JP4913750B2 - Photosensitive transfer material, partition wall and method for forming the same, optical element and method for manufacturing the same, and display device - Google Patents

Description

  The present invention relates to a display device such as a liquid crystal display and a liquid crystal color television, an optical element used in the display device and a manufacturing method thereof, a partition provided in the optical element, a method of forming the partition, and a photosensitive transfer used for forming the partition. Regarding materials.

In recent years, the demand for liquid crystal displays for personal computers and liquid crystal color televisions has been increasing, and there has been an increasing demand for improved characteristics and cost reduction of color filters indispensable for such displays.
Conventionally, as a method for producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like have been performed.
For example, in the dyeing method, a water-soluble polymer material layer that is a dyeing material is formed on a transparent substrate, patterned into a desired shape by a photolithography process, and the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern. By repeating these steps three times while changing the color, a colored layer composed of three colored portions of R (red), G (green), and B (blue) is formed.
In addition, the pigment dispersion method has been actively performed in recent years, and a monochromatic pattern is obtained by forming a photosensitive resin layer in which a pigment is dispersed on a transparent substrate and patterning it. By repeating this process three times while changing the color, a colored layer composed of colored portions of R, G, and B is formed.

In the electrodeposition method, a transparent electrode is patterned on a transparent substrate, and the first substrate is electrodeposited by immersing the transparent substrate in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, and the like. This process is repeated three times while changing the color to form a colored layer composed of colored portions of R, G, and B, and finally fired.
In the printing method, a pigment is dispersed in a thermosetting resin, and printing using the obtained dispersion is repeated three times while changing the color, so that R, G, and B are separately applied, and then the resin is thermoset. By doing so, a colored layer is formed.
In any of these production methods, a protective layer is generally formed on the obtained colored layer.

  The point common to these methods is that it is necessary to repeat the same process three times in order to form red, green and blue three-color pixels, resulting in high costs. Furthermore, since the number of processes is large, the yield tends to decrease.

In order to overcome these problems, in recent years, a color filter manufacturing method in which a black matrix is formed by a pigment dispersion method and RGB pixels are manufactured by an ink jet method has been studied. In this inkjet method, pixels are formed by sequentially applying R, G, and B colors to the recesses of the black matrix. The method using the ink jet method has an advantage that the manufacturing process is simple and the cost is low.
In addition, the inkjet method is not limited to the manufacture of color filters, but can also be applied to the manufacture of other optical elements such as electroluminescence elements.

  An electroluminescence element has a structure in which a thin film containing a fluorescent inorganic and organic compound is sandwiched between a cathode and an anode, and excitons are obtained by injecting electrons and holes into the thin film and recombining them. Is generated by utilizing the emission of fluorescence or phosphorescence when the exciton is deactivated. Each color fluorescent material used for such an electroluminescence element can be applied to a substrate on which an element such as a TFT is formed by an ink jet method to form a light emitting layer to constitute the element.

As described above, the ink jet method or the like method for applying droplets can be applied to the manufacture of optical elements such as color filters and electroluminescence elements because the manufacturing process can be simplified and the cost can be reduced. However, in the manufacture of such an optical element by the ink jet method, as a specific problem, there are “white spots”, “extruding ink”, “color mixing” and other “thickness unevenness in pixels” as shown in FIG. is there.
Hereinafter, the above problem will be described by taking a case of producing a color filter as an example.

Ink protrusion is a phenomenon in which when the black matrix is used as the partition 51 and ink is applied to the opening (pixel portion) of the black matrix to form a colored portion, the ink overflows beyond the black matrix serving as the partition. In addition, color mixing is a phenomenon in which overflowed ink is mixed between adjacent colored portions.
White spots are a phenomenon in which the wettability between the glass surface of the opening or the side wall of the partition wall and the ink is poor, the ink does not spread sufficiently in the opening, or a gap is formed between the side wall and the filled ink. It is.
The thickness unevenness in the pixels 53A to 53C is a phenomenon in which the thickness of the ink is different in one pixel, and occurs because the ink is raised and applied to the opening (pixel portion) of the black matrix. In particular, when an ink-repellent treatment is performed on the partition wall in order to prevent color mixing, it tends to occur at the four corners of the pixel, and the four corners often become thin.
These white spots, protrusions, mixed colors, and uneven thickness in pixels cause display defects such as uneven color and a decrease in contrast.

  As a technique for preventing color mixing, a method of patterning a water- and oil-repellent silicone rubber layer to form a partition wall for preventing color mixing (see, for example, Patent Document 1), or black serving as a light shielding layer There has been proposed a method of forming a silicone rubber layer on a matrix and using it as a partition wall for preventing color mixing (see, for example, Patent Document 2 or 3). In these methods, the ink repellency exhibited by the surface layer of the partition wall is insufficient, and a sufficient effect cannot be obtained.

As a method of using a fluorine compound that exhibits higher oil repellency and water repellency than a silicone compound, an ink repellent treatment example using CF ₄ plasma has been tried (see, for example, Patent Document 4). When ink repellent treatment was performed by this method, ink mixing between adjacent pixels could be effectively prevented, but there was a drawback that white spots were likely to occur. This is a problem that occurs because the ink repellent treatment is not limited to the upper surface of the partition wall but extends to the substrate surface and the side surface of the partition wall. In addition, a large capital investment is required to perform the plasma treatment.
As a method that does not require a large capital investment, there is a method using a wettability adjusting agent having a reactive group. For example, an ink repellent treatment example using a fluorine-containing silane coupling agent is disclosed as a wettability adjusting agent having a reactive group (see, for example, Patent Document 5). When ink repellent treatment was performed by this method, ink mixing between adjacent pixels could be effectively prevented, and the side wall of the partition was not processed, so that no bubbles (repelling) were generated near the partition. However, it is necessary to apply a fluorine-containing silane coupling agent with a solvent that does not dissolve the photoresist layer in order to recoat it on the black photoresist layer previously applied. Perfluoro (2-butyltetrahydrofuran) It was necessary to use a special expensive solvent such as
In addition, any of these methods needs to provide a dedicated process for the ink repellent treatment, which is a cost burden.

In addition, a method for simultaneously improving color mixing and white spots has been proposed (see, for example, Patent Document 6). By forming the partition wall from an ink repellent layer and a familiar layer, color mixing and white spots are simultaneously prevented. ing. However, even in that case, there remains a problem of improving the thickness unevenness in the pixel.
JP 4-123005 A JP-A-5-241011 JP-A-5-241012 JP 2003-344640 A JP-A-9-127327 JP 2002-139612 A

  Therefore, a photosensitive transfer material that can form a photosensitive resin layer imparted with ink repellency only on a desired surface, mixed colors, white spots, protrusions, and uneven thickness in pixels that are produced when pixels are formed are effective. Partition that can be prevented automatically, a method of forming the partition that can be easily formed, an optical element that is free of color mixing, white spots and protrusions, and unevenness in thickness within the pixel, and the optical element can be stably obtained There is a need for an optical element manufacturing method and a display device free from display defects.

The present inventor has reached the present invention in view of the above situation.
According to a first aspect of the present invention, there is provided a photosensitive transfer material having a temporary support, a surface treatment layer containing a fluorine compound having a polymerizable group, and a photosensitive resin layer in contact with the surface treatment layer in this order. provide.

  In a second aspect of the present invention, the photosensitive transfer material having the photosensitive resin layer and the surface treatment layer is used, and the photosensitive transfer material is pressure-bonded to the substrate so that the photosensitive resin layer is in contact with the substrate. Then, there is provided a method for forming a partition wall, in which the photosensitive resin layer is subjected to pattern exposure through the surface treatment layer, and the photosensitive resin layer is developed in this order.

  The third aspect of the present invention provides a partition formed by the above method.

  According to a fourth aspect of the present invention, there is provided a method for producing an optical element, wherein a pixel is formed by applying droplets to the recesses defined by the partition walls by an ink jet method.

    According to a fifth aspect of the present invention, there is provided at least a plurality of pixels and a partition formed so as to partition the pixels on the substrate, and the fifth aspect is manufactured by the manufacturing method according to the fourth aspect. An optical element is provided.

  According to a sixth aspect of the present invention, there is provided a display device comprising the optical element of the fifth aspect.

The photosensitive transfer material of the present invention has at least a surface treatment layer and a photosensitive resin layer on a temporary support, and the surface treatment layer has a polymerizable group (hereinafter referred to as “polymerizable group-containing fluorine compound”). It may be referred to as “.”).
By including a polymerizable group-containing fluorine compound in the surface treatment layer, the photosensitive resin layer or partition formed on the substrate using the photosensitive transfer material is ink repellent only on the upper surface (the surface opposite to the substrate). Sex can be imparted.
Hereinafter, in describing the present invention in detail, each of the layers constituting the photosensitive transfer material will be described first.

<Surface treatment layer>
The surface treatment layer refers to a layer formed so as to be in contact with the surface of the photosensitive resin layer on the temporary support side and for treating the surface of the photosensitive resin layer on the side of the temporary support. Specifically, for example,
(1) As shown in FIG. 2B, in the photosensitive transfer material in which the thermoplastic resin layer 40, the intermediate layer 20, and the photosensitive resin layer 10 are formed on the temporary support 30 so as to contact each other in this order, The intermediate layer 20 is
(2) As shown in FIG. 2A, in the photosensitive transfer material in which the intermediate layer 20 and the photosensitive resin layer 10 are formed on the temporary support 30 so as to contact each other in this order, the intermediate layer 20 is indicated. Also,
(3) In the photosensitive transfer material formed so that the thermoplastic resin layer and the photosensitive resin layer are in contact with each other in this order on the temporary support, the thermoplastic resin layer is
(4) In a photosensitive transfer material in which a thermoplastic resin layer, an intermediate layer, another layer as a surface treatment layer and a photosensitive resin layer are formed on a temporary support so that they are in contact with each other in this order, the other layers Point to. In the case where the photosensitive transfer material is pressure-bonded to a substrate for the purpose of forming a partition wall, etc., it is excellent in prevention of mixing of each layer, oxygen barrier property, adhesion at the time of pressure bonding, and economical efficiency. The photosensitive transfer material is particularly preferably the embodiment (1).

  By applying the surface treatment layer coating solution containing a polymerizable group-containing fluorine compound, the polymerizable group-containing fluorine compound is concentrated on the air interface side. Further, by forming a photosensitive resin layer thereon (on the air interface side), a polymerizable group-containing fluorine compound is densely packed at the interface on the photosensitive resin layer side in the surface treatment layer. Next, in this state, the photosensitive resin layer is exposed from the surface treatment layer side. Then, a polymerization reaction occurs due to the initiator in the photosensitive resin layer, and the photosensitive resin layer is cured. In this exposure curing process, the polymerizable group-containing fluorine compound in the surface treatment layer causes an interaction such as chemical bonding or physical adsorption with the photosensitive resin layer, and is fixed to the surface treatment layer side interface. Thus, ink repellency can be imparted only to the surface treatment layer side interface of the photosensitive resin layer. Further, after the exposure, the surface treatment layer is removed by c) development described later, whereby a partition wall having ink repellency can be produced only on the upper surface (the surface on the opposite side of the substrate). Heating the surface treatment layer and the photosensitive resin layer before a) pressure bonding or between a) pressure bonding and b) exposure is also preferable because the interaction can be further strengthened.

Since the polymerizable group-containing fluorine compound fixed on the surface of the photosensitive resin layer by the interaction is not removed by development, a partition having ink repellency is produced only on the upper surface (the surface on the opposite side of the substrate) as described above. can do.
As described above, the surface treatment layer can achieve its purpose if it has a film thickness of about one molecule, and therefore the film thickness of the surface treatment layer is not particularly limited. However, it is preferably 15.0 μm or less, more preferably 3.0 μm or less, from the viewpoints of economy and developability.

  In addition, it is preferable that a 0.1 μm or less polymerizable group-containing fluorine compound layer is present on the surface of the photosensitive resin layer after exposure and development. In this case, when the panel is formed, the fluorine compound does not cry into the liquid crystal, and the liquid crystal drive is not hindered. In addition, the film thickness of the partition wall does not become larger than the desired film thickness. In this case, the cell gap can be easily set to a desired value, and problems such as unevenness do not occur.

  The amount of the polymerizable group-containing fluorine compound fixed to the photosensitive resin layer surface by exposure is preferably such that the number of fluorine atoms / number of carbon atoms on the upper surface measured by ESCA is 0.10 or more, and 0.30 or more It is more preferable that

  Here, the measurement of ESCA was performed by preparing a solid sample for measurement with a solid exposure at a predetermined exposure amount, and the atomic ratio of the surface was measured by ESCA (manufactured by ULVAC-PHI, PHI-5300, detection angle 45 °). .

