WO2007108186A1

WO2007108186A1 - Cleaning treatment liquid

Info

Publication number: WO2007108186A1
Application number: PCT/JP2006/324768
Authority: WO
Inventors: Toshiyuki Masuda; Mitsutoshi Tanaka
Original assignee: Fujifilm Corporation
Priority date: 2006-03-20
Filing date: 2006-12-12
Publication date: 2007-09-27
Also published as: JP2007254510A; CN101400775A; KR20080113359A; CN101400775B; TW200801177A

Abstract

A cleaning treatment liquid that excels in cleaning removing capability for stain, such as development residue, and that is free from environmental problems and would not deteriorate even in shower idling; and using the cleaning treatment liquid, a method of forming color images, process for producing a color filter and process for producing an array substrate with color filter. There is provided a cleaning treatment liquid characterized by containing a basic compound and at least one surfactant selected from among a phenoxyoxyalkylene surfactant, alkyl ether surfactant and acetylene surfactant having at least one hydroxyl, and containing a naphthalene surfactant.

Description

Specification

Cleaning treatment liquid

Technical field

The present invention relates to a cleaning treatment liquid, a method for forming a colored image using the same, a method for producing a color filter, and a method for producing an array substrate with a color filter.

Background art

Conventionally, color filters have been widely used in liquid crystal display devices, sensors, color separation devices, and the like. As a method for producing this color filter, a method of patterning a dyeable resin (for example, natural gelatin or casein) and dyeing the resin with a dye to form a pixel has been adopted. However, the pixel formed by the above method has a problem that heat resistance and light resistance are inferior due to restrictions on the material.

Therefore, in recent years, a method for producing a color filter using a photosensitive transfer material in which a pigment is dispersed has been proposed for the purpose of improving heat resistance and light resistance. According to this proposal, the manufacturing method has been simplified, and it has been praised for the stability of the image obtained and the length of its lifetime.

[0004] However, in the manufacturing method of the color filter, there have been problems such as development residue, contamination of the pixel surface, and disturbance of the pixel edge, which are difficult to develop the photoresist in which the pigment is dispersed. In addition, since contamination such as development residue leads to a decrease in contact resistance when forming an image on a TFT active matrix substrate such as COA and HA, development of a developer that does not generate development residue has been attempted. However, sufficient results were not obtained in either proposal, and further improvement was desired.

[0005] In order to solve this problem, it has been devised to clean a substrate immediately after development using a cleaning treatment liquid containing polyoxyethylene nouryl ether. In this method, most of the development residue was removed, the pixel surface was smooth, and the pixel edge was not disturbed, and a good image could be formed.

However, the polyoxyethylene nonyl phenyl ether has an endocrine disrupting action on fish and is a subject of endocrine regulation, so that it cannot be used due to environmental problems. [0006] In order to solve this problem, cleaning treatment liquids using a surfactant disclosed in Patent Document 1 and Patent Document 2 have been proposed. This cleaning agent has solved not only environmental problems but also problems such as development residue. However, in recent years, the construction of the color filter production line has changed with the increase in size of the substrate, etc., and the time for empty showering of the cleaning device (spraying only the shower and the substrate does not flow) has become longer. Degradation has become a problem.

[0007] Patent Document 1: Japanese Unexamined Patent Publication No. 2003-336097

Patent Document 2: JP-A-2005-146171

Disclosure of the invention

Problems to be solved by the invention

[0008] An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is excellent in cleaning and removal of stains such as development residues, has no environmental problems, does not deteriorate even in an empty shower operation, and a colored image forming method using the cleaning processing liquid, It is an object to provide a method for producing a color filter and a method for producing an array substrate with a color filter.

Means for solving the problem

Means for solving the above-described problems are as follows. That is,

<1> a basic compound and at least one surfactant selected from an acetylene surfactant containing at least one hydroxyl group, an alkyl ether surfactant, and a phenoxyalkylene surfactant; A cleaning liquid characterized by containing a naphthalene surfactant.

