound 8> <Compound 9>

<Compound 10> <Compound 11> <Compound 12>

<Compound 13> <Compound 14> <Compound 15>

<Compound 16> <Compound 17> <Compound 18>

<Compound 19> <Compound 20> <Compound 21>

<Compound 22> <Compound 23> <Compound 24>

<Compound 25> <Compound 26> <Compound 27>

<Compound 28> <Compound 29> <Compound 30>

<Compound 31> <Compound 32> <Compound 33>

<Compound 34> <Compound 35> <Compound 36>

<Compound 37> <Compound 38> <Compound 39>

<Compound 40> <Compound 41> <Compound 42>

<Compound 43> <Compound 44> <Compound 45>

<Compound 46>

In addition, the present invention provides a coating liquid composition containing an acrylic compound (containing both an aromatic substituent and an aliphatic substituent) represented by the above [Formula 1].

Here, as a specific example of the coating liquid composition, it includes 1 to 80% by weight (wt) of the acrylic compound (A) represented by [Formula 1]; 19 to 80% by weight (wt) of a multifunctional acrylic monomer compound (B) polymerizable with the acrylic compound (A); And it may include 0.1 to 20 weight (wt)% of a polymerization initiator (D).

Meanwhile, the component of the acrylic compound (A) having a specific structure represented by [Formula 1] in the coating liquid composition according to the present invention is one type represented by [Formula 1], or 2 represented by [Formula 1]. It refers to a mixture containing a mixture of more than one type of compound. That is, in the specification of the present invention, the acrylic compound (A) represented by [Formula 1] '1 to 80 wt%' refers to 'an acrylic compound represented by [Formula 1] or a plurality of acrylics represented by [Formula 1]. This means that the 'mixed component of compounds' is '1 to 80 wt%', preferably the acrylic compound represented by [Formula 1] alone or the mixed component of 2 to 5 types of acrylic compounds represented by [Formula 1]. It can be used, and this is interpreted similarly to the components of the 'multifunctional acrylic compound (B)' described in detail below.

Here, the multifunctional acrylic compound (B) is a compound containing two or more polymerizable acrylic or methacrylic groups in the molecule, and has the effect of increasing the crosslinking speed of the final film produced and improving the hardness and toughness of the film. can increase.

Therefore, when the multifunctional acrylic compound (B) is included in an appropriate ratio in the coating liquid composition according to the present invention, the photocuring rate of the coating liquid composition can be increased, and the reliability of the resulting film can be increased to reduce the risk that may occur during inorganic layer coating. It is particularly useful for flexible substrates because it can prevent the haze phenomenon, and can be used as a coating liquid composition for organic thin film displays.

Here, in the coating liquid composition, the multifunctional acrylic compound (B) polymerizable with the acrylic compound (A) is composed of two or more acrylic groups that can be polymerized with the acrylic compound (A) to form a polymer or oligomer. Alternatively, any compound having a methacrylic group can be used without limitation in type.

In the present invention, a more preferable structure of the polymerizable multifunctional acrylic compound (B) is di(meth)acrylate having two (meth)acrylic groups, polyfunctional having three or more (meth)acrylic groups in the molecule ( It may be a monomer compound containing at least one selected from polyfunctional compounds such as meta)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and polyester (meth)acrylate.

More specifically, the multifunctional acrylic compound (B) is 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. , 1,10-decanediol di(meth)acrylate, 1,12-dodecane diol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,14-tetradecanediol diol ( A structure in which two (meth)acrylic groups are substituted for an alkanediol with a linear methylene structure, such as meta)acrylate, 1,16-hexadecanediol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. , polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Polyethylene glycol, structure in which two (meth)acrylic groups are substituted in polypropylene glycol, tricyclodecane dimethanol diacrylate, adaman (meth)acrylates with cyclic structures such as tan-1,2-dinyldiacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol (poly)ethoxytri(meth)acrylate, pentaerythritol (poly) Propoxytri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol(poly)ethoxytetra(meth)acrylate, pentaerythritol(poly)propoxytetra(meth)acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol (poly)caprolactone penta(meth)acrylate, dipentaerythritol (poly)ethoxypenta(meth)acrylate, dipentaerythritol (poly)propoxy penta(meth)acrylate , dipentaerythritol hexa(meth)acrylate, dipentaerythritol(poly)caprolactone hexa(meth)acrylate, dipentaerythritol(poly)ethoxyhexa(meth)acrylate, dipentaerythritol(poly)propoxyhexa(meth)acrylate (meth)acrylate, polypentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane(poly)ethoxytri(meth)acrylate, trimethylolpropane(poly)propoxytri (meth)acrylate, dimethylolpropane tetra(meth)acrylate, polyfunctional (meth)acrylate of polyhydric alcohol such as glycerol tri(meth)acrylate, acid such as 2,2,2-trisacryloxymethylsuccinic acid Polyfunctional (meth)acrylates having a silicone skeleton such as modified polyfunctional (meth)acrylate and silicon hexa(meth)acrylate can be mentioned.

Here, the content of the acrylic compound (A) represented by [Formula 1] of the present invention may include 1 to 80% by weight, preferably 10 to 74% by weight, based on the total composition. and, more preferably, may contain 13 to 70% by weight.

In addition, the content of the multifunctional acrylic compound (B) may include 19 to 80% by weight, preferably 25 to 80% by weight, and more preferably 28 to 80% by weight, based on the total composition. It may contain 80% by weight.

