WO2024048892A1

WO2024048892A1 - Compound, photosensitive resin composition including same, and color filter

Info

Publication number: WO2024048892A1
Application number: PCT/KR2023/005396
Authority: WO
Inventors: 장춘근; 권장현; 전광일; 정의수; 최규범; 신인섭; 문희조; 류지현; 박백성
Original assignee: 삼성에스디아이 주식회사
Priority date: 2022-08-30
Filing date: 2023-04-20
Publication date: 2024-03-07
Also published as: KR20240030438A

Abstract

Provided are a compound represented by chemical formula 1, a photosensitive resin composition including the compound, and a color filter manufactured using the photosensitive resin composition. An embodiment provides a compound represented by chemical formula 1: [Chemical formula 1] (in chemical formula 1, each substituent is as defined in the specification).

Description

Compound, photosensitive resin composition containing the same, and color filter

This disclosure relates to compounds, photosensitive resin compositions containing the same, and color filters.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent adhesion to integrated circuits, and its range of use is expanding to notebook computers, monitors, TV images, etc. there is.

This liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed; and an upper substrate on which an active circuit part consisting of a liquid crystal layer, a thin film transistor, and a storage capacitor layer and an ITO pixel electrode are formed.

Additionally, the color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels; and pixel units in which a plurality of colors (typically three primary colors of red (R), green (G), and blue (B)) are arranged in a predetermined order to form each pixel.

The pigment dispersion method, which is one of the methods of implementing a color filter, forms a colored thin film using a photosensitive resin composition containing a pigment as a colorant. Specifically, a series of processes including a process of forming a resin film by coating a photosensitive resin composition on a transparent substrate provided with a black matrix, a process of exposing a pattern on the resin film, and a process of removing the unexposed area with a solvent and heat curing it. By repeating this, a colored thin film is formed.

However, when using the pigment dispersion method, the manufacturing process of the color filter is difficult, and the quality of the manufactured color filter also has limitations. First, in order to stabilize the dispersion state of the pigment in the photosensitive resin composition and form a fine and elaborate pattern, it is necessary to use pigments with a finer particle size or to use various additives such as dispersants. In addition, storage and transportation conditions for maintaining the quality of the manufactured photosensitive resin composition at optimal levels are difficult. Moreover, the final color filter has limitations in luminance and contrast ratio resulting from the pigment particle size.

Accordingly, dyes are attracting attention as materials to replace or complement pigments. However, apart from excellent optical properties such as brightness and contrast ratio, the dyes known to date have problems with inferior heat resistance and chemical resistance compared to pigments.

One embodiment is to provide a compound that has excellent optical properties, heat resistance, chemical resistance, etc., and can replace or supplement pigments.

Another embodiment is to provide a photosensitive resin composition containing the above compound.

Another embodiment is to provide a photosensitive resin film manufactured using the photosensitive resin composition.

Another embodiment is to provide a color filter including the photosensitive resin film.

One embodiment provides a compound represented by Formula 1:

[Formula 1]

In Formula 1,

A and B are each independently a C6 to C20 aromatic ring, or a C2 to C20 heteroaromatic ring containing 1 to 3 heteroatoms each independently selected from the group consisting of N, O and S;

Y ¹ and Y ² are each independently *-O-*, *-S-*, or *-CR ¹ R ² -*; Here, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group;

R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

x and y are each independently integers from 1 to 18.

A and B may each independently be a benzene ring or a naphthalene ring.

At least one of A and B may be a naphthalene ring.

Y ¹ and Y ² may each independently be *-O-*, *-S-*, or *-C(CH ₃ ) ₂ -*.

Y ¹ and Y ² may be different from each other.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkyl group; The substituent for the C1 to C20 alkyl group may be a sulfurous acid (*-SO ₃ ) group, a (meth)acrylate group, or an epoxy group.

R ¹ and R ² may be different from each other.

R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group; The substituent for the C1 to C20 alkyl group may be a sulfurous acid (*-SO ₃ ) group, a (meth)acrylate group, or an epoxy group.

R ³ and R ⁴ may be the same.

The maximum absorption wavelength (λmax) of the compound may be 500 nm to 580 nm.

The molar extinction coefficient (ε) of the compound may be 90,000 L mol ^-1 cm ^-1 to 120,000 L mol ^-1 cm ^-1 .

The compound may be selected from the following formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

The definitions of Y ¹ , Y ² , and R ¹ to R ⁴ are the same as in clause 1;

x1 is an integer from 1 to 6, y1 is an integer from 1 to 4;

x2 and y2 are each independently an integer from 1 to 4;

x3 and y3 are each independently integers from 1 to 6.

The compound may be selected from the group comprising:

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

[Formula 1-1-6]

[Formula 1-1-7]

[Formula 1-1-8]

[Formula 1-1-9]

[Formula 1-1-10]

[Formula 1-1-11]

[Formula 1-1-12]

[Formula 1-1-13]

[Formula 1-1-14]

[Formula 1-1-15]

[Formula 1-1-16]

[Formula 1-1-17]

[Formula 1-1-18]

[Formula 1-1-19]

[Formula 1-1-20]

[Formula 1-1-21]

[Formula 1-1-22]

[Formula 1-1-23]

[Formula 1-1-24]

[Formula 1-1-25]

[Formula 1-1-26]

[Formula 1-1-27]

[Formula 1-1-28]

[Formula 1-1-29]

[Formula 1-1-30]

[Formula 1-1-31]

[Formula 1-1-32]

[Formula 1-1-33]

[Formula 1-1-34]

[Formula 1-1-35]

[Formula 1-1-36]

[Formula 1-2-1]

[Formula 1-2-2]

[Formula 1-2-3]

[Formula 1-2-4]

[Formula 1-2-5]

[Formula 1-2-6]

[Formula 1-2-7]

[Formula 1-2-8]

[Formula 1-2-9]

[Formula 1-2-10]

[Formula 1-2-11]

[Formula 1-2-12]

[Formula 1-2-13]

[Formula 1-2-14]

[Formula 1-2-15]

[Formula 1-2-16]

[Formula 1-2-17]

[Formula 1-2-18]

[Formula 1-2-19]

[Formula 1-2-20]

[Formula 1-2-21]

[Formula 1-2-22]

[Formula 1-2-23]

[Formula 1-2-24]

[Formula 1-2-25]

[Formula 1-2-26]

[Formula 1-2-27]

[Formula 1-2-28]

[Formula 1-2-29]

[Formula 1-2-30]

[Formula 1-2-31]

[Formula 1-2-32]

[Formula 1-2-33]

[Formula 1-2-34]

[Formula 1-2-35]

[Formula 1-2-36]

[Formula 1-3-1]

[Formula 1-3-2]

[Formula 1-3-3]

[Formula 1-3-4]

[Formula 1-3-5]

[Formula 1-3-6]

[Formula 1-3-7]

[Formula 1-3-8]

[Formula 1-3-9]

[Formula 1-3-10]

[Formula 1-3-11]

[Formula 1-3-12]

[Formula 1-3-13]

[Formula 1-3-14]

[Formula 1-3-15]

[Formula 1-3-16]

[Formula 1-3-17]

[Formula 1-3-18]

[Formula 1-3-19]

[Formula 1-3-20]

[Formula 1-3-21]

[Formula 1-3-22]

[Formula 1-3-23]

[Formula 1-3-24]

[Formula 1-3-25]

[Formula 1-3-26]

[Formula 1-3-27]

[Formula 1-3-28]

[Formula 1-3-29]

[Formula 1-3-30]

[Formula 1-3-31]

[Formula 1-3-32]

[Formula 1-3-33]

[Formula 1-3-34]

[Formula 1-3-35]

[Formula 1-3-36]

.