<2> The basic compound is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, potassium carbonate, metasilicic acid. The cleaning solution according to the above item 1>, which is at least one kind of inorganic alkaline compound in which sodium and potassium metasilicate are also selected.

<3> The cleaning liquid according to any one of <1> to <2>, wherein the content of the basic compound in the cleaning liquid is 0.01 to 50% by mass.

<4> wherein the acetylene surfactant is an acetylenic diol surfactant.

The cleaning liquid according to any one of <1> to <3>. <5> The cleaning treatment solution according to any one of 1> to 4>, wherein the phenoxyalkylene surfactant is represented by the following structural formula (1):

[Chemical 3]

^{Ph-- 0- ( "CH CH 2 -} .. 0 structural formula (1) where the structural formula (1), Ph represents R is a full group, represents n is a hydrogen atom or an alkyl group Represents an integer of 1 or more.

<6> Naphtalene-based surfactant power The cleaning treatment solution according to <1> to <5> represented by the following structural formula (2).

[Chemical 4]

SM structural formula (2)

However, in said structural formula (2), R represents an alkyl group, R is a hydrogen atom or an alkyl group

1 2

Represents. M represents Na, K or H.

<7> The cleaning treatment liquid according to any one of <1> to <6>, wherein the cleaning treatment liquid is applied to an object to be treated under a pressurized condition.

<8> The cleaning treatment liquid according to <7>, wherein the pressure is 0.01 to 100 MPa.

<9> Pressurizing force The cleaning treatment liquid according to any one of <7> to <8>, which is performed by at least one of a brush, a sponge, and a hydraulic pressure.

<10> The cleaning treatment liquid according to any one of <7> to <9>, wherein the object to be processed is a transfer material in which at least a photosensitive layer and an oxygen blocking layer are sequentially stacked on a substrate. is there.

<11> The cleaning treatment solution according to any one of <1> to <10>, wherein the cleaning solution is used by diluting 5 to 1,000 times with a diluted solution.

<12> a photosensitive layer forming step of forming on the substrate a photosensitive layer capable of alkali development; A colored image comprising at least an exposure and development step for exposing and developing a layer, and a cleaning treatment step for performing a washing treatment using the washing treatment liquid according to any one of the above <1> Karaku 11> It is the formation method.

<13> The <12>, wherein the photosensitive layer is formed of a transfer material containing at least a resin having an acid value of 20 to 300, a pigment, a monomer containing a photopolymerizable unsaturated bond, and a photopolymerization initiator. This is a colored image forming method.

<14> Forming a plurality of colored images on the same substrate, including at least a photosensitive layer forming step for forming an alkali developable photosensitive layer on the substrate, and an exposure and developing step for exposing and developing the photosensitive layer. A method for producing a color filter, further comprising a washing treatment step of washing with the washing treatment liquid according to any one of <1> to 11 above. is there.

<15> a photosensitive layer forming step of forming an alkali-developable photosensitive layer on the TFT array substrate, and an exposure and developing step of exposing and developing the photosensitive layer, and a plurality of colored images on the same TFT array substrate A method for producing an array substrate with a color filter that forms a color filter, comprising a cleaning process step of cleaning using the cleaning process liquid according to any one of the above items 1> Karaku 11> This is a method of manufacturing an attached array substrate.

The invention's effect

[0010] The cleaning treatment liquid of the present invention is selected from a basic compound, an acetylene surfactant containing at least one hydroxyl group, an alkyl ether surfactant, and a phenoxyalkylene surfactant. It contains at least one surfactant and a naphthalene surfactant.

As a result, a colored image can be formed without deterioration even in an empty shower operation that is excellent in cleaning and removing dirt such as development residues and has no environmental problems.