  The partition wall produced by the above method has ink repellency only on the top surface and no ink repellency site on the side surface. For this reason, there is an advantage that white-out failure hardly occurs. Further, the thickness of the partition wall can be made the same as the thickness of the photosensitive resin layer, and there is an advantage that the problem due to the variation in the thickness does not occur.

  In addition, it is preferable that the said surface treatment layer does not contain a photoinitiator or a photoinitiator system. Here, “does not contain” means that no photopolymerization initiator or photopolymerization initiator system is added when the surface treatment layer coating solution is prepared. If the surface treatment layer does not contain a photopolymerization initiator or a photopolymerization initiator system, the surface treatment layer does not harden during exposure, and the partition wall thickness does not become larger than the desired thickness. In this case, the cell gap can be set to a desired value, and problems such as unevenness do not occur.

  In addition, the surface treatment layer is a layer formed from a coating solution in which an aqueous layer (25% by mass or more (more preferably 40% by mass or more) of the solvent) is water from the viewpoint of coating with the photosensitive resin layer. ) Is preferable.

-Fluorine compound having a polymerizable group-
Examples of the polymerizable group-containing fluorine compound used in the present invention include a polymer compound having a fluorine atom and a polymerizable unsaturated double bond (hereinafter sometimes referred to as “polymerizable group-containing fluorine-containing polymer”). Can be mentioned. Furthermore, this polymer compound is preferably soluble in an alkaline aqueous solution. In this case, it becomes possible to remove the unreacted polymer compound by development, and there is less labor and a process with excellent environmental compatibility. It becomes possible to provide. Moreover, from the viewpoint of dissolving in the coating solution for the surface treatment layer, the polymer compound preferably contains a water-soluble group.
That is, as the polymerizable group-containing fluorine compound in the present invention, a copolymer of a fluorine-containing monomer part and a double bond-containing monomer part is preferably used, and further preferably includes a hydrophilic monomer part.

Here, several methods for synthesizing copolymers of the fluorine-containing monomer part and the double bond-containing monomer part are listed. However, the method for synthesizing the copolymer is not limited thereto.
For example, using an oil-repellent and water-repellent monomer such as a fluorine-containing monomer, (a) a method of copolymerizing a fluorine-containing monomer, a hydrophilic monomer, and a monomer having an ethylene addition polymerizable unsaturated group in the side chain, (b) A method in which a fluorine-containing monomer, a hydrophilic monomer and a monomer having a double bond precursor are copolymerized, and then a double bond is introduced into a polymer obtained by treatment with a base or the like; (c) hydrophilicity such as carboxylic acid Examples include a method of reacting a fluorine-containing polymer having a functional group with a compound having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (a) a method of copolymerizing a fluorine monomer, a hydrophilic monomer, and a monomer having an ethylene addition polymerizable unsaturated group in the side chain is particularly preferable.

  Examples of the monomer having an ethylene addition polymerizable unsaturated group in the side chain used in the method (a) include an allyl group-containing monomer, specifically, allyl (meth) acrylate, 2-allyloxyethyl methacrylate. Is mentioned.

Examples of the monomer having a double bond precursor used in the method (b) include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate and 2- (2-bromo-2-methyl-1). -Oxopropoxy) ethyl methacrylate.
The method of “introducing a double bond into a polymer obtained by treatment with a base” will be described in more detail. By having a base act, a fluorine-containing monomer, a hydrophilic monomer, and a double bond precursor are included. In this method, the deoxidation reaction of the monomer copolymer is promoted to convert the double bond precursor into a double bond. Here, inorganic and organic bases can be used as the base, and organic bases are preferable, and tertiary alkylamines such as triethylamine, diisopropylethylamine, diazabicycloundecene, diazabicyclononene, and the like are particularly used. preferable.

Furthermore, in the method (c), it is used for introducing an unsaturated group by utilizing a reaction between a carboxyl group, an amino group or a salt thereof in a fluorine-containing polymer and a functional group such as a hydroxyl group or an epoxy group. Examples of the compound having an ethylene addition polymerizable unsaturated group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate and the like.
In general, the monomer having an ethylene addition polymerizable unsaturated group is a monomer having a highly reactive ethylene addition polymerizable unsaturated group from the viewpoint of increasing the sensitivity of the water repellent (ink repellent) reaction. It is preferable that the monomer has a long main chain (the number of main chain carbon atoms is 5 or more, more preferably 8 or more).

-Fluorine-containing monomer-
Next, a fluorine-containing monomer that is used in the methods (a) and (b) and also serves as a raw material for the fluorine-containing polymer having a hydrophilic functional group in the method (c) will be described.
Examples of the fluorine-containing monomer include at least one fluorine-containing monomer selected from the group consisting of the following general formulas (I), (II), (III), (IV), and (V).

CH ₂ = CR ¹ COOR ² R ^f (I)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents —C _p H _2p —, —C (C _p H _{2p + 1} ) H—, —CH ₂ C (C _p H _{2p + 1} ) H. - or -CH ₂ CH ₂ O-, the ^{_{R f -C n F 2n + 1}} , - (CF 2) n H, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF _{2) p OC m H 2m C} i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1 or _{-N (C p H 2p + 1} ) SO 2 C n F 2n + 1 represents. However, p is 1-10, n is 1-16, m is 0-10, i is an integer of 0-16.)

CF ₂ = CFOR ^g (II)
(In the formula, R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CHR ^g (III)
(In the formula, R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

_{^{CH 2 = CR 3 COOR 5 R}} j R 6 OCOCR 4 = CH 2 ··· (IV)
Wherein R ³ and R ⁴ are hydrogen atoms or methyl groups, R ⁵ and R ⁶ are —C _q H _2q —, —C (C _q H _{2q + 1} ) H—, —CH ₂ C (C _q H _{2q + 1} ) H— or —CH ₂ CH ₂ O—, R ^j represents —C _t F _2t —, where q is an integer of 1 to 10 and t is an integer of 1 to 16.

^{_{CH 2 = CR 7 COOCH 2 CH}} (CH 2 R k) OCOCR 8 = CH 2 ··· (V)
(Wherein R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ^k represents —C _y F _{2y + 1} , where y is an integer of ₁ to 16)

Hereinafter, although the specific example of the fluorine-containing monomer which can be used for this invention is given, this invention is not restrict | limited to this.
Examples of the monomer represented by the general formula (I) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH _2. OCOC (CH ₃ ) = CH ₂ , C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH _{2 , CF 3 (CF 2) 4} CH (CH 3) OCOC (CH 3) = CH 2, CF 3 (CF 2) 4 OC _{2 CH 2 OCOC (CH 3)} = CH 2, C 2 F 5 CON (C 2 H 5) CH 2 OCOCH = CH 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH ₂ , H (CF ₂ ) ₆ CH (C ₂ H ₅ ) OCOC (CH ₃ ) = CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH _{2 and the} like.

Examples of the fluoroalkylated olefin represented by the general formulas (II) and (III) include C ₃ F ₇ CH═CH ₂ , C ₄ F ₉ CH═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , C ₃ such as _{F 7 OCF = CF 2, C} 7 F 15 OCF = CF 2 and C ₈ F ₁₇ OCF = CF ₂ and the like.

The monomer represented by the general formula (IV) and (V) for _{example, CH 2 = CHCOOCH 2 (CF} 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = CH _{2 and the} like can be mentioned.

In addition to the monomers represented by the general formulas (I) to (V), CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ (CH ₂ CH ₂ O) ₂ CH ₂ OCOCH═CH ₂ , a fluorine-containing monomer of (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH═CH ₂ can also be preferably used.

Among these, from the viewpoint of improving water repellency (ink repellency), it is preferable that the perfluoro group has a larger number of main chain carbon atoms, and 6 or more is particularly effective. _{Specifically, CF 3 (CF 2) 7} CH 2 CH 2 OCOCH = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₆ CH (C ₂ H ₅ ) OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF _{3 (CF 2) 7 SO 2} N (CH 3) (CH 2) 10 OCOCH = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3 _{(CH 2) 4 OCOCH = CH} 2, C 10 F 21 CH = CH 2, C 7 F 15 OCF = CF 2, C 8 F 17 OCF = CF 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17 ) OCOCH = CH ₂ is preferred.

Moreover, it is also preferable that the terminal of a perfluoro group is a fluorine atom. _{Specifically, CF 3 (CF 2) 7} CH 2 CH 2 OCOCH = CH 2, CF 3 CH 2 OCOCH = CH 2, CF 3 (CF 2) 4 CH 2 CH 2 OCOC (CH 3) = CH 2, _{C 7 F 15 CON (C 2} H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH 2, CF 3 (CF 2 ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₄ CH _{(CH 3) OCOC (CH 3} ) = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2 _{C 2 F 5 CON (C 2} H 5) CH 2 OCOCH = CH 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 CH ( _{C 2 H 5) OCOC (CH} 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 _{N (CH 3) (CH 2} ) 10 OCOCH = CH 2, C 2 F 5 SO 2 N (C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH ₃ ) (CH ₂ ) ₄ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH ₂ , C ₃ F ₇ CH═CH _{2 , C 4 F 9 CH = CH} 2, C 10 F 21 CH = CH 2, C 3 F 7 OCF = CF 2, C 7 F 15 OCF = CF 2, C 8 F 17 OCF _{CF 2, CF 3 CH 2 OCH} 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2 Is preferred.

In addition, from the viewpoint of good compatibility with other components in the surface treatment layer, it is also preferable to contain S, N, and the like. _{Specifically, C 7 F 15 CON (C} 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH 2, CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) _{7 SO 2 N (CH 3) CH} 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2, C 2 F 5 SO 2 _{N (C 2 H 5) CH} 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 _{COCH = CH 2, C 2 F} 5 SO 2 N (C 2 H 5) C (C 2 H 5) HCH 2 OCOCH = CH 2 and the like.

-Hydrophilic monomer-
Next, a hydrophilic monomer that is used in the methods (a) and (b) and also serves as a raw material for the fluorine-containing polymer having a hydrophilic functional group in the method (c) will be described.
The hydrophilic monomer useful in the present invention is a monomer having a positive charge such as ammonium or phosphonium, or a negative charge or negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group. And monomers having an acidic group that can be dissociated. In addition, for example, a hydrophilic monomer having a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, a cyano group, or an ethylene oxide group can be used.

In the present invention, specific examples of particularly useful hydrophilic monomers include the following monomers. For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethylaminoethyl (medium) ) Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.
Among these, nonionic ones are more preferable because they are less likely to be mixed with impurities in the liquid crystal layer. Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meta ) Acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) acrylate.

-Other monomers-
The polymerizable group-containing fluoropolymer in the present invention may be copolymerized with other monomers in addition to the monomer having a fluorine atom and a polymerizable unsaturated double bond group as its constituent elements. These monomers are used to increase the solvent solubility of the polymer compound of the present invention. Although it does not specifically limit as a monomer used for such a purpose, Acrylic acid ester, such as (meth) acrylic acid methyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid methoxyethyl ester, should be used. Can do.
In addition, since the polymerizable group-containing fluoropolymer in the present invention has a lower Tg, ink repellency is more likely to proceed, and it is preferable that such a monomer is copolymerized. Specifically, an alkyl acrylate having 3 or more carbon atoms and an alkyl group can be used.

  The polymerizable group-containing fluorine compound obtained from the monomer is preferably a resin represented by the following structural formula (1).

In the structural formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁶ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^{11 to} R ¹⁴ and R ¹⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. An alkyl group of 3 is preferred, and a methyl group is particularly preferred.
Among the above, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁶ are preferably a hydrogen atom or a methyl group.

In the structural formula (1), R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms in total, or an aryl group having 6 to 20 carbon atoms in total.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁵ include an alkyl group having no functional group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, An alkyl group having a functional group such as a hydroxyethyl group, a hydroxybutyl group, a hydroxypropyl group, a dihydroxypropyl group, a trimethylammonium ethyl group, a dimethylbenzylammonium ethyl group is preferable, among which an alkyl group having 1 to 4 carbon atoms is preferable, A methyl group and a propyl group are particularly preferable.
As the aryl group having 6 to 20 carbon atoms represented by R ¹⁵ , for example, a phenyl group, a methoxyphenyl group, a methylphenyl group, an octoxyphenyl group, a dimethylaminophenyl group and the like are preferable, and a phenyl group, a methoxyphenyl group Is particularly preferred.
Among the above, R ¹⁵ is preferably a hydrogen atom, a methyl group, a propyl group, or a hydroxyethyl group.

In the structural formula (1), L ₁ and L ₂ each independently represent a single bond or a divalent linking group.
The divalent linking group represented by L ₁ and L ₂ is preferably an alkylene group or an arylene group, which may be unsubstituted or substituted, and may be a hydroxy group, an ester group, a monoether bond, or an ester. You may have a bond and a urethane bond.