In addition, the film produced from the multifunctional acrylic compound (B) in the present invention has excellent adhesion to metal and low curing shrinkage, so that the composition containing the multifunctional acrylic compound (B) forms a reliable thin film. can do.

Additionally, when the coating liquid composition according to the present invention includes the multifunctional acrylic compound (B), it can be used alone or in a mixture of 2 to 5 types.

In addition, as an embodiment according to the present invention, the polymerizable component in the coating liquid composition may consist only of an acrylic compound (A) represented by Chemical Formula 1 and a multifunctional acrylic compound (B) polymerizable with the acrylic compound (A). there is.

In addition, the coating liquid composition according to the present invention includes an acrylic compound (A) represented by [Formula 1]; A multifunctional acrylic compound (B) polymerizable with the acrylic compound (A) represented by the above [Formula 1]; and polymerization initiator (D); As an additional monomer in the component, a monofunctional acrylic monomer (C) may be optionally included in an amount of 0 to 50% by weight based on 100% by weight of the coating liquid composition.

When the monofunctional acrylic monomer (C) in the present invention is additionally included in the coating liquid composition of the present invention, the physical properties of the coating liquid composition can be improved.

That is, the coating composition of the present invention takes into account the physical properties (viscosity, dielectric constant, adhesion, thermal stability) of the finally obtained resin composition, and includes an acrylic compound (A) represented by Formula 1; A multifunctional acrylic compound (B) polymerizable with the acrylic compound (A) represented by the above formula (1); In addition to the polymerization initiator (D), it may additionally include a monofunctional compound (C) used to control physical properties, and the content of the monofunctional compound (C) is 0 to 50, based on the entire composition. It may be in the range of weight% (wt%), preferably in the range of 1 to 40 weight% (wt%), and more preferably in the range of 2 to 30 weight% (wt%).

In addition, when the coating liquid composition according to the present invention additionally includes a monofunctional compound (C) used for controlling the physical properties, the monofunctional compound (C) polymerizes with the acrylic compound (A) and the acrylic compound (B). Any compound containing one acrylic group or methacrylic group capable of forming a polymer or oligomer can be used without limitation in type. In this case, the monofunctional compound (C) can be used alone or within the above range in the entire composition. 2 to 5 types can be mixed and used.

Here, more preferable examples of the monofunctional compound (C) used for controlling the physical properties include a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₄ to C ₂₅ cycloalkyl group, or a substituted or unsubstituted C 4 to C 25 alkyl group. Substituted C ₉ ~ C ₃₅ aliphatic polycyclic cycloalkyl group, substituted or unsubstituted C ₄ ~ C ₂₅ alkenyl group, substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, substituted or unsubstituted C ₇ ~ C ₅₀ It may be a monofunctional (meth)acrylic monomer containing at least one substituent selected from arylalkyl groups, preferably a (meth)acrylate containing an alkyl group having 1 to 30 carbon atoms, and a cycloalkyl group having 6 to 25 carbon atoms. meth)acrylate containing, (meth)acrylate containing an aliphatic polycyclic cycloalkyl group having 10 to 30 carbon atoms, (meth)acrylate containing an aryl group having 6 to 18 carbon atoms. It may be a monomer compound containing one or more selected from among, but is not limited to this.

Specific examples of the monofunctional monofunctional compound (C) used to control the physical properties include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl ( Meth)acrylate, octyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and hexadecyl (meth)acrylate. , isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclofentanyl (meth)acrylate, benzyl (meth)acrylate, phenoxybenzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate ) Acrylate, 2-ethoxyethyl (meth)acrylate, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxy 1 to 5 selected from cyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-ethyloxetane-3-methyl (meth)acrylate, and (meth)acrylamide monomer Compounds can be used.

Meanwhile, the coating liquid composition according to the present invention may optionally use an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain in order to control pattern characteristics and provide thin film properties such as heat resistance.

The acrylic polymer is a copolymer of monomers containing the monomers described below. Examples of the monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and hexadecyl (meth)acrylate, isobornyl (meth)acrylate ) Acrylate, damantyl (meth)acrylate, dicyclofentanyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Acrylic acid, methacrylic acid, styrene, acetoxystyrene, glycidyl acrylate, glycidyl methacrylate, itaconic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl fumarate, 3,4-epoxybutyl ( Meth)acrylate, 2,3-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-ethyloxetane-3-methyl(meth)acrylate, N-methyl Maleimide, N-butylmaleimide, N-phenylmaleimide, (meth)acrylamide, etc. can be mentioned, and these can be used individually or by polymerizing two or more types, where the content of the acrylic polymer is determined by the solvent. When containing, it is preferable to include 0 to 40% by weight based on 100% by weight of the coating liquid composition.

In addition, the coating liquid composition may additionally optionally include a polymerization initiator: or a photopolymerizable monomer. More specifically, the polymerization initiator (D) may be a photopolymerization initiator or a thermal initiator capable of performing a photocuring reaction. there is.

The content of the polymerization initiator (D) of the present invention is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.5 to 7% by weight, based on 100% by weight of the total amount of the coating liquid composition. You can use it.

The thermal polymerization initiator may be azo-based, peroxy-based, etc., and the photopolymerization initiator may be benzoin-based, triazine-based, acetophenone-based, benzophenone-based, anthraquinone-based, ketal-based, thioxanthone-based, benzophenone-based, Any one selected from the phosphine oxide type and the oxime type may be used alone, or two or more types may be mixed.