In another embodiment, a color material for electronic materials containing the above compound is provided.

The compound may be used as a core and may further include a shell surrounding the core.

The shell can be represented by the following formula (2):

[Formula 2]

In Formula 2,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group;

Z ¹ and Z ² are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group;

X ¹ and X ² are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group;

a1 and a2 are each independently integers from 0 to 4;

n is an integer from 2 to 10.

Another embodiment provides a photosensitive resin composition containing any one of the above compound and the color material for electronic materials.

The photosensitive resin composition may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

Another embodiment provides a display device including the color filter.

Details of other aspects of the invention are included in the detailed description below.

The compound according to one embodiment is a compound that exhibits excellent optical properties, heat resistance, chemical resistance, etc. in the photosensitive resin composition and resin film, and can be usefully used in the manufacture of color filters by replacing or supplementing pigments.

Figure 1 is a diagram showing the cage width of the shell represented by Formula 2 above.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

(용어의 정의)(Definition of Terms)

Unless otherwise specified herein, “substituted” or “substituted” means that one or more hydrogen atoms in the functional groups of the present invention are halogen atoms (F, Br, Cl or I), hydroxy groups, nitro groups, cyano groups, amino groups ( NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), where R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other and are each independently a C1 to C10 alkyl group), an amidino group, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic groups.

Unless otherwise specified herein, “alkyl group” means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and “cycloalkyl group” means a C3 to C20 cycloalkyl group, specifically C3 refers to a C1 to C18 cycloalkyl group, “alkoxy group” refers to a C1 to C20 alkoxy group, specifically refers to a C1 to C18 alkoxy group, and “aryl group” refers to a C6 to C20 aryl group, specifically refers to a C6 to C20 aryl group. means a C18 aryl group, “alkenyl group” means a C2 to C20 alkenyl group, specifically means a C2 to C18 alkenyl group, and “alkylene group” means a C1 to C20 alkylene group, specifically a C1 to C18 alkylene group, and “arylene group” refers to a C6 to C20 arylene group, specifically, a C6 to C16 arylene group.

Unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid”. This means that both are possible.

Unless otherwise defined herein, “combination” means mixing or copolymerization. Additionally, “copolymerization” refers to block copolymerization to random copolymerization, and “copolymer” refers to block copolymerization to random copolymerization.

Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

As used herein, cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of the following formulas 2-1 to 2-11 is included in the backbone of the resin.

Additionally, unless otherwise defined in the specification, “*” means a portion connected to the same or different atom or chemical formula.

(화합물)(compound)

One embodiment provides a compound represented by Formula 1:

[Formula 1]

In Formula 1,

x and y are each independently integers from 1 to 18.

Squarine (SQ)-based compounds generally known in the electronic materials field are 1,3-squarene-based compounds as follows.

The 1,3-squarene-based compound has a maximum absorption wavelength (λmax) of 650 nm to 850 nm, and is used as a green dye.

On the other hand, the above embodiment presents a 1,2-squarene-based compound, which is a structural isomer of the 1,3-squarene-based compound, and is an unknown compound in the electronic materials field.

The 1,2-squarene-based compound has a maximum absorption wavelength (λmax) of 500 nm to 580 nm and can function as a yellow dye, which can produce a completely different color from the 1,3-squarene-based compound.

Moreover, the molar extinction coefficient (ε) of the generally known yellow dye is about 500,000 L mol ^-1 cm ^-1 to 60,000 L mol ^-1 cm ^-1 , while the 1,2-squarene-based compound is 900,000 L mol ^-1 It has a significantly high molar extinction coefficient (ε) ranging from ¹ cm ^-1 to 100,000 L mol ^-1 cm ^-1 .

Here, “high molar extinction coefficient” means “a large amount of light absorbed by one molecule.” Accordingly, compared to the generally known yellow dye, the 1,2-squarene-based compound can exhibit a high level of color reproducibility even when the amount applied to the photosensitive resin composition is reduced, and other solids in the photosensitive resin composition (e.g. It can also contribute to increasing the amount of application of photopolymerizable compounds, etc.).

Hereinafter, the compound according to the above embodiment will be described in more detail.

A and B may each independently be a benzene ring or a naphthalene ring.

Specifically, at least one of A and B may be a naphthalene ring. In this case, compared to the case where both A and B are benzene rings, the maximum absorption wavelength (λmax) of the compound may be higher.

For example, one of A and B may be a naphthalene ring, and the other may be a benzene ring. In this way, in the case of an asymmetric structure, the molar extinction coefficient of the compound may be higher compared to the case of a symmetric structure. In the case of a symmetrical structure, the left and right D structures in the electron donating (Donor, D) - electron accepting (Acceptor, A) - electron donating (D) structure of the molecule are the same, which makes it easy to overlap between molecules. As a result, Interference of electronic levels occurs due to interactions between molecules, which tends to reduce the intensity of the absorption graph and widen the half width. On the other hand, the asymmetric structure is in the form of D-A-D’, which makes it relatively difficult to overlap between molecules, reducing interactions between molecules. Additionally, if a substituent is introduced outside the aromatic ring of the donor with an asymmetric structure, the above advantages can become more advantageous. The effect of a high molar extinction coefficient is as described above.

Y ¹ and Y ² may each independently be *-O-*, *-S-*, or *-C(CH ₃ ) ₂ -*.

Specifically, Y ¹ and Y ² may be different from each other. In the case of such an asymmetric structure, the molar extinction coefficient of the compound may be higher compared to the case of a symmetric structure. The effect of a high molar extinction coefficient is as described above.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkyl group; The substituent of the C1 to C20 alkyl group may be a sulfurous acid (*-SO ₃ ) group, a (meth)acrylate group, or an epoxy group.

Specifically, here, the C1 to C20 alkyl group may be terminally substituted with a sulfurous acid (*-SO ₃ ) group, a (meth)acrylate group, or an epoxy group. When the parent core structure of the compound is the same, the properties of the compound may vary depending on the type of terminal substituent. For example, if the terminal substituent is a sulfurous acid (*-SO ₃ ) group, the ( ) effect can be strengthened, if the terminal substituent is a (meth)acrylate group, heat resistance can be strengthened, and if the terminal substituent is an epoxy group, chemical resistance can be strengthened.

Meanwhile, R ¹ and R ² may be different from each other. In the case of such an asymmetric structure, the molar extinction coefficient of the compound may be higher compared to the case of a symmetric structure. The effect of a high molar extinction coefficient is as described above.

Here, the C1 to C20 alkyl group may be terminally substituted with a sulfurous acid (*-SO ₃ ) group, a (meth)acrylate group, or an epoxy group. The effects of the terminal substituents are as described above.

Meanwhile, R ³ and R ⁴ may be the same.

As previously mentioned, the maximum absorption wavelength (λmax) of the compound may be 500 nm to 580 nm.

Specifically, when both A and B are benzene rings, the maximum absorption wavelength (λmax) of the compound may be 500 nm to 550 nm. On the other hand, when at least one of A and B is a naphthalene ring, the maximum absorption wavelength (λmax) of the compound may be increased to 550 nm to 580 nm.

As described previously, the compound exhibits a maximum absorption wavelength (λmax) in the range of 500 nm to 580 nm. Among them, the steeper the slope of the absorbance graph (i.e., absorbance/wavelength) in the wavelength range of 520 nm to 550 nm, the molar extinction coefficient. is high.

