KR20160139985A - Low-temperature thermosetting composition for printing, flexible color filter and method for preparing flexible color filter using the same - Google Patents

Abstract

The present invention relates to a low-temperature thermosetting composition for printing, a flexible color filter prepared using the composition, and a preparation method of the color filter, and more specifically, to a low-temperature thermosetting composition for printing comprising novolak resin as a binder resin, a curing agent represented by chemical formula 1, a coloring agent and a solvent; to a flexible color filter prepared from the composition; and to a preparation method of the color filter. The composition is capable of being cured at low temperature, and a flexible filter obtained by using the composition and through the preparation method may not only address the problem of heat deformation in conventional plastic substrates, but also form a high-resolution pattern that cannot be realized on the plastic substrate, and patterns can be diversified without being constrained by substrate film materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a low-temperature thermosetting composition for printing, a flexible color filter manufactured therefrom, and a method of manufacturing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a low temperature thermosetting composition for printing capable of realizing high quality image quality by securing fine pattern formation properties and adhesion even under low temperature conditions, a flexible color filter manufactured therefrom, and a method for manufacturing the same.

As the amount of information that the Internet becomes universal and communication explosively increases, an environment of "ubiquitous display" in which information can be accessed anytime and anywhere will be created in the future. Accordingly, notebooks and electronic notebooks And the role of portable displays such as PDAs have become important. In order to realize such a ubiquitous display environment, it is required that the display is portable so that information can be directly accessed at a desired time and place, and a large screen characteristic for displaying various multimedia information is also required. Therefore, in order to satisfy such portability and large-screen characteristics at the same time, the display should be flexible so that it can be used when it functions as a display, and it can be folded and stored when carrying. Flexible displays are flexible, bendable and versatile next-generation displays that can be used in a variety of forms, including mobile and portable displays, wearable and fashionable displays, and paper-like displays. Research and development is underway.

A typical type of a flat panel display device widely used today is a liquid crystal display (LCD) and an organic light-emitting diode (OLED).

OLED has the advantage of being able to realize a very light and thin screen compared to the conventional LCD, a wide color reproduction range, a fast response time and a high contrast ratio (CR), and besides, it is most suitable for implementing a flexible display It is being actively developed as a display.

Particularly, a white organic light-emitting diode (WOLED) using a white light source instead of a conventional blue light source has high efficiency, high resolution and long life characteristics, and is realized not only as a large-area high- Due to the possibility, studies are being conducted in earnest by researchers at home and abroad.

For WOLED, a color filter is used for full color implementation. The color filter used herein is formed by forming a black matrix (BM) pattern and red, green, blue, and white patterns on a glass substrate.

However, since the glass substrate used in the color filter is large in weight and easily broken by a small external impact, the portability and the display characteristics of a large screen are limited. Therefore, a plastic substrate which is light in weight, strong in impact, and has a flexible characteristic is used.

In addition, there is an increasing need to form the line width and the line spacing of the pattern more finely, as the color filter is required to be miniaturized, light in weight, diversified in performance, and advanced in the WOLED.

For example, a conductive pattern for forming an electrode in various electronic devices, a black matrix of a color filter, or a resist pattern for forming a conductive pattern are widely used, and they are formed more finely as the size and performance of the electronic device are improved There is a need.

The conventional method for forming the pattern varies depending on the application, but typically includes photolithography, inkjet, and printing.

The photolithography method is a method capable of forming a pattern by forming a photosensitive layer with a photosensitive material, selectively exposing and developing it, and patterning.

However, the photolithography process basically proceeds at a high temperature of about 230 ° C., and the cost for the photosensitive material and the etching liquid, which are not included in the final product, disappear and the cost for disposal of the photosensitive material and the etchant increases. . There is also a problem of environmental pollution due to disposal of the above materials. In addition, the method requires a large number of steps and is complicated, resulting in a long time and cost.

The inkjet method is a method of forming a pattern by ejecting ink into a barrier rib pattern through a nozzle. In order to form a pattern of a certain shape and thickness, it is necessary to have a pattern that can act as a partition wall. There is a limit to the formation.

Korean Patent Publication No. 2010-0047029 refers to an electron beam low-temperature curing method capable of curing at a temperature of 100 ° C or lower in the manufacture of a color filter for an electronic display.

Korean Patent Laid-Open Publication No. 2004-0097228 discloses a method of separating a glass substrate and an image receiving layer by irradiating a light such as a laser to a separation layer after sequentially forming a separation layer, a thin film device, an adhesive layer, and a temporary substrate on a glass substrate Method is disclosed.