The colored image forming method of the present invention includes at least a photosensitive layer forming step, an exposure and development step, and a washing treatment step. In the colored image forming method of the present invention, a photosensitive layer capable of alkali development is formed on a substrate in the photosensitive layer forming step, and the photosensitive layer is exposed and developed in the exposure and development steps. In the cleaning process, Wash with a bright cleaning solution.

[0012] According to the present invention, a conventional cleaning treatment solution that can solve various problems in the prior art, is excellent in cleaning removal of dirt such as development residues, has no environmental problems, and does not deteriorate even in an empty shower operation, It is possible to provide a colored image forming method, a color filter manufacturing method, and a method of manufacturing an array substrate with a color filter.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] (Cleaning solution)

The cleaning treatment liquid of the present invention comprises at least one selected from a basic compound, an acetylene surfactant containing at least one hydroxyl group, an alkyl ether surfactant, and a phenoxyalkylene surfactant. It contains a surfactant and a naphthalene surfactant, and further contains other components as necessary.

[0014] Basic compounds

The basic compound is not particularly limited as long as it exhibits basicity, and can be appropriately selected according to the purpose. Examples thereof include inorganic alkali compounds and organic alkali compounds.

[0015] Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, potassium carbonate, Examples thereof include sodium silicate such as sodium metasilicate, potassium metasilicate, and the like, and potassium hydroxide, potassium carbonate, and the like. These inorganic alkali compounds may be used alone or in combination of two or more.

[0016] Examples of the organic alkali compound include triethanolamine, diethanolamine, butyramine, phenol hydrazine, tetramethyl ammonium hydroxide, and the like. These organic alkali compounds may be used alone or in combination of two or more.

Of these, inorganic alkaline compounds are preferred from the viewpoint of handleability such as no odor. [0017] As the basic compound, it is preferable to use a salt of a weak acid from the viewpoint of not damaging the pixels when the cleaning treatment of the present invention and a brush are used at the same time. Specifically, carbonates and / or phosphates are preferably used as the weak acid salts.

Examples of the carbonate and / or phosphate include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, sodium hydrogen phosphate, potassium phosphate, hydrogen phosphate. Examples include potassium, potassium phosphate-hydrogen hydrogen, sodium pyrophosphate, potassium pyrophosphate, and hydrated salts thereof. These may be used alone, for example, sodium carbonate and sodium bicarbonate, potassium carbonate and potassium bicarbonate, sodium phosphate and sodium phosphate, potassium phosphate and hydrogen phosphate In addition, it is preferable to combine those having an approximate number of substitutions of hydrogen as an acid with metal in an equimolar ratio or a ratio close to this in order to suppress pH change. From the viewpoint of waste liquid treatment, carbonate is most preferable.

The carbonate and / or phosphate of the present invention is described in the form of a salt added as a raw material. Needless to say, in the actual cleaning liquid of the present invention, some of these salts are present in a dissociated state. No.

[0018] The content of the basic compound in the cleaning treatment liquid is preferably 0.01 to 50% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.05 to 15% by mass. It is particularly preferably 0.1 to 10% by mass. If the content is less than 0.01% by mass, the resolution may be insufficient, and if it exceeds 50% by mass, the photoresist itself may peel off the substrate.

[0019] Phenoxyoxyalkylene surfactant

The phenoxyalkylene surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those having a structure represented by the following structural formula (1).

[0020] [Chemical 5]

Ph—— 0— (-CH CH ₂ — 0 ^ Structural formula ( In the structural formula (1), Ph represents a phenyl group.

R represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert butyl group, a pentyl group, a neopentyl group, and a hexyl group. The ru group is preferred. n represents an integer of 1 or more, preferably 1 to 50.

[0022] Among the phenoxyalkylene surfactants represented by the structural formula (1), the phenoxyoxyalkylene surfactant described in [0021] Koki et al. [0037] of JP-A-2005-146171. It is preferable to use a surfactant.