Accordingly, the above compound has a significantly higher molar extinction coefficient compared to generally known yellow dyes.

More specifically, the molar extinction coefficient (ε) of the compound may be 90,000 L mol ^-1 cm ^-1 to 120,000 L mol ^-1 cm ^-1 .

Here, when the compound has a symmetric structure, the molar extinction coefficient (ε) of the compound may be 90,000 L mol ^-1 cm ^-1 to 100,000 L mol ^-1 cm ^-1 . On the other hand, when the compound has an asymmetric structure, the molar extinction coefficient (ε) of the compound can be as high as 100,000 L mol ^-1 cm ^-1 to 120,000 L mol ^-1 cm ^-1 .

The compound may be selected from the following formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

The definitions of Y ¹ , Y ² , and R ¹ to R ⁴ are the same as in clause 1;

x1 is an integer from 1 to 6, y1 is an integer from 1 to 4;

x2 and y2 are each independently an integer from 1 to 4;

x3 and y3 are each independently integers from 1 to 6.

Among Formulas 1-1 to 1-3, the one with the highest maximum absorption wavelength (λmax) and molar extinction coefficient (ε) is the compound of Formula 1-1 in which at least one of A and B has an asymmetric structure as a naphthalene ring. You can.

The compound may be selected from the group comprising:

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

[Formula 1-1-6]

[Formula 1-1-7]

[Formula 1-1-8]

[Formula 1-1-9]

[Formula 1-1-10]

[Formula 1-1-11]

[Formula 1-1-12]

[Formula 1-1-13]

[Formula 1-1-14]

[Formula 1-1-15]

[Formula 1-1-16]

[Formula 1-1-17]

[Formula 1-1-18]

[Formula 1-1-19]

[Formula 1-1-20]

[Formula 1-1-21]

[Formula 1-1-22]

[Formula 1-1-23]

[Formula 1-1-24]

[Formula 1-1-25]

[Formula 1-1-26]

[Formula 1-1-27]

[Formula 1-1-28]

[Formula 1-1-29]

[Formula 1-1-30]

[Formula 1-1-31]

[Formula 1-1-32]

[Formula 1-1-33]

[Formula 1-1-34]

[Formula 1-1-35]

[Formula 1-1-36]

[Formula 1-2-1]

[Formula 1-2-2]

[Formula 1-2-3]

[Formula 1-2-4]

[Formula 1-2-5]

[Formula 1-2-6]

[Formula 1-2-7]

[Formula 1-2-8]

[Formula 1-2-9]

[Formula 1-2-10]

[Formula 1-2-11]

[Formula 1-2-12]

[Formula 1-2-13]

[Formula 1-2-14]

[Formula 1-2-15]

[Formula 1-2-16]

[Formula 1-2-17]

[Formula 1-2-18]

[Formula 1-2-19]

[Formula 1-2-20]

[Formula 1-2-21]

[Formula 1-2-22]

[Formula 1-2-23]

[Formula 1-2-24]

[Formula 1-2-25]

[Formula 1-2-26]

[Formula 1-2-27]

[Formula 1-2-28]

[Formula 1-2-29]

[Formula 1-2-30]

[Formula 1-2-31]

[Formula 1-2-32]

[Formula 1-2-33]

[Formula 1-2-34]

[Formula 1-2-35]

[Formula 1-2-36]

[Formula 1-3-1]

[Formula 1-3-2]

[Formula 1-3-3]

[Formula 1-3-4]

[Formula 1-3-5]

[Formula 1-3-6]

[Formula 1-3-7]

[Formula 1-3-8]

[Formula 1-3-9]

[Formula 1-3-10]

[Formula 1-3-11]

[Formula 1-3-12]

[Formula 1-3-13]

[Formula 1-3-14]

[Formula 1-3-15]

[Formula 1-3-16]

[Formula 1-3-17]

[Formula 1-3-18]

[Formula 1-3-19]

[Formula 1-3-20]

[Formula 1-3-21]

[Formula 1-3-22]

[Formula 1-3-23]

[Formula 1-3-24]

[Formula 1-3-25]

[Formula 1-3-26]

[Formula 1-3-27]

[Formula 1-3-28]

[Formula 1-3-29]

[Formula 1-3-30]

[Formula 1-3-31]

[Formula 1-3-32]

[Formula 1-3-33]

[Formula 1-3-34]

[Formula 1-3-35]

[Formula 1-3-36]

.

In the group consisting of the above, the highest absorption wavelength (λmax) and molar extinction coefficient (ε) are those of formulas 1-1-1 to 1-1- where at least one of A and B is a naphthalene ring and has an asymmetric structure. It may be a compound of 36.

On the other hand, when the structure of the parent nucleus in the group consisting of the above is the same, the properties of the compound may partially vary depending on the terminal substituents of R ³ and R ⁴ . The effects of the terminal substituent are as described above.

(전자재료용 색재료)(Color materials for electronic materials)

Here, “electronic materials” are not particularly limited, but include display devices such as liquid crystal displays (LCDs) and organic light emitting devices (OLEDs); Image sensors such as charge coupled device (CCD) and complementary metal-oxide semiconductor (CMOS) image sensors; Electronic and electrical components such as prepreg, resin sheets, build-up materials, non-conductive films, metal foil-clad laminates, and printed wiring boards; Refers to materials used in, etc.

As described above, the compound has a maximum absorption wavelength (λmax) of 500 nm to 580 nm and can function as a yellow dye. Moreover, since the compound has a significantly high molar extinction coefficient (ε) of 90,000 L mol ^-1 cm ^-1 to 100,000 L mol ^-1 cm ^-1 , a high level of color reproducibility is achieved even when the amount applied to the photosensitive resin composition is reduced. It can also contribute to increasing the application amount of other solids (for example, photopolymerizable compounds, etc.) in the photosensitive resin composition.

Hereinafter, descriptions that overlap with the above-mentioned content will be omitted, and the color material for electronic materials will be described.

Since the above compound has sufficiently excellent durability, it has excellent storage stability even when used alone.

In order to supplement the storage stability of the compound, a core-shell compound can be prepared using the compound as a core and further comprising a shell surrounding the core.

Specifically, the shell may be represented by the following formula (2):

[Formula 2]

In Formula 2,

a1 and a2 are each independently integers from 0 to 4;

n is an integer from 2 to 10.

The shell represented by Formula 2 is a rotaxane-based macrocyclic compound and contains an amide bond (-CONH-). Accordingly, the hydrogen atom included in the amide bond of the shell represented by Formula 2 may form a non-covalent bond with the oxygen atom of the compound represented by Formula 1. Specifically, the two atoms form a hydrogen bond, which can enhance the durability of the core-shell compound.

Specifically, one of Z ¹ and Z ² may be *-CH-* or a nitrogen atom, and the other may be *-CH-*. When introducing a nitrogen atom as either of Z ¹ and Z ² , compared to the case where it is not introduced at all, the non-covalent bond between the shell and the core, or the non-covalent bond inside the shell increases, so that the core- The durability of the shell compound can be further strengthened.

X ¹ and X ² are each independently a halogen group, and d1+d2 may be an integer of 1 to 8. When introducing a fluorine atom as at least one of X ¹ ^and there is. For example, both X ¹ and X ² may be fluorine atoms (i.e., F), and a1+a2 may be 8.