The thermal initiator may represent an organic peroxide or hydroperoxide, an azo compound, an oxidation-reduction compound, etc., and any one of these may be used alone, or two or more types may be mixed. Additionally, a photopolymerization initiator and a thermal initiator can be mixed and used.

Here, specific examples of the polymerization initiator (D) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 -one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, oligo[2-hydride Acetophenones such as oxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; Thioxanthone such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones, such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; Phosphorus such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide. Examples include pinoxides, and one or more initiators selected from the above polymerization initiators may be used alone or in a mixture of two or more, but are not limited to the above polymerization initiators.

On the other hand, this coating liquid composition can be formed as a solvent-free type that does not contain a solvent, and when the coating liquid composition is a solvent-free type, the content (wt%) of the components of each composition is the acrylic compound (A) represented by the formula (1) ), the content of each component will be set as weight percent based on the total weight of the composition according to the total of the acrylic compound (A), the polymerizable multifunctional acrylic compound (B), the polymerization initiator (D), and the total of components that may be additionally included. You can.

Additionally, the coating composition of the present invention can be prepared by mixing and dissolving each component. For example, inject each ingredient into a round bottom flask equipped with a stirring device and a thermometer and stir for 0.5 to 6 hours in a vacuum at 20 to 80 ℃, preferably 40 to 80 ℃ to remove moisture and unnecessary solvents. A pure composition can be obtained.

In addition, the coating liquid composition according to the present invention can be manufactured as a composition containing a solvent when the viscosity is high, and when the organic light emitting device composition contains a solvent, the content (% by weight) of the components of the coating liquid composition is expressed in the formula 1 An acrylic compound (A) represented by, a multifunctional monomer compound (B) polymerizable with the acrylic compound (A), and a polymerization initiator (D), wherein the content of the solvent is the acrylic compound (A) represented by Formula 1. ), the multifunctional acrylic compound (B) polymerizable with the compound (A), the polymerization initiator (D), and the additional monomer component (C) are not taken into account when calculating the content. That is, when calculating each content in the coating liquid composition according to the present invention, the content of the solvent is not reflected based on the entire composition, but is based on the total composition based on the total weight of the composition according to the sum of the remaining components. .

Meanwhile, when using a solvent in the present invention, not only can the viscosity of the coating composition be adjusted, but also excellent coating properties and a transparent thin film can be obtained, and it is generally preferable to use an organic solvent.

The organic solvent is preferably ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, and propylene glycol. Methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexamethylene Rice paddy, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, Daigle Diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, One or more types selected from toluene, xylene, hexane, heptane, and octane may be used, where the content of the solvent is preferably 5 to 70% by weight based on 100% by weight (including solvent) of the coating liquid composition.

As a method for depositing the coating liquid composition of the present invention on a substrate, an inkjet method, roll coat method, spin coat method, die coat method, vapor deposition method, etc. may be used.

In addition, in the means for performing the step of curing the deposited coating composition, the light source for curing includes electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, there is. In the present invention, among these, ultraviolet rays, laser rays, visible rays or electron beams are preferred. Particularly preferably, ultraviolet rays or visible rays are used, and types of light sources include high-pressure mercury lamps, metal halide lamps, and LED lamps.

Specifically, an LED lamp may be used as a light source for photocuring for the purpose of minimizing damage to other materials. In general, LED lamps are said to have weaker irradiation energy compared to high-pressure mercury lamps or metal halide lamps. When curing is performed with an LED lamp, the emission wavelength can be used in the range of 315 to 550 nm. For example, 365 nm, 385 nm, 390 nm, 395 nm, and 405 nm are available as commercial products, but all lamps are close to visible light. It is necessary to select a photopolymerization initiator having an absorption band on the relatively long wavelength side, and in that case, a photopolymerization initiator of phosphine oxides is preferable, and among them, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is used alone. You may use it, or you may mix two or more types.

Additionally, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzyl (diphenyl) phosphine oxide, or a mixture thereof can be used as a mixing initiator.

In addition, the present invention provides a coating composition comprising an acrylic compound (A) represented by Formula 1, a multifunctional acrylic compound (B) polymerizable with the acrylic compound (A), and a polymerization initiator (D) by heat curing or light curing. Provided is a photocured or heat-cured organic coating film manufactured by curing.

The coating composition can be cured to a heat or light cure rate of 85% or more, more preferably 90% to 99%, and even more preferably 91% to 97%, and within this range, curing shrinkage after curing. It is suitable for use in encapsulation purposes as it creates a layer with low stress and no shift.

In the present invention, the substrate on which the coating composition is formed is not particularly limited and includes PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), TAC (triacetylcellulose), and PC (polymethylene terephthalate). Carbonate), PI (polyimide), various resin films such as PMMA (polymethyl methacrylate), various metal sheets such as aluminum sheets, glass substrates, etc., if a monomer layer can be formed, gas barrier film, optical film, protective film Various base films used in various functional films such as these are available. Glass substrates are often used in organic light-emitting devices (organic EL displays). In order to manufacture a flexible organic light emitting device (organic EL display), the substrate must be flexible, and since high dimensional stability and heat resistance are required, thin-film glass substrates, PEN, PI, or their composite materials are often used.

Meanwhile, the organic coating film according to the present invention may additionally include an organic layer or an inorganic layer.

The inorganic layer includes at least one selected from metal, metal oxide, metal fluoride, metal nitride, metal oxynitride, metal boride, metal oxyboride, and metal silicide, and the metal is silicon (Si), indium (In ), germanium (Ge), tin (Sn), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), bismuth (Bi), transition metals, and lanthanide metals. It can be included.

