Color filter for low temperature applications

Color filters for low temperature applications

The present invention relates to a color filter comprising a substrate and a photosensitive photoresist composition containing a cured pigment; its manufacturing method and its use in devices such as electrophoretic displays, polymer dispersed liquid crystal displays and OLED displays.

Electrophoretic display (so-called electronic paper) is an emerging technology that allows rewriting text on a sheet of paper. The "paper" is actually made of organic electronic devices that use conductive plastic containing small balls that can respond to electrical charges and change the page in roughly the same way as the pixels on a computer monitor change.

Electronic paper overcomes some limitations of computer monitors. For example, the backlight of a monitor makes human eyes feel uncomfortable, and electronic paper reflects light almost like normal paper. Compared with flat screen monitors, it is easier to read from a certain angle. Since it is made of plastic, e-paper has the potential to be flexible. It is lightweight and potentially inexpensive.

Electronic paper was first developed by Nick Sheridon at Xerox's Palo Alto Research Center in the 1970s. The original electronic paper was called Gyricon, which consisted of small balls charged with static electricity. One side of the small balls was black and the other side was white. The "text" of this paper is changed by the presence of an electric field, which makes the ball rotate up or down.

In the 1990s, another type of electronic paper was invented by Joseph Jacobson. This electronic paper uses small microcapsules filled with charged white particles suspended in colored oil. In the early version, the underlying circuit controlled the white particles to be at the top of the capsule (hence the appearance of white to the viewer) or at the bottom of the capsule (hence the colour of the oil that the viewer sees). This is basically a re-introduction of the well-known electrophoretic display technology, but the use of microcapsules allows the display to be used on flexible plastic sheets instead of glass. There are many ways to prepare electronic paper, and many companies develop technologies in this field. Other technologies applied to electronic paper include liquid crystal displays, electrochromic displays, and Kyushu University's improvement of the electronic equivalent of sketch etching. One form or another electronic paper is being developed by Gyricon (a derivative company of Xerox), Philips Electronics, Kent Displays (cholesterol display), Ntera (electrochromic Nanochromic display) and many other companies.

It is necessary to develop a color electronic paper display. In principle, there are two different ways to obtain a color display. First, the white particles can be replaced with colored (RGB/CYM) particles, and alternatively, a color filter can be applied on top of the electrophoretic display.

Hard electrophoretic displays can use color filters made on separate glass substrates. However, this is an expensive approach and is not easy to implement because it is necessary to laminate the second glass substrate and the color filter on top of the electronic paper. Flexible electronic paper cannot use this lamination method at all.

An alternative and cheaper method is to pattern the color filter directly on the e-paper layer. The photosensitive resist composition is used to form a color filter. The composition requires high sensitivity, adhesion to the substrate, chemical resistance and similar properties. Generally speaking, in order to use such photosensitive photoresist composition to form a color filter, a light-shielding layer pattern is formed on a transparent substrate, and a photosensitive photoresist composition in which the colorant is dispersed is coated on the substrate, and The mask is exposed to radiation for development, and the unexposed part is dissolved with a developer to form a pixel pattern. Use red, green, and blue colorants as colorants. The standard colored photoresist composition includes a resin containing an acidic functional group (such as (meth)acrylic acid), a multifunctional monomer (such as isopentaerythritol tri(meth)acrylate), and a photopolymerization initiator.

However, with the existing color filter photoresist, it is difficult to directly pattern the color filter on the electronic paper layer. This is because the photoresist is usually inadequately cured by exposure to light and usually needs to be cured. The final curing step performed at a temperature of at least 200°C. At this temperature, the capsule containing the dispersion containing black and white particles will be completely destroyed. Omitting the subsequent baking step will only achieve the degree of light-initiated crosslinking of acrylate monomers up to about 40% to 50% depending on the color, because the color filter is composed of three layers of R, G and B formed in sequence , So the degree of cross-linking is not enough to produce sufficient chemical resistance to the second and third layers.

Color filter photoresists for low temperature applications are described in, for example, JP 2004-083754 A and JP 2003-330184 A. However, basically additional additives (epoxides, peroxides) are used in the photoresist to lower the curing temperature. It is not implied that the heat curing step can be omitted.

KR 10-2009-0104670 A discloses a photosensitive photoresist composition, which can form a patterned structure or a protective film by low-temperature heating or without heat treatment. The composition includes a (meth)acrylic derivative of polyglycidyl ether as a polymerizable compound and includes a resin having a branched chain and/or alicyclic structure in the side chain.

WO 2007/113107 A1 discloses a photosensitive photoresist composition for low-temperature color filter photoresist, which uses a polyacrylate monomer containing two glycidyl acrylate groups. However, the physical resistance of the cross-linked film and the adhesion especially on glass, SiN-coated substrates or plastic substrates do not meet the requirements for suitable color filters. The irradiated part is often separated from the substrate after development.

Therefore, one object of the present invention is to overcome these shortcomings and provide a color filter with improved adhesion between the cured photosensitive photoresist composition layer and the substrate.

Another object of the present invention is to provide a color filter for low temperature applications.

Another object of the present invention is to provide a color filter used in a display device (such as an electrophoretic display).

Therefore, in the first aspect, the present invention relates to a color filter comprising a substrate and a cured layer of a photosensitive photoresist composition, the photosensitive photoresist composition comprising

(A) Polyacrylate monomer of the following formula<img file="TW201214031A_D0001.tif" />, Where R¹Is methyl or CH₂OR⁵, R², R³, R⁴And R⁵Independently of each other as H or<img file="TW201214031A_D0002.tif" />Group or formula<img file="TW201214031A_D0003.tif" />The group; R⁶Independently of each other are H or methyl, and the restriction is that there are at least three groups of formula (II);

(B) Adhesives, which contain alkali-soluble copolymers with side chains containing ethylenic unsaturated bonds, and the restriction is that the copolymer does not include other structural units containing branched chains and/or alicyclic structures in the side chains ;

(C) Pigment; and

(D) Photopolymerization initiator.

Preferably, each R of the polyacrylate monomer⁶The same and are H or methyl.

Alkyl (e.g. C₁-C₄Alkyl, C₁-C₈Alkyl or C₁-C₁₂Alkyl) can be straight or branched (if possible) within the limits of a given C atom. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl Base, n-hexyl, 1,1,3,3-tetramethylpentyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, undecyl and Dodecyl. Alkoxy is alkyl-O-.

Alkylene (e.g. C₂-C₁₈Alkylene, C₁-C₆Alkylene or C₁-C₄(Alkylene) can be methylene, ethylene, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sine Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl Alkyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.

Arylene (e.g. C₆-C₁₂Aryl or C₆-C₁₈Arylene) can be phenylene or naphthylene, such as o-phenylene, meta-phenylene, p-phenylene, 1,4-naphthylene, 1,5-naphthylene or biphenyl-4 ,4'. Two bases.

The above groups may be substituted by one or more substituents. Possible substituent is C₁-C₈Alkyl, OH, C₁-C₈Alkoxy and halogen. If the substituent occurs more than once in the group, it can be different at each occurrence. Halogen means I, Br, Cl or F, especially Br or Cl.

The (meth)acryloyl group in (meth)acrylic acid or (meth)acrylate means an acryloyl group and/or a methacryloyl group.

The term "cured layer of photosensitive photoresist composition" or "pixel" as used herein means the final developed and optionally dried color filter coating film, in other words, after coating the composition on a substrate and drying , Color filter coating film formed after exposure, development and optionally drying. Generally speaking, only when you still need to remove any volatile substances, you need to choose drying according to the situation.

Preferably, the polyacrylate monomer (A) is trimethylolethane triglyceride tri(meth)acrylate or isopentaerythritol tetraglyceride tetra(meth)acrylate.

In R¹For CH₂OR⁵Under the circumstances, R², R³, R⁴Or R⁵One of them can be H or the formula<img file="TW201214031A_D0004.tif" />The group replacement, where R⁶It is H or methyl.

Since the polyacrylate monomer of formula (I) can exist in the form of a mixture of polyacrylate monomers of formula (I), the polyacrylate monomer or a mixture thereof can be used as the component (A) in the present invention. If necessary, the monomer can be separated by a method known to those skilled in the art (for example, chromatography, etc.). However, in the context of the present invention, there is no need to separate a single monomer from the mixture, as long as the required content of three groups of formula (II) is present in the polyacrylate monomer of formula (I) in the mixture .