L ¹ and L ² may each independently be a C1 to C10 alkylene group. In this case, solubility is excellent and it is easy to form a structure in which the shell surrounds the core. For example, both L ¹ and L ¹ may be methylene groups (ie, *-CH ₂ -*).

The n may be 2.

The shell may be represented by any of the following formulas 2-1 to 2-4:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

.

Among 2-1 to 2-4, when the structure of the parent nucleus is the same, there is an effect of shifting the maximum absorption peak of the core-shell compound using a shell substituted with a fluorine atom to a longer wavelength region.

The cage width of the shell may be 6.5 Å to 7.5 Å, and the volume of the shell may be 10 Å to 16 Å. As used herein, the cage width refers to the distance inside the shell, for example, the distance between two different phenylene groups with methylene groups connected to both sides in the shell represented by Chemical Formula 2 (see Figure 1). When the shell has a cage width within the above range, a core-shell compound having a structure surrounding the core represented by Formula 1 can be obtained, and accordingly, when the core-shell compound is added to the photosensitive resin composition, durability is increased. A photosensitive resin film with excellent and high brightness can be realized.

Meanwhile, the core-shell compound may include a core containing the compound represented by Formula 1 and the shell at a molar ratio of 1:1. When the core and shell are present in the above molar ratio, a coating layer (shell) surrounding the core containing the compound represented by Formula 1 can be well formed.

X ¹ and X ² are each independently *-CR ¹ R ² -*, *-O-* or *-S-*; R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

Specifically, X ¹ and X ² are each independently *-CR ¹ R ² -*, and R ¹ and R ² may each independently be a substituted or unsubstituted C1 to C5 alkyl group. For example, R ¹ and R ² may both be CH ₃ , and X ¹ and X ² may both be *-C(CH ₃ ) ₂ -*.

Y ¹ to Y ⁴ are each independently a hydrogen atom, a halogen atom, a furanyl group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group; At least one of Y ¹ to Y ⁴ is a C1 to C20 alkoxy group whose terminal is substituted with a furanyl group.

Specifically, one of Y ¹ and Y ² may be a C1 to C20 alkoxy group whose terminal end is substituted with a furanyl group, and the other may be a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. For example, Y ² may be a C1 to C20 alkoxy group whose terminal is substituted with a furanyl group, and Y ¹ may be a hydrogen atom.

In addition, one of Y ³ and Y ⁴ may be a C1 to C20 alkoxy group whose terminal end is substituted with a furanyl group, and the other may be a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. For example, Y ³ may be a C1 to C20 alkoxy group whose terminal is substituted with a furanyl group, and Y ⁴ may be a hydrogen atom.

A ¹ and A ² are each independently an anionic substituent or a C1 to C20 alkyl group containing an anionic substituent at the terminal.

Specifically, the anionic substituent may be a substituent represented by any one of the following Formulas A-1 to Formula A-5:

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

.

L ¹ to L ³ are each independently, the same or different, *-O-*, *-CO-*, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group. am.

Specifically, L ¹ and L ³ may each independently be a substituted or unsubstituted C1 to C10 alkylene group. For example, L ¹ and L ³ may each independently be a substituted or unsubstituted C1 to C5 alkylene group.

Additionally, L ² may be a substituted or unsubstituted C1 to C10 alkylene group. For example, L ² may be a substituted or unsubstituted C1 to C5 alkylene group.

a to c may each independently be an integer of 1 to 10, specifically an integer of 1 to 5, for example, an integer of 1 to 3.

Representative examples of compounds represented by Formula 1 are as follows:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

.

The compound represented by Formula 1 may have maximum absorbance in the wavelength range of 450 nm to 780 nm.

(감광성 수지 조성물)(Photosensitive resin composition)

Another embodiment provides a photosensitive resin composition containing any one of the compound and the color material for electronic materials.

As it contains either the compound or the color material for electronic materials, it exhibits excellent optical properties, heat resistance, chemical resistance, etc., and can be usefully used in the production of a yellow color filter.

The photosensitive resin composition may include any one of the compound and the color material for electronic materials as a dye, and may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Hereinafter, each of the above components will be described in detail.

coloring agent

The colorant includes a dye, and the dye may include any one of the compound and the color material for electronic materials.

The dye may be a yellow dye.

In addition to including any one of the compound and the coloring material for electronic materials, the colorant may further include an organic solvent-soluble dye.

Examples of the organic solvent-soluble dye include triarylmethane-based compounds, anthraquinone-based compounds, benzylidene-based compounds, xanthene-based compounds, phthalocyanine-based compounds, azaporphyrin-based compounds, and indigo-based compounds.

The colorant may further include a pigment in addition to the dye.

The pigment may include blue pigment, violet pigment, red pigment, green pigment, yellow pigment, etc.

Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Blue Pigment 16, C.I. Blue Pigment 22, C.I. Blue Pigment 60, C.I. Blue Pigment 64, C.I. Blue pigment 80 or a combination thereof may be mentioned.

Examples of the violet pigment include C.I. Violet pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet Pigment 27, C.I. Violet Pigment 28, C.I. Violet Pigment 29, C.I. Violet Pigment 30, C.I. Violet Pigment 32, C.I. Violet Pigment 37, C.I. Violet Pigment 40, C.I. Violet Pigment 42, C.I. Violet Pigment 50 or a combination thereof may be mentioned.

Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red Pigment 179, C.I. Red pigment 89, etc. can be mentioned.

Examples of the green pigment include C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Pigment Green 58, C.I. and halogenated phthalocyanine-based pigments such as Pigment Green 59.

Examples of the yellow pigment include C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, etc. can be mentioned, and these can be used alone or in a mixture of two or more types.

The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment within the solvent.

The solid pigment is 1% to 20% by weight, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% by weight to 10% by weight, based on the total amount of the pigment dispersion. It may be included at 15% by weight.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid. Salts, alkylamide alkylene oxide adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more.

Examples of commercially available dispersants include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 1% to 20% by weight based on the total amount of the pigment dispersion. When the dispersant is included within the above range, an appropriate viscosity can be maintained and the dispersibility of the photosensitive resin composition is excellent. As a result, optical, physical and chemical qualities can be maintained when the product is applied.

Solvents for forming the pigment dispersion include ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono)methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc.

The colorant may be included in an amount of 5% to 30% by weight, for example, 5% to 25% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the color reproduction rate is excellent, and the curability and adhesion of the pattern are excellent.

binder resin

The binder resin may include an acrylic binder resin, a cardo-based binder resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; These can be mentioned, and these can be used alone or in a mixture of two or more.

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Examples include, but are not limited to, acrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and these may be used alone or in combination of two or more types. there is.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate when manufacturing a color filter.

The acid value of the acrylic binder resin may be 15 mgKOH/g to 60 mgKOH/g, for example, 20 mgKOH/g to 50 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cardo-based binder resin may include a repeating unit represented by the following formula (3).

[Formula 3]

In Formula 3 above,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

L ³ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ (wherein R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following Any one of the linking groups represented by Formulas 4-1 to 4-11,

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Formula 4-5 above,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.)

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

L ⁴ is an acid dianhydride residue,

m1 and m2 are each independently integers from 0 to 4.

The cardo-based binder resin may include a functional group represented by the following formula (5) at at least one of both ends.

[Formula 5]

In Formula 5 above,

Z ³ may be represented by the following formulas 6-1 to 6-7.