Among these, the following groups or groups having the following structures are preferable.

  Y is more preferably a single bond and a substituent having the following structure. In the following substituent, n represents an integer of 1 to 6.

In Structural Formula (1), X ₁ represents an ester group, an amide group, an arylene group which may have a substituent, or a linking group having these, and X ₂ and X ₃ are each independently an ether A group, an ester group, an amide group, an arylene group which may have a substituent, a heterocyclic residue, or a linking group having these.

The arylene group represented by X ₁ , X ₂ and X ₃ is preferably an arylene group having a total carbon number of 6 to 20, and examples thereof include phenylene, naphthylene, anthracenylene and biphenylene, and these include o-, p-, It may be m-substituted. Among these, an arylene group having 6 to 12 carbon atoms is more preferable, and phenylene and biphenylene are particularly preferable.

As the heterocyclic residue represented by X ₂ and X ₃ , for example, a 5-membered ring or a 6-membered ring containing a nitrogen atom or an oxygen atom as a member of the ring is preferable, and a pyridine ring, a pyrimidine ring, a pyrazine ring, Thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, isoxazole ring, pyrazole ring, imidazole ring, quinoline ring, thiadiazole ring, caprolactam ring, pyrrolidone ring, etc. are preferred, pyridine ring, thiadiazole ring, caprolactam ring, A pyrrolidone ring is more preferred.

Among the above, X ₁ is preferably a linking group having the following linking group or the following structure.

Here, R _x represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms in total, or an aryl group having 6 to 20 carbon atoms in total.
All of the alkyl group having 1 to 12 carbon atoms and the aryl group having 6 to 20 carbon atoms have the same meaning as in R ¹⁵ , and preferred embodiments thereof are also the same.

Among the above, X ₂ and X ₃ are preferably the following linking groups or linking groups having the following structure. Here, R _x has the same meaning as R _x described above.

In the structural formula (1), Rf ² represents a substituent containing fluorine. As the substituent containing fluorine, the following fluorine-containing groups or fluorine-containing groups having the following structures are suitable. Here, m in the fluorine group represents an integer of 1 to 20, l represents an integer of 1 to 10, and n represents an integer of 1 to 20.

  Examples of the polymerizable group-containing fluorine compound used in the present invention are shown below. However, the present invention is not limited to these.

  The molecular weight (Mw) of the polymerizable group-containing fluoropolymer that can be used in the present invention is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 2000 to 100,000, and most preferably in the range of 2000 to 40,000. Within this molecular weight range, an excellent water repellency effect and solubility in a solution can be achieved. A molecular weight of 1000 or more is preferable because it is easy to achieve both ink repellency and solubility. Moreover, it is preferable that it is 1 million or less because the solubility does not deteriorate.

As the solid content ratio of the polymerizable group-containing fluorine compound in the surface treatment layer increases, ink repellency (oil repellency and water repellency) can be obtained with a smaller exposure amount. It becomes difficult to form the resin layer. Therefore, 1-50 mass% is preferable and, as for the ratio of the polymeric group containing fluorine compound in solid content of a surface treatment layer, 5-30 mass% is more preferable.

  As described above, examples of the surface treatment layer in the present invention include an intermediate layer, a thermoplastic resin layer, and other layers. Next, the intermediate layer and the thermoplastic resin layer will be described.

<Intermediate layer>
The photosensitive transfer material of the present invention preferably has an intermediate layer for preventing mixing of components at the time of coating a plurality of coating layers and during storage after coating. As described above, when the intermediate layer corresponds to the surface treatment layer, it is essential to contain a polymerizable group-containing fluorine compound, and from the viewpoint of separate coating from the photosensitive resin layer, an aqueous system is included. (A layer formed by a coating solution in which 25% by mass or more of the solvent is water).

As the intermediate layer, an intermediate layer having an oxygen blocking function described in paragraphs [0014] to [0015] of JP-A-5-72724 as “separation layer” is preferable. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
The dry thickness of the intermediate layer is generally 0.2 to 5 μm, preferably 0.5 to 3 μm, particularly preferably 1 to 2.5 μm.

<Thermoplastic resin layer>
The photosensitive transfer material of the present invention may have a thermoplastic resin layer as necessary. As described above, when the thermoplastic resin layer corresponds to the surface treatment layer, it is essential to contain a polymerizable group-containing fluorine compound.
Such a thermoplastic resin layer is alkali-soluble and contains at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support (substrate) can be exhibited during the formation of the partition walls.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples include saponified products of acid ester copolymers, saponified products of poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate, and the like.

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. An activator, a release agent and the like can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate.

<Temporary support>
The temporary support in the photosensitive transfer material of the present invention can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers.

<Photosensitive resin layer>
The photosensitive resin layer in the present invention is coated with a photosensitive resin composition containing at least (1) an alkali-soluble binder, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or a photopolymerization initiator system. Is preferably formed. From the viewpoint of obtaining light shielding properties, the composition preferably further includes (4) a colorant. It is more preferable that the photosensitive resin layer has a light shielding property in that it has a function of a partition black matrix.
Hereinafter, the components (1) to (4) will be described.

(1) Alkali-soluble binder The alkali-soluble binder in the present invention (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone, or may be used in the state of a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the photosensitive resin composition. The rate is generally 20 to 50% by mass, and preferably 25 to 45% by mass.

(2) Monomer or Oligomer The monomer or oligomer in the present invention is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.
Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. % Is preferred.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system in the present invention, a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, US The acyloin ether compound described in Japanese Patent No. 2448828, the aromatic acyloin compound substituted with α-hydrocarbon described in US Pat. No. 2,722,512, US Pat. Nos. 3,046,127 and 2,951,758 No. 3,549,367, a combination of a triarylimidazole dimer and a p-aminoketone, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and a trihalomethyl- s-triazine compounds, described in US Pat. No. 4,239,850 Trihalomethyl - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A No. 11-133600 can also be mentioned as a preferable example, and further described in paragraph numbers 0028 to 0042 of JP-A No. 2000-310707. Photopolymerization initiators can also be used as suitable.

These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

(4) Colorant It is preferable that the said photosensitive resin composition contains a colorant as needed. As the colorant, organic pigments, inorganic pigments, dyes and the like can be suitably used. When the photosensitive resin layer is required to have light shielding properties, metal oxides such as carbon black, titanium oxide, and iron oxide are used. In addition to the light-shielding agent such as powder, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used. Among these, carbon black is particularly preferable because of its excellent light shielding properties.

Furthermore, a solvent, a surfactant, a thermal polymerization inhibitor, an ultraviolet absorber and the like can be added to the photosensitive resin composition.
-Solvent-
The photosensitive resin composition in the present invention may further contain an organic solvent in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

-Surfactant-
Conventionally used optical elements (color filters, etc.) have a problem that the color of each pixel becomes dark in order to realize high color purity, and the unevenness of the film thickness of the pixel is recognized as the color unevenness as it is. It was. Therefore, it has been demanded to improve the film thickness variation during the formation (application) of the photosensitive resin layer, which directly affects the pixel film thickness.
In the photosensitive transfer material of the present invention, it is possible to control to a uniform film thickness, and from the viewpoint of effectively preventing coating unevenness (color unevenness due to film thickness fluctuation), an appropriate surface activity in the photosensitive resin composition. It is preferable to contain an agent.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

-Thermal polymerization inhibitor-
The photosensitive resin composition in the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-Supplementary dyes and pigments-
The photosensitive resin composition in the present invention may contain a known colorant in addition to the colorant (pigment) as necessary for the purpose of obtaining higher light-shielding properties. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the photosensitive resin composition, so that the particle size is 0.1 μm or less, particularly 0.08 μm or less. preferable.
Specific examples of the known colorant include color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And pigments described in JP-A-2005-17521 [0080] to [0088] can be preferably used.

-UV absorber-
The photosensitive resin composition in this invention can contain a ultraviolet absorber as needed. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like.

  Moreover, the photosensitive resin composition in this invention can contain the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, another additive, etc. other than the said additive.

  The photosensitive resin composition for forming the partition wall of the present invention is: (a) a non-high-ortho-type cresol novolak resin obtained by reacting phenols containing at least p-cresol with an aldehyde under an acid catalyst, or (B) A positive photoresist composition containing a quinonediazide group-containing compound may be used. Furthermore, in the positive photoresist composition, it is preferable that the dinuclear content of p-cresol in the component (a) is less than 2.0% in the GPC (gel permeation chromatography) method. Examples of the positive photoresist composition include those described in paragraphs [0007] to [0026] of Japanese Patent No. 3624718. When the positive photoresist composition is used, it is difficult to generate sublimates even when subjected to high-temperature baking, and it is possible to form a resist pattern close to a rectangle with a high residual film ratio as well as excellent sensitivity and resolution. .

  The resin composition of the present invention may contain a thermoplastic resin having a mass reduction rate of 2% by mass or less when heated at 230 ° C. for 1 hour. When the resin is used, the color characteristics of optical elements (color filters, etc.) due to discoloration due to the deterioration of the resin are not deteriorated even by a heating process exceeding 200 ° C. such as ITO film preparation and alignment film preparation. A display device (for example, a liquid crystal display) excellent in color quality can be provided. Examples of the resin include resins described in paragraph numbers 0013 to 0016 of JP-A-11-194214.

  The resin composition of the present invention may contain inorganic fine particles having an average particle size (for example, about 1 to 100 nm) smaller than the exposure wavelength. The inorganic fine particles can be composed of colloidal silica which may have a functional group (for example, a photosensitive group). The photosensitive resin composition may be either a negative type or a positive type, and may be water or alkali developable. By containing the inorganic fine particles, oxygen plasma resistance, heat resistance, dry etching resistance, sensitivity and resolution can be greatly improved. Examples of the inorganic fine particles include those described in paragraph numbers 0036 to 0047 of JP-A No. 11-327125.

  The resin composition of the present invention may contain retardation reducing particles. By including the retardation-reducing particles, the absolute value of the retardation can be reduced to 15 nm or less. Accordingly, the color filter using this resin composition is excellent in viewing angle dependence, and high-quality by using the color filter. It is possible to provide a liquid crystal display device capable of obtaining the above image. Specific examples of the retardation-reducing particles include those described in JP-A 2000-187114, paragraphs 0014 to 0035.

  The resin composition of the present invention may contain a light stabilizer. As the light stabilizer, at least one compound selected from phosphites, benzotriazoles, benzophenones, hindered amines, salicylic acid esters, triazines, hindered phenols and thioethers is preferred. Specific examples of the light stabilizer include those described in paragraphs 0007 to 0014 of JP-A No. 2000-214580. The resin composition containing the light stabilizer has both excellent light resistance and curability of the composition, and is excellent in image forming property. When used, the resin composition is high quality and low cost by the pigment dispersion method. A highly reliable color filter can be realized.

  When the resin composition of the present invention contains a green organic pigment, the amount of tetrachlorophthalic acid, tetrachlorophthalic anhydride and tetrachlorophthalimide in the green organic pigment is analyzed, and the total of them is 500 ppm or less. Is preferred. Examples of the method for obtaining the pigment in the preferred range include the methods described in paragraph Nos. 0005 to 0020 of JP-A No. 2000-32417. Further, by the same method, impurities of pigments other than green can be reduced. The resin composition using the organic pigment does not cause omission or peeling in the pattern during development, and does not cause display defects such as image sticking when used as a display panel. It is possible to provide a color filter that is excellent in mechanical strength, and has good adhesion to the substrate of the pattern and a good pattern shape.

  The pigment used in the resin composition of the present invention is preferably a pigment selected or processed so that the voltage holding ratio is 80% or more. Examples of the pigment within the preferable range include pigments described in paragraph Nos. 0005 to 0026 of JP-A No. 2000-329929. By using pigments that have been selected or processed so that the voltage holding ratio is 80% or more, the pixel pattern at the time of development is not lost or peeled off, and it has excellent developability and the display panel is burned. Therefore, a color filter having excellent mechanical strength after film formation, good adhesion to the pixel substrate, and good pattern shape can be provided.

  The resin composition of the present invention comprises a polymer having a glass transition temperature Tg of 60 to 120 ° C. and a weight average molecular weight of 10,000 to 100,000, and a polyfunctional monomer having a viscosity at 25 ° C. of 10 to 8000 cps. And a colorant. Examples of the preferable resin composition include combinations described in paragraph Nos. 0016 to 0033 of JP-A No. 10-1515917. Since the resin layer formed from the resin composition has an appropriate viscosity in the range of 20 to 30 ° C., the use efficiency of the material is excellent.