These patents attempt to improve the thermal instability caused by the use of a plastic substrate, because the plastic material to which the low temperature heat treatment (curing) method can be applied has to be limited, not.

Korean Patent Publication No. 2010-0047029 Korean Patent Publication No. 2004-0097228

Therefore, the inventor of the present invention fabricated a color filter on a WOLED device itself, not on a method of manufacturing a color filter having R, G, B, W, and BM patterns on a plastic substrate and then bonding the WOLED device with the WOLED device, In order to form a pattern through R, G, B, W and BM patterns using a composition which can be heat-treated at a low temperature during the formation of R, G, B, W and BM patterns, thermal deformation problems The present invention has been completed.

Accordingly, an object of the present invention is to provide a low-temperature thermosetting composition for printing which can obtain a fixed three-pattern which is difficult to realize in a conventional plastic substrate and can solve the thermal instability of the plastic substrate.

Another object of the present invention is to provide a flexible color filter formed by using the low temperature thermosetting composition for printing and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a process for producing a color filter comprising a binder resin, a curing agent, a colorant and a solvent,

Wherein the binder resin comprises a novolac resin,

Wherein the curing agent comprises a compound represented by the following general formula (1).

[Chemical Formula 1]

(Wherein R ₁ to R ₄ and n is as described in the specification.)

At this time, the low temperature thermosetting composition for printing further comprises a polyfunctional monomer having an ethylenically unsaturated double bond.

The present invention also provides a flexible color filter comprising a pattern made of the low temperature thermosetting composition for printing.

In this case, the pattern is a BM or RGBW pattern.

In addition,

Forming an RGBW pattern on a planarization layer of a white organic light-emitting diode (WOLED) by a printing process;

Heat-treating the formed RGBW pattern;

Forming a BM pattern between the heat-treated RGBW patterns;

Heat treating the formed BM pattern;

Coating a composition for forming a flattening layer over the RGBW and BM patterns to form a planarization layer; And

Bonding the substrate film coated on one side of the adhesive layer with the planarizing layer,

Wherein the RGBW and BM patterns are made of the low temperature thermosetting composition for printing.

In addition, the present invention provides a flexible white organic light emitting display including the flexible color filter integrated WOLED device.

The low temperature thermosetting composition for printing according to the present invention can overcome the problem of thermal deformation and limitation of formation of fine patterns that occur when a conventional plastic substrate is used.

The flexible color filter using the low temperature thermosetting composition for printing has no deformation of the substrate and can form a fixed three patterns, and it is possible to apply a base film of various plastic materials.

In addition, the flexible color filter is easily applied to a curved surface such as a column, and has excellent color reproduction characteristics as compared with the conventional color filter due to the fixed three-dimensional structure, thereby realizing a vivid image quality.

1 schematically illustrates a reverse offset printing method according to an embodiment of the present invention.
FIGS. 2 to 6 are cross-sectional views of respective steps of a method for manufacturing a flexible color filter integrated WOLED device according to an embodiment of the present invention.

The present invention provides a low temperature thermosetting composition for printing that can be used as a color filter of a flexible white organic light emitting display.

The heat treatment, curing, curing, and baking referred to throughout this specification mean the same process.

The color filter formed a fine pattern by a photolithographic method using a photoresist on a glass substrate to form a fine pattern. However, in the photolithography method, the process is not only performed at a high temperature of about 230 ° C., but also the necessary equipment and various processes such as exposure, development, heat treatment, etching,

Flexible display devices, which have recently been attracting attention, use plastic substrates instead of glass substrates for flexibility, which is unsuitable for high temperature processes and various chemical processes in photolithographic processes. Specifically, the plastic substrate has a low rigidity and a low heat distortion temperature, so that the plastic substrate undergoes a process accompanied by a heat treatment at a high temperature to cause thermal deformation such as warping, twisting, expansion and contraction of the plastic substrate. Therefore, when the process is directly conducted on the plastic substrate, the heat treatment conditions and the like are limited, and the final obtained fine pattern is difficult to control.

Accordingly, the present invention provides a novolak resin as a binder resin and a low-temperature curable thermosetting composition containing a curing agent represented by the formula (1) as an essential component. The reaction between the novolac resin and the curing agent represented by the formula As a result, it is possible to form a fine pattern directly on the device, and the problem caused by thermal deformation of the plastic substrate can be fundamentally eliminated. Further, it is possible to obtain a fixed pattern of a pattern difficult to be implemented on a plastic substrate, and it is possible to diversify the plastic substrate without restriction on the material.