[Formula 6-1]

(In Formula 6-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

(In Formula 6-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Formula 6-6]

[Formula 6-7]

The cardo-based binder resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic acid dianhydride, perylene tetracarboxylic acid dianhydride. , anhydride compounds such as tetrahydrofuran tetracarboxylic acid dianhydride and tetrahydrophthalic acid anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; Solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the cardo-based binder resin is used together with the acrylic binder resin described above, a photosensitive resin composition with excellent adhesion and high-resolution and high-brightness characteristics can be obtained.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 3,000 g/mol to 30,000 g/mol. If the weight average molecular weight of the cardo-based binder resin is within the above range, a pattern can be easily formed without residue when manufacturing a color filter, there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may have an acid value of 100 mgKOH/g to 140 mgKOH/g.

The binder resin may be included in an amount of 1% to 10% by weight, for example, 1% to 7% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability, and adhesion can be obtained.

photopolymerizable compound

The photopolymerizable compound may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern with excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization upon exposure to light in the pattern formation process.

Specific examples of photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di. (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Rate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate ) acrylate, tris (meth)acryloyloxyethyl phosphate, novolak epoxy (meth)acrylate, etc.

Examples of commercially available photopolymerizable compounds are as follows. Examples of the monofunctional ester of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® manufactured by Toagosei Chemical Co., Ltd.; Nippon Kayaku Co., Ltd.'s KAYARAD TC-110S ^® , KAYARAD TC-120S ^® , etc.; Examples include V-158 ^® and V-2311 ^® manufactured by Osaka Yuki Chemical Co., Ltd. Examples of the above-mentioned difunctional ester of (meth)acrylic acid include Aronics M-210 ^® , M-240 ^® , and M-6200 ^® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , HX-220 ^® , R-604 ^® , etc.; Examples include V-260 ^® , V-312 ^® , and V-335 HP ^® manufactured by Osaka Yuki Chemical Engineering Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronics M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , and M manufactured by Toagosei Chemical Co., Ltd. -710 ^® , M-8030 ^® , M-8060 ^® , etc.; Nippon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , DPCA-20 ^® , Dong-30 ^® , Dong-60 ^® , Dong-120 ^® , etc.; Examples include V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , and Dong-400 ^® manufactured by Osaka Yuki Kayaku Kogyo Co., Ltd. The above products can be used alone or in combination of two or more types.

The photopolymerizable compound may be used by treating it with an acid anhydride to provide better developability.

The photopolymerizable compound may be included in an amount of 5% to 15% by weight, for example, 5% to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, and also excellent resolution and adhesion.

photopolymerization initiator

The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. You can use it.

Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

Examples of the oxime-based compounds include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime) )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime- O-acetate, etc. can be mentioned.

In addition to the above compounds, the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and fluorene-based compounds.

The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 0.1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure during the pattern formation process to obtain excellent reliability, the heat resistance, light resistance, and chemical resistance of the pattern are excellent, resolution and adhesion are also excellent, and the non-reacted initiator is used. This can prevent a decrease in transmittance due to

menstruum

The solvent may be a material that is compatible with, but does not react with, a compound, a pigment, a binder resin, a photopolymerizable compound, and a photopolymerization initiator according to one embodiment.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Alkyl oxyacetic acid esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionate esters such as methyl 2-oxy-2-methyl propionate, ethyl 2-oxy-2-methyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as ethyl methyl propionate; esters such as ethyl 2-hydroxy propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxy acetate, and 2-hydroxy-3-methyl methyl butanoate; Keto acid esters such as ethyl pyruvate, and others include N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can be mentioned.

Among these, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate may be used.

The solvent may be included in a residual amount, for example, 40% by weight to 80% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, thereby improving processability when manufacturing the photosensitive resin film in the color filter.

Other additives

The photosensitive resin composition contains malonic acid to prevent stains or spots upon application, to improve leveling performance, and to prevent the creation of residues due to non-development; 3-amino-1,2-propanediol; Silane-based coupling agents having reactive substituents such as carboxyl group, methacryloyl group, isocyanate group, and epoxy group; leveling agent; Fluorine-based surfactant; It may further include additives such as a radical polymerization initiator.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ-gly. Sidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be used alone or in combination of two or more.

The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

The photosensitive resin composition may further include an epoxy compound to improve adhesion to the substrate.

Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the above range, adhesion, storage, etc. are excellent.

Additionally, the photosensitive resin composition may further include a surfactant, if necessary, to improve coating properties and prevent defects.

A fluorine-based surfactant may be used as the surfactant, and examples of the fluorine-based surfactant include DIC's F-482, F-484, F-478, and F-554, but are not limited thereto.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, coating uniformity is ensured, stains do not occur, and wetting on the glass substrate is excellent.

Additionally, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within the range that does not impair the physical properties.

(감광성 수지막, 컬러 필터 및 디스플레이 장치)(Photosensitive resin film, color filter and display device)

According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition is provided. According to another embodiment, a color filter including the photosensitive resin film is provided.

The pattern formation process within the color filter is as follows.

A process of applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing, etc.; A step of drying the applied photosensitive resin composition to form a photosensitive resin composition film; A process of exposing the photosensitive resin composition film; A process of developing the exposed photosensitive resin composition film with an aqueous alkaline solution to produce a photosensitive resin film; and a step of heat treating the photosensitive resin film. Since the above process conditions are widely known in the field, detailed description will be omitted in this specification.

According to another embodiment, a display device including the color filter is provided. The display device may be a liquid crystal display (LCD), an organic light emitting diode (OLED), or the like.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

(화합물의 합성)(Synthesis of compounds)

합성예 1: 화학식 1-1-1로 표시되는 화합물의 합성Synthesis Example 1: Synthesis of a compound represented by Formula 1-1-1

A) An ethanol (10 fold) solution containing 1 equivalent of 3-butyl-2-methylnaphtho[2,1-d][1,3]oxazol-3-ium iodide is mixed with 1 equivalent of triethylamine and ethyl scour. It was added dropwise to an ethanol (1 fold) solution containing 1 equivalent of arate at room temperature, stirred for 20 hours, and then heated to reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

B) 3-ethoxy-4-{[(2Z)-3-butyl-2H,3H-naphtho[2,1-d][1,3]oxazol-2-ylidene]methyl obtained from A) } Reflux an ethanol (10fold) solution containing 1 equivalent of cyclobutane-1,2-dione, 1 equivalent of 3-butyl-2-methyl-1,3-benzooxazol-3-ium iodide, and 0.1 equivalent of triethylamine. Heated. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.78-6.57(m,4H), 5.32(s,1H), 4.56(s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 1.71-1.65(m,4H), 1.54-1.47(m,4H), 1.00( t,6H); LC-MS(m/z): 509.6

[Formula 1-1-1]

합성예 2: 화학식 1-1-5로 표시되는 화합물의 합성Synthesis Example 2: Synthesis of a compound represented by Formula 1-1-5

3-Ethoxy-4-{[(2Z)-3-butyl-2H,3H-naphtho[2,1-d][1,3]oxazole-2-, a compound obtained in A) of Synthesis Example 1 [ylidene]methyl}ethanol (10fold) containing 1 equivalent of cyclobutane-1,2-dione, 1 equivalent of 3-butyl-2-methyl-1,3-benzothiazol-3-ium iodide, and 0.1 equivalent of triethylamine. ) The solution was heated to reflux. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography. ¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.81-6.59(m,4H), 5.48(s,1H), 4.56 (s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 1.71-1.65(m,4H), 1.54-1.47(m,4H), 1.00( m,6H); LC-MS(m/z): 525.7

[Formula 1-1-5]