Therefore, component (A) may preferably be of formula<img file="TW201214031A_D0005.tif" />or<img file="TW201214031A_D0006.tif" />The mixture of the polyacrylate monomer and the polyacrylate monomer of formula (I), where R², R³, R⁴And R⁵Independently of each other as H or<img file="TW201214031A_D0007.tif" />Group or formula<img file="TW201214031A_D0008.tif" />The group; R⁶They are H or methyl independently of each other, and the restriction is that there are at least three groups of formula (II) in the monomer.

Component (A) is in particular a polyacrylate monomer of formula (I) comprising trimethylolethane triglyceride tri(meth)acrylate or isopentaerythritol tetraglyceride tetra(meth)acrylate The mixture. The content of trimethylolethane triglyceride tri(meth)acrylate based on the total weight of the polyacrylate monomer of formula (I) may be 15% by weight or more than 15% by weight, preferably at least 20% by weight %, more preferably at least 25% by weight and most preferably at least 40% by weight. The content of isopentaerythritol tetraglyceride tetra(meth)acrylate based on the total weight of the polyacrylate monomer of formula (I) may be 15% by weight or more than 15% by weight, preferably at least 20% by weight, More preferably, it is at least 25% by weight and most preferably at least 40% by weight.

The polyacrylate monomer can be used alone or in the form of a mixture of two or more. In addition to the polymerizable compound of formula (I), the photosensitive resin may also include a polymerizable compound having an ethylenically unsaturated bond. The other polymerizable compound may be selected from polymerizable compounds known in the art. Preferably, only the polyacrylate monomer of formula (I) as defined above or a mixture of these monomers is present in the photosensitive composition.

The amount of the polyacrylate monomer (A) in the photosensitive resist composition is generally at least 5 parts by weight based on 100 parts by weight of the binder (B), preferably 5 to 500 parts by weight, and more preferably 20 to 500 parts by weight. Parts by weight. The amount of at least 5 parts by weight can provide excellent polymerization curability during exposure, so that it is no longer necessary to perform the conventional post-baking step at 200°C after development.

The polyacrylate monomer can be prepared by a known method. For example, the compound of formula (I) can be prepared by reacting a base alcohol with epichlorohydrin to form the corresponding polyglycidyl ether, and some of these reactants are commercially available. Subsequently, the polyglycidyl ether can be reacted with an appropriate amount of acrylic compound (such as (meth)acrylic acid) in the presence of a polymerization inhibitor and a catalyst at a high temperature (such as 80°C to 110°C) for several hours until the reactants disappear completely. A variety of catalysts can be used, such as triethylamine, dimethylaniline, boron trifluoride, triphenylphosphine, various metal salts, or any other epoxide ring-opening catalysts known to those skilled in the art. The catalyst may be added all at once at the beginning of the reaction, or may be added continuously or in an incremental manner at regular time intervals during the reaction. Use inhibitors to prevent undesirable polymerization of (meth)acrylates. Examples include, for example, hydroquinone, hydroquinone ethers (such as hydroquinone monomethyl ether), di-tertiary butylcatechol, phenothiazine, p-phenylenediamine, methylene blue, hindered phenols, and nitrophenols (such as TEMPO), And it is widely known by those who are familiar with this technology. The proportion of inhibitors used individually or in the form of a mixture may generally be in the range of about 0.01% by weight to about 1% by weight based on the weight of the entire reaction mixture.

The compound of formula (I) can also be prepared by the Williamson synthesis by reacting the alcohol as described above with allyl bromide or allyl chloride to form the corresponding allyl ether. This can be done, for example, as described in Organic Syntheses, Coll. Vol. 5, Page 251 (1973) or Vol. 46, Page 28 (1966). Allyl ether can also be similar to the method disclosed by M. Stojanowa-Antoszcyszyn et al., Comptes Rendus de l'Academie Bulgare des Sciences, 2001, 54(3), 51, by applying Wilhelm Mussen under phase transfer catalysis Synthesis method to prepare. The polyallyl ether can then be epoxidized by methods known in the art, such as percarboxylic acid or hydroperoxide. The resulting polyglycidyl ether can be reacted to the corresponding polyacrylate under the conditions described above.

The binder (component B) used in the present invention contains an alkali-soluble copolymer having a side chain containing ethylenic unsaturated bonds. Preferably, the limitation is that the copolymer does not include branched chains and / Or other structural units of the alicyclic structure. In a preferred aspect, the adhesive includes the following copolymer, which has a structural unit containing an acidic group and the formula<img file="TW201214031A_D0009.tif" />The structural unit, where X is O, NH or NR⁸, Preferably O, R⁸Is C₁-C₄Alkyl or phenyl; Y is C with -CH(OH)- or -O-CO-NH-₂-C₁₈A divalent organic group with aliphatic and/or aromatic structure, the Y is optionally mixed with O; Z is<img file="TW201214031A_D0010.tif" />or<img file="TW201214031A_D0011.tif" />; R⁷, R⁹And R¹⁰Independently of each other are H or methyl.

C₂-C₁₈Examples of aliphatic and/or aromatic structures include C which can be linear or branched (if possible)₂-C₁₈Alkylene and may contain terminal or interrupted aromatic structures, such as 1,3-phenylene or 1,4-phenylene and C₆-C₁₈Arylene (such as biphenyl-4,4'-diyl). These groups are mixed with -CH(OH)- or -O-CO-NH-, and one or more O is further mixed as appropriate.

The acidic group can be -COOH group, -SO₂NHCO- group, -SO₃H group, phenolic hydroxyl group, -SO₂NH- group or -CO-NH-CO- group. The copolymer preferably contains an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as "carboxyl group-containing unsaturated monomer").

Examples of unsaturated monomers containing carboxyl groups include unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids (anhydrides), such as cis Butenedioic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, methyl maleic acid, methyl maleic anhydride and methyl fumaric acid; Unsaturated polycarboxylic acids (anhydrides) with at least 3 carboxyl groups in the molecule; mono(meth)acryloyloxyalkyl esters of non-polymerizable dicarboxylic acids, such as mono(2-acryloyloxy) of succinic acid Of mono(2-methacryloxyethyl) succinic acid, mono(2-acryloxyethyl) phthalic acid and phthalic acid Mono(2-methacryloxyethyl) ester; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate and the like. These carboxyl group-containing unsaturated monomers can be used alone or in the form of a mixture of two or more.

Preferably, the copolymer of component (B) contains acrylic acid and/or methacrylic acid as structural units.

Z is preferably<img file="TW201214031A_D0012.tif" />or

<chemistry general="n"><img file="TW201214031A_D0013.tif" /></chemistry>

Where R⁹And R¹⁰Independently of each other are H or methyl.

Preferred groups of formula (IV) are, for example

<chemistry general="n"><img file="TW201214031A_D0014.tif" /></chemistry>

<img file="TW201214031A_D0015.tif" />, Where R⁷, R⁹And R¹⁰Independently of each other are H or methyl, R¹¹, R¹², R¹³, R¹⁴And R¹⁵Independently of each other as C₁-C₆Alkylene, preferably C₁-C₄Alkylene, or phenylene, especially methylene, ethylene, prop-1,2-diyl, prop-2,2-diyl, 1,3-phenylene or 1,4-phenylene Phenyl; and p is 0, 1, 2 or 3, preferably p is 0 or 1.

The groups of formula (IVa), (IVb) or (IVc) may exist alone or in the form of a mixture of two or more.

Especially preferred groups of formula (IV) are<img file="TW201214031A_D0016.tif" />; The group of formula (IVa), wherein p is 1 and R¹¹Is 1,4-phenylene, ethylene or propyl-1,2-diyl; group of formula (IVb), wherein R¹²With R¹³Same, preferably ethylene or propyl-1,2-diyl; group of formula (IVc), wherein R¹⁴Ethylene or propyl-1,2-diyl, R¹⁵Is methylene, ethylene or propyl-1,2-diyl, the R¹⁵It can be attached to the substituted benzene ring in the meta or para position. Groups of formula (IVd) are of particular interest.