In addition to the novolak resin and the curing agent represented by the formula (1), the low temperature thermosetting composition for printing according to the present invention includes a colorant, a solvent and a polyfunctional monomer having an ethylenically unsaturated double bond.

Each composition will be described below.

The binder resin has heat-activatability, compatibility with other components in the composition, and serves as a binder. The binder resin should have excellent heat resistance, chemical resistance, and mechanical properties when forming a pattern.

In the present invention, the binder resin is a resin containing a hydroxyl group (-OH) capable of reacting with a curing agent described later, and is preferably a novolak resin.

The novolak resin can be obtained by copolymerizing at least one phenol compound and an aldehyde compound.

The phenol compound is not particularly limited and includes, for example, phenols, cresols such as p-cresol, m-cresol and o-cresol, Xylenols such as 3,5-xylenol, 2,5-xylenol, 2,3-xylenol and 3,4-xylenol; 2,3-dimethylphenol, 2,4-dimethylphenol , Dimethylphenol such as 2,5-dimethylphenol, 2,6-dimethylphenol, 3-dimethylphenol and 3,5-dimethylphenol; 2,3,4-trimethylphenol, 2,3,5- Trimethylphenols such as 3,4,5-trimethylphenol and 2,4,5-trimethylphenol;? -Butylphenols such as 2-t-butylphenol, 3-t-butylphenol and 4-t-butylphenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol and 2,3-dichlorophenol; m-methoxyphenol, p-methoxyphenol, o-methoxyphenol, Methoxyphenols such as phenol, 2,5-dimethoxyphenol and 3,5-dimethoxyphenol; p-butoxyphenol; ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 3 , Ethylphenols such as 4,5-triethylphenol, resorcinols such as resorcinol, 2-methyl resorcinol, 4-methyl resorcinol and 5-methyl resorcinol, p-isopropylphenol, Naphthols such as naphthol and? -Naphthol; and methylene bisphenol, methylene bis p-cresol, catechol, and 4-methylresorcin. These may be used alone or in combination of two or more.

The aldehyde compound is not particularly limited and includes, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylaldehyde,? -Phenylpropylaldehyde,? -Hydroxybenzaldehyde, -Hydroxybenzaldehyde, p-hydroxybenzaldehyde, glutaraldehyde, glyoxal, o-methylbenzaldehyde, p-methylbenzaldehyde and the like. These may be used alone or in combination of two or more.

The novolak resin of the present invention can be prepared by the following method. For example, it is a resin obtained by reacting the above-mentioned one or more phenolic compounds and aldehyde compounds in the presence of an acid catalyst at a temperature of 110 to 220 ° C. Specifically, examples of the phenol compound include p-cresol, m-cresol, 3,5-dimethylphenol and the like. As the aldehyde compound, formaldehyde, paraformaldehyde, acetaldehyde and the like can be used. The acid catalyst is not particularly limited, and examples thereof include weak acids such as organic carboxylic acids such as oxalic acid and acetic acid. Of these, either a single compound or a mixture of two or more compounds may be used.

The novolak resin of the present invention preferably has a weight average molecular weight measured by GPC in the range of 1000 to 10000, more preferably in the range of 2500 to 8000. By setting the weight average molecular weight within the above range, moldability and adhesion Can be improved. The weight average molecular weight was calculated on the basis of a calibration curve prepared using a polystyrene standard material. GPC measurement can be carried out by using a differential refractometer as a detector under conditions of a flow rate of 1.0 ml / min and a column temperature of 40 캜 with tetrahydrofuran as an elution solvent.

The novolac resin may be contained in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on 100% by weight of the total composition. When used within the above range, the binding agent and the pattern transfer rate can be increased to improve yield and process efficiency.

The curing agent reacts with the above-mentioned binder resin to form a bridge. The crosslinking reaction is carried out by reacting an isocyanate group (-NCO) in a curing agent with a hydroxyl group. The conventional curing agent is highly reactive and reacts with a binder resin having a hydroxyl group even at room temperature prior to the thermal curing process, There is a problem that application and fine pattern formation are difficult.

Therefore, the curing agent in the present invention includes a compound represented by the following formula (1) wherein the carbon atom of the isocyanate group is not double bonded to the nitrogen atom and is protected by another substituent group.