합성예 3: 화학식 1-1-9로 표시되는 화합물의 합성Synthesis Example 3: Synthesis of a compound represented by Formula 1-1-9

3-Ethoxy-4-{[(2Z)-3-butyl-2H,3H-naphtho[2,1-d][1,3]oxazole-2-, a compound obtained in A) of Synthesis Example 1 Ethane]methyl}ethanol (10fold) solution containing 1 equivalent of cyclobutane-1,2-dione, 1 equivalent of 3-butyl-2-methyl-1,1'-ㅣmethylindolium iodide, and 0.1 equivalent of triethylamine. was heated to reflux. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography. ¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.81-6.59(m,4H), 5.48(s,1H), 4.56 (s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 1.71-1.65(m,4H), 1.54-1.47(m,4H), 1.37( s, 6H), 1.01(m, 6H); LC-MS(m/z): 535.2

[Formula 1-1-9]

합성예 4: 화학식 1-1-10으로 표시되는 화합물의 합성Synthesis Example 4: Synthesis of a compound represented by Formula 1-1-10

A) An ethanol (10 fold) solution containing 1 equivalent of 3-(4-sulfonebutyl)-2-methylnaphtho[2,1-d][1,3]oxazol-3-ium iodide was mixed with triethylamine. It was added dropwise to an ethanol (1 fold) solution containing 1 equivalent of ethyl squarate at room temperature, stirred for 20 hours, and then heated to reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

B) 3-ethoxy-4-{[(2Z)-3-(4-sulfonbutyl)-2H,3H-naphtho[2,1-d][1,3]oxazole-2 obtained from A) -ylidene]methyl}cyclobutane-1,2-dione, 1 equivalent, 3-(4-sulfonbutyl)-2-methyl-1,1'-dimethylindolium iodide, 1 equivalent, and 0.1 equivalent of triethylamine. The ethanol (10fold) solution was heated to reflux. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.81-6.59(m,4H), 5.48(s,1H), 4.56 (s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 3.06(t,2H), 3.00(t,2H), 1.71-1.65(m, 4H), 1.54-1.47(m, 4H), 1.37(s, 6H); LC-MS(m/z): 693.1

[Formula 1-1-10]

합성예 5: 화학식 1-1-11로 표시되는 화합물의 합성Synthesis Example 5: Synthesis of a compound represented by Formula 1-1-11

A) An ethanol (10 fold) solution containing 1 equivalent of 3-(4-acryloylbutyl)-2-methylnaphtho[2,1-d][1,3]oxazol-3-ium iodide was triturated. It was added dropwise to an ethanol (1 fold) solution containing 1 equivalent of ethylamine and 1 equivalent of ethyl squarate at room temperature, stirred for 20 hours, and then heated to reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

B) 3-Ethoxy-4-{[(2Z)-3-(4-acryloylbutyl)-2H,3H-naphtho[2,1-d][1,3]oxazole obtained from A) -2-ylidene]methyl} 1 equivalent of cyclobutane-1,2-dione and 1 equivalent of 3-(4-acryloylbutyl)-2-methyl-1,1'-dimethylindolium iodide, triethylamine A solution containing 0.1 equivalent of ethanol (10 fold) was heated to reflux. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.81-6.59(m,4H), 6.37(dd,2H), 6.08(dd,2H), 5.95(dd,2H), 5.48(s,1H), 4.56 (s,1H), 4.16(m,4H), 3.71(dd,2H), 3.54 -3.45(m,4H), 1.71-1.65(m,4H), 1.54-1.47(m,4H), 1.37(s, 6H); LC-MS(m/z): 675.2

[Formula 1-1-11]

합성예 6: 화학식 1-1-12로 표시되는 화합물의 합성Synthesis Example 6: Synthesis of a compound represented by Formula 1-1-12

A) An ethanol (10 fold) solution containing 1 equivalent of 3-(4-epoxybutyl)-2-methylnaphtho[2,1-d][1,3]oxazol-3-ium iodide was mixed with triethylamine. It was added dropwise to an ethanol (1 fold) solution containing 1 equivalent of ethyl squarate at room temperature, stirred for 20 hours, and then heated to reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

B) 3-ethoxy-4-{[(2Z)-3-(4-epoxybutyl)-2H,3H-naphtho[2,1-d][1,3]oxazole-2 obtained from A) -Ylidene]methyl}cyclobutane-1,2-dione, 1 equivalent, 3-(4-epoxybutyl)-2-methyl-1,1'-dimethylindolium iodide, 1 equivalent, and 0.1 equivalent of triethylamine. The ethanol (10fold) solution was heated to reflux. After 2 hours, completion of the reaction was confirmed using thin layer chromatography, heating was stopped, and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography.

¹ H-NMR (δ ppm): 7.67-7.61(m,2H), 7.23-7.18(m,2H), 7.10(d,1H), 7.08(d,1H), 6.81-6.59(m,4H), 5.48(s,1H), 4.56 (s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 2.86-2.81(m,2H), 2.59-2.55(m,2H), 2.47- 2.41(m,2H), 1.71-1.65(m,4H), 1.56-1.47(m,8H), 1.37(s, 6H); LC-MS(m/z): 618.2

[Formula 1-1-12]

합성예 7: 화학식 1-2-1로 표시되는 화합물의 합성Synthesis Example 7: Synthesis of a compound represented by Formula 1-2-1

An ethanol (10 fold) solution containing 2 equivalents of 3-butyl-2-methylbenzoxazol-3-ium iodide is mixed with an ethanol (1 fold) solution containing 1 equivalent of triethylamine and 1 equivalent of ethyl squarate at room temperature. After the dropwise addition, the mixture was stirred for 20 hours and then heated under reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography. ¹ H-NMR (δ ppm): 6.78-6.57(m,8H), 4.56 (s,2H), 3.71(dd,2H), 3.66(t,2H), 3.54(t,2H), 1.71.65( m,4H), 1.54-1.47(m,4H), 1.02(t,6H); LC-MS(m/z): 458.03

[Formula 1-2-1]

합성예 8: 화학식 1-3-1로 표시되는 화합물의 합성Synthesis Example 8: Synthesis of a compound represented by Formula 1-3-1

An ethanol (10 fold) solution containing 2 equivalents of 3-butyl-2-methylnaphtho[2,1-d][1,3]oxazol-3-ium iodide is mixed with 1 equivalent of triethylamine and ethyl squarate. It was added dropwise to a solution containing 1 equivalent of ethanol (1 fold) at room temperature, stirred for 20 hours, and then heated to reflux for 3 hours. The completion of the reaction was confirmed using thin layer chromatography, and after completion of the reaction, heating was stopped and the solvent was removed using a rotary concentrator. The remaining product was purified using silica chromatography. ¹ H-NMR (δ ppm): 7.67-7.61(m,4H), 7.23-7.18(m,4H), 7.10(d,2H), 7.08(d,2H), 5.48(s,1H), 4.56 ( s,1H), 3.71(dd,2H), 3.54-3.45(m,4H), 1.71-1.65(m,4H), 1.54-1.47(m,4H), 1.03(m,6H); LC-MS(m/z): 559.3

[Formula 1-3-1]

비교합성예 1: 화학식 A로 표시되는 화합물의 합성Comparative Synthesis Example 1: Synthesis of the compound represented by Formula A

By the method described in KR 10-2194873 B1, a compound represented by the following formula A (CAS No. 1982310-13-3) was synthesized:

[Formula A]

(감광성 수지 조성물의 합성)(Synthesis of photosensitive resin composition)

실시예 1Example 1

The photosensitive resin composition according to Example 1 was prepared by mixing the components mentioned below in the composition shown in Table 1 below.

Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Then, an acrylic binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 2 hours. Next, a compound (dye) and a pigment (in the form of a pigment dispersion) represented by Chemical Formula 1-1-1 as a colorant were added to the obtained reaction product and stirred at room temperature for 1 hour. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%)

배합원료Mixed raw materials			함량content
착색제coloring agent	염료dyes	화학식 1-1-1로 표시되는 화합물Compound represented by formula 1-1-1	5.05.0
착색제coloring agent	안료 분산액pigment dispersion	Pigment Y138 안료 분산액Pigment Y138 pigment dispersion	15.015.0
알칼리 가용성 수지Alkali soluble resin		(A)/(B)=15/85(w/w), 분자량(Mw)=22,000g/mol (A): 메타크릴산 (B): 벤질메타크릴레이트(A)/(B)=15/85(w/w); Molecular weight (Mw)=22,000g/mol (A): Methacrylic acid (B): Benzyl methacrylate	3.53.5
광중합성 화합물photopolymerizable compound		디펜타에리트리톨헥사아크릴레이트(DPHA)Dipentaerythritol hexaacrylate (DPHA)	8.08.0
광중합 개시제photopolymerization initiator		1,2-옥탄디온1,2-octanedione	1.01.0
광중합 개시제photopolymerization initiator		2-디메틸아미노-2-(4-메틸-벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one	0.50.5
용매menstruum		사이클로헥사논Cyclohexanone	37.037.0
용매menstruum		PGMEA(Propylene Glycol Monomethyl Ether Acetate)Propylene Glycol Monomethyl Ether Acetate (PGMEA)	30.030.0
총량(Total)Total			100.00100.00

Example 2 A photosensitive resin composition was prepared in the same manner as Example 1, except that the compound represented by Formula 1-1-5 was used instead of the compound represented by Formula 1-1-1.

실시예 3Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-1-9 was used instead of the compound represented by Formula 1-1-1.

실시예 4Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-1-10 was used instead of the compound represented by Formula 1-1-1.

실시예 5Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-1-11 was used instead of the compound represented by Formula 1-1-1.

실시예 6Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-1-12 was used instead of the compound represented by Formula 1-1-1.

실시예 7Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-2-1 was used instead of the compound represented by Formula 1-1-1.

실시예 8Example 8

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-3-1 was used instead of the compound represented by Formula 1-1-1.

비교예 1Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula A was used instead of the compound represented by Formula 1-1-1.

평가 1: 광 특성Evaluation 1: Optical properties

The optical properties were evaluated using the compounds prepared in Synthesis Examples 1 to 8 and Comparative Synthesis Example 1.

Specifically, the compounds prepared in Synthesis Examples 1 to 8 and Comparative Synthesis Example 1 were mixed with a diluent solvent (PGMEA) to prepare a diluted solution with a concentration of 0.005 wt%, which was measured using an ultraviolet-visible spectrophotometer (model name: UV- 2550, manufacturer: Shimazu Seisakusho (島津製作所), and an absorption spectrum was obtained.

In each absorption spectrum for the compounds prepared in Synthesis Examples 1 to 8 and Comparative Synthesis Example 1, the wavelength (λmax) and molar extinction coefficient (ε) representing the maximum absorbance were determined and listed in Table 2 below.

	최대 흡수 파장(nm)Maximum absorption wavelength (nm)	몰 흡광계수(L mol^-1　cm^-1)Molar extinction coefficient (L mol ^-1 cm ^-1 )
합성예 1Synthesis Example 1	512512	97,24097,240
합성예 2Synthesis Example 2	510510	98,16098,160
합성예 3Synthesis Example 3	517517	114,100114,100
합성예 4Synthesis Example 4	519519	113,200113,200
합성예 5Synthesis Example 5	518518	101,485101,485
합성예 6Synthesis Example 6	519519	103,425103,425
합성예 7Synthesis Example 7	504504	89,16089,160
합성예 8Synthesis Example 8	517517	93,10093,100
비교합성예 1Comparative Synthesis Example 1	432432	45,33345,333

According to Table 3, the compounds of Synthesis Examples 1 to 8 have a maximum absorption wavelength (λmax) of 500 nm to 580 nm and can function as a yellow dye, which is 1, which has a maximum absorption wavelength (λmax) of 700 nm to 850 nm. It is possible to achieve a completely different color from 3-squarene-based compounds. In addition, the molar extinction coefficient (ε) of the generally known yellow dye (Comparative Synthesis Example 1) is about 40,000 L mol ^-1 cm ^-1 to 60,000 L mol ^{- 1} cm ^-1 , whereas the compounds of Synthesis Examples 1 to 8 have a significantly higher molar extinction coefficient (ε) of 90,000 L mol ^-1 cm ^-1 to 100,000 L mol ^-1 cm ^-1 .

Accordingly, the compounds of one embodiment, represented by the compounds of Synthesis Examples 1 to 8, can exhibit a high level of color reproducibility even when the amount applied to the photosensitive resin composition is reduced compared to the generally known yellow dye, and the photosensitive resin composition It can also contribute to increasing the application amount of other solids (for example, photopolymerizable compounds, etc.).

Meanwhile, among the compounds of Synthesis Examples 1 to 8, those with the highest maximum absorption wavelength (λmax) and molar extinction coefficient (ε) are the compounds (Synthesis Examples 1 to 6) having an asymmetric structure including a naphthalene ring on at least one side. .

평가 2: 색 특성(휘도), 내열성 및 내화학성Evaluation 2: Color characteristics (brightness), heat resistance and chemical resistance

The photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Example 1 were applied to a thickness of 1 ㎛ to 3 ㎛ on a degreased 1 mm thick glass substrate using a spin coater at 250 rpm to 350 rpm. After coating under the conditions, prebaking was performed on a hot plate at 90°C. Afterwards, full exposure was performed under the condition of 50mJ/cm ² in the exposure machine, and then development was performed for 60 seconds and water washing for 60 seconds using 111x KOH developer in the developer under the condition of washing solution/developer = 1/0.8 to obtain the development history. gave it After development, post-baking was performed in an oven at 230°C/20 minutes to complete the production of color chips.

(1) Color characteristics: The color characteristics of the produced color specimen were evaluated based on C light source using MCPD (Otsuka) equipment, and the luminance (RY) was calculated based on Rx 0.658, and are shown in Table 4 below. It was.

(2) Heat resistance: After the color specimen produced above was additionally treated at 230°C/60 minutes using a convection oven, the color change before and after treatment was measured using MCPD (Otsuka) equipment to determine the color characteristics based on the C light source. The evaluation was performed, and the ΔEab* value was calculated and the results are shown in Table 4 below.

(3) 　Chemical resistance: After producing the above-produced color specimen in a size of 1㎝ Analysis was conducted. After obtaining the ABS and quantitative curves for each color specimen, the amount eluted was calculated and shown in Table 3 below.