These copolymers are known in the art and can be used, for example, as disclosed in US 2006/229376 A1, US 2003/232259 A1, JP 2005-062621 A, WO 01/13175 A2 and WO 2008/4705 A1. Known methods to prepare. The binder component of the photosensitive photoresist composition may preferably be a copolymer (B) containing acrylic acid and/or methacrylic acid units and units of formula (IV). Optionally, one or more other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as "other unsaturated monomers") may be present in the copolymer.

Preferably, after forming the linkage of the main chain of the copolymer according to a known method of free radical polymerization technology, the ethylenic unsaturated bond is incorporated via an appropriate functional group.

In order to incorporate the structural unit of formula (IVa) (where p is 0) into the copolymer, firstly, at least (meth)acrylic acid can be polymerized as a monomer to form the main chain part of the copolymer, and then The carboxyl group of (meth)acrylic acid reacts with glycidyl (meth)acrylate. However, in this situation, it is necessary to adjust the amount of glycidyl (meth)acrylate, because the content of the carboxyl group of (meth)acrylic acid is too low to cause insufficient alkali solubility.

When p is different from 0, the structural unit of formula (IVa) can be derived from the hydroxyl-substituted (meth)acrylate of the following formula:<img file="TW201214031A_D0017.tif" />, Where R⁷And R¹¹Is as defined above.

The OH- group can then be reacted with glycidyl (meth)acrylate as described above.

In order to incorporate the structural unit of formula (IVb) into the copolymer, first, the main chain part of the copolymer can be formed by copolymerizing the hydroxyl-substituted (meth)acrylate of the following formula with other monomers

<chemistry general="n"><img file="TW201214031A_D0018.tif" /></chemistry>

Where R⁷And R¹²Is as defined above. Then, the hydroxyl group can be reacted with an isocyanate-terminated compound of the following general formula:<img file="TW201214031A_D0019.tif" />, Where R¹³And R⁹Is as defined above.

Therefore, the structural unit of formula (IVc) can be prepared.

Examples of other unsaturated monomers as mentioned above include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, o-chlorostyrene , M-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-vinylbenzyl methyl ether and p-vinylbenzyl glycidyl ether ; Unsaturated carboxylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxy (meth)acrylate Ethyl, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (methyl) ) 4-hydroxybutyl acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate and methoxytriethylene glycol (meth)acrylate; unsaturated Carboxylic acid amino alkyl esters, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, (methyl) ) 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth)acrylate and 3-dimethylaminopropyl (meth)acrylate; unsaturated glycidyl carboxylic acid, such as (former Base) glycidyl acrylate; vinyl carboxylate, such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, allyl glycid Glyceryl ether and methallyl glycidyl ether; cyanide vinyl compounds, such as (meth)acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides and unsaturated amides, such as (form Yl)acrylamide, α-chloroacrylamide, N-(2-hydroxyethyl)(meth)acrylamide, maleimide, N-phenylmaleimide and N-cyclohexyl maleimide; aliphatic conjugated dienes, such as 1,3-butadiene; macromonomers having a single (meth)acrylic acid group at the end of the polymer molecular chain , Such as polystyrene, polymethyl (meth)acrylate, poly n-butyl (meth)acrylate and polysiloxane; and the like. These other unsaturated monomers can be used alone or in the form of a mixture of two or more.

Preferably, the copolymer (B) contains at least one monomer unit selected from the group consisting of styrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, N-Butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, phenyl(meth)acrylate, mono(meth)acrylate ) Glyceryl acrylate, N-phenyl maleimide, polystyrene macromonomer and polymethyl (meth)acrylate macromonomer.

In a preferred aspect, the copolymer (B) consists of the following:

(a) A structural unit having an acidic group, preferably (meth)acrylic acid;

(b) At least one monomer selected from the group consisting of: styrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate Ester, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, glycerol mono(meth)acrylate, N- Phenyl maleimide, polystyrene macromonomer and polymethyl (meth)acrylate macromonomer, preferably methyl (meth)acrylate, n-butyl (meth)acrylate , Styrene, 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate; and

(c) The monomer unit of formula (IV) is preferably the monomer unit of formula (IVa).

More preferably, the copolymer (B) may consist of the following:

(a) 5% to 50% by weight based on the total weight of the copolymer, preferably 10% to 40% by weight and more preferably 10% to 30% by weight of monomer units containing acidic groups, preferably (Methacrylate;

(b) 40% to 90% by weight based on the total weight of the copolymer, preferably 50% to 85% by weight, and more preferably 60% to 80% by weight of at least one monomer unit selected from the group consisting of the following : Styrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl meth)acrylate, phenyl(meth)acrylate, glycerol mono(meth)acrylate, N-phenylmaleimide, polystyrene macromonomer and poly(methyl) Methyl acrylate macromonomer;

(c) 2% to 30% by weight, preferably 5% to 20% by weight, based on the total weight of the copolymer, of monomer units of formula (IV), preferably monomer units of formula (IVa), more preferably It is a monomer unit of formula (IVd).

The condition adjusts the content ratio of each structural unit constituting the molecular structure of the copolymer (B). Adjust the amount of acidic monomer to meet the required alkali solubility and the required solvent solubility. Adjust the amount of monomers containing ethylenic unsaturated bonds to meet the desired degree of photocurability (sensitivity).

The proportion of the carboxyl group-containing unsaturated monomer in the component (B) is generally 5 wt% to 50 wt%, more preferably 10 wt% to 40 wt%, more preferably 10 wt% to 30 wt%. When the proportion of carboxyl group-containing unsaturated monomer is less than 5 wt%, the solubility of the resulting radiation-sensitive composition in alkali developer tends to decrease, and when the proportion is greater than 50 wt%, the formed pixel pattern uses alkali The developer tends to fall off from the substrate or the surface of the pixel tends to become rough during development.

Preferably, the copolymer (B) consists of the following:

(a) 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%, and more preferably 10 wt% to 30 wt% (meth)acrylic acid based on the total weight of the copolymer;

(b) 40% to 90% by weight based on the total weight of the copolymer, preferably 50% to 85% by weight and more preferably 60% to 80% by weight of at least one monomer unit selected from the group consisting of the following : Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate;

(c) 2% to 30% by weight, preferably 5% to 20% by weight of the monomer unit of formula (IVa) based on the total weight of the copolymer.

Therefore, in a preferred aspect, the present invention relates to a color filter comprising a substrate and a cured layer of a photosensitive photoresist composition, the photosensitive photoresist composition comprising

(A) Polyacrylate monomer of the following formula<img file="TW201214031A_D0020.tif" />, Where R¹Is methyl or CH₂OR⁵, R², R³, R⁴And R⁵Independently of each other as H or<img file="TW201214031A_D0021.tif" />Group or formula<img file="TW201214031A_D0022.tif" />The group; R⁶Independently of each other are H or methyl, and the restriction is that at least three groups of formula (II) exist; or contain trimethylolethane triglyceride tri(meth)acrylate or isopentaerythritol tetraglycerol A mixture of polyacrylate monomers of formula (I) of ester tetra(meth)acrylate;

(B) Alkali-soluble copolymer composed of:

(a) 5% to 50% by weight, preferably 10% to 40% by weight, and more preferably 10% to 30% by weight of monomer units containing acidic groups based on the total weight of the copolymer;

(b) 40% to 90% by weight based on the total weight of the copolymer, preferably 50% to 85% by weight and more preferably 60% to 80% by weight of at least one monomer unit selected from the group consisting of the following : Methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate or benzyl (meth)acrylate;

(c) 2% to 30% by weight, preferably 5% to 20% by weight of the monomer unit of formula (IV) based on the total weight of the copolymer;

(C) Pigment; and

(D) Photopolymerization initiator.

Generally, the amount of monomers containing ethylenic unsaturated bonds in the copolymer (B) is lower than that of monomers containing acidic groups. For example, the molar ratio of monomers containing ethylenic unsaturated bonds to monomers containing acidic groups may be in the range of 1:19 to 1:2, preferably in the range of 1:9 to 1:3 It is better to be in the range of 1:6 to 1:4.

Therefore, in a preferred aspect, the present invention relates to a color filter in which the copolymer (component (B)) in the photosensitive photoresist composition contains the structural unit of the acidic group and the formula (IV) The molar ratio of the structural unit of) is 9:1 to 3:1, preferably 6:1 to 4:1.