(In the formula 1,

,

또는

이고,R ₁ is an alkyl group having 1 to 5 carbon atoms,

,

or

ego,

R ₂ is an alkylene group having 1 to 10 carbon atoms,

R ₃ and R ₄ are the same or different and are each independently an alkyl group having 1 to 5 carbon atoms,

and n is an integer of 1 to 3)

The alkyl group referred to in the present invention refers to a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms and having no unsaturation and bonded to the remainder of the molecule by a single bond. The alkyl group is preferably a straight or branched alkyl group having 1 to 5 carbon atoms. Examples of such unsubstituted alkyl groups include methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, t - butyl and pentyl.

The curing agent according to the present invention has an activity of isocyanate group when heat is applied at a predetermined temperature (about 100 ° C. or more) without reaction with hydroxyl groups at room temperature by using the compound represented by the above formula (1) And it hardens.

The compound of Formula 1 may be prepared directly or commercially available.

Such a curing agent may be contained in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight, in 100% by weight of the total composition. If the amount is less than the above range, the degree of crosslinking may be insignificant and the degree of curing of the pattern may be decreased. On the contrary, if the amount exceeds the above range, the storage stability of the entire composition may be deteriorated.

The coloring agent is used for displaying color, and it plays a role of expressing each color in RGB pattern, and it can play a role of preventing light leakage by giving light blocking property to BM pattern.

The colorant is not particularly limited in the present invention, and all known colorants such as organic pigments, dyes, and black pigments may be used. These colorants may be used alone or in admixture of two or more.

For example, organic pigments are compounds classified as pigments in the color index (CI, published by The Society of Dyers and Colors, Inc.), specifically color indexes (CIs) such as: Quot; name "

C.I. Pigment yellow No. 1, C.I. Pigment yellow No. 12, C.I. Pigment yellow No. 13, C.I. Pigment yellow No. 14, C.I. Pigment yellow No. 15, C.I. Pigment yellow No. 16, C.I. Pigment yellow No. 17, C.I. Pigment yellow No. 20, C.I. Pigment yellow No. 24, C.I. Pigment yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow No. 86, C.I. Pigment yellow 93, C.I. Pigment Yellow 94, C.I. Pigment yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment yellow No. 128, C.I. Pigment yellow No. 137, C.I. Pigment yellow 138, C.I. Pigment yellow No. 139, C.I. Pigment yellow No. 147, C.I. Pigment yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment yellow 153, C.I. Pigment yellow 154, C.I. Pigment yellow No. 155, C.I. Pigment yellow 166, C.I. Pigment Yellow No. 168, C.I. Pigment yellow No. 173, C.I. Pigment yellow 180, C.I. Pigment yellow No. 211;

C.I. Pigment Orange No. 5, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 14, C.I. Pigment Orange No. 24, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 34, C.I. Pigment orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment orange No. 40, C.I. Pigment orange No. 42, C.I. Pigment orange No. 43, C.I. Pigment Orange No. 46, C.I. Pigment Orange No. 49, C.I. Pigment Orange No. 51, C.I. Pigment orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment orange No. 64, C.I. Pigment orange No. 65, C.I. Pigment orange No. 68, C.I. Pigment orange No. 70, C.I. Pigment orange No. 71, C.I. Pigment orange No. 72, C.I. Pigment Orange No. 73, C.I. Pigment Orange No. 74;

C.I. Pigment red No. 1, C.I. Pigment red No. 2, C.I. Pigment red No. 5, C.I. Pigment red No. 9, C.I. Pigment red No. 17, C.I. Pigment red No. 31, C.I. Pigment red No. 32, C.I. Pigment red No. 41, C.I. Pigment red No. 97, C.I. Pigment red No. 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment red No. 144, C.I. Pigment red No. 149, C.I. Pigment Red 166, C.I. Pigment Red No. 168, C.I. Pigment red No. 170, C.I. Pigment Red 171, C.I. Pigment red No. 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment red No. 180, C.I. Pigment red No. 185, C.I. Pigment red No. 192, C.I. Pigment Red No. 194, C.I. Pigment red No. 202, C.I. Pigment red No. 206, C.I. Pigment red No. 207, C.I. Pigment red No. 208, C.I. Pigment red No. 209, C.I. Pigment Red 214, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment red No. 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red No. 264, C.I. Pigment red No. 265, C.I. Pigment red No. 272;

C.I. Pigment Blue No. 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment blue No. 16, C.I. Pigment blue No. 60, C.I. Pigment blue No. 80;

C.I. Pigment purple No. 1, C.I. Pigment purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38;

C.I. Pigment Green No. 7, C.I. Pigment green No. 36, C.I. Pigment green No. 58;

C.I. Pigment brown No. 23, C.I. Pigment brown No. 25;

C.I. Pigment black No. 1, C.I. Pigment black No. 7.