[0023] The content of the phenoxyalkylene surfactant in the cleaning treatment liquid is preferably 0.01 to 50% by mass, more preferably 0.05 to 10% by mass. When the content is less than 0.01% by mass, the resolution may be insufficient, and when it exceeds 50% by mass, the storage stability of the liquid is deteriorated.

[0024] When the phenoxyalkylene surfactant is used in combination with other surfactants, the use of the phenoxyalkylene surfactant as a main component enables removal of development residues and the like more efficiently. Is preferable.

[0025] An acetylene surfactant containing at least one hydroxyl group

The acetylene surfactant containing at least one hydroxyl group can be appropriately selected depending on the purpose without particular limitation. For example, an acetylene monool surfactant having one hydroxyl group, a hydroxyl group having 2 hydroxyl groups, and the like. These include acetylene glycol surfactants, and among these, acetylene glycol surfactants are preferred.

[0026] As the acetylene glycol surfactant, for example, the acetylene glycol surfactant described in [0042] to [0045] of JP-A-2005-146171 is preferable.

[0027] The content of the acetylene surfactant containing at least one hydroxyl group in the cleaning treatment liquid is preferably 0.01 to 50% by mass, more preferably 0.05 to 5% by mass. When the content is less than 0.01% by mass, the resolution may be insufficient. On the other hand, when the content exceeds 50% by mass, the storage stability of the liquid may be deteriorated.

[0028] The acetylene surfactant containing at least one hydroxyl group is combined with another surfactant. When used in combination, development residues and the like can be efficiently removed even with a low content. Further, using the phenoxyalkylene surfactant as a main component and the acetylene surfactant containing at least one hydroxyl group (particularly, acetylene glycol surfactant is preferred) is used in combination. It is preferable in that it can remove development residues more efficiently.

[0029] One alkyl ether surfactant

The alkyl ether surfactant used in the cleaning solution of the present invention is not particularly limited. For example, JP 2005-1461 A can be selected as appropriate according to the purpose.

71. Alkyl ether surfactants described in JP-A No. 71 [0050] to [0053] are preferred.

[0030] The content of the alkyl ether surfactant in the cleaning treatment liquid is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 0 to 5% by mass.

[0031] Furthermore, as other surfactants, polycarboxylic acid type polymer surfactants, polyon acid type dispersants such as polysulfonic acid type polymer surfactants; polyoxyethylene / polyoxypropylene block polymers, etc. A non-one dispersant or the like can be added.

[0032] Naphthalene surfactant

The naphthalene-based surfactant can be appropriately selected according to the purpose without any particular restriction, and examples thereof include those having a structure represented by the following structural formula (2).

[Chemical 6]

S ○ ₃ M Structural formula (2)

1 2

Represents. M represents Na, K or H.

M is preferably Na or K from the viewpoint of water solubility. -SO M is in position 1 or 2

Three

Although it can be attached, the position 2 is preferred from the viewpoint of residue removal.

R represents an alkyl group. From the viewpoint of residue removal, a butyl group or a propyl group is preferred. R represents a hydrogen atom or an alkyl group. From the standpoint of residue removal, R is a butyl group. Or prefer propyl group U.

Among these, those represented by the following structural formula (3) are most preferable from the viewpoint of residue removal.

[Chemical 7]

Structural formula (3)

[0034] The content of the naphthalene surfactant in the cleaning liquid is preferably 0.01 to 50% by mass, more preferably 0.05 to 10% by mass. When the content is less than 0.01% by mass, the resolution may be insufficient, and when it exceeds 50% by mass, the storage stability of the liquid is deteriorated.

[0035] In the present invention, at least one surfactant selected from the group consisting of an acetylene surfactant containing at least one hydroxyl group, an alkyl ether surfactant, and a phenoxyalkylene surfactant is used. The content of the cleaning treatment liquid containing at least one kind and containing a naphthalene surfactant is preferably 0.01 to 50% by mass, more preferably 0.01 to 20% by mass. More preferably, it is 05-15 mass%.