The amount of other unsaturated monomers (c) in the polymer main chain can be 40 mol% to 90 mol% based on the total amount of monomers in the main chain, preferably 40 mol% to 80 mol%, And it is more preferably 50 mol% to 80 mol%, and most preferably 60 mol% to 75 mol%. A particularly preferred copolymer is a copolymer comprising (meth)acrylic acid and at least one other unsaturated monomer with a molar ratio of 1:4 to 1:1, preferably 1:1.5 to 1:2.5 before functionalization , Wherein the molar ratio of monomers containing ethylenic unsaturated bonds to monomers containing acidic groups can be in the range of 1:19 to 1:2 after functionalization, preferably in the range of 1:9 to 1:3 Within the range, more preferably within the range of 1:6 to 1:4.

Therefore, the preferred copolymer is composed of the following monomer units:

(a) (meth)acrylic acid,

(b) At least one monomer unit selected from the group consisting of: methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate or (methyl) ) Benzyl acrylate; and

(c) The monomer unit of formula (IVa) is preferably the monomer unit of formula (IVd).

Particularly preferred copolymers can be obtained by the following steps:

(a) (Meth) acrylic and

(b) At least one monomer selected from the group consisting of: methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate or (meth) Benzyl acrylate is polymerized at a molar ratio of (a) and (b) from 1:4 to 1:1; then the acid group of (a) is functionalized to form at least one formula<img file="TW201214031A_D0023.tif" />The molar ratio of (a) to (IVd) in the final copolymer is 9:1 to 3:1, preferably 6:1 to 4:1.

A particularly preferred copolymer (B) can be obtained by the following steps:

(a) (Meth) acrylic and

(b) At least one monomer selected from the group consisting of: methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate or (meth) Benzyl acrylate is polymerized at a molar ratio of (a) and (b) from 1:1.5 to 1:2.5; then the acid group of (a) is functionalized to form at least one unit of formula (IVd), wherein The molar ratio of (a) to (IVd) in the final copolymer is 6:1 to 4:1.

The copolymer (B) of the binder component may be a random copolymer or may be a block copolymer. Likewise, mixtures of the above-mentioned copolymers can be used in the composition of the present invention.

The weight average molecular weight of the copolymer (hereinafter referred to as "weight average molecular weight" Mw) measured by gel permeation chromatography (GPC: tetrahydrofuran as solvent) based on polystyrene is usually 1,000 g/mol to 300,000 g/mol , Preferably 2,000 g/mol to 100,000 g/mol, more preferably 5,000 g/mol to 50,000 g/mol, and most preferably 5,000 g/mol to 25,000 g/mol. The ratio of the weight average molecular weight to the number average molecular weight is preferably 1 to 5, more preferably 1.5 to 4, especially 2 to 3.5.

By using a binder with the specific weight average molecular weight, a radiation-sensitive composition with excellent developability can be obtained, whereby a pixel array with a clear pattern edge can be formed, and during development, except for the pixels where the pixels are formed on the substrate Smudges, film residues, or the like are hardly generated in areas other than the part.

The amount of the binder used in the present invention is generally 10 to 1,000 parts by weight, preferably 20 to 500 parts by weight, based on 100 parts by weight of the pigment (C).

Specifically, the dissolution of the copolymer (B) of the acidic group-containing structural unit, the ethylenically unsaturated bond-containing structural unit, and optionally the presence of another unsaturated monomer in the above-mentioned specified ratio in the alkali developer Excellent sex. In a radiation-sensitive composition containing the copolymer as a binder, few undissolved products remain after development with an alkali developer, and almost no stains or film residues are generated in the area of the substrate except for the part where the pixels are formed. The pixel pattern obtained from the composition is not excessively dissolved in the alkali developer, has excellent adhesion to the substrate, and does not fall off from the substrate.

In the present invention, a binder resin other than the copolymer (B) may be used within a certain range to achieve the purpose of the present invention. Other binder resins may be copolymers containing at least two monomers selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid Ethyl, n-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl(meth)acrylate, styrene, polystyrene macromonomers and poly(meth)acrylate macromolecules monomer. Among them, preferred are copolymers of (meth)acrylic acid and benzyl (meth)acrylate; copolymers of (meth)acrylic acid, benzyl (meth)acrylate and styrene; and benzene (meth)acrylate Copolymer of methyl ester and styrene; copolymer of benzyl (meth)acrylate and styrene macromonomer; and the like.

The pigment (C) in the present invention is not limited to a specific color, and is appropriately selected according to the application purpose of the color filter. It can be an organic or inorganic pigment. Preferably, the photosensitive photoresist composition contains a pigment (C) selected from the group consisting of organic pigments and carbon black. It is better to use organic pigments.

Examples of inorganic pigments also include inorganic salts called "extender pigments" and the like. Since the color filter requires highly accurate color development and heat resistance, the pigment used in the present invention preferably has high color development characteristics and high heat resistance, especially high heat decomposition resistance. Organic pigments and/or carbon black are generally used, and organic pigments and/or carbon black are particularly preferred.

Examples of organic pigments that can be used in the photosensitive composition as described herein are shown below with color index numbers.

For the red composition used to form the red filter section, red pigments can be used, such as CI Pigment Red 2, 4, 5, 7, 9, 14, 23, 41, 48:1, 48:2, 48: 3. 48: 4, 52: 2, 53: 1, 57, 57: 1, 81: 1, 81: 2, 81: 3, 88, 89, 97, 101, 104, 112, 122, 123, 144, 146, 149, 166, 168, 177, 178, 180, 181, 184, 185, 187, 190, 192, 194, 200, 202, 204, 206, 207, 208, 210, 214, 215, 216, 217, 220, 221, 222, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 262, 264, 270, 272, 279, Vat Red 74, 3,6-bis(3'-cyanide Phenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione or 3-phenyl-6-(4'-tertiary butylphenyl)-2, 5-Dihydropyrrolo[3,4-c]pyrrole-1,4-dione. A yellow pigment or an orange pigment can be additionally used in the red composition.

For the yellow composition used to form the yellow filter section, yellow pigments can be used, such as CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 184, 185, 187, 188, 191, 191-1, 193, 194, 199, 213 or 214.

For the orange composition used to form the orange filter section, orange pigments such as CI Pigment Orange 5, 13, 16, 34, 36, 40, 43, 48, 49, 51, 55, 59, 61, 64, 71 or 73.

For the green composition used to form the green filter section, green pigments such as CI Pigment Green 7, 10, 17, 36, 37, 50, or 58 can be used. A yellow pigment may be additionally used in combination in the green composition.

For the blue composition used to form the blue filter section, blue pigments can be used, such as CI Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6 , 16, 22, 28, 29, 58, 60, 64, 66, or 80. Violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be additionally used in the blue composition.

For the cyan composition used to form the cyan filter section, a blue pigment, such as CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 16 or 81, can be used. Green pigments such as CI Pigment Green 7 can be additionally used in the cyan color composition.

For the magenta composition used to form the magenta filter section, purple pigments and red pigments, such as CI Pigment Violet 1 and 19, and CI Pigment Reds 144, 146, 177, 169, and 81 can be used. A yellow pigment can be additionally used in the magenta composition.

In addition, as black pigments for the black matrix, carbon black, titanium black, aniline black, anthraquinone black pigment, perylene black pigment, especially CI pigment black 1, 6, 7, 12, 20, 27, 30, 31 can be used. Or 32. Among them, carbon black is preferred. The surface of carbon black can be treated with resin, for example.

In addition, the preferred black pigment is of the formula<img file="TW201214031A_D0024.tif" />The two-side oxydihydro-indolyl-benzodifuranone colorant or its cis-trans isomer, which can be differently substituted as described in, for example, WO 00/24736 A1, especially The compound of Example 12b, the patent is incorporated herein. These pigments are further described in WO 09/10521, WO 2010/81624 and WO 2010/81624. The pigment is preferably unsubstituted.