These organic pigments may be subjected to a surface treatment using a pigment derivative in which a rosin treatment, an acidic group or a basic group is introduced, a surface graft treatment using a polymer compound or the like, a fine particle treatment using sulfuric acid, Cleaning treatment or the like may be performed.

In addition to this, pigments for use in printing ink, ink jet, etc., and pigments for use in water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacreotide pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxins, anthraquinones, Anthanthrone, indanthrone, pravanthrone, pyranthrone pigments, and the like can be used.

The black pigment may be aniline black, perylene black, titanium black or carbon black, and any of them may be used without particular limitation as far as it is light shielding.

Examples of usable carbon black include CHBK-17 from Mikuni Color; HS, SISO 3HHAF-HS, Sisato NH, Sisato 3M, Sisso 300HAF-LS, Sisso 116HMMAF-HS, Sisato 116MAF, Sisito FMFEF- HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Diagram Black, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR , # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, , # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN- 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black that is the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

The carbon black, which is the black pigment, may be a resin-coated carbon black. Since the carbon black coated with the resin has a lower conductivity than that of the carbon black not coated with the resin, excellent electrical insulation can be imparted at the time of forming the black matrix pattern.

As the dye, for example, C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent Yellow No. 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 63; C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91: 1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197; C.I. Solvent Purple No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59; C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70; C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7, and the like.

Such a colorant may be contained in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, in 100% by weight of the total composition. The content can be controlled according to the required color characteristics within the above range, and when it is out of the above range, the curing property or the driving upon introduction into the apparatus may cause a problem.

The colorant in the present invention can be used together with a dispersant and a dispersion aid, if necessary.

As the dispersing agent, for example, a suitable dispersing agent such as a cationic, anionic, or nonionic type can be used, but a polymeric dispersant is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like. DISPERBYK-2000, DISPERBYK-2001, BYK-LPN6919 and BYK-LPN21116 (manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol), and the like are commercially available. DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170 and DisperBYK-182 (manufactured by BYK SUSPERSE 24000 (manufactured by Lubrizol) as polyethyleneimine, DisperBYK-2010 (BYK) as polyester, Ajisper PB821, Ajisper PB822, Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) ) And the like.

Examples of the dispersion aid include pigment derivatives, specifically, copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

These dispersants may be used alone or in combination of two or more. The content of the dispersing agent is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the colorant. If the content of the dispersing agent is too large, there is a possibility that developability and the like are damaged.

Any solvent may be used as long as it can dissolve or disperse the above-mentioned composition, and the solvent is not particularly limited in the present invention.

The solvent is preferably an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether in consideration of solubility, dispersibility of the colorant, coating property, and the like; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, methanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; and cyclic esters such as? -butyrolactone. These may be used alone or in combination of two or more.

Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C in the solvent is preferably used from the viewpoint of coatability and dryness, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but it is preferably 40 to 90% by weight, preferably 45 to 85% by weight based on 100% by weight of the total weight of the composition.

In addition, the low temperature thermosetting composition for printing of the present invention may further include a multifunctional monomer having an ethylenically unsaturated double bond in the above components.

The multifunctional monomer having an ethylenically unsaturated double bond is used for enhancing the strength of the pattern, and includes monofunctional monomers. Specific examples include monofunctional compounds such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N- Monomer; (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Bifunctional monomers such as 3-methylpentanediol di (meth) acrylate; Trifunctional monomers such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

The multifunctional monomer having an ethylenically unsaturated double bond may be contained in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on 100% by weight of the whole composition. When used in the above content range, good pattern strength can be obtained.

In addition, the low temperature thermosetting composition for printing of the present invention may further comprise at least one additive selected from an adhesion promoter, a surfactant, a dispersant, an antioxidant, an ultraviolet absorber, a thermal polymerization inhibitor, and a leveling agent.