  When using a copper phthalocyanine pigment in the resin composition of the present invention, the content of free copper contained in the pigment is preferably 200 ppm or less. Examples of the pigment include those described in paragraph Nos. 0011 to 0020 of JP-A No. 2004-189852. By using the pigment, the storage stability of the composition can be enhanced.

  When carbon black is used for the resin composition of the present invention, carbon black having a primary particle size of 20 to 50 nm, a DBP absorption of 140 ml / 100 g or less, and a pH of 2.5 to 4 is preferable. Examples of the carbon black include those described in paragraph numbers 0010 to 0014 of JP-A No. 2004-292672. By using the carbon black, partition walls (black matrix, colored layer, etc.) excellent in both developability and OD value can be formed.

  When the resin composition of the present invention contains a metal compound, the specific gravity of the resin composition is preferably 2.5 or more. As the resin composition, those described in paragraph Nos. 0007 to 0013 of JP-A No. 2004-352890 are preferable. By producing a pattern (such as a partition wall) using the resin composition, a black pattern that cannot be achieved conventionally can be formed.

  In the resin composition of the present invention, the hardness of the formed pattern (partitions etc.) is 3H or more and 9H or less in pencil hardness, and the resin layer obtained after exposure is made into an aqueous alkaline solution at 25 ° C. with stirring at 100 rpm. It is preferable that the resin composition has a transmittance (average of 400 to 780 nm) of 98% or more and 100% or less at a portion where the non-exposed portion of the resin layer dissolved after 120 seconds is immersed. Examples thereof include the resin compositions described in paragraph numbers 0007 to 0075 of JP-A-2005-10663. When a pattern is formed using the resin composition, both high surface hardness and good developability can be achieved.

  When a nitrogen atom-containing dispersant is used in the resin composition of the present invention, the residual ratio of the total nitrogen amount when the dispersant is heated at 230 ° C. for 30 minutes (the mass of the total nitrogen amount after heating with respect to the total nitrogen amount before heating) The ratio is preferably 60% by mass or less. Examples of the dispersant include those described in paragraph Nos. 0043 to 0047 of JP-A No. 2004-325968. A color filter (such as a partition wall or a colored pixel) using the dispersant has very little influence on the voltage holding ratio of the liquid crystal. Therefore, display defects such as display unevenness and image sticking hardly occur, and an extremely high quality display device is manufactured. be able to.

When an overcoat layer is provided when producing a color filter as the optical element of the present invention, the indentation hardness of the overcoat is preferably within the range of the following formula (1). In addition, whether the overcoat layer is provided or not, it is preferable that the indentation hardness of the color filter is within the range represented by the formula (2). Within the above range, display unevenness of the liquid crystal display device due to non-uniform cell gap is unlikely to occur. Examples of means for achieving the preferred range of hardness include the methods described in paragraph Nos. 0012 to 0061 of JP-A No. 11-271525.
kP / gh ² ≧ 30 (1)
kP / gh ² ≧ 40 (2)
(Where P: indentation load at the time of hardness evaluation (mN), h: indentation depth in PmN (μm), g: gravitational acceleration (= 9.807 m / s ² ), k: constant determined by the shape of the indenter. )

  The color filter is preferably formed of a colored layer having an average refractive index of 1.60 or more and 1.90 or less and an absolute value of birefringence of 0.01 or less. Since the retardation of the color filter using the colored layer (including the partition walls) within the preferable range is reduced, a liquid crystal display device having excellent display characteristics can be provided. Examples of means for producing a color filter within the preferable range include the methods described in paragraph Nos. 0007 to 0042 of JP-A No. 2000-136253.

Further the specific surface area of the pigments used in the color filter is preferably in the range of ^{35m 2 · g -1 ~120m 2 ·} g -1. Examples of means for obtaining a pigment having a preferable specific surface area range include the methods described in paragraph Nos. 0015 to 0022 of JP-A No. 2001-42117. A composition (ink) using the pigment can obtain a colored film having both high transmittance and high color purity while maintaining good flow characteristics. As a result, a color filter with improved color characteristics can be obtained, and further, the color characteristics of the display device can be improved.

<Protective film>
It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

<Method for producing photosensitive transfer material>
The photosensitive transfer material of the present invention is essential to have the surface treatment layer and the photosensitive resin layer on the temporary support, and as described above, the thermoplastic resin layer and the intermediate layer on the temporary support. It is preferable to have the photosensitive resin layers so that they are in contact with each other in this order.
Here, the manufacturing method of the photosensitive transfer material of the said preferable aspect is demonstrated. Apply a coating solution (thermoplastic resin layer coating solution) in which the additive for the thermoplastic resin layer is dissolved on the temporary support, and provide the thermoplastic resin layer by drying, and then thermoplastic the thermoplastic resin layer. It consists of a solvent that does not dissolve the resin layer, and a solution of the intermediate layer material (including the polymerizable group-containing fluorine compound) is applied and dried, and then the photosensitive resin layer is applied and dried with a solvent that does not dissolve the intermediate layer. It can produce by providing.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. It can also be produced by pasting together.

  In the photosensitive transfer material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. preferable. Although not particularly limited, the preferred film thickness of each of the other layers is as follows: the temporary support is 15 to 100 μm, the thermoplastic resin layer is 2 to 30 μm, the intermediate layer is 0.5 to 3.0 μm, The protective film is generally preferably 4 to 40 μm.

  In addition, although application | coating in the said preparation method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to apply | coat with the slit-shaped nozzle which has a slit-shaped hole in the part which discharges a liquid. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

<Method for forming partition wall>
The partition wall of the present invention is at least a) using the photosensitive transfer material, and being pressure-bonded to the substrate so that the photosensitive resin layer side of the transfer material is in contact with the substrate, and b) the photosensitive resin through the surface treatment layer. It is preferable to form the layer by pattern exposure and c) developing the photosensitive resin layer in this order. c) By removing the surface treatment layer by development, a partition wall having ink repellency can be produced only on the upper surface (surface opposite to the substrate). In addition, as described above, it is also preferable to heat the surface treatment layer and the photosensitive resin layer before a) pressure bonding or between a) pressure bonding and b) exposure because the interaction can be further strengthened. Furthermore, it is also preferable to b) the obtained partition wall after c) development.
The partition wall of the present invention thus obtained can selectively impart ink repellency (oil repellency and water repellency) only to the upper surface 4 (surface opposite to the substrate), and also the substrate surface of the pixel portion and the side walls of the partition wall. (For example, in FIGS. 3 and 4, the concave portion 3 and the side wall 5 of the partition wall) are not fluorinated and do not have ink repellency.

-Board-
In the present invention, as the substrate on which the partition is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with the photosensitive resin transfer material by performing a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

-Crimping-
The pressure bonding is, for example, contacting by applying pressure like a laminate, and using the photosensitive resin transfer material of the present invention, a photosensitive resin layer formed in a film shape is heated and / or pressurized. Alternatively, the transfer material of the present invention can be attached to the substrate by pressure bonding or thermocompression bonding with a flat plate. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint of quantity, it is preferable to use the method described in JP-A-7-110575.
Further, a multi-cutter laminator may be used as the laminator. Examples of the multi-cutter laminator include those described in paragraph numbers 0007 to 0039 of JP-A-2004-333616. By using a multi-catch laminator, a laminator (multi-catch laminator) that can supply a plurality of transfer materials with a width smaller than the transfer area width in parallel can be used for laminating a wide width without depending on the application width of the resin transfer material. realizable.

-Pattern exposure and development-
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask and the surface treatment layer, and then developed with a developer, whereby the present invention is performed. A partition can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is 5-300 mJ / cm < ² > normally, Preferably it is 10-200 mJ / cm < ² >.
The pattern exposure may be exposure using a laser light source described in paragraph Nos. [0061] to [0205] of Japanese Patent Application Laid-Open No. 2004-240216 other than the exposure using the mask.

The developer is not particularly limited, and a known developer such as that described in JP-A-5-72724 can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be included.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
The developer may further contain a known surfactant. The concentration of the surfactant in the developer is preferably 0.01% by mass to 10% by mass.

As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline liquid having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, or the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

-Bake-
In the baking process, the image formed by the pattern exposure and development is heated and cured to obtain the partition wall of the present invention.
Various conventionally known methods can be used as the baking method. That is, a method of storing a plurality of substrates in a cassette and processing them with a convection oven, a method of processing one by one with a hot plate, a method of processing with an infrared heater, and the like. Moreover, as baking temperature (heating temperature), it is 150-280 degreeC normally, Preferably it is 180-250 degreeC. Although the heating time varies depending on the baking temperature, when the baking temperature is 220 ° C., it is preferably 5 to 30 minutes in the intermediate baking process and 60 to 200 minutes in the final baking process.
In baking in the method for forming a partition wall of the present invention, the partition wall formed by the pattern exposure / development prevents uneven film loss and prevents precipitation of components such as UV absorbers contained in the photosensitive resin layer. From the viewpoint, post-exposure may be performed before baking. When post-exposure is performed before the baking (heating) treatment is performed, it is possible to effectively prevent a minute foreign matter swollen during laminating and causing a defect.

-Post exposure-
As a light source for the post-exposure, any light source capable of irradiating light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount may be an exposure amount that supplements the pattern exposure, and is usually 50 to 5000 mJ / cm ² , preferably 200 to 2000 mJ / cm ² , more preferably 500 to 1000 mJ.
/ Cm ² .

-Example of partition wall formation method-
Here, an example of a method for forming the partition is shown below. However, the present invention is not limited to this.
i) Substrate cleaning An alkali-free glass substrate is used, but cleaning is performed to remove surface contamination. For example, a glass cleaning solution adjusted to 25 ° C. (trade names: T-SD1, T-SD2 Fuji Photo Film Co., Ltd.) is sprayed with a rotating brush with nylon hair while spraying for 20 seconds in a shower, and then pure water Perform shower cleaning.

ii) Silane coupling treatment In order to increase the adhesion of the photosensitive resin layer by lamination, it is preferable to carry out a silane coupling treatment. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, Shin-Etsu Chemical) is sprayed for 20 seconds by a shower, and pure water shower washing is performed. Thereafter, the reaction is carried out by heating. Although a heating tank may be used, the reaction can be advanced by preheating the substrate in a laminator.

iii) Laminate This substrate is heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator. Thereby, lamination can be performed uniformly.
After peeling off the protective film of the photosensitive transfer material of the present invention, it is laminated on a substrate heated to 100 ° C. using a laminator at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min. . The rubber roller temperature is preferably 70 to 150 ° C, more preferably 80 to 130 ° C. By setting it within this range, the transfer material is not wrinkled and can be laminated on the substrate with good adhesion.

iv) Pattern exposure After lamination, exposure is performed with a proximity type exposure machine with an ultra-high pressure mercury lamp. The temporary support may be peeled off after exposure (in this case, the photosensitive resin layer is exposed through the temporary support and the surface treatment layer), or the temporary support is peeled off before exposure. (In this case, the photosensitive resin layer is exposed through the surface treatment layer). However, the surface treatment layer must adhere to the photosensitive resin layer at the time of exposure.
When the substrate size is 50 centimeters or more, it is preferable to expose the substrate and the mask (quartz exposure mask having an image pattern) in a vertical state from the viewpoint of preventing the deflection of the mask. The shorter the distance between the exposure mask surface and the substrate-side surface, the better the resolution, but foreign matter tends to adhere, so it is set to 100 to 300 μm. The exposure amount is 10 to 300 mJ / cm ² . As a result, the pattern is exposed.

v) Removal of thermoplastic resin layer and intermediate layer After removal of the temporary support and exposure, a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoaming agent) Content, trade name: T-PD1, Fuji Photo Film Co., Ltd.) and the like to remove the thermoplastic resin layer and the intermediate layer. At this time, ideally, other conditions are set so that the photosensitive resin layer is not developed at all. For example, the developer is supplied in a shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa.
In addition, when a thermoplastic resin layer and an intermediate | middle layer do not correspond to the surface treatment layer in this invention, you may remove together at the time of peeling of a temporary support body.

vi) Development of photosensitive resin layer Subsequently, the photosensitive resin layer is developed with an alkaline solution to form an image. For example, Na carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% by weight of sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T-CD1, Fuji Photo Film Co., Ltd.) is used.
As conditions, for example, shower development is performed at 35 ° C. for 35 seconds and a cone type nozzle pressure of 0.15 MPa. As a developing solution, KOH type or TMA type may be used.

vii) Residue removal Subsequently, detergent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer included, trade name: T-SD1, Fuji Photo Film Co., Ltd., or sodium carbonate, phenoxypolyoxyethylene series Surfactant-containing, trade name: T-SD2, Fuji Photo Film Co., Ltd.) and the like are used. The conditions are 33 ° C. for 20 seconds, cone type nozzle pressure of 0.02 MPa, and the residue is removed by a rotating brush having a shower and nylon hair. Thereby, the remaining components of the photosensitive resin layer in the unexposed area are removed.

viii) Post exposure Subsequently, the substrate is exposed to about 1000 mJ / cm ² from the resin layer side with an ultrahigh pressure mercury lamp. You may implement from both surfaces, and you may select in the range of 100-5000mJ / cm < ² >. By carrying out post exposure, the effect of polymerization in subsequent baking is enhanced, and the sectional shape of the partition wall after baking can be adjusted by the amount of post exposure.

ix) Bake Bake to make a hard film by reacting monomer or oligomer. The bake is preferably heat-treated at 200 to 240 ° C. for 30 to 180 minutes. These temperature and time are more preferably set to a higher temperature and a shorter time so as not to reduce production tact.
Through the above steps, the partition wall of the present invention can be formed.