	휘도 (%)Luminance (%)	내열성 (@230℃, 60min)Heat resistance (@230℃, 60min)	내화학성 (ppm)Chemical resistance (ppm)
합성예 1Synthesis Example 1	18.2418.24	2.152.15	1.21.2
합성예 2Synthesis Example 2	18.1718.17	2.242.24	1.31.3
합성예 3Synthesis Example 3	18.1518.15	2.362.36	1.31.3
합성예 4Synthesis Example 4	18.1318.13	1.341.34	1.11.1
합성예 5Synthesis Example 5	18.2218.22	0.950.95	0.80.8
합성예 6Synthesis Example 6	18.2418.24	1.281.28	0.70.7
합성예 7Synthesis Example 7	18.1518.15	2.262.26	1.31.3
합성예 8Synthesis Example 8	18.2118.21	2.142.14	1.11.1
비교합성예 1Comparative Synthesis Example 1	17.7517.75	1.041.04	0.90.9

The compounds of Synthesis Examples 1 to 8 are all superior in brightness, heat resistance, and chemical resistance compared to the compounds of Comparative Synthesis Example 1. Meanwhile, among the compounds of Synthesis Examples 1 to 8, when the structures of the parent nucleus are the same, the properties of the compounds are partially different depending on the terminal substituent. The properties of the compound may vary depending on the type of terminal substituent. For example, if the terminal substituent is a sulfurous acid (Sulfite, *-SO ₃ ) group, water solubility (Synthesis Example 4), if the terminal substituent is a (meth)acrylate group, heat resistance (Synthesis Example 5), and if the terminal substituent is an epoxy group, chemical resistance (Synthesis Example 6) will be strengthened. You can.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and this also applies to the present invention. It is natural that it falls within the scope of the invention.

Claims

Compound represented by Formula 1:

[Formula 1]

In Formula 1,

A and B are each independently a C6 to C20 aromatic ring, or a C2 to C20 heteroaromatic ring containing 1 to 3 heteroatoms each independently selected from the group consisting of N, O and S;

Y 1 and Y 2 are each independently *-O-*, *-S-*, or *-CR 1 R 2 -*; Here, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group;

R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

x and y are each independently integers from 1 to 18.
According to paragraph 1,

A compound wherein A and B are each independently a benzene ring or a naphthalene ring.
According to paragraph 2,

A compound wherein at least one of A and B is a naphthalene ring.
According to paragraph 1,

Y 1 and Y 2 are each independently *-O-*, *-S-*, or *-C(CH 3 ) 2 -*.
According to paragraph 4,

A compound in which Y 1 and Y 2 are different from each other.
According to paragraph 1,

R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1 to C20 alkyl group; A compound in which the substituent of the C1 to C20 alkyl group is a sulfurous acid (*-SO 3 ) group, a (meth)acrylate group, or an epoxy group.
According to clause 6,

A compound in which R 1 and R 2 are different from each other.
According to paragraph 1,

R 3 and R 4 are each independently a substituted or unsubstituted C1 to C20 alkyl group; A compound in which the substituent of the C1 to C20 alkyl group is a sulfurous acid (*-SO 3 ) group, a (meth)acrylate group, or an epoxy group.
According to clause 8,

R 3 and R 4 are the same compound.
According to paragraph 1,

A compound whose maximum absorption wavelength (λmax) is 500 nm to 580 nm.
According to paragraph 1,

The compound has a molar extinction coefficient (ε) of 90,000 L mol -1 cm -1 to 120,000 L mol -1 cm -1 .
According to paragraph 1,

The compound is selected from the following formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

The definitions of Y 1 , Y 2 , and R 1 to R 4 are the same as in clause 1;

x1 is an integer from 1 to 6, y1 is an integer from 1 to 4;

x2 and y2 are each independently an integer from 1 to 4;

x3 and y3 are each independently integers from 1 to 6.
According to paragraph 1,

The compound is selected from the group comprising:

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

[Formula 1-1-6]

[Formula 1-1-7]

[Formula 1-1-8]

[Formula 1-1-9]

[Formula 1-1-10]

[Formula 1-1-11]

[Formula 1-1-12]

[Formula 1-1-13]

[Formula 1-1-14]

[Formula 1-1-15]

[Formula 1-1-16]

[Formula 1-1-17]

[Formula 1-1-18]

[Formula 1-1-19]

[Formula 1-1-20]

[Formula 1-1-21]

[Formula 1-1-22]

[Formula 1-1-23]

[Formula 1-1-24]

[Formula 1-1-25]

[Formula 1-1-26]

[Formula 1-1-27]

[Formula 1-1-28]

[Formula 1-1-29]

[Formula 1-1-30]

[Formula 1-1-31]

[Formula 1-1-32]

[Formula 1-1-33]

[Formula 1-1-34]

[Formula 1-1-35]

[Formula 1-1-36]

[Formula 1-2-1]

[Formula 1-2-2]

[Formula 1-2-3]

[Formula 1-2-4]

[Formula 1-2-5]

[Formula 1-2-6]

[Formula 1-2-7]

[Formula 1-2-8]

[Formula 1-2-9]

[Formula 1-2-10]

[Formula 1-2-11]

[Formula 1-2-12]

[Formula 1-2-13]

[Formula 1-2-14]

[Formula 1-2-15]

[Formula 1-2-16]

[Formula 1-2-17]

[Formula 1-2-18]

[Formula 1-2-19]

[Formula 1-2-20]

[Formula 1-2-21]

[Formula 1-2-22]

[Formula 1-2-23]

[Formula 1-2-24]

[Formula 1-2-25]

[Formula 1-2-26]

[Formula 1-2-27]

[Formula 1-2-28]

[Formula 1-2-29]

[Formula 1-2-30]

[Formula 1-2-31]

[Formula 1-2-32]

[Formula 1-2-33]

[Formula 1-2-34]

[Formula 1-2-35]

[Formula 1-2-36]

[Formula 1-3-1]

[Formula 1-3-2]

[Formula 1-3-3]

[Formula 1-3-4]

[Formula 1-3-5]

[Formula 1-3-6]

[Formula 1-3-7]

[Formula 1-3-8]

[Formula 1-3-9]

[Formula 1-3-10]

[Formula 1-3-11]

[Formula 1-3-12]

[Formula 1-3-13]

[Formula 1-3-14]

[Formula 1-3-15]

[Formula 1-3-16]

[Formula 1-3-17]

[Formula 1-3-18]

[Formula 1-3-19]

[Formula 1-3-20]

[Formula 1-3-21]

[Formula 1-3-22]

[Formula 1-3-23]

[Formula 1-3-24]

[Formula 1-3-25]

[Formula 1-3-26]

[Formula 1-3-27]

[Formula 1-3-28]

[Formula 1-3-29]

[Formula 1-3-30]

[Formula 1-3-31]

[Formula 1-3-32]

[Formula 1-3-33]

[Formula 1-3-34]

[Formula 1-3-35]

[Formula 1-3-36]

.
A color material for electronic materials containing the compound of claim 1.
According to clause 14,

A color material for electronic materials, comprising the compound of claim 1 as a core and further comprising a shell surrounding the core.
According to clause 15,

The shell is a color material for electronic materials represented by the following formula (2):

[Formula 2]

In Formula 2,

L 1 and L 2 are each independently a substituted or unsubstituted C1 to C10 alkylene group;

Z 1 and Z 2 are each independently *-CR-* or a nitrogen atom, where R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group;

X 1 and X 2 are each independently a halogen group or a substituted or unsubstituted C1 to C10 alkyl group;

a1 and a2 are each independently integers from 0 to 4;

n is an integer from 2 to 10.
A photosensitive resin composition comprising any one of the compounds of claims 1 to 13 and the color materials for electronic materials of claims 14 to 16.
According to clause 17,

The photosensitive resin composition further includes a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
A photosensitive resin film manufactured using the photosensitive resin composition of claim 18.
A color filter comprising the photosensitive resin film of claim 19.
A display device comprising the color filter of claim 20.