In addition, examples of inorganic pigments include titanium oxide, barium sulfate, zinc sulfide, lead sulfate, lead yellow, zinc yellow, red iron oxide (III), cadmium red, navy blue, Prussian blue, chromium oxide green, cobalt Green, amber and synthetic iron black. Inorganic pigments can be used in combination with organic pigments to ensure excellent coating characteristics, sensitivity, development characteristics and the like, while balancing chromaticity and brightness.

The photosensitive composition described herein may contain dyes for toning in an amount that does not reduce heat resistance. Preferably, no dye is used in the composition of the present invention.

Among inorganic pigments, carbon black is particularly preferred.

In the present invention, the above-mentioned pigments can be used alone or in the form of a mixture of two or more.

The surface of each of these pigments can be modified by the polymer before use.

The polymer used to modify the surface of the pigment may be a polymer disclosed in JP 08-259876 A, a commercially available polymer or oligomer used for dispersing pigments, or the like.

In the present invention, the pigment can be used in combination with a dispersant or a dispersing aid.

Examples of dispersants include polycarboxylates, such as polyurethanes and polyacrylates; unsaturated polyamides; (part of) amine, ammonium and alkylamine salts of polycarboxylic acids; polysiloxanes ; Long-chain polyamino amide phosphate; hydroxyl-containing polycarboxylate; and modified products thereof; formed by reacting polyester with free carboxylic acid group with poly(low-carbon alkyleneimine) Amide and its salts; and its analogues, their brand names are as follows:<img file="TW201214031A_D0025.tif" />-130, 101, 160, 161, 162, 163, 164, 165, 166, 170, 171, 182, 2000, 2001, 2050, 2070 and the like;<img file="TW201214031A_D0026.tif" /> 44, 46, 47, 48, 4010, 4015, 4020, 4044, 4046, 4047, 4050, 4055, 4060, 4330, 4340 and the like; Ajisper PB-821, 822, 823,<img file="TW201214031A_D0027.tif" /> 13240, 13940, 17000, 24000GR, 28000, 20000, 12000, 27000, 32000, 32500 and the like.

The dispersant or dispersing aid is, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant, or a silicone-based or fluorine-based surfactant.

Examples of surfactants include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers, such as polyoxyethylene octyl Phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol diesters, such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid ester; Fatty acid-modified polyester; tertiary amine-modified polyurethane; poly(ethyleneimine); and its analogs, the trade names of which are as follows: KP, Polyflow, F-Top, Megafax, Florade, Asahi Guard and Surflon and their analogs.

These dispersants can be used alone or in the form of a mixture of two or more.

The amount of the dispersant is generally 50 parts by weight or less than 50 parts by weight based on 100 parts by weight of the pigment, preferably 20 parts by weight to 40 parts by weight.

The dispersing aid may be a pigment derivative obtained by treating the pigment with an acid, a base, or a polymer. Examples of the dispersing aid include blue pigment derivatives, such as copper phthalocyanine derivatives; yellow pigment derivatives; and the like.

In addition to the above-mentioned pigments, the pigments may also include pigment derivatives. Pigment derivatives are generally C₄-C₃₀Alkyl, C₄-C₃₀Alkoxy, C₄-C₃₀Alkylthio, aminomethyl, sulfo, carboxyl, amidosulfonyl or amidocarbonyl non-polar groups or (usually) polar group-substituted pigment chromophores. These pigment derivatives are often referred to as synergists in the field of color filters. Any known pigment derivatives can be used.

Known synergists include, for example, commercially available products, such as<img file="TW201214031A_D0028.tif" />5000, 12000 or 22000.

The term "photopolymerization initiator (D)" as used herein means a compound that can form a radical, cationic, or anionic active substance capable of starting polymerization of component (A) due to bond decomposition or cleavage caused by exposure.

The photopolymerization initiator is a compound having a bisimidazole ring, a compound based on benzoin, a compound based on acetophenone, a compound based on benzophenone, a compound based on α-diketone, a compound based on polynuclear quinone, a compound based on<img file="TW201214031A_D0029.tif" />The compound or the triazine-based compound, as disclosed in WO 2007/113107 A1, page 22, line 16 to page 25, line 4, for example.

An example of a compound based on bisimidazole is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole And 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis (2,4-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5' -Tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole. These bisimidazole-based compounds have excellent solubility in solvents and do not produce foreign substances, such as undissolved products and deposits. In addition, it has high sensitivity, and the curing reaction can be fully promoted by exposure to a small amount of energy, providing high contrast and no curing reaction in the unexposed part. Therefore, the exposed coating film containing these compounds is clearly divided into a cured part that is insoluble in the developer and an uncured part that is highly soluble in the developer, so that the pixel pattern can be formed without partial or complete loss or bottom. Cut the color filter.

Examples of benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzylbenzoate, and the like.

Examples of acetophenone-based compounds include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4- Isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,2- Dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-(4-methylthienyl)-2-(N-morpholinyl)-1-prop-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2- Dimethoxy-1,2-diphenylethan-1-one and its analogues.

Examples of benzophenone-based compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Examples of α-diketone-based compounds include diacetyl, biphenylmethyl, methyl benzoate, and the like.

Examples of polynuclear quinone-based compounds include anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,4-naphthoquinone, and the like.

based on<img file="TW201214031A_D0030.tif" />Examples of compounds include<img file="TW201214031A_D0031.tif" />, 9-oxysulfur<img file="TW201214031A_D0032.tif" />, 2-Chloro-9-oxysulfur<img file="TW201214031A_D0033.tif" />And its analogues.

Examples of triazine-based compounds include 1,3,5-ginseng (trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)- s-triazine, 1,3-bis(trichloromethyl)-5-(4'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2' -Methoxyphenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(2'-furan Ethylene)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxystyryl)-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-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(2'-thienylethylene)-4,6-bis(trichloromethyl)-s-triazine and their analogs.

Among the above-mentioned benzoin-based compounds, acetophenone-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds,<img file="TW201214031A_D0034.tif" />Among the compounds and triazine-based compounds, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-(4-methylthienyl)-2-(N-morpholine) Yl)-1-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)butan-1-one are preferred because The formed pixel pattern hardly falls off from the substrate during development, and the pixel intensity and sensitivity are high.

The above-mentioned photoinitiators can be used alone or in a combination of two or more.

In the present invention, the above-mentioned photoinitiator may be used in combination with at least one member selected from the group consisting of: a sensitizer, a curing accelerator, and a photocrosslinking agent or sensitizer composed of a polymer compound as needed.

Examples of sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminobenzene Ethyl ketone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4 '-Diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzyl) coumarin, 4-(diethylamine Base) Chalcone and its analogs.

Examples of curing accelerators include chain transfer agents such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-Mercapto-4,6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, 3-mercapto-4-methyl-4H-1,2,4-tetrazole and their analog.

In addition, the polymeric photocrosslinker/sensitizer is a polymer compound having a functional group that can serve as a photocrosslinker and/or sensitizer in the main chain and/or side chain.

Examples of polymeric photocrosslinkers/sensitizers include the condensate of 4-azidobenzaldehyde and polyvinyl alcohol, the condensate of 4-azidobenzaldehyde and phenolic novolac resin, and 4-acryloylbenzene Homopolymers and copolymers of phenylpropenyl esters, 1,4-polybutadiene, 1,2-polybutadiene and the like.

In the present invention, the amount of the photopolymerization initiator is generally 0.01 to 200 parts by weight, preferably 1 to 120 parts by weight, and particularly preferably 1 to 50 parts by weight based on a total of 100 parts by weight of component (A). When the amount of the photopolymerization initiator is less than 0.01 parts by weight, the curing caused by exposure is insufficient, so the pixel pattern may be partially or completely lost or undercut. On the other hand, when the amount is greater than 200 parts by weight, the formed pixel pattern is likely to fall off from the substrate during development, and smudges or film residues are likely to be generated in areas other than the portion where the pixels are formed.

The photosensitive resist composition may further contain various additives.

The photosensitive photoresist composition may contain a storage stabilizer that stabilizes the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chloride, such as benzyltrimethyl chloride and diethylhydroxylamine; organic acids, such as lactic acid and oxalic acid and its methyl ether; tertiary butylcatechol; organic phosphine , Such as tetraethylphosphine and tetraphenylphosphine; and phosphorous acid salts. The amount of storage stabilizer can be 0.1% to 10% by weight based on the weight of the pigment (C).