In addition, the coating composition according to the present invention may have a light transmittance of 95% or more, specifically 95% to 99%, after curing, and can increase visibility when used as a coating film within this range.

Additionally, the coating liquid composition according to the present invention can be used in any one selected from organic light-emitting devices, electrochromic devices, photochromic devices, solar cells, lighting devices, integrated circuits, LCD devices, light-emitting diodes, and encapsulants.

In addition, the present invention can provide an encapsulated device comprising a photo-cured or thermo-cured organic coating film prepared by thermally or photo-curing the coating composition, wherein the encapsulated device is an organic light-emitting device. , can be used as any one selected from electrochromic devices, photochromic devices, solar cells, lighting devices, integrated circuits, LCD devices, and light-emitting diodes.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Preparation example: Preparation of acrylate compound (A) represented by Formula 1

Synthesis Example 1: Synthesis of Compound 3

Synthesis Example 1-1: Synthesis of Compound 3

Add 113.6 g (489 mmol) of Compound 3-1 to a 3L reactor, dissolve in 1 L of ethanol, cool the internal temperature to 0°C, and slowly add 11.1 g (294 mmol) of sodium borohydride dropwise, raise the temperature to room temperature, and stir for 6 hours. The reaction mixture was distilled under reduced pressure to remove ethanol, then 1L of ethyl acetate was added, extracted using an aqueous sodium chloride solution, the organic layer was dried with anhydrous magnesium sulfate, concentrated, and the obtained organic matter was dissolved in 1L of dichloromethane and cooled to an internal temperature of 0°C. Then, 99.1 g (979 mmol) of triethylamine and 53.2 g (587 mmol) of acrylic chloride were slowly added dropwise and stirred for 2 hours while maintaining the temperature. The reaction mixture was filtered through a filter filled with Celite, the produced salts were removed, the filtrate was washed with 1L of distilled water, the organic layer was dried with anhydrous magnesium sulfate, and the obtained organic matter was concentrated and filtered through a column with a mixture of ethyl acetate and normal hexane. Proceeding to obtain 100.1g (yield: 71%) of target compound 3 as a clear liquid.

^1H NMR (δ ppm; DMSO _- d6 ): 7.28~7.26 (m, 5H), 6.17(m, 1H), 5.95(m, 1H), 5.49(m, 1H), 5.14(m, 1H), 1.54(m) , 2H), 1.21~1.15(m, 10H), 0.78(m, 3H)

MS( m/e ): 260.2

Synthesis Example 2: Synthesis of Compound 6

Synthesis Example 2-1: Synthesis of Compound 6

In the same manner as Synthesis Example 1-1, 100.0 g (347 mmol) of compound 6-1, 7.9 g (208 mmol) of sodium borohydride, 70.2 g (693 mmol) of triethylamine, 37.7 g (416 mmol) of acrylic chloride, 1 L of ethanol, dichloromethane. Using 1L, 82.4g (yield: 69%) of target compound 6 as a clear liquid was obtained.

^1H NMR (δ ppm; DMSO _- d6 ): 7.28~7.26 (m, 5H), 6.17(m, 1H), 5.95(m, 1H), 5.49(m, 1H), 5.14(m, 1H), 1.54(m) , 2H), 1.21~1.15(m, 22H), 0.78(m, 3H)

MS( m/e ): 344.3

Synthesis Example 3: Synthesis of Compound 12

Synthesis Example 3-1 Synthesis of Compound 12

In the same manner as Synthesis Example 1-1, 100.0 g (384 mmol) of compound 12-1, 8.7 g (230 mmol) of sodium borohydride, 77.7 g (768 mmol) of triethylamine, 48.2 g (461 mmol) of methacrylic chloride, 1 L of ethanol, and dichloride were added. Using 1L of methane, 91.4g (yield: 72%) of target compound 12 as a transparent liquid was obtained.

^1H NMR (δ ppm; DMSO _- d6 ): 7.28~7.26 (m, 5H), 6.38 (m, 1H), 6.30(m, 1H), 5.14(m, 1H), 1.91(m, 3H), 1.54(m) , 2H), 1.21~1.15(m, 18H), 0.78(m, 3H)

MS( m/e ): 330.3

Synthesis Example 4: Synthesis of Compound 14

Synthesis Example 4-1: Synthesis of Compound 14

In the same manner as Synthesis Example 1-1, 100.0 g (316 mmol) of compound 14-1, 7.2 g (190 mmol) of sodium borohydride, 63.9 g (632 mmol) of triethylamine, 39.6 g (379 mmol) of methacrylic chloride, 1 L of ethanol, and dichloride were added. Using 1L of methane, 78.2g (yield: 64%) of the target compound 14 as a transparent liquid was obtained.

^1H NMR (δ ppm; DMSO _- d6 ): 7.28~7.26 (m, 5H), 6.38 (m, 1H), 6.30(m, 1H), 5.14(m, 1H), 1.91(m, 3H), 1.54(m) , 2H), 1.21~1.15(m, 26H), 0.78(m, 3H)

MS( m/e ): 386.3

Synthesis Example 5: Synthesis of Compound 16

Synthesis Example 5-1: Synthesis of Compound 16

In the same manner as Synthesis Example 1-1, 100.0 g (384 mmol) of Compound 16-1, 8.7 g (230 mmol) of sodium borohydride, 77.7 g (768 mmol) of triethylamine, 41.7 g (461 mmol) of acrylic chloride, 1 L of ethanol, and dichloromethane. Using 1L, 81.9g (yield: 67%) of target compound 16 as a clear liquid was obtained.