<Inkjet partition>
In forming the pixels of the optical element by the ink jet method, the partition walls separating the pixels are the partition walls of the present invention in which ink repellency is selectively imparted only to the upper surface (the surface on the opposite side of the substrate). It is possible to prevent the applied ink from flowing into or bleeding into other pixels without causing omission, color mixing, ink overflow, or uneven thickness within the pixel. When manufacturing a color filter, it is preferable to use a light-shielding layer that shields light between adjacent pixels. In that case, a black matrix or a black stripe may be used.

Here, the optical element of the present invention provided with the partition walls will be described using a color filter as an example.
FIG. 3 or 4 is a cross-sectional view schematically showing the color filter of the present invention. In FIG. 3 or 4, only the rightmost concave portion 3 is shown in a state where a colored layer is not formed for easy understanding.
In FIG. 3 or 4, for the sake of clarity, only five partition walls 1 and four recesses 3 are shown, but a necessary number is provided. For example, in the case of a striped color filter, if 640 pixels are required, three color filters of RGB per pixel are required, so 1921 partition walls 1 and 1920 recesses 3 are required. . In the liquid crystal display element, a color filter pattern may be formed from the precision of the substrate gap to the periphery of the display pixel where display is not performed.

  In the case of a stripe pattern, the partition wall 1 may not be formed in the longitudinal direction, but the periphery of the pixel 2 may be completely surrounded by the partition wall 1. In particular, in the case of a mosaic color filter, the periphery of the pixel 2 is surrounded by a partition wall 1.

In the present invention, the partition wall 1 for dividing the pixel (colored layer) 2 is formed on the substrate 6 in a linear shape or a lattice shape. The shape of the partition wall 1 may be such that the recessed portion 3 partitioned by the partition wall 1 corresponds to the pixel 2. For example, when forming a striped color filter, it is formed in a linear shape, and in order to correspond to the square pixel 2, it is formed in a lattice shape. Since this is appropriately determined depending on the shape of the pixel 2, various shapes such as a radial shape and a circumferential shape are also conceivable. In FIG. 4, 7 indicates a non-colored pixel.
The partition wall 1 is advantageously used as a black mask in a liquid crystal display element or the like. For this reason, in the following description, the partition 1 will be described based on an example in which the partition 1 is also used as a black mask. However, when the partition 1 is not a black mask, a black material or the like may not be used.

The partition wall in the present invention plays a role of preventing the sprayed ink from flowing into or bleeding into other pixels when coloring by the inkjet method. Therefore, the height of the partition walls is preferably high to some extent. However, since it is also required that the flatness of the entire color filter is high, a height close to the thickness of the colored layer is preferable.
Specifically, although it depends on the amount of ink deposited to obtain a desired colored layer, it is usually about 0.1 to 3 μm.
If the ink remains on the upper surface of the partition wall (the upper surface 4 in FIG. 3 or 4), the flatness and the color uniformity between the pixels are impaired. Is effectively suppressed. Further, the partition wall of the present invention is not subjected to ink repellent treatment on its side surface (side surface 5 in FIG. 3 or 4), that is, the top surface of the partition wall has a property of repelling ink and the side surface has a property of hardly repelling ink. have. Further, the pixel portion (the concave portion 3 in FIG. 3 or 4) is not subjected to fluorination treatment, and the pixel portion has a property of hardly repelling ink. Accordingly, the optical element using the partition wall according to the present invention is less likely to cause white spots, and can effectively prevent color mixing and ink leakage and thickness unevenness in the pixels.

  Here, “ink repellency” on the upper surface of the partition wall means a property of repelling liquid (= ink) applied to the opening (pixel portion) of the partition wall in order to produce an optical element. Since ink varies depending on the optical element to be manufactured, the contact angle of water is shown in the present invention as a universal measure of ink repellency.

The degree of ink repellency on the upper surface of the partition wall is preferably a water contact angle of 90 to 140 °. If this is less than 90 °, the ink tends to remain on the upper surface of the partition wall, and if it exceeds 140 °, the coloring of the pixel tends to be hindered or the smoothness of the upper surface of the partition wall may be lost. Moreover, it is more preferable that it is 100-125 degrees.
Here, the contact angle of water can be measured by a contact angle meter DM300 manufactured by Kyowa Interface Science Co., Ltd., and the contact angle of ink can be obtained in the same manner.

  The degree of ink repellency can be controlled by the content of the polymerizable group-containing fluorine compound in the surface treatment layer, the pattern exposure amount for the photosensitive resin layer, and the like.

-Black mask-
The black mask according to the present invention is a light-blocking partition that is formed in a linear shape when forming a striped color filter, and formed in a lattice shape to correspond to a square pixel. is there. Since this is appropriately determined depending on the shape of the pixel, various shapes such as a radial shape and a circumferential shape are also conceivable.
A black mask can be manufactured by using a colorant having a light shielding property for the photosensitive resin layer.

<Optical element>
The optical element of the present invention can be produced by forming a colored layer (pixel) by an inkjet method between the partition walls formed on the substrate using the photosensitive transfer material of the present invention. Examples of the optical element of the present invention include optical elements such as a color filter and an electroluminescence element.
Examples of the color filter include a mode in which rectangular images such as red, green, and blue are arranged in a matrix on a substrate such as glass, and a partition such as a black mask is arranged at the boundary. On the other hand, as an example of an electroluminescence device, a thin film containing a fluorescent inorganic and organic compound is sandwiched between a cathode and an anode, and recombination is performed by injecting electrons and holes into the thin film. An element that emits light by utilizing the emission of fluorescence or phosphorescence when excitons are generated by the generation of the excitons and the excitons are deactivated. A fluorescent material used for such an electroluminescence element can be applied to a substrate on which an element such as a TFT is formed by an ink jet method to form a light emitting layer, whereby the element can be configured.

  A method of applying droplets such as an ink jet method is applied to manufacture of optical elements such as a color filter and an electroluminescence element because the manufacturing process can be simplified and the cost can be reduced.

-Inkjet system-
In the present invention, an inkjet method is used to form pixels. As an ink jet method, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and a method in which ink is heated and intermittently ejected using its foam Various methods can be employed.

  The ink used can be both oily and water-based. The coloring material contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. Moreover, the oil-based coloring ink (colored resin composition) used for preparation of a well-known color filter can also be used.

The ink according to the present invention may include a component that is cured by heating or is cured by energy rays such as ultraviolet rays in consideration of a process after coloring. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, the photosensitive resin composition containing a coloring material such as a pigment described in the above section <Photosensitive resin layer> can be preferably used.

Further, the color filter (colored pixel) composed of at least three colors has white display coordinates (u ′ _white , v ′ _white ) and black that are calculated based on the tristimulus values “X, Y, Z” of each film. The display coordinates (u ′ _black , v ′ _black ) are coordinates P ₁ (0.18, 0.52), coordinates Q ₁ (0.25, 0.52), coordinates R ₁ (0.23, 0.42). ), Which is within the range of a straight line connecting the four coordinates of coordinates S ₁ (0.15, 0.42). Examples of the color filter include those described in JP-A-2005-25175, paragraph numbers 0008 to 0047. A display device using the color filter can appropriately balance the pixels, and the display color can be easily adjusted. In particular, it can be preferably used as a color filter for television.

  The contrast of the colored pixels formed with the ink is preferably 2000 or more. As a method for increasing the contrast, means described in paragraph No. 0025 of JP-A-2005-25206 can be given. A display device using a color filter having a high contrast can be used as an EBU standard TV liquid crystal display device having excellent color reproducibility.

  In manufacturing a color filter, three colors of color filters are formed by spraying three colors of ink, usually by an inkjet method. However, the present invention is not limited to the three RGB colors, and a multicolor filter of four colors or more can also be formed. This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

  The optical element of the present invention including the color filter effectively suppresses defects such as bleeding of each color ink, protrusion, and color mixture with adjacent pixels.

<Display device>
The optical element of the present invention is used in various display devices as described above, and is also preferably used as a liquid crystal display element in which a liquid crystal material is sealed between a pair of opposed substrates.
The color filter according to the present invention is formed on the counter substrate of the liquid crystal display device (the substrate on the side having no active element such as TFT), the COA method formed on the TFT substrate side, and only black on the TFT substrate side. A BOA method to be formed or an HA method having a high aperture structure on the TFT substrate can also be used.
An overcoat film or a transparent conductive film can be further formed on the color filter as necessary. Thereafter, liquid crystal is sealed between the color filter and the counter substrate, and a liquid crystal display device is manufactured. The liquid crystal display method is not particularly limited and is appropriately selected according to the purpose. For example, ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), OCB (Optically Compensatory Bend), VA (Val) Hybrid Aligned Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), GH (Guest Host), FLC (ferroelectric liquid crystal), AFLC (antiferroelectric liquid crystal), PDLC (polymer dispersion type liquid crystal) ) And other display methods.

  Hereinafter, the present invention will be described in more detail by way of examples. In the following, “part” and “%” are based on mass unless otherwise specified.

(Polymer synthesis)
(Synthesis Example 1. Synthesis of polymer a)
The polymer a is synthesized through the following two steps.
<Step 1: Copolymerization of 2- (perfluorooctyl) -ethyl methacrylate (FAMAC), methacrylic acid (MA), and methacrylic acid 2-hydroxyethyl ester (HEMA) (FAMAC / MA / HEMA monomer mass ratio = 33 / 33/34)>
Under a nitrogen atmosphere, 30 g of N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) was placed in a 300 ml three-necked flask equipped with a condenser and heated to 65 ° C. in a water bath. Here, 30 g of DMAc, 2.54 g (0.0194 mol) of methacrylic acid 2-hydroxyethyl ester (HEMA, Tokyo Chemical Industry) and 10.0 g of 2- (perfluorooctyl) -ethyl methacrylate (FAMAC, manufactured by Daikin Fine Chemical Laboratories) (0.0188 mol) and methacrylic acid (MA, Tokyo Chemical Industry) 1.62 g (0.0188 mol) and 2,2′-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries) 0.66 g (0.0029 mol) The homogeneous solution in which was dissolved was dropped into the flask with a plunger pump at a rate of 0.54 ml / min. After completion of the dropping, the contents of the flask were stirred for 5 hours to stop the reaction.
The reaction solution was reprecipitated with 1500 ml of methanol, and the precipitated solid was collected by suction filtration. It was vacuum-dried for 3 hours to obtain a white powder (copolymer). (Yield 7.84 g)

<Introduction of Double Bond to Step2 Copolymer>
3.0 g of the copolymer obtained in Step 1 and 0.0325 g of hydroquinone (Wako Pure Chemical Industries, Ltd.) were placed in a 300 ml three-necked flask equipped with a cooling tube, and 40 g of DMAc was added and stirred at room temperature to obtain a uniform solution.
While stirring the solution, 1.53 g (0.00983 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 1 drop of di-n-butyltin dilaurate (Tokyo Kasei Kogyo) was added and heated with a water bath at 65 ° C. while stirring. After 5 hours, the reaction was stopped and the mixture was naturally cooled to room temperature. The reaction solution was reprecipitated with 1500 ml of methanol, and the precipitated solid was collected by suction filtration to obtain polymer a. (Yield 2.4 g)
In addition, molecular weight (GPC, THF, polystyrene conversion) was Mw25000. Moreover, the result of having performed IR measurement (KBr) (measured using Excalibur FTIR-8300 (SHIMAZU)) is shown below.
3390 (b), 2965 (b), 1735 (s), 1640 (s) cm ⁻¹

(Synthesis Example 2. Synthesis of polymer b)
In a 1000 ml three-necked flask equipped with a condenser and a thermometer, acrylic acid (Tokyo Kasei Co., Ltd.) 50.0 g (0.694 mol), N, N-dimethylacrylamide (Tokyo Kasei Co., Ltd.) 70.0 g (0.71 mol) ), 2- (perfluorooctyl) -ethyl methacrylate (Unimatec) 80.0 g (0.16 mol), n-propanol 400.0 g, n-dodecyl mercaptan (Tokyo Chemical Industry) 9.47 g (46.8) × 10 ⁻³ mol) was added and stirred. This reaction solution was heated in an oil bath, and the internal temperature was set to 70 ° C. 0.32 g (1.56 × 10 ⁻³ mol) of 2,2′-azobis (isobutyric acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 2.0 g of n-propanol and dropped into the reaction solution. After the dropwise addition of 2,2′-azobis (isobutyric acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd.), the temperature of the reaction solution reached 96 ° C. The three-necked flask containing the reaction solution was once lifted from the oil bath, cooled in the air, and stabilized at 70 ° C. 2,2′-azobis (isobutyric acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise 2.5 hours later, and 2,2′-azobis (isobutyric acid) dimethyl dissolved in 2.0 g of n-propanol again. 0.359 g (1.56 × 10 ⁻³ mol) (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into the reaction solution. Further 1.5 hours later, 0.359 g (1.56 × 10 ⁻³ mol) of 2,2′-azobis (isobutyric acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd.) similarly dissolved in 2.0 g of n-propanol was used. Was dropped into the reaction solution. Thereafter, the internal temperature was raised to 80 ° C. and the polymerization reaction was carried out for 5.3 hours.