Examples of additives include dispersion aids for blue pigment derivatives (such as copper phthalocyanine derivatives and yellow pigment derivatives); fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and polyethylene Alcohol monoalkyl ether and poly(fluoroalkyl acrylate); surfactants, such as nonionic surfactants, cationic surfactants and anionic surfactants; adhesion promoters, such as vinyl trimethoxysilane, Vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, N-(2-aminoethyl)-3-aminopropylmethyl dimethoxy silane, N- (2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane Propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis(4-methyl-6-third Butylphenol) and 2,6-di-tert-butylphenol; UV absorbers such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotris Azoles and alkoxy benzophenones; and coalescence inhibitors, such as sodium polyacrylate.

Generally, all the aforementioned components of the photosensitive photoresist composition of the present invention except for component (C) are dissolved in a suitable solvent to prepare a liquid composition.

Any solvent is acceptable as long as it can disperse or dissolve the components and additives, does not react with them, and has appropriate volatility.

Examples of solvents include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono N-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetate, such as ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers, such as diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate, such as 2 -Methyl hydroxypropionate and ethyl 2-hydroxypropionate; other esters, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isoacetate Propyl ester, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate Esters, methyl pyruvic acid, ethyl pyruvic acid, n-propyl pyruvic acid, methyl acetylacetate, ethyl acetylacetate and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; Carboxyamides, such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; and the like. These solvents can be used alone or in the form of a mixture of two or more.

High boiling point solvents can be used in combination with solvents such as benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol , Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and ethylene glycol monophenyl ether acetic acid ester. These high boiling point solvents can be used alone or in the form of a mixture of two or more.

Among the above solvents, from the perspective of solubility, pigment dispersibility and coating characteristics, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol Dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate Esters, isopropyl butyrate, n-butyl butyrate and ethyl pyruvic acid are preferred, and among the above-mentioned high boiling point solvents, γ-butyrolactone is preferred.

The amount of the solvent in the present invention is generally 100 to 10,000 parts by weight, preferably 500 to 5,000 parts by weight, based on 100 parts by weight of the binder (B).

In a preferred aspect, the present invention relates to a color filter, in which the photosensitive photoresist composition in an uncured state contains a bonding agent in an amount of 10 to 1,000 parts by weight based on 100 parts by weight of the pigment (C) Agent (B); 5 to 500 parts by weight of polyacrylate monomer (A) based on 100 parts by weight of binder (B); and 0.01 based on a total of 100 parts by weight of polyacrylate monomer (A) Up to 200 parts by weight of the photopolymerization initiator (D).

The photosensitive composition described herein can be prepared in the form of a solvent-developed or alkali-developed colored photoresist. Photoresist can be prepared by dispersing pigments and other substances mentioned above. Preferably, particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more than 0.5 μm are removed from the photosensitive composition by means of, for example, centrifugal separation, a sintered filter or a membrane filter. And mixed dust.

The color filter preferably includes a cured layer of the photosensitive photoresist composition as defined in any aspect above formed on a substrate, especially formed on a transparent substrate, wherein the content of the pigment in the layer is 0.02 g/m²Up to 1.5 g/m²。

The color filter may include pixels arranged on a transparent substrate, and optionally, the color filter includes a black matrix, wherein the pixels and/or the black matrix are formed by curing the photosensitive photoresist composition of the present invention.

Preferably, the color filter includes pixels composed of at least three colors on a transparent substrate and includes a black matrix separating the pixels, and the pixels and/or the black matrix are formed by curing the photosensitive photoresist composition form. More preferably, the color filter includes at least one red filter section, at least one green filter section, and at least one blue filter section.

The color filter of the present invention generally has at least one filter section formed using the photosensitive composition described herein. The color filter includes an additive mixture type, which includes at least one red filter section, at least one green filter section, and at least one blue filter section; and a subtractive mixture type ( subtractive mixture type), which includes at least one magenta filter section, at least one cyan filter section, and at least one yellow filter section.

The substrate used to form the color filter can be a glass substrate or a plastic substrate. Usually, the substrate is made of glass (such as soda glass, Pyrex(R) glass or quartz glass) or flexible glass material (such as alkali-free glass without alkali components in the glass, for example, "1737 glass available from Corning" ")production. In addition, SiN-coated substrates, silicon or plastic substrates (such as polycarbonate, polyester, aromatic polyamide, polyimide, polyimide, polyether chloride, or the like) are suitable. Suitable pretreatments can be performed on the transparent substrate, such as chemical treatment with silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction process or vacuum vapor deposition. Transparent substrates such as glass substrates or polyester sheets, especially polyethylene terephthalate (PET) sheets or substrates with transparent conductive films are preferred.

The photosensitive photoresist composition described herein is particularly useful for temperature-sensitive substrates suitable for devices such as electrophoretic displays (EPD), LCD displays or organic light emitting diode displays (OLED).

The photosensitive photoresist composition can be coated on an electrophoretic display such as electronic paper. The electrophoretic display generally includes a plastic film containing electrophoretic particles. For example, the composition can be coated on the plastic film of the electrophoretic display or on the transparent conductive film provided thereon. The composition can also be coated on a liquid crystal display (such as a polymer dispersed liquid crystal display (PDLC)), which generally contains liquid crystal droplets dispersed in a solid polymer matrix. For example, the composition can be coated on the polymer substrate or coated on the transparent conductive film provided thereon. In addition, the composition may be coated on an organic light emitting diode display (OLED), for example, on an outer layer (such as a conductive film, such as an ITO film).

Therefore, in a preferred aspect of the present invention, the substrate is a temperature-sensitive substrate, which includes a display device, such as an electrophoretic display, a polymer dispersed liquid crystal display, or an organic light-emitting diode display. The term "temperature-sensitive substrate" means a substrate that can withstand temperatures up to 90°C without damage.

In the second aspect, the present invention relates to a method of manufacturing a color filter, the method includes the following steps: coating a photosensitive photoresist composition as defined above on a substrate, then drying, exposing and developing ,Form a film.

The resulting color filter is also an aspect of the present invention. It is advisable not to perform the post-baking step at a temperature of at least 200°C after development. Generally, after development, the resulting layer is dried at room temperature (20°C to 25°C) up to 90°C, preferably at a lower temperature (about 50°C to 70°C) to remove any volatile substances or solvents.

Preferably, the method of manufacturing the color filter as defined above includes the following steps: coating a photosensitive photoresist composition on a substrate, followed by drying, exposing, developing to form a film, and then at 20°C to 70°C, Preferably, the developed film is dried at a temperature of 50°C to 70°C.

The color filter of the present invention can be prepared by using a photosensitive composition to form individual filter sections on a substrate by a photolithography method.

The respective color filter sections can be formed by the photolithography method as follows. That is, by coating methods (such as spray coating, spin coating, slit coating, or roll coating), the photosensitive composition prepared in the form of a solvent-developed or alkali-developed colored photoresist is coated on a transparent substrate to 0.2 μm when dry To a thickness of 5 μm. Then, the dried coating is exposed to ultraviolet rays in a contact or non-contact state through a mask having a predetermined pattern to be provided on the coating. Next, the uncured portion is removed by immersing the coating in a solvent or alkali developer or by spraying the developer onto the coating with, for example, a sprayer. For other colors, similar operations are repeated to prepare color filters. The photolithography method can produce color filters with higher accuracy than color filters made by printing methods.

An aqueous solution of, for example, sodium carbonate or sodium hydroxide can be used as the alkali developer. Organic bases such as dimethylbenzylamine or triethanolamine can also be used. A defoamer or a surfactant can be added to the developer. An aqueous developer is preferred.

In addition, water-soluble or alkali-soluble resin (such as polyvinyl alcohol or water-soluble acrylic resin) can be coated on the coated and dried colored photoresist, and the coated resin can be dried to prevent oxygen After causing the polymerization inhibition film to increase the sensitivity to ultraviolet light, it is exposed to ultraviolet light.

A more detailed description of the method of forming a color filter using the photosensitive photoresist composition described herein is provided later.