Examples of the adhesion promoter include methacrylate such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyldimethoxysilane, methacryloyloxypropyltriethoxysilane, and methacryloyloxypropyldimethoxysilane. At least one member selected from the group consisting of octyltrimethoxysilane, dodecyltrimethoxysilane, and octadecyltrimethoxysilane may be used as the alkyltrimethoxysilane. Species can be used.

Examples of the surfactant include MCF 350SF, F-475, F-488 and F-552 (manufactured by DIC), but the present invention is not limited thereto.

As the dispersant and leveling agent, any of those commonly used in the art can be used.

Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol, t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxybenzophenone and the like. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4-thiobis t-butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole and the like.

The production of the above-mentioned low temperature thermosetting composition for printing is not particularly limited in the present invention, and follows the well-known production method of the thermosetting composition.

For example, the coloring agent is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the coloring agent becomes about 0.2 μm or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin may be blended. The rest of the binder resin, the curing agent, other components to be used if necessary, and, if necessary, additional solvent are further added to the obtained dispersion (hereinafter, also referred to as a mill base) so as to have a predetermined concentration to obtain a desired low- To obtain a composition.

The present invention also provides a method of manufacturing a flexible color filter and a flexible color filter integrated WOLED device having a pattern made of the above-mentioned low temperature thermosetting composition for printing.

The pattern may be a BM, RGBW pattern.

In particular, the pattern can be formed by printing the low temperature thermosetting composition for printing on the WOLED element.

The printing process may be a roll printing, an offset printing, a gravure offset printing, or a reverse offset printing method. Preferably, a reverse offset printing method can be used.

1 schematically shows an embodiment of a reverse offset printing method. 1, the reverse offset printing method includes applying a printing low-temperature thermosetting composition 11 to a blanket 10 made of polydimethylsiloxane (PDMS) rubber, applying a blanket 10 to a concavo- A desired pattern is formed on the blanket 10 by contacting the clit 15 formed with the pattern 14 on the blanket 10 and the pattern is transferred to one surface of the printed material 16. [ Such a reverse offset printing method can form various patterns of various shapes and sizes into a uniform thin film pattern with a thickness of several micro or less.

The flexible color filter of the present invention using the above-described reverse offset printing method is formed by directly forming BM and RGBW patterns on a flexible white organic light emitting display element and then performing a heat treatment.

2 to 6 are cross-sectional views of respective steps of a method for manufacturing a flexible color filter integrated WOLED device 100 according to an embodiment of the present invention.

As shown in FIGS. 2 to 6, the flexible color filter integrated WOLED device 100 according to the present invention includes

Forming a RGBW pattern 103 on a planarization layer of a white organic light-emitting diode (WOLED) 101 in a printing process;

Heat-treating the formed RGBW pattern 103;

Forming a BM pattern (105) between the heat-treated RGBW patterns (103);

Heat-treating the formed BM pattern 105;

Applying a composition for forming a planarization layer over the entire RGBW and BM patterns to form a planarization layer 107; And

And bonding the base film 111, on which the adhesive layer 109 is coated on one side, with the planarization layer 107. [

Hereinafter, each step will be described in more detail with reference to the drawings.

First, an RGBW pattern 103 is formed on a planarization layer of a prepared white organic light-emitting diode (WOLED) 101 by a printing process (see FIG. 2)

The RGBW pattern 103 is formed using the low temperature thermosetting composition for printing of the present invention, and the printing process is as described above.

Next, the formed RGBW pattern 103 is heat-treated.

Since the printing low temperature thermosetting composition of the present invention having the RGBW pattern 103 can be cured at a lower temperature, it is possible to form a pattern under more relaxed conditions. Accordingly, the heat treatment is preferably performed at 90 to 110 ° C for 10 to 30 minutes.

Next, a BM pattern 105 is formed between the heat-treated RGBW patterns 103 (see FIG. 3).

The BM pattern 105 is formed using the low temperature thermosetting composition for printing of the present invention, and the printing process is as described above.

Next, the formed BM pattern 105 is heat-treated.

Since the BM pattern 105 of the present invention is also made of the low-temperature thermosetting composition for printing, pattern formation is possible at lower temperature conditions.

The heat treatment temperature range and time are as described above.

Next, a composition for forming a planarization layer is applied over the RGBW 103 and the BM pattern 105 to form a planarization layer 107 (see FIG. 4).

The planarization layer 107 is formed over the entire surface on which the pattern is formed for protection of the RGBW 103 and BM pattern 105 and planarization of the color filter surface.