This reaction liquid was returned to room temperature, 0.059 g of 2,5-di-amylhydroquinone (glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 2.0 g of n-propanol), 59.2 g (0.42 mol), and 100 g of n-propanol. 0.92 g (8.32 × 10 ⁻³ mol) of 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 12.4 g of n-propanol was added and stirred to obtain a uniform solution. This reaction solution was heated in an oil bath to set the internal temperature to 70 ° C. After 14 hours, the heating was stopped and the temperature was returned to room temperature to complete the reaction.
When the molecular weight was measured by GPC (polystyrene conversion, tetrahydrofuran solvent), the weight average molecular weight was 3,500. Further, the composition was measured by NMR (Brucker 300 MHz), and the ratio of carboxyl group-containing monomer unit: glycidyl group-containing monomer unit: amide group-containing monomer unit: perfluoro group-containing monomer unit = 18: 27: 45: 10 It was found that it was introduced at (molar ratio).

(Synthesis Example 3. Synthesis of Polymer c)
The polymer c is synthesized through the following two steps.
<Step 1: Copolymerization of 2- (perfluorooctyl) -ethyl acrylate (FAAC) with acrylic acid (AA) and dimethylacrylamide (DMAAm) (FAAC / AA / DMAAm monomer mass ratio = 40/25/35)>
Under a nitrogen stream, 300 g of propylene glycol monomethyl ether (MFG) was placed in a 2000 ml three-necked flask equipped with a condenser and heated to 70 ° C. with a water bath. 400 g of MFG, 125 g (1.73 mol) of acrylic acid (AA, Tokyo Chemical Industry), 200 g (0.39 mol) of 2- (perfluorooctyl) -ethyl acrylate (FAAC, manufactured by Unimatec Co., Ltd.) and dimethylacrylamide ( DMAAm, Tokyo Chemical Industry Co., Ltd.) 2.68 g (0.01 mol) of 2,2′-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries, Ltd.) was dissolved in a solution of 175 g (1.77 mol) dissolved in DMAAm and 300 g of MFG. Each solution was added dropwise over 2 hours with a plunger pump. After completion of dropping, the mixture was stirred for 5 hours to obtain a copolymer solution (c1) having a FAAC / AA / DMAAm monomer mass ratio = 40/25/35.

<Introduction of Double Bond to Step2 Copolymer>
In the copolymer solution (c1) obtained in Step 1, 0.5 g of di-t-pentylhydroquinone (Wako Pure Chemical Industries) and 3.26 g (0.032 mol) of triphenylphosphine were added to 2000 ml of a condenser tube. The solution was placed in a three-necked flask and the solution was stirred to obtain a uniform solution. The internal temperature was adjusted to 90 ° C., and 148 g (1.04 mol) of glycidyl methacrylate (Tokyo Chemical Industry) was added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 12 hours to obtain the target polymer c.
In addition, molecular weight (GPC, THF, polystyrene conversion) was Mw10000.

(Synthesis Example 4. Synthesis of Polymer d)
The polymer d is synthesized through the following two steps.
<Step 1: Copolymerization of 2- (perfluorooctyl) -ethyl acrylate (FAAC) with acrylic acid (AA) and hydroxyethyl acrylate (HEA) (FAAC / AA / HEA monomer mass ratio = 40/25/35) >
Under a nitrogen stream, 30 g of propylene glycol monomethyl ether (MFG) was placed in a 300 ml three-necked flask equipped with a condenser and heated to 70 ° C. with a water bath. Here, 40 g of MFG, 12.5 g (0.173 mol) of acrylic acid (AA, Tokyo Chemical Industry), 20 g (0.039 mol) of 2- (perfluorooctyl) -ethyl acrylate (FAAC, manufactured by Unimatec) and hydroxy A solution in which 17.5 g (0.151 mol) of ethyl acrylate (HEA, Tokyo Chemical Industry) is dissolved, 30 g of MFG, 2,2′-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries) 0.251 g (0.001 mol) ) Was dissolved dropwise with a plunger pump over 2 hours. After completion of dropping, the mixture was stirred for 5 hours to obtain a copolymer solution (d1) having a FAAC / AA / HEA monomer mass ratio of 40/25/35.

<Introduction of Double Bond to Step2 Copolymer>
To the copolymer solution (d1) obtained in Step 1, 0.15 g of di-t-pentylhydroquinone (Wako Pure Chemical Industries), 0.305 g (0.0028 mol) of 2-ethyl-4-methylimidazole, The solution was placed in a 300 ml three-necked flask, and the solution was stirred to obtain a uniform solution. The internal temperature was adjusted to 90 ° C., and 14.8 g (0.104 mol) of glycidyl methacrylate (Tokyo Chemical Industry) was added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 12 hours to obtain the target polymer d.
In addition, molecular weight (GPC, THF, polystyrene conversion) was Mw11000.

(Synthesis Example 5. Synthesis of Polymer e)
The polymer e is synthesized through the following two steps.
<Step 1: Copolymerization of 2- (perfluorooctyl) -ethyl acrylate (FAAC) with acrylic acid (AA) and dimethylacrylamide (DMAAm) (FAAC / AA / DMAAm monomer mass ratio = 50/10/40)>
Under a nitrogen stream, 100 g of propylene glycol monomethyl ether (MFG) was placed in a 500 ml three-necked flask equipped with a condenser and heated to 70 ° C. with a water bath. Here, 150 g of MFG, 25 g (0.35 mol) of acrylic acid (AA, Tokyo Chemical Industry), 125 g (0.24 mol) of 2- (perfluorooctyl) -ethyl acrylate (FAAC, manufactured by Unimatec Co., Ltd.) and dimethylacrylamide ( DMAAm, Tokyo Chemical Industry Co., Ltd.) 100 g (1.01 mol) of a solution in which MFG 130 g was dissolved, 2,2′-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries, Ltd.) 3.97 g (0.01 mol) was dissolved. Each solution was added dropwise over 2 hours with a plunger pump. After completion of the dropping, the mixture was stirred for 5 hours to obtain a copolymer solution (e1) having a FAAC / AA / DMAAm monomer mass ratio = 50/10/40.

<Introduction of Double Bond to Step2 Copolymer>
To the copolymer solution (e1) obtained in Step 1, 0.23 g of di-t-pentylhydroquinone (Wako Pure Chemical Industries) and 3.52 g (0.035 mol) of triphenylphosphine were added to 500 ml of a condenser tube. The solution was placed in a three-necked flask and the solution was stirred to obtain a uniform solution. The internal temperature was adjusted to 90 ° C., and 49 g (0.37 mol) of glycidyl methacrylate (Tokyo Chemical Industry) was added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 12 hours to obtain the target polymer e.
In addition, molecular weight (GPC, THF, polystyrene conversion) was Mw14000.

Example 1
[Production of photosensitive transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation C was applied and dried using a slit nozzle. Next, a coating solution for a surface treatment layer having the following formulation P1 was applied and dried. Furthermore, the photosensitive resin composition K1 described in Table 1 below was applied and dried. Thus, a thermoplastic resin layer having a dry film thickness of 6.0 μm, a surface treatment layer having a dry film thickness of 1.6 μm, and a photosensitive layer having a dry film thickness of 2.4 μm are provided on the temporary support. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive transfer material K1 in which the temporary support, the thermoplastic resin layer, the surface treatment layer (oxygen barrier film), and the black (K) photosensitive layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation C>
Methanol 11.1 parts Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd., MMPG-Ac (the same material is used below)) 6.36 parts Methyl ethyl ketone 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
Molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37,
(Average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (BPE-500, Shin-Nakamura Chemical Co., Ltd.) 9.1 parts, interface Activator 1 0.54 parts

<Coating liquid for surface treatment layer: prescription P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Saponification degree = 88%, polymerization degree 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan, K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts · Polymer a 0.59 parts

Here, preparation of the colored photosensitive resin composition K1 described in Table 1 will be described.
In the photosensitive resin composition K1, first, the pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, 1, methyl ethyl ketone, binder 1, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethylamino) -3′-bromophenyl] -s -Triazine, hydroquinone monomethyl ether and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C (± 2 ° C), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C (± 2 ° C).

In addition, among the compositions described in the photosensitive resin composition K1, the compositions of the pigment dispersion 1, the binder 1, the DPHA liquid, and the surfactant 1 are as follows.
(Pigment dispersion 1)
Carbon black (trade name Special Black 250, manufactured by Degussa) 13.1 partsN, N′-bis- (3-diethylaminopropyl) -5
{4- [2-oxo-1- (2-oxo-2,3-dihydro-1H
-Benzimidazol-5-ylcarbamoyl) -propylazo]
-Benzoylamino] -isophthalamide 0.65 parts polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer, weight average molecular weight 37,000) 6.72 parts, propylene glycol monomethyl ether acetate 79.53 parts

(Binder 1)
・ Benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer, weight average molecular weight 44,000 27 parts, propylene glycol monomethyl ether acetate 73 parts

(DPHA solution)
・ Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts ・ Propylene glycol monomethyl ether acetate 24 parts

(Surfactant 1)
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ : 40 parts and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ : 55 parts and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : 5 Department and
Copolymer, weight average molecular weight 30,000 30 parts, methyl ethyl ketone 70 parts

[Partition formation]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After the protective film of the photosensitive transfer material K1 is peeled off, the remainder is laminated on a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), with a rubber roller temperature of 130 ° C. and a wire. Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, the rest is a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 200 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, FUJIFILM Electronics Materials Co., Ltd.) was diluted 100 times with pure water and shower developed at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues, and an image of matrix-like black (K) was obtained. Thereafter, the substrate is further post-exposed with 1000 mJ / cm ² light from the side of the resin layer with an ultrahigh pressure mercury lamp, and further 1000 mJ / cm with an ultrahigh pressure mercury lamp from the side opposite to the resin layer. ^The film was post-exposed with the light No. ² and then heat-treated at 220 ° C. for 30 minutes.

[Evaluation of ink repellency]
With respect to the upper surface of the black matrix and the glass surface (concave portion) of the black matrix (partition wall) substrate after the heat treatment, the contact angle with pure water was measured by the method described above. The black matrix surface was measured on a frame having a width of 5 mm provided around the fine pattern, and the glass substrate surface was measured at a location where the black matrix pattern outside the frame was not provided. The results are shown in Table 3.

Further, the amount of fluorine on the upper surface of the black matrix was measured by ESCA.
A solid sample for measurement was prepared in which the pattern exposure was a solid exposure with the same exposure amount, and the ratio of the number of fluorine atoms to the number of carbon atoms (number of fluorine atoms / number of carbon atoms) on the surface was measured. As a measuring device, PHI-5300 (detection angle 45 °) manufactured by ULVAC-PHI was used.

[Preparation of ink]
Next, each of R, G, and B inks was prepared with the following composition using an acrylic copolymer having the following composition as a thermosetting component.