^1H NMR (δ ppm; DMSO _- d6 ): 7.28~7.26 (m, 5H), 6.17 (m, 1H), 5.95(m, 1H), 5.49(m, 1H), 5.13(m, 1H), 2.35(m) , 1H), 1.21~1.15(m, 16H), 0.80~0.78(m, 6H)

MS( m/e ): 316.2

Synthesis Example 6: Synthesis of Compound 23

Synthesis Example 6-1: Synthesis of Compound 21

In the same manner as Synthesis Example 1-1, 100.0 g (290 mmol) of compound 23-1, 6.6 g (174 mmol) of sodium borohydride, 58.7 g (580 mmol) of triethylamine, 31.5 g (348 mmol) of acrylic chloride, 1 L of ethanol, dichloromethane. Using 1L, 54.5g (yield: 59%) of the target compound 23 as a clear liquid was obtained.

^1H NMR (δ ppm; DMSO- d ₆ ): 7.02 (d, 1H), 6.93 (s, 1H), 6.87 (d, 1H), 6.17 (m, 1H), 5.95 (m, 1H), 5.49 (m, 1H) ), 5.14(m, 1H), 2.24(m, 6H), 1.54(m, 2H), 1.21~1.15(m, 26H), 0.78(m, 3H)

MS( m/e ): 400.3

Synthesis Example 7: Synthesis of Compound 24

Synthesis Example 7-1: Synthesis of Compound 24

In the same manner as Synthesis Example 1-1, 110.0 g (357 mmol) of compound 24-1, 8.1 g (214 mmol) of sodium borohydride, 72.2 g (713 mmol) of triethylamine, 38.7 g (428 mmol) of acrylic chloride, 1 L of ethanol, dichloromethane. Using 1L, 88.4g (yield: 68%) of the target compound 24 as a clear liquid was obtained.

^1H NMR (δ ppm; DMSO _- d6 ): 7.42~7.28 (m, 9H), 6.17(m, 1H), 5.95(m, 1H), 5.49(m, 1H), 5.14(m, 1H), 1.54(m) , 2H), 1.21~1.15(m, 14H), 0.78(m, 3H)

MS( m/e ): 336.2

Synthesis Example 8: Synthesis of Compound 27

Synthesis Example 8-1: Synthesis of Compound 27

In a 3L reactor, 100.0g (403mmol) of Compound 27-1 was dissolved in 1L of dichloromethane, the internal temperature was cooled to 0°C, then 81.5g (805mmol) of triethylamine and 43.7g (483mmol) of acrylic chloride were slowly added dropwise and the temperature was adjusted to Maintain stirring for 2 hours. The reaction mixture was filtered through a filter filled with Celite, the salts produced were removed, the filtrate was washed with 1L of distilled water, the organic layer was dried with anhydrous magnesium sulfate, and the obtained organic matter was concentrated and filtered through a column with a mixture of ethyl acetate and normal hexane. Proceeding to obtain 92.1g (yield: 68%) of the target compound 25 as a transparent liquid.

^1H NMR (δ ppm; DMSO- d ₆ ): 7.14 (d, 2H), 7.06 (d, 2H), 6.17 (m, 1H), 5.95 (m, 1H), 5.49 (m, 1H), 2.24 (m, 3H) ), 1.76~1.72 (m, 4H), 1.21~1.15(m, 10H), 0.80~0.78(m, 6H)

MS( m/e ): 302.2

Synthesis Example 9: Synthesis of Compound 42

Synthesis Example 9-1: Synthesis of compound [42-2]

Add 100.0 g (430 mmol) of Compound 42-1 to a 3L reactor, dissolve it in 475 g (10,329 mmol) of formamide, add 99.1 g (2,152 mmol) of formic acid, raise the internal temperature to 190°C, and stir for 6 hours. Add 79.2 g (1,721 mmol) of formic acid to the reaction mixture, cool to room temperature, and stir for 6 hours. Add 1.5 L of distilled water to the reaction mixture, add 1.5 L of ethyl acetate, extract using aqueous sodium chloride solution, dry the organic layer with anhydrous magnesium sulfate, and then concentrate. The resulting organic material was diluted with 1 L of ethanol and 1.5 L of distilled water, and then added with 35% hydrochloric acid to 1,366.6 m. Add g (8,607 mmol) and stir for 8 hours. Afterwards, ethanol and hydrochloric acid are removed through reduced pressure distillation, cooled to 0°C, and ammonium aqueous solution is added dropwise until the pH reaches 10. Then, after adding 1 L of ethyl iser, extraction was performed using an aqueous sodium chloride solution, the organic layer was dried with anhydrous magnesium sulfate, and then concentrated. The obtained organic material was column-processed using a mixture of methylene chloride, ethyl hacetate, methanol, and triethylamine to produce a clear liquid. 81.4 g (yield: 81%) of intermediate compound [42-2] was obtained.

Synthesis Example 9-2: Synthesis of Compound 42

In the same manner as Synthesis Example 8-1, the target compound 42 as a transparent liquid was prepared using 81.4 g (349 mmol) of compound 42-1, 70.6 g (697 mmol) of triethylamine, 43.7 g (418 mmol) of methacrylic chloride, and 1 L of dichloromethane. 59.9g (yield: 57%) was obtained.