First, a light-shielding layer is formed to define the part where pixels are formed on the surface of the transparent substrate. A liquid photosensitive photoresist composition, such as a red pigment, dispersed on the substrate is coated to form a layer. Thereafter, the layer is exposed to radiation through a photomask and developed with an alkali developer to dissolve and remove the unexposed part of the coating film to form an array of red pixels arranged in a predetermined pattern.

After that, apply, expose and develop the liquid photosensitive resist composition dispersed with green pigment and the liquid photosensitive resist composition dispersed with blue pigment in sequence in the same manner as described above to be on the same substrate An array of green pixels and blue pixels is formed. Therefore, a color filter in which three pixel arrays of red, green and blue are arranged on the substrate is obtained.

The radiation-sensitive liquid composition can be coated on the transparent substrate using spin coating, cast coating, roll coating, or the like.

The thickness of the layer or coating after drying is generally 0.1 to 10 μm, preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm.

The radiation used to form the color filter is selected from visible light, ultraviolet light, extreme ultraviolet light, electron beam, X-ray and the like. It preferably has a wavelength of 190 to 450 nm.

The radiation energy is preferably 1 mJ/cm²Up to 1,000 mJ/cm²。

The alkali developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5 -Aqueous solution of diazabicyclo[4.3.0]-5-nonene or its analogues. The alkali developer may contain a suitable amount of a water-soluble organic solvent (such as methanol or ethanol) and a surfactant. Alkaline developer can generally be washed away with water.

The development is carried out by performing shower development, spray development, immersion development, mixed development or similar methods at room temperature for 5 to 300 seconds.

It is particularly preferable to use the color filter of the present invention in an electrophoretic display. In addition, another aspect of the present invention is to provide an electrophoretic display device including at least one color filter of the present invention.

As mentioned above, the photosensitive photoresist composition is particularly suitable for manufacturing color filters related to low-temperature substrates and/or displays (such as electrophoretic displays).

However, in principle, every flexible display that uses a substrate other than glass requires a low-temperature color filter method. New technologies that do not require patterning (such as inkjet, direct printing, etc.) are about to appear, and the coated pixels need to be cured (solvent removal, hardening, etc.). For example, inkjet often uses radiation curing instead of thermal curing (see, for example, JP 2002-371216). For these technologies, the photosensitive photoresist composition of the present invention also provides powerful advantages.

Therefore, a preferred embodiment of the present invention relates to a method for manufacturing a color filter by using the above-mentioned photosensitive photoresist composition to print a filter material. It is used in printing red, green and blue filter materials to manufacture color filters for displays (such as liquid crystal displays (LCD), polymer-dispersed LC-based displays (PDLC) or monochromatic emission OLED displays) There are specific applications.

Therefore, one purpose is to manufacture color filters used in liquid crystals (especially polymer-dispersed liquid crystal-based displays (PDLC)), organic light-emitting diode devices (OLED) (especially monochromatic emission OLED displays) or similar devices It is achieved by providing a way to successfully use an inkjet printing system to prevent the ink from flowing out of the designated unit to which it is delivered by using a physical barrier to deposit the colored ink on a predetermined position. Colored inks can be deposited in an extremely precise manner by ink jet or photo-like methods, in which colored thermoplastics or wax are transferred to the substrate (because the resolution of these devices is greater than that required for color filters). Make sure that the background is fully saturated and the continuity between the color points is good to make the color transition smooth. The colors remain separated and pure, and there is a sharp transition between each color and the black matrix.

By using a photolithography step or a high-resolution printing step to place a raised black mask on a glass or polymer sheet, a barrier containing ink or toner can actually be formed. Then use an inkjet or laser printer mechanism to "print" the color filter. With methods such as this, only one lithography step is required, which provides comparison marks, etc. and is also used to prevent color mixing, thereby ensuring a very clear distinction between pure colors and colors. It is important that for this method to work effectively, the thickness of the black matrix (mask) must be significantly thicker than the thickness seen in current LCDs. Physical barrier can mean any member that prevents liquid from moving and can include barriers, surface wetting phenomena, and so on. It is important to note that the present invention will be effective for the future pixel size of LCDs.

Therefore, the present invention relates to the use of the above-mentioned color filter in an electrophoretic display (electronic paper), a liquid crystal display device (preferably a display device based on polymer dispersed liquid crystal), or an organic light emitting diode display device. use.

In another aspect, the invention therefore relates to a device comprising a color filter as described in any aspect of the invention, which is an electrophoretic display (EPL), a polymer dispersed liquid crystal display (PDLC) or an organic Light-emitting diode display (OLED).

All the definitions and preferred ones provided for the color filter or photosensitive composition above are also applicable to other aspects of the present invention.

The use of the photosensitive photoresist composition of the present invention can enhance the degree of crosslinking of the film obtained during the exposure step without the need for a post-baking step after development. In addition, the drying temperature can be reduced up to 90°C and even lower, for example 70°C. By combining specific copolymers and highly reactive monomers, the cured layer obtained has higher adhesiveness and greater flexibility than the photoresist composition used in the prior art.

The adhesion of these films to substrates, especially glass substrates, SiN-coated substrates and plastic substrates has been significantly improved to prevent separation or tearing of the inner layer. In addition, the films are excellent in stability and they exhibit excellent chemical and physical resistance to the second and third layer photoresists that are subsequently colored. The photoresist composition of the present invention forms accurate and fine patterns.

The use of selected polyacrylate monomers achieves a higher degree of crosslinking and maintains compatibility with physical properties such as excellent dispersion stability, solubility and chemical resistance.

The omission of post-baking steps makes it possible to manufacture color filters directly on electronic paper displays or plastic substrates (that is, using current flexible, temperature-sensitive substrates). In addition, removing the post-baking step can reduce the number of steps, making the process cheaper.

In addition, since the parallax effect is reduced, that is, the distance between the pixel filter and the display is much smaller, the optical quality is significantly improved.

The following examples are provided for the purpose of further illustrating the present invention, but these examples should never be regarded as limiting. If not otherwise stated, "%" is by weight.

<b>Instance</b>

<b>Synthetic polyacrylate monomer</b>

<b>Example 1:</b>Trimethylolethane Polyglycerol Polyacrylate

Mix 65 g trimethylolethane triglycidyl ether (0.5 mol epoxy equivalent (from¹H NMR measurement); EEW 130 g, ERISYS GE-31/CVC Chemicals), 0.55 g (5 mmol) tetramethylammonium chloride (relative to epoxy equivalent 1 mol%) and 100 mg hydroquinone monomethyl ether And heated to a temperature of 90°C. 36 g (0.5 mol) acrylic acid was added dropwise within 30 minutes, keeping the temperature at 90°C. Next, the mixture was stirred at 90°C until NMR analysis showed complete conversion (9 hours). The mixture was cooled to room temperature to obtain trimethylolethane polyglyceride polyacrylate containing trimethylolethane triglyceride triacrylate in the form of a viscous clear yellow liquid.

¹H NMR (500 MHz, CDCl₃,δ ppm): 0.92(t,3H),3.32-3.81(m,28H),4.04(m,2H),4.2(m,4H),5.85(d,3H),6.12(dd,3H),6.43 (d, 3H).

<b>Example 2:</b>Isopentaerythritol polyglycerol ester polyacrylate

Mix 96 g isoprene erythritol polyglycidyl ether (0.5 mol epoxy equivalent (from¹H NMR measurement); EEW 216, Denacol EX-411/Nagase Chemicals), 0.55 g (5 mmol) of tetramethylammonium chloride and 100 mg of hydroquinone monomethyl ether and heated to a temperature of 90°C. 36 g (0.5 mol) of acrylic acid was added dropwise within 30 minutes, keeping the temperature at 90°C. Next, the mixture was stirred at 90°C until NMR analysis showed complete conversion (10 hours). The mixture was cooled to room temperature to obtain isopentaerythritol polyglyceryl polyacrylate containing isopentaerythritol tetraglyceride tetraacrylate in the form of a viscous clear yellow liquid.

¹H NMR (500 MHz, CDCl₃,δ ppm): 3.4-3.8(m,58H),4.0(s,4H),4.2(m,6H), 5.86(d,4H), 6.14(dd,4H), 6.42(d,4H).