(Curing component)
Methyl methacrylate 50 parts Hydroxyethyl methacrylate 30 parts N-methylolacrylamide 20 parts

(R ink)
C. I. Acid Orange 148 3.5 parts C.I. I. Acid Red 289 0.5 part Diethylene glycol 30 parts Ethylene glycol 20 parts Ion-exchanged water 40 parts The above curing component 6 parts

(G ink)
C. I. Acid Yellow 23 2 parts Zinc phthalocyanine sulfoamide 2 parts Diethylene glycol 30 parts Ethylene glycol 20 parts Ion-exchanged water 40 parts The above curing component 6 parts

(B ink)
C. I. Direct Blue 199 4 parts Diethylene glycol 30 parts Ethylene glycol 20 parts Ion-exchanged water 40 parts The above curing component 6 parts

  Next, R, G, and B pigment dispersions prepared by the above-described method in the openings (recesses) of the black matrix (partitions) on the glass substrate using an inkjet recording apparatus equipped with a piezo-type head having a nozzle resolution of 180 dpi. Ink was applied to the desired concentration.

  Next, heat treatment was performed at 230 ° C. for 1 hour to cure the ink, and a color filter having R, G, and B colored portions was formed.

[Evaluation of color filter]
The obtained color filter was evaluated for ink protrusion and color mixture. The evaluation of ink protrusion and color mixture was observed using an optical microscope, and the presence or absence of ink protrusion and color mixture was observed for any 3000 pixels of the color filter. Ink overflow and color mixing refer to the phenomenon shown in FIG.
The results are shown in Table 3. Allowable is A rank, B rank or C rank for all items.
A rank: Nothing B rank: 1-2 places C rank: 3-4 places D rank: 5-10 places E rank: 11 places or more

[Step measurement (thickness unevenness evaluation)]
Next, thickness unevenness evaluation within the pixel was performed.
The surface shape of an arbitrary pixel was measured with a surface roughness meter P-10 manufactured by Tencor, and the difference in height between the most raised part in the pixel and the lowest part in the pixel was obtained. The allowable step is 0.2 μm or less.

[Production of liquid crystal display devices]
-Overcoat layer-
Thereafter, the color filter on which the pixels are formed is washed with a clean-tech low-pressure mercury lamp UV cleaning device to remove residues and foreign matters, and then a transparent overcoat agent is added so that the film thickness becomes 1.5 μm. After coating the entire surface, baking was performed at 230 ° C. for 40 minutes. At this time, in order to form a transparent overcoat layer, a polyamic acid of the following chemical formula (A) and an epoxy compound of the chemical formula (B) were mixed at a mass ratio of 3: 1.

-Formation of ITO pattern (PVA mode)-
The glass substrate on which the overcoat layer is formed is put in a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. Then, an ITO pattern was formed by a photo process, and unnecessary ITO was etched with aqua regia to complete pattern formation.

-Spacer formation-
With respect to the substrate after the ITO formation, the formulation of the photosensitive resin composition K1 in the partition wall prepared above is changed to the following coating solution formulation S1 for the photosensitive resin layer, and the surface treatment layer is changed to the following formulation PC1. A spacer was produced using the same method except that described above.
However, the following methods were used for exposure, development, and baking.
Proximity exposure was performed at 300 mJ / cm ² with an ultrahigh pressure mercury lamp through a predetermined photomask. After the exposure, the unexposed portion of the photosensitive resin layer was dissolved and removed using a KOH developer [CDK-1 (trade name) 100-fold diluted solution (pH = 11.8), manufactured by Fuji Photo Film Co., Ltd.]. .
Subsequently, baking was performed at 230 ° C. for 30 minutes to form a transparent columnar spacer pattern having a diameter of 16 μm and an average height of 3.7 μm on the ITO film on the glass substrate.

* Prescription of coating solution for photosensitive resin layer: S1
-Methacrylic acid / allyl methacrylate copolymer: 108 parts (molar ratio = 20/80, molecular weight 40000)
Dipentaerythritol hexaacrylate (polymerizable monomer) 64.7 parts 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl ] -S-triazine 6.24 parts, hydroquinone monomethyl ether 0.00.03 parts, Victoria Pure Blue BOHM (Hodogaya Chemical Co., Ltd.) 0.874 parts, MegaFuck F780F 0.856 parts (Made by Co., Ltd .; surfactant)
・ Methyl ethyl ketone: 328 parts ・ 1-methoxy-2-propyl acetate: 475 parts ・ Methanol: 16.6 parts

* Intermediate layer coating solution: Prescription PC1
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (APS Japan, K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts

  Using the liquid crystal display device substrate obtained above, the liquid crystal display device of Example 1 was produced using the method described in the first example [0079] to [0082] of JP-A-11-242243. did. Specifically, a liquid crystal display device was produced as follows.

  First, the gate patterns 200 and 210 and the common patterns 300 and 310 are formed by depositing and patterning a metal film on the substrate 100. Next, the gate insulating film 400, the amorphous silicon layer 800, and the doped amorphous silicon layer 900 are sequentially deposited, and the amorphous silicon layer 800 and the doped amorphous silicon layer 900 are patterned together. .

  Next, a chromium layer and an aluminum layer are sequentially deposited in thicknesses of about 500 mm and 2000 mm, respectively. Next, after the aluminum film 502 is patterned, the chromium film 501 is patterned. Thus, the data line 500, the source electrode 510, the drain electrode 620, and the pixel patterns 600 and 610 are formed. Then, the doped amorphous silicon layer 900 not covered with the source electrode 510 and the drain electrode 620 is etched to complete the resistive contact layers 910 and 920.

  Finally, a protective film 700 is deposited on the entire surface of the substrate.

[Evaluation of liquid crystal display devices]
Various images were displayed on the liquid crystal display device, and it was visually evaluated whether normal display was possible as a normal liquid crystal display. The results are shown in Table 3.

(Example 2)
Surface treatment layer coating solution of Example 1: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polymer a0.59 part of the formulation P1 was changed to 4.66 parts of polymer a.

(Example 3)
Coating liquid for surface treatment layer of Example 1: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polymer a0.59 part of the formulation P1 was changed to 10.3 part of the polymer a1.

Example 4
In Example 3, a liquid crystal display device was prepared and evaluated in the same manner as in Example 3 except that the thickness of the thermoplastic resin layer was changed to 14.6 μm and the method for forming the partition walls was changed as follows. Went.

-Formation of partition walls-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After the protective film of the photosensitive transfer material K1 is peeled off, the remainder is laminated on a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), with a rubber roller temperature of 130 ° C. and a wire. Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, the rest is a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 200 mJ / cm ² . Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) diluted 12 times with pure water at 30 ° C. for 50 seconds, flat Shower development was performed at a nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the surface treatment layer were removed.
Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing photosensitive agent, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water and shower-developed at 29 ° C. for 30 seconds and cone-type nozzle pressure of 0.15 MPa. Was developed to obtain a patterning partition wall.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD3 (Fuji Photo Film Co., Ltd.)”) diluted 10 times with pure water. The residue was removed with a rotating brush having a shower and nylon bristles at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa to obtain a black (K) image. Thereafter, the substrate was further post-exposed with 1000 mJ / cm ² of light from the resin layer side with an ultrahigh pressure mercury lamp, and then heat treated at 220 ° C. for 30 minutes.

(Example 5)
Coating liquid for surface treatment layer of Example 1: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that 0.59 part of polymer a in formulation P1 was changed to 4.66 parts of polymer b. .

(Example 6)
A liquid crystal display device was prepared and evaluated in the same manner as in Example 5 except that the thickness of the thermoplastic resin layer was changed to 14.6 μm and the method for forming the partition walls was changed as follows.

-Formation of partition walls-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After the protective film of the photosensitive transfer material K1 is peeled off, the remainder is laminated on a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), with a rubber roller temperature of 130 ° C. and a wire. Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, the rest is a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 200 mJ / cm ² . Next, a triethanolamine developer (containing 30% triethanolamine, containing a nonionic surfactant, containing a polypropylene antifoaming agent, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) with pure water Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa with a solution diluted 12 times, and the thermoplastic resin layer and the surface treatment layer were removed.
Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing photosensitive agent, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water and shower-developed at 29 ° C. for 30 seconds and cone-type nozzle pressure of 0.15 MPa. Was developed to obtain a patterning partition wall.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD3 (Fuji Photo Film Co., Ltd.)”) diluted 10 times with pure water. The residue was removed with a rotating brush having a shower and nylon bristles at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa to obtain a black (K) image. Thereafter, the substrate was further post-exposed with 1000 mJ / cm ² of light from the resin layer side with an ultrahigh pressure mercury lamp, and then heat treated at 220 ° C. for 30 minutes.

Moreover, the manufacturing method of the board | substrate for liquid crystal display devices was changed as follows.
-Production of substrates for liquid crystal display devices-
Without providing an overcoat layer, a transparent electrode film was formed by sputtering ITO on a color filter on which RGB pixels had been formed. A liquid crystal display device was produced in the same manner as in Example 1 except that liquid crystal alignment control protrusions were formed on the ITO-formed substrate by the following method.

-Formation of liquid crystal alignment control protrusions-
In the partition wall produced in Example 1, the formulation of the photosensitive resin composition K1 was changed to the following coating solution formulation T1 for photosensitive resin layer, the surface treatment layer was changed to formulation PC1, and the thermoplastic resin layer was changed to 14. A liquid crystal alignment control protrusion was produced using the same method as in Example 1 except that the thickness was 6 μm.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine was arranged so that the predetermined photomask was at a distance of 100 μm from the surface of the photosensitive resin layer, and the proximity exposure was performed through the photomask with an irradiation energy of 150 mJ / cm ² with an ultrahigh pressure mercury lamp. Thereafter, a solution obtained by diluting a triethanolamine developer (trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water is sprayed onto a substrate at 30 ° C. for 60 seconds using a shower type developing device. Then, the thermoplastic resin layer and the surface treatment layer were dissolved and removed. At this stage, the photosensitive resin layer was not substantially developed.
Subsequently, the 2.38% tetramethylammonium hydroxide aqueous solution was developed while sprayed onto a substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer were developed and removed. On the color filter side substrate, a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned in a desired shape was formed.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form liquid crystal alignment control protrusions on the liquid crystal display device substrate.

* Composition of photosensitive resin layer coating solution T1 and positive resist solution (FUJIFILM Electronics
Materials Co., Ltd., FH-2413F) 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Megafac F-780F (Dainippon Ink Chemical Co., Ltd.) 0.04 parts

* Intermediate layer coating solution: Formula PC1
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (APS Japan, K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts

(Example 7)
Surface treatment layer coating solution: same as Example 1 except that the polymer a0.59 part of the formulation P1 was changed to polymer a12.3 part and the method for producing the substrate for liquid crystal display device was changed as follows. A liquid crystal display device was prepared and evaluated.

-Production of substrates for liquid crystal display devices-
-Overcoat layer-
The color filter on which the pixels are formed is cleaned with a clean-tech low-pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign matters, and then the transparent overcoat agent is applied to a film thickness of 1.5 μm. After coating the entire surface, baking was performed at 230 ° C. for 40 minutes. At this time, the polyamic acid represented by the chemical formula (A) and the epoxy compound represented by the chemical formula (B) were mixed at a mass ratio of 3: 1 to form a transparent overcoat layer.

-Formation of liquid crystal alignment control protrusions-
In the partition wall produced in Example 1, the formulation of the photosensitive resin composition K1 was changed to the coating solution formulation T1 for the photosensitive resin layer, the surface treatment layer was changed to the formulation PC1, and the thermoplastic resin layer was changed to 14 A liquid crystal alignment control protrusion was produced using the same method as in Example 1 except that the thickness was set to 0.6 μm.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine was arranged so that the predetermined photomask was at a distance of 100 μm from the surface of the photosensitive resin layer, and the proximity exposure was performed through the photomask with an irradiation energy of 150 mJ / cm ² with an ultrahigh pressure mercury lamp. Thereafter, a solution obtained by diluting a triethanolamine developer (trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water is sprayed onto the substrate at 30 ° C. for 60 seconds with a shower type developing device. Then, the thermoplastic resin layer and the surface treatment layer were dissolved and removed. At this stage, the photosensitive resin layer was not substantially developed.
Subsequently, the 2.38% tetramethylammonium hydroxide aqueous solution was developed while sprayed onto a substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer were developed and removed. On the color filter side substrate, a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned in a desired shape was formed.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form liquid crystal alignment control protrusions on the liquid crystal display device substrate.

(Example 8)
In the method for producing a substrate for a liquid crystal display device of Example 6, an overcoat layer is provided in the same manner as in Example 1, and the same as in Example 6 except that the pattern exposure on the photosensitive resin layer is 250 mj / cm ^2. A liquid crystal display device was prepared and evaluated.

Example 9
In Example 5, liquid crystal display was performed in the same manner as in Example 5 except that the development time with the KOH-based developer was 40 seconds and the pattern exposure on the photosensitive resin layer was 250 mj / cm ² when the partition walls were formed. A device was created and evaluated.