^1H NMR (δ ppm; DMSO- d ₆ ): 7.93 (s, 1H), 7.30 (m, 2H), 7.19-7.17 (m, 3H), 5.89 (m, 1H), 5.60 (m, 1H), 4.77 (m , 1H), 1.88(s, 3H), 1.74(m, 2H), 1.21~1.15(m, 14H), 0.78(m, 3H)

MS( m/e ): 301.2

Synthesis Example 10: Synthesis of Compound 45

Synthesis Example 10-1: Synthesis of Compound 45

In the same manner as Synthesis Example 1-1, 100.0 g (399 mmol) of compound 45-1, 9.1 g (240 mmol) of sodium borohydride, 80.8 g (799 mmol) of triethylamine, 43.4 g (479 mmol) of acrylic chloride, 1 L of ethanol, dichloromethane. Using 1L, 88.1g (yield: 72%) of the target compound 45 as a transparent liquid was obtained.

^1H NMR (δ ppm; DMSO- d ₆ ): 7.24 (m, 2H), 7.07 (m, 2H), 6.17 (m, 1H), 5.95 (m, 1H), 5.49 (m, 1H), 5.14 (m, 1H) ), 1.54(m, 2H), 1.21~1.15(m, 14H), 0.78(m, 3H)

MS( m/e ): 306.2

It is obvious to those skilled in the art that Synthesis Examples 1 to 10 describe specific examples and do not limit the synthesis method.

Physical property evaluation of coating liquid composition

The components of the coating liquid composition used in Examples 1 to 15 and Comparative Examples 1 to 6 are shown below.

(A) Acrylate compound (A) represented by Formula 1

(A-1) 1-phenyl-1-decyl acrylate (Compound 3)

(A-2) 1-phenyl-1-tetradecylacrylate (Compound 6)

(A-3) 1-phenyl-1-dodecyl methacrylate (Compound 12)

(A-4) 1-phenyl-1-hexadecyl methacrylate (Compound 14)

(A-5) 1-phenyl-2-butyl-1-octylacrylate (Compound 15)

(A-6) 1-(2,4-dimethylphenyl)-1-hexadecel acrylate (Compound 21)

(A-7) 4-Biphenyl-1-decyl acrylate (Compound 24)

(A-8) 4-methylphenyl-1-ethyl-1-octylacrylate (Compound 25)

(A-9) 1-phenyl-1-decylacrylamide (Compound 40)

(A-10) 1-(4-fluorophenyl)-1-tetradecylacrylate (Compound 40)

(B) A multifunctional acrylic compound (B) polymerizable with the acrylate compound (A) represented by Formula 1

(B-1) 1,10-decanediol diacrylate

(B-2) 1,12-dodecanediol diacrylate

(B-3) 1,8-octanediol diacrylate

(B-4) Tricyclodecane dimethanol dimethacrylate

(B-5) Trimethylolpropane triacrylate

(C) Additional monofunctional acrylic compound (C)

(C-1) Octyl methacrylate

(C-2) Lauryl acrylate

(C-3) dicyclofentanyl methacrylate

(D) Photoinitiator

(D-1) Phosphorus photoinitiator (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide)

(D-1: Darocur TPO)

(D-2) Oxime-based photoinitiator ((E)-2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl) octan-1-one)

(D-2: Irgacure OXE-01)

(E) Monofunctional acrylic compound used as a comparative example

(E-1) 1-phenyl-1-pentyl methacrylate

(E-2) Phenoxyethyl methacrylate

(E-3) Phenoxybenzyl acrylate

(E-4) o-phenylphenoxyethyl acrylate

In addition, the contents of each component of the coating liquid composition used in Examples 1 to 15 and Comparative Examples 1 to 6 are shown in Table 1 below.

division Composition (% by weight) Aromatic monofunctional monomer (A) Polymerizable multifunctional compound (B) additionally available
monofunctional compounds
(C) Polymerization initiator (D) Example 1 A-1(60) B-1(38) - D-1(2) Example 2 A-2(60) B-2(38) - D-1(2) Example 3 A-3(60) B-3(38) - D-1(2) Example 4 A-4(60) B-4(38) - D-1(2) Example 5 A-5(60) B-5(38) - D-1(2) Example 6 A-6(60) B-1(38) - D-1(2) Example 7 A-7(60) B-2(38) - D-1(2) Example 8 A-8(74) B-3(14), B-4(10) - D-1(2) Example 9 A-9(25) B-5(51), B-1(20) - D-2(4) Example 10 A-10(18) B-2(40),B-3(37) - D-2(5) Example 11 A-1(40), A-2(30) B-1(28) - D-1(2) Example 12 A-3(48), A-4(25) B-3(25) - D-1(2) Example 13 A-5(20), A-6(10) B-2(63) C-1(5) D-2(2) Example 14 A-7(30), A-8(28) B-5(25) C-2(15) D-2(2) Example 15 A-7(15) B-1(48), B-2(15) C-3(20) D-2(2) Comparative Example 1 E-1(58) B-1(40) D-1(2) Comparative Example 2 E-2(58) B-2(40) D-1(2) Comparative Example 3 E-3(58) B-3(40) D-1(2) Comparative Example 4 E-4(58) B-4(40) D-1(2) Comparative Example 5 E-1(40)E-2(28) B-5(30) D-1(2) Comparative Example 6 E-4(50) B-1(38) C-1(10) D-1(2)

Experimental evaluation example 1: relative dielectric constant

The coating composition prepared according to the above Examples and Comparative Examples was applied to a copper electrode of 30 mm It was measured using .