<b>combine</b><b>Functionalized polyacrylate</b>

<b>Example 3</b>

a) Degas 112.5 g of methoxypropyl acetate with nitrogen at room temperature for 60 minutes, and then heat to 140°C under a nitrogen atmosphere. A homogeneous blend of 60.0 g benzyl methacrylate, 14.3 g methacrylic acid and 0.38 g di-tert-butyl peroxide was added dropwise within 1.5 hours, maintaining the temperature at 135°C to 140°C. Then, the mixture was stirred at 140°C for 4 hours and cooled to room temperature. The resulting clear viscous polymer solution had a solid content of 37.7% by weight (halogen dryer, 150°C). The final polymer solution was adjusted to 25 wt% by adding 91 g of methoxypropyl acetate. The molecular weight of the polymer was determined by GPC (THF): Mn 5.300, Mw 13.700, pdi 2.6. Viscosity (Brookfield, 20°C, 100 rpm): 438 mPas.

b) Functionalized polymer of Example 3a

70 g of the polymer mixture (25 wt% solids) obtained in Example 3a was degassed at room temperature for 60 minutes, and then heated to 130°C under a nitrogen atmosphere. During the heating phase, 0.03 g of tetramethylammonium chloride and several crystals of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (about 10 mg) were added to the polymer In the mixture. At 130°C, a solution of 1.25 g glycidyl methacrylate in 2.5 g methoxypropyl acetate was added dropwise within 45 minutes, keeping the temperature at 130°C. Then, the mixture was stirred at 130°C for 4 hours and cooled to room temperature. The resulting yellowish polymer solution had a solid content of 24.5 wt% (halogen dryer, 150°C). Viscosity (Brockfield, 20°C, 100 rpm): 245 mPas.

<b>Example 4</b>

a) Degas 101.6 g of methoxypropyl acetate with nitrogen at room temperature for 60 minutes, and then heat to 140°C under a nitrogen atmosphere. A homogeneous blend of 48.4 g of benzyl methacrylate, 11.5 g of methacrylic acid and 0.61 g of di-tert-butyl peroxide was added dropwise within 1.5 hours, maintaining the temperature at 135°C to 140°C. Then, the mixture was stirred at 140°C for 4 hours and cooled to room temperature. The resulting clear viscous polymer solution has a solid content of 35.1 wt% (halogen dryer, 150°C). The final polymer solution was adjusted to 25 wt% by adding 58 g of methoxypropyl acetate. The molecular weight of the polymer was determined by GPC (THF): Mn 5.300, Mw 12.500, pdi 2.4. Viscosity (Brockfield, 20°C, 100 rpm): 249 mPas.

b) Functionalized polymer of Example 4a

84 g of the polymer mixture (25 wt% solids) obtained in Example 4a was degassed with nitrogen at room temperature for 60 minutes, and then heated to 130°C under a nitrogen atmosphere. During the heating phase, 0.04 g of tetramethylammonium chloride and several crystals of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (about 10 mg) were added to the polymer In the mixture. At 130°C, a solution of 1.50 g glycidyl methacrylate in 3.0 g methoxypropyl acetate was added dropwise within 45 minutes, keeping the temperature at 130°C. Then, the mixture was stirred at 130°C for 4 hours and cooled to room temperature. The resulting yellowish polymer solution had a solid content of 24.1 wt% (halogen dryer, 150°C). Viscosity (Brockfield, 20°C, 100 rpm): 151 mPas.

<b>Application example: Color filter application</b>

<b>Example 5</b>

Mix 1.5 g with stirring <img file="TW201214031A_D0035.tif" />Red BK-CF (CI Pigment Red 254; Ciba), 0.6 g Ajisper PB 821 (pigment dispersant; Ajinomoto Japan), 7.65 g propylene glycol monomethyl ether acetate (PGMEA) and 4.0 g of the polymer obtained in Example 3b . 30 g of zirconia beads (0.5 mm) are added, and the mixture is shaken in Skandex for about 15 hours. Next, the dispersion liquid and the beads are separated by sieving.

7.0 g of the obtained dispersion was mixed with 0.35 g of isopentaerythritol polyglyceride polyacrylate obtained in Example 2 and 3.5 g of PGMEA, and then 0.14 g was added <img file="TW201214031A_D0036.tif" /> OXE02 (photoinitiator; Ciba). The mixture was shaken for 1 hour.

The mixture was spin-coated onto a clean and dried polyester substrate at 1000 rpm for 30 seconds, and dried on a hot plate at 65°C for 2 minutes. Through the mask (Karl S<img file="TW201214031A_D0037.tif" />ss Mirror mask aligner, MA 6) Expose the dry film to ultraviolet light for about 15 seconds.

The unexposed film was washed with 0.05% potassium hydroxide aqueous solution containing 0.25% surfactant, rinsed with water, and dried on a spin coater at 2000 rpm for 30 seconds.

<b>Examples 6 and 7</b>

Repeat Example 5 twice, and in Example 6, change<img file="TW201214031A_D0038.tif" />Replace red BK-CF with 1.65 g Heliogen Green 9365 (CI Pigment Green 36, BASF) and 0.85 g <img file="TW201214031A_D0039.tif" />A mixture of yellow LY2 (CI Pigment Yellow 150, Ciba), and in Example 7, the<img file="TW201214031A_D0040.tif" />Replace the red BK-CF with 1.44 g CI Pigment Blue 15:6, 0.03 g Solsperse 5000 and Solsperse 12'000 (two pigment derivatives).

Align the green layer on the red substrate of Example 5 and align the blue layer on the red and green layers of Examples 6 and 7, respectively.

For the green layer, use Karl S<img file="TW201214031A_D0041.tif" />The exposure time of the ss MA 6 mask aligner is 20 seconds, and for the blue layer, it is 50 seconds.

<b>Examples 5A to 7A</b>

Examples 5 to 7 were repeated on the glass substrate. The same excellent results regarding adhesion as in Examples 5 to 7 were obtained. The results of Examples 5A to 7A show that the formed delta structure with three-color pixels (R, G, and B) and the size is about 100×150 μm²Precise pixel pattern. The distance between pixels is 10 to 20 μm.

The results on both polyester and glass substrates are well-defined three-color filters with excellent adhesion properties.

<b>Comparative example 8</b>

Mix with stirring 1.44 g CI Pigment Blue 15.6, 0.03 g Solsperse 5000 (pigment derivative), 0.03 g Solsperse 12'000 (pigment derivative), 8.3 g PGMEA and 4.0 g general binder (approximately 20 mol% of armour) Copolymer of acrylic acid and about 80 mol% benzyl methacrylate). 30 g of zirconia beads (0.5 mm) are added, and the mixture is shaken in Skandex for about 15 hours. Next, the dispersion liquid and the beads are separated by sieving.

Mix 7.0 g of the obtained dispersion with 0.83 g glycerol 1,3-diglyceride diacrylate (GDDA), 1.22 g general-purpose binder and 4.5 g PGMEA, and then add 0.11 g <img file="TW201214031A_D0042.tif" /> OXE02 (photoinitiator). The mixture was shaken for 1 hour.

Using a resolution test mask, the mixture was spin-coated as a single component on glass substrates and polyester substrates. A loss of adhesion of almost all details can be observed.

<b>Example 9</b>

Repeat Example 8, except that the trimethylolethane polyglyceride polyacrylate of Example 1 was used instead of glycerol 1,3-diglyceride diacrylate, and the functionalized polymer obtained in Example 3b was used instead of universal bonding Agent (copolymer of methacrylic acid and aromatic methacrylate).

Use the resolution test mask to coat the material as a single-component material on the glass substrate and the polyester substrate. The adhesion is significantly improved compared to the coated material of Comparative Example 8, and even the smallest details (such as digits) can be seen.

In order to examine the adhesion and undercutting under extremely strict conditions much stronger than normal conditions during development, a resolution test mask was used in Comparative Example 8 and Example 9. This mask can show specific details from 10 μm down to 1.5 μm, which are much smaller than those in standard pixel designs for conventional color filters of 5 to 6 inches (12.7 to 15.24 cm).

Compared with the layer of Comparative Example 8, the adhesion quality of the layer of Example 9 is significantly improved. On the glass substrate of Comparative Example 8, most of the small details detached during development, which can be seen elsewhere on the glass substrate.

For the coated polyester substrate of Example 9, the same improved results were obtained.