The material of the planarization layer 107 is not particularly limited in the present invention, and may be a commonly used polyacrylate, polyimide, polyester, or the like.

Next, the base film 111 having the adhesive layer 109 coated on one side thereof is bonded to the planarization layer 107 (Fig. 5).

The base film 111 may be any of those usually used for optical transparent films, but it is preferable to use a film excellent in flexibility, transparency, thermal stability, moisture barrier property, uniformity of phase difference, isotropy and the like. By using the base film (111), it is possible to prevent damage during manufacture, transportation and storage of the color filter and to handle it easily.

The material of the usable base film 111 is, for example, polyethylene terephthalate, polyethylene, polystyrene, polycarbonate, polyimide and the like.

The adhesive layer 109 is used to bond the base film 111 and the planarization layer 107 of the color filter and is disposed on one side of the base film 111 or the planarization layer 107. The adhesive that can be used is a photocurable adhesive, which does not require a separate drying step after photocuring, and the manufacturing process is simple, thereby improving the productivity. The photocurable adhesive used in the present invention can be formed using the photocurable adhesive used in the art without any particular limitation. For example, a composition comprising an epoxy compound or an acrylic monomer may be included.

Further, in the photocuring of the adhesive layer 109, an electron beam, a proton ray, a neutron beam and the like can be used in addition to electromagnetic waves such as light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays and infrared rays, X rays and? Curing by ultraviolet irradiation is advantageous from the curing rate, ease of obtaining the irradiation apparatus, price, and the like.

As the light source for irradiating the ultraviolet ray, a high pressure mercury lamp, an electrodeless lamp, a super high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light and the like can be used.

In addition, the substrate film and / or the planarization layer may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, ultraviolet irradiation, primer coating treatment, and saponification treatment to improve adhesion between the layers.

Finally, a flexible color filter integrated WOLED device 100 having a flexible color filter according to the present invention shown in Fig. 6 can be obtained.

The flexible color filter and the flexible color filter integrated WOLED device according to the present invention can be fabricated by forming a pattern using a reverse offset printing method using the above-mentioned low temperature thermosetting composition for printing, heat-treating the substrate, and laminating a base material film of a plastic material.

In this manufacturing method, since a process is directly performed on the flexible white organic light emitting display device, a separate substrate for forming a color filter is not required, and problems such as quality deterioration or malfunction due to thermal deformation of the plastic substrate can be solved. In addition, since a fixed pattern of fine patterns which are difficult to be implemented in a plastic substrate can be formed, it is possible to realize more precise pixels and it is possible to use various base film according to the purpose.

The present invention also provides a flexible white organic light emitting display device including the flexible color filter.

Specifically, a flexible color filter and a touch sensor according to the present invention, a POL integrated touch or window film may be provided on a white organic light-emitting diode (WOLED).

Therefore, the display device including the flexible color filter of the present invention solves the problems caused by thermal deformation of the plastic material, and thus can be applied to various fields such as automation devices, smart phones, displays, solar cells, and electronic paper that require flexibility and flexibility It can be applied in a free form.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, it should be understood that the present invention is not limited thereto.

Example  1 and Comparative Example  1. Preparation of low temperature thermosetting composition for printing

[Example 1]

50% by weight of carbon black (MA8, manufactured by Mitsubishi Chemical Corporation) and 3% by weight of a polyester dispersant (DisperBYK-2010, manufactured by BYK) were mixed to prepare a mill base.

Subsequently, a binder resin (50% by weight of the obtained mill base and 2% by weight of a binder resin having a weight average molecular weight (MW) of 5,000 (m-cresol and p-cresol were contained in a weight ratio of 6: 4 and polymerization and formaldehyde copolymerization), dipentaerythritol hexa 1% by weight of acrylate (manufactured by TOAGOSEI CORPORATION), 0.5% by weight of BI-7983 (manufactured by Baxenden) as a curing agent, 1% by weight of TF-1535 (manufactured by DIC) as a surfactant and propylene glycol monomethyl ether acetate Lt; / RTI >

The mixture was stirred at 23 占 폚 for 3 hours to prepare a low temperature thermosetting composition for printing.

[Comparative Example 1]

The binder resin of Example 1 was prepared in the same manner except that a copolymer of methacrylic acid and benzyl methacrylate having a weight average molecular weight (MW) of 8,000 was used.