(Example 10)
In the production of the photosensitive transfer material of Example 1, the thermoplastic resin layer was not provided, the coating liquid formulation P1 for the surface treatment layer was changed to the following formulation EV1, and the dry film thickness of the surface treatment layer was changed to 16 μm. A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer material EV1 was formed and the partition wall formation method was changed as follows.

* Surface treatment layer coating solution formulation: EV1
・ Ethylene-ethyl acrylate copolymer resin 10 parts (Mitsui-DuPont Polychemical Co., Ltd., trade name: EVAFLEX-EEA-709)
・ Toluene 100 parts ・ Polymer a 1.1 parts

-Formation of partition walls-
After the protective film of the photosensitive transfer material EV1 is peeled off, the rest is laminated on a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), with a rubber roller temperature of 100 ° C. and a wire. Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 1.2 m / min.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the photosensitive resin The distance between the layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 200 mJ / cm ² .
Next, the temporary support was peeled off together with the surface treatment layer, leaving only the photosensitive resin layer on the substrate.
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer, and then a KOH-based developer (KOH, containing nonionic surfactant, trade name: CDK-1, Fuji) Film Electronics Materials Co., Ltd.) was diluted 100 times with pure water and shower developed at 23 ° C. for 40 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues, and an image of matrix-like black (K) was obtained. Thereafter, the substrate is further post-exposed with 1000 mJ / cm ² light from the side of the resin layer with an ultrahigh pressure mercury lamp, and further 1000 mJ / cm with an ultrahigh pressure mercury lamp from the side opposite to the resin layer. ^The film was post-exposed with the light No. ² and then heat-treated at 220 ° C. for 30 minutes.

(Example 11)
In Example 8, the coating solution for the surface treatment layer: implemented except that 4.66 parts of the polymer b in the formulation P1 was changed to 10.3 parts of the polymer b, and that the RGB ink was changed to that prepared by the following method. A liquid crystal display device was prepared and evaluated in the same manner as in Example 8.

-Preparation of ink-
(R ink)
Among the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for R (red) pixels.
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, weight average molecular weight 37,000) 3 parts ・ First epoxy resin (novolak type epoxy resin,
Epicoat 154 manufactured by Yuka Shell Co., Ltd.) 2 parts ・ Second epoxy resin (neopentylglycol diglycidyl ether) 5 parts ・ Curing agent (trimellitic acid) 4 parts ・ Solvent: 80 parts ethyl 3-ethoxypropionate

(G ink)
In the R ink composition, C.I. I. Pigment Red 254 instead of C.I. I. A colored ink composition for G (green) pixels was prepared in the same manner as for the colored ink composition for R pixels except that the same amount of pigment green 36 was used.

(B ink)
Further, C.I. I. Pigment Red 254 instead of C.I. I. A colored ink composition for B (blue) pixels was prepared in the same manner as for the colored ink composition for R pixels except that the same amount of Pigment Blue 15: 6 was used.

(Example 12)
A liquid crystal display device was prepared and evaluated in the same manner as in Example 8 except that the formulation of the photosensitive resin composition for the black matrix in Example 8 was changed to K2 below.

Here, preparation of the photosensitive resin composition K2 described in Table 2 will be described.
In the photosensitive resin composition K2, first, pigment dispersions 2 to 6 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2 were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then The remaining components described in Table 2 were weighed out, added in the order described in Table 2 at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.). .

In addition, each composition of the composition as described in the photosensitive resin composition K2 is as follows.
(Pigment dispersion 2)
・ C. I. P. R. 177 (manufactured by Ciba Specialty Chemicals,
Product name: Chromophthaled Red A2B) 18 parts benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 72/28 Weight average molecular weight = 40% of 30000
Propylene glycol monomethyl acetate solution] 12 parts ・ Cyclohexanone 60 parts ・ Propylene glycol monomethyl acetate 10 parts

(Pigment dispersion 3)
・ C. I. P. B. 15: 6
(Product name: Heliogen Blue L6700F, manufactured by BASF Japan Ltd.) 18 parts benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 72/28 Weight average molecular weight = 40% of 30000
Propylene glycol monomethyl acetate solution] 15 parts, cyclohexanone 50 parts, propylene glycol monomethyl acetate 17 parts

(Pigment dispersion 4)
・ C. I. P. Y. 139 (manufactured by Ciba Specialty Chemicals,
Product name: Irgaphor Yellow 2R-CF) 18 parts benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 72/28 Weight average molecular weight = 40% of 30000
Propylene glycol monomethyl acetate solution] 15 parts, cyclohexanone 50 parts, propylene glycol monomethyl acetate 17 parts

(Pigment dispersion 5)
・ C. I. P. V. 23 (manufactured by Clariant Japan,
Product name: Hostaperm Violet RL-NF) 12 parts benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 72/28 Weight average molecular weight = 40% of 30000
Propylene glycol monomethyl acetate solution] 18 parts, 60 parts of cyclohexanone, 10 parts of propylene glycol monomethyl acetate

(Pigment dispersion 6)
Carbon black (Degussa, trade name: Special Black 250) 15 parts Benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 72/28 Weight average molecular weight = 40% of 30000
Propylene glycol monomethyl acetate solution] 23 parts / cyclohexanone 60 parts / propylene glycol monomethyl acetate 10 parts

(Example 13)
Surface treatment layer coating solution: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that 0.59 parts of polymer a in formulation P1 was changed to 10.3 parts of polymer c.

(Example 14)
Surface treatment layer coating solution: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that 0.59 part of polymer a in formulation P1 was changed to 18.3 parts of polymer d.

(Example 15)
Surface treatment layer coating solution: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that 0.59 part of polymer a in formulation P1 was changed to 36.7 parts of polymer d.

(Example 16)
Surface treatment layer coating solution: A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that 0.59 parts of polymer a in formulation P1 was changed to 36.7 parts of polymer e.
(Example 17)
A liquid crystal display device was prepared and evaluated in the same manner as in Example 8, except that the formulation of the photosensitive resin composition for black matrix in Example 8 was changed to K3.

(Comparative Example 1)
The surface treatment layer coating liquid P1 of Example 1 was changed to the surface treatment layer coating liquid PC1 used for forming the spacer of Example 1, and the RGB ink was changed to the ink shown in Example 11 Produced a liquid crystal display device in the same manner as in Example 1 and evaluated it.

(Comparative Example 2)
First, a partition wall was prepared in the same manner as in Comparative Example 1. Next, a liquid crystal display device was prepared and evaluated in the same manner as in Comparative Example 1 except that the partition walls were fluorinated by the following method.

-Plasma treatment-
Plasma treatment was performed under the following conditions using a plasma treatment apparatus (apparatus described in FIG. 12 of JP-A-2003-344640).
Gas used: O ₂ gas Pressure: 25 Pa
RF power: 100W
Processing time: 60 sec

-Plasma treatment-
Plasma treatment was further performed under the following conditions using the same plasma treatment apparatus as described above.
Gas used: CF ₄ gas Pressure: 25 Pa
RF power: 100W
Processing time: 60 sec

(Comparative Example 3)
A liquid crystal display device was prepared in the same manner as in Comparative Example 1 except that the photosensitive transfer material K1 of Comparative Example 1 was changed to the following one consisting of the first layer and the second layer, and the exposure and development method was changed to the following. And evaluated.

(Formation of partition walls)
The first layer had a thickness of 0.5 μm, and the second layer had a thickness of 1.5 μm.
Base film 75 μm thick polyethylene terephthalate film 1st layer Base resin: 30 parts of methyl methacrylate / hydroxyethyl methacrylate copolymer Photopolymerizable monomer: 25 parts of trimethylolpropane triacrylate Photopolymerization initiator: manufactured by Ciba Geigy "Irgacure 907" 10 parts Fluorine-based compound: "Florard FC-430" manufactured by Sumitomo 3M 5 parts-Second layer "V-259BK resist" manufactured by Nippon Steel Chemical Co., Ltd.

  Lamination was performed in the same manner as in Comparative Example 1, and then pattern exposure was performed from the base film side using a photomask for forming a partition wall. Then, the base film was peeled and removed, and then an alkali developer (“V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.). ) Was used to develop the first layer and the second layer, thereby forming a partition wall having an opening of 80 μm × 220 μm.

  In Comparative Example 2, although the contact angle between the black matrix and pure water was large, the contact angle with ink was very small, and a failure such as color mixing occurred.

FIG. 6 is a plan view schematically showing a conventional color filter in which ink overflows, mixed colors, and white spots occur. It is typical sectional drawing which shows the photosensitive transfer material of 3 layer structure of this invention. It is typical sectional drawing which shows the photosensitive transfer material of 4 layer structure of this invention. 1 is a schematic cross-sectional view of a color filter (for a white light display device (LCD)) according to the present invention. 1 is a schematic cross-sectional view of a color filter (for a blue light display device (EL)) according to the present invention.

Claims (13)

  A photosensitive transfer material comprising a temporary support, a surface treatment layer containing a fluorine compound having a polymerizable group, and a photosensitive resin layer in contact with the surface treatment layer in this order. The fluorine compound having a polymerizable group is a polymer compound prepared using at least one fluorine-containing monomer selected from the group consisting of the following general formulas (I) to (V). Item 2. The photosensitive transfer material according to Item 1.
CH ₂ = CR ¹ COOR ² R ^f (I)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents —C _p H _2p —, —C (C _p H _{2p + 1} ) H—, —CH ₂ C (C _p H _{2p + 1} ) H. - or -CH ₂ CH ₂ O-, the ^{_{R f -C n F 2n + 1}} , - (CF 2) n H, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF _{2) p OC m H 2m C} i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1 or _{-N (C p H 2p + 1} ) SO 2 C n F 2n + 1 represents. However, p is 1-10, n is 1-16, m is 0-10, i is an integer of 0-16.)
CF ₂ = CFOR ^g (II)
(In the formula, R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CHR ^g (III)
(In the formula, R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
^{_{CH 2 = CR 3 COOR 5 R}} j R 6 OCOCR 4 = CH 2 ··· (IV)
Wherein R ³ and R ⁴ are hydrogen atoms or methyl groups, R ⁵ and R ⁶ are —C _q H _2q —, —C (C _q H _{2q + 1} ) H—, —CH ₂ C (C _q H _{2q + 1} ) H— or —CH ₂ CH ₂ O—, R ^j represents —C _t F _2t —, where q is an integer of 1 to 10 and t is an integer of 1 to 16.
^{_{CH 2 = CR 7 COOCH 2 CH}} (CH 2 R k) OCOCR 8 = CH 2 ··· (V)
(Wherein R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ^k represents —C _y F _{2y + 1} , where y is an integer of ₁ to 16) The photosensitive transfer material according to claim 1, wherein the fluorine compound having a polymerizable group is at least a resin represented by the following structural formula (1).

(In the above structural formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in total, and R ¹⁵ represents a hydrogen atom. Represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ₁ is an ester group, an amide group, an arylene group which may have a substituent, or these X ₂ and X ₃ each independently represent an ether group, an ester group, an amide group, an arylene group which may have a substituent, a heterocyclic residue, or a linking group having these. L ₁ and L ₂ each independently represents a divalent linking group which may be a single bond, Rf ² represents a substituent containing fluorine, a, b, c and d each represents a mass ratio. , A represents 0 to 30, b represents 1 to 30, c represents 1 to 30, and d represents 20 to 98. ) Using the photosensitive transfer material according to claim 1 having a photosensitive resin layer and a surface treatment layer, the photosensitive transfer material is pressure-bonded to the substrate so that the photosensitive resin layer is in contact with the substrate,
Pattern exposure of the photosensitive resin layer through the surface treatment layer,
Developing the said photosensitive resin layer The formation method of the partition which has this order.   5. The method for forming a partition wall according to claim 4, wherein, in the pattern exposure, the surface of the photosensitive resin layer opposite to the side in contact with the substrate is fluorinated.   The method for forming a partition wall according to claim 4, wherein in the development, the surface treatment layer is removed.   A partition wall formed by the method according to claim 4.   The partition wall according to claim 7, wherein the surface of the photosensitive resin layer opposite to the side in contact with the substrate is fluorinated by the surface treatment layer, and the fluorinated surface is exposed.   The partition wall according to claim 7, which has a light shielding property.   8. A method of manufacturing an optical element, wherein a pixel is formed by applying droplets to the recesses defined by the partition walls according to claim 7 by an ink jet method.   The method of manufacturing an optical element according to claim 10, wherein the droplet contains a colorant.   An optical element comprising at least a plurality of pixels and a partition formed so as to divide the pixels on a substrate and manufactured by the manufacturing method according to claim 10.   A display device comprising the optical element according to claim 12.

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