Experimental Evaluation Example 2: Plasma etch rate evaluation

The sealing material composition prepared in Table 1 was applied to a silicon wafer and then photocured, and the film thickness of the organic layer was measured (T1: ㎛). More specifically, after treating the organic layer with inductively coupled plasma using ICP CVD, the film thickness of the organic layer was measured and the etch rate was calculated using Equation 1) below.

Equation 1) Etching rate (%): (T1-T2)/T1×100

Experimental evaluation example 3: Crosscut tape test (adhesion measurement)

After applying the coating liquid composition for sealing material prepared in Table 1 to a silicon wafer to a thickness of 10 ㎛ and photocuring, the organic layer was cut into 7×7 pieces at 1 mm intervals using a crosscut tape test knife, and the cut surface was Clean it up with a soft brush.

After attaching the adhesive tape (25 mm, 4.3 N), the tape was removed by pulling at an angle of 180 degrees within 90 ± 30 seconds, and the adhesive was classified and measured according to the grades of 0B to 5B based on the standards shown in Table 2 below.

Rating standard 5B The cutting surface is clean and the grid squares are not separated. 4B Small pieces of coating separate at the intersection.
Less than 5% of grid area 3B Small pieces of the coating separate along edges and at cut intersections.
1-15% of grid area 2B The cut edge of the coating and part of the square are separated.
15-35% of grid area 1B The coating peeled off significantly along the edges of the cut and the squares separated.
35~65% of grid area 0B More deprived and separated than 1B
More than 65% of grid area

Experimental Example 4: Measurement of shrinkage rate

Shrinkage rate was measured using the volume difference before and after curing of the composition, and the shrinkage rate was calculated by injecting the composition at a certain height (H1) into a glass tube with an inner diameter of 5 mm and using the height (H2) after curing by exposure to UV, Equation 2).

Equation 2) Shrinkage rate (%): (H1-H2)/H1×100

The evaluation results measured in Experimental Examples 1 to 4 are shown in Table 3 below.

division permittivity Plasma etch rate (%) cross cut tape
test shrinkage rate
(%) Example 1 2.65 5.2 5B 5.3 Example 2 2.54 5.4 4B 5.2 Example 3 2.66 5.3 5B 5.5 Example 4 2.53 5.6 5B 5.1 Example 5 2.68 5.5 5B 5.4 Example 6 2.57 5.3 4B 5.5 Example 7 2.69 5.3 5B 5.5 Example 8 2.51 5.4 4B 5.3 Example 9 2.64 5.5 5B 5.1 Example 10 2.58 5.3 5B 5.3 Example 11 2.60 5.7 5B 5.6 Example 12 2.51 5.5 5B 5.6 Example 13 2.58 5.9 5B 5.8 Example 14 2.60 6.0 4B 5.1 Example 15 2.61 6.2 5B 5.2 Comparative Example 1 3.22 6.2 2B 6.6 Comparative Example 2 3.13 5.9 1B 6.2 Comparative Example 3 3.20 6.3 2B 6.4 Comparative Example 4 3.01 6.4 3B 6.3 Comparative Example 5 3.15 6.1 2B 6.0 Comparative Example 6 2.94 6.2 3B 6.3

As shown in Table 3, the sealing material compositions of Examples 1 to 15 of the present invention showed excellent performance in dielectric constant, plasma resistance, adhesion, and shrinkage characteristics compared to the compositions of Comparative Examples 1 to 6.

To explain this in more detail, it can be seen that in Examples 1 to 15, when R ₃ used an alkyl group having 6 or more carbon atoms, the dielectric constant and adhesive strength were superior to those when R ₃ used pentyl with 5 carbon atoms in Comparative Examples 1 and 5. there is.

In addition, in Comparative Example 6, a monomer was added to adjust the physical properties, which can be seen as a contrast to Examples 13 to 15. However, when crosslinking was performed using E-4 as an aromatic monofunctional monomer, even if a monofunctional monomer was added, electrons were polarized. It can be seen that the dielectric constant increases and the thin film becomes hard, resulting in less good adhesion than in the example.

In addition, in the comparative examples, examples containing many functional groups and aromatic ring compounds show no difference in plasma resistance, but show a large difference in dielectric constant, which is the most important item, compared to the examples according to the present invention, and also show low performance in adhesive strength. It can be seen that it shows, and it is presumed that the presence of many functional groups and aromatic ring compounds causes polarization of electrons, greatly affecting the dielectric constant.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can be made by those skilled in the art using the basic concept of the present invention as defined in the following claims. It falls within the scope of invention rights.

Claims (18)

An acrylic compound containing both an aromatic substituent and an aliphatic substituent, represented by the following [Chemical Formula 1].
[Formula 1]