Experimental Example  1. Evaluation

(1) Pattern adhesion

The composition of Example 1 and Comparative Example 1 was coated on a glass substrate using a spin coater. The glass substrate coated with the composition was subjected to pre-baking under the conditions of 100 DEG C and 120 seconds, left at room temperature, and then heated and cured at 120 DEG C for 30 minutes.

The heat-cured coating film was subjected to a tape peeling test using JIS K5400 to examine the degree of the total of 100 grid-tearing peaks. The adhesion was evaluated according to the following criteria. The obtained results are shown in Table 1 below.

<Standard>

○: Maintains more than 90 grid patterns

DELTA: Maintains 80 to 90 grid patterns

X: Less than 80 grid patterns

(2) Chemical resistance

The coating film prepared in (1) of Experimental Example 1 was immersed in a 1% potassium hydroxide aqueous solution (alkaline), MA-So2 (Dongwoo Fine Chemical Co., Ltd.) (acid resistance) and SAM-19 And the chemical resistance was evaluated by changing the adhesion after immersion for 2 minutes. Tape peeling test using JIS K5400 was carried out for the change of adhesion, and the degree of the total of 100 gratings was examined.

At this time, the adhesion was evaluated according to the following criteria. The obtained results are shown in Table 1 below.

<Standard>

○: Maintains more than 90 grid patterns

DELTA: Maintains 80 to 90 grid patterns

X: Less than 80 grid patterns

Adhesiveness Chemical resistance My alkalinity Acid resistance My peeling liquor Example 1 ○ ○ ○ ○ Comparative Example 1 △ △ X △

Referring to Table 1, both Example 1 and Comparative Example 1 were patterned through a low temperature curing process at 100 ° C. However, in Example 1 according to the present invention, it was confirmed that the pattern formed was excellent in adhesion to the substrate and chemical resistance Respectively.

The low temperature thermosetting composition for printing according to the present invention is introduced into a color filter of a flexible white organic light emitting display device and can maintain a high quality and adhesion property to realize a high quality and vivid image quality.

10: Blanket 11: Low temperature thermosetting composition for printing
12: Application of low temperature thermosetting composition for printing
13: slit die coater 14: concave / convex portion
15: cliche 16:
100: Flexible color filter integrated WOLED device
101: Flexible white organic light emitting display element
103: RGBW pattern 105: BM pattern
107: planarization layer 109: adhesive layer
111: substrate film

Claims (9)

A binder resin, a curing agent, a colorant and a solvent,
Wherein the binder resin comprises a novolac resin,
Wherein the curing agent is a low temperature thermosetting composition for printing comprising a compound represented by the following Formula 1:
[Chemical Formula 1]

(In the formula 1,
R ₁ is an alkyl group having 1 to 5 carbon atoms,

,

or

ego,
R ₂ is an alkylene group having 1 to 10 carbon atoms,
R ₃ and R ₄ are the same or different and are each independently an alkyl group having 1 to 5 carbon atoms,
and n is an integer of 1 to 3) The low-temperature thermosetting composition for printing according to claim 1,
0.1 to 20% by weight of a binder resin,
0.01 to 5% by weight of a curing agent,
5 to 40% by weight of a colorant, and
Wherein the low temperature thermosetting composition for printing comprises 40 to 90% by weight of a solvent. The low temperature thermosetting composition for printing according to claim 1, wherein the low temperature thermosetting composition for printing further comprises a multifunctional monomer having an ethylenically unsaturated double bond. A flexible color filter comprising a pattern made of the low temperature thermosetting composition for printing according to claim 1. The flexible color filter according to claim 4, wherein the pattern is a BM or RGBW pattern. Forming an RGBW pattern on a planarization layer of a white organic light-emitting diode (WOLED) by a printing process;
Heat-treating the formed RGBW pattern;
Forming a BM pattern between the heat-treated RGBW patterns;
Heat treating the formed BM pattern;
Coating a composition for forming a flattening layer over the RGBW and BM patterns to form a planarization layer; And
And bonding the substrate film coated on one side with the planarizing layer with an adhesive layer,
Wherein the RGBW and BM patterns are made of the low temperature thermosetting composition for printing of claim 1. 7. The method of claim 6, wherein the printing process is roll printing, offset printing, gravure offset printing, or reverse offset printing. [7] The method of claim 6, wherein the heat treatment is performed in a range of 90 to 110. [ A white organic light-emitting diode (WOLED);
Color filters; And
A touch sensor, a POL integrated touch or window film,
Wherein the color filter is a flexible color filter according to claim 4.

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