In [Formula 1] above,
R ₁ is any one selected from hydrogen, deuterium, and a substituted or unsubstituted C1 to C10 alkyl group,
The X is any one selected from oxygen (O), sulfur (S), or -NR'-,
R' and R ₂ are each the same or different, and are independently hydrogen, deuterium, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C1~C30 halogenated alkyl group, or a substituted or unsubstituted C6. Any one selected from ~C24 aryl group, substituted or unsubstituted C4~C24 heteroaryl group containing 1 to 2 O, N or S as heteroatoms,
R ₃ is a substituted or unsubstituted C6 to C30 alkyl group. R ₃ is a substituted or unsubstituted C6 to C30 alkyl group and a substituted or unsubstituted C6 to C30 halogenated alkyl group,
and a substituted or unsubstituted C6~C30 halogenated alkyl group,
Ar ₁ is any one selected from a substituted or unsubstituted C6 to C24 aryl group and a substituted or unsubstituted C4 to C24 heteroaryl group containing 1 to 2 heteroatoms O, N or S,
In Formula 1, 'substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C2-C10 alkene. Nyl group, C2-C10 alkynyl group, C1-C10 heteroalkyl group, C6-C18 aryl group, C7-C19 arylalkyl group, C7-C19 alkylaryl group, C1-C10 alkoxy group, C1-C10 alkyl group Substituted with any one substituent selected from the group consisting of oneyl group, C1-C10 alkylamino group, C6-C18 arylamino group, C1-C10 alkylsilyl group, C6-C18 arylsilyl group, and C6-C12 aryloxy group. It means becoming.
According to paragraph 1,
An acrylic compound wherein R ₁ is selected from hydrogen, deuterium, or an unsubstituted alkyl group of C1 to C5.
According to paragraph 1,
R' and R ₂ are each the same or different, and are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C18 aryl group. Characterized by acrylic compounds.
According to paragraph 1,
An acrylic compound wherein R ₃ is a substituted or unsubstituted C7 to C20 alkyl group.
According to paragraph 1,
An acrylic compound, wherein X is oxygen (O).
According to paragraph 1,
The acrylic compound is characterized in that Ar1 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.
According to paragraph 1,
The acrylic compound represented by Formula 1 is an acrylic compound selected from compounds 1 to 46 below.

<Compound 1><Compound2><Compound3>

<Compound 4><Compound5><Compound6>

<Compound 7><Compound8><Compound9>

<Compound 10><Compound11><Compound12>

<Compound 13><Compound14><Compound15>

<Compound 16><Compound17><Compound18>

<Compound 19><Compound20><Compound21>

<Compound 22><Compound23><Compound24>

<Compound 25><Compound26><Compound27>

<Compound 28><Compound29><Compound30>

<Compound 31><Compound32><Compound33>

<Compound 34><Compound35><Compound36>

<Compound 37><Compound38><Compound39>

<Compound 40><Compound41><Compound42>

<Compound 43><Compound44><Compound45>

<Compound 46>
A coating liquid composition comprising the acrylic compound according to any one of claims 1 to 7.
According to clause 8,
The coating liquid composition further optionally includes a polymerization initiator: or a photopolymerizable monomer.
1 to 80% by weight of the acrylic compound (A) according to any one of claims 1 to 7; 19 to 80% by weight of a multifunctional acrylic compound (B) polymerizable with the acrylic compound (A); and 0.1 to 20% by weight of a polymerization initiator (D).
According to clause 10,
The multifunctional compound (B) is 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,16-Hexadecanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, adamantane-1,2- Dinyldiacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol(poly)ethoxytri(meth)acrylate, pentaerythritol(poly)propoxytri(meth)acrylate, pentaerythritol tetra(meth)acrylate , pentaerythritol (poly) ethoxytetra (meth)acrylate, pentaerythritol (poly) propoxy tetra (meth)acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol (poly) caprolactone penta (meth) ) Acrylate, dipentaerythritol (poly)ethoxypenta (meth)acrylate, dipentaerythritol (poly)propoxypenta (meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol (poly) Caprolactone hexa(meth)acrylate, dipentaerythritol (poly)ethoxyhexa(meth)acrylate, dipentaerythritol (poly)propoxy hexa(meth)acrylate, polypentaerythritol poly(meth)acrylate, trimethyl Rollpropane tri(meth)acrylate, trimethylolpropane(poly)ethoxytri(meth)acrylate, trimethylolpropane(poly)propoxytri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, glycerol A coating liquid composition characterized in that compounds 1 to 5 selected from tri(meth)acrylate, 2,2,2-trisacryloxymethylsuccinic acid, and silicon hexa(meth)acrylate are used.
According to clause 10,
The coating liquid composition includes compound (A) represented by [Formula 1]; A multifunctional compound (B) polymerizable with the compound (A); In addition, 0 to 50% by weight of monofunctional acrylic monomer (C); A coating liquid composition comprising:
According to clause 12,
The monofunctional acrylic monomer (C) is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and octyl (meth)acrylate. , cyclohexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adaman Til (meth)acrylate, dicyclofentanyl (meth)acrylate, benzyl (meth)acrylate, phenoxybenzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate ) Acrylate, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4 - A coating liquid composition characterized in that 1 to 5 compounds selected from epoxycyclohexylmethyl (meth)acrylate, 3-ethyloxetane-3-methyl (meth)acrylate, and (meth)acrylamide monomer are used.
According to clause 9,
A coating liquid composition, characterized in that the polymerization initiator (D) is a photopolymerization initiator.
According to clause 10,
The coating liquid composition is characterized in that it additionally contains 5 to 70 parts by weight of an organic solvent, based on the total amount of the entire composition.
A photo-cured or thermo-cured organic coating film, characterized in that it is manufactured by thermally curing or photo-curing the coating liquid composition according to any one of claims 8 to 15.
According to clause 16,
The organic coating film is characterized in that the organic coating film additionally includes an organic layer or an inorganic layer.
The coating liquid composition according to any one of claims 8 to 15 can be used in any one selected from organic light-emitting devices, electrochromic devices, photochromic devices, solar cells, lighting devices, integrated circuits, LCD devices, light-emitting diodes, and encapsulants. A coating liquid composition characterized in that it is used.