[0036] One other component

The following are preferably added to the cleaning agent of the present invention for the purpose of storage stability of the liquid, prevention of alteration during processing, and prevention of reattachment of residues.

Chelating agents (EDTA-sodium salt, EDTA tetrasodium salt, EGTA, 0.5 1 to 0. 5 mass ^_0/0), a polymer (poly Bulle pyrrolidone, methylcellulose hydroxypropyl methyl cellulose, gelatin, Agarosu, 0. 1 0.5 wt%), antifoaming agent (manufactured by Shin-Etsu chemical Siri corn oil KS- 502 Kusumoto chemicals OX- 66 OX- 715 OX- 1930N 1934 Maruzen pharmaceutical chemistry en Chicks # 100 0.1 01-0. 1 mass ^_0/0 )

[0037] The cleaning treatment liquid of the present invention is used by being applied to an object to be processed, and is preferably used by being applied to an object to be processed under a pressure condition. Therefore, it is extremely excellent in cleaning and removing dirt. In addition, when the object to be processed has a configuration in which a photosensitive layer is provided on a substrate, in particular, a case in which the target object has a configuration in which a photosensitive layer, an oxygen blocking layer, and the like are sequentially stacked on the substrate. In this case, a development residue or the like is likely to occur on the substrate or the photosensitive layer surface. By using the cleaning solution of the present invention, preferably by applying under pressure conditions, development residues and the like in the substrate and the photosensitive layer can be efficiently removed, surface smoothness, edge shape is good, and resolution is improved. High V and colored images can be formed.

The photosensitive layer and the oxygen blocking layer will be described in detail in the colored image forming method of the present invention.

[0038] As the pressurizing condition, the method described in [0058] Force et al. [0059] of JP-A-2005-146171 is preferably used.

[0039] The cleaning treatment solution of the present invention is preferably used after diluting it 5 to 1,000 times with a diluent, and more preferably 10 to 200 times.

The diluting solution can be appropriately selected according to the purpose without any particular limitation. For example, tap water, water, pure water, distilled water, various organic solvents, a mixed solvent of water and various organic solvents, Etc. are used.

[0040] (Method for forming colored image)

The colored image forming method of the present invention includes a photosensitive layer forming process, an exposure process and a developing process, and further includes a cleaning process, and includes other processes as necessary.

In the present invention, the cleaning treatment step may be provided before or after the photosensitive layer forming step, or may be provided before or after the exposure and development steps. However, when the purpose is to clean the substrate, it is preferably provided before the photosensitive layer forming step, and when the purpose is to remove the development residue, after the exposure and image forming steps. Preferably it is provided.

[0041] Photosensitive layer forming step

The photosensitive layer formed in the photosensitive layer forming step can be alkali-developable and is preferably formed from the colored image forming material described below.

Colored image forming material>

The colored image-forming material is alkali-developable and has photosensitivity! / If there is no particular limitation, it is not limited, but it is a resin, a colorant such as a pigment 'dye, a monomer containing a photopolymerizable unsaturated bond, And it is preferable to contain a photoinitiator and other components. Specific examples are JP-A-2005-146171 describes in [0064] to [0099]. Also, JP-A-2 005-146171, [0100] to [0121] describe a method for forming a photosensitive layer, a method for preparing a coating solution for a photosensitive layer, a thermoplastic resin layer, an oxygen barrier layer, and others. .

[0042] Exposure and development process

Throughout the exposure and development steps, the exposure of the photosensitive layer formed on the substrate can be suitably performed by a method of irradiating the photosensitive layer with an actinic ray in an image-like manner. The film can be cured. In the exposure, an oxygen blocking film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 m, and the exposure may be performed thereon.

Preferred examples of the active light source include carbon arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and visible light lasers. Using these light sources, actinic rays are irradiated in the form of an image by pattern exposure through a photomask or direct drawing by scanning.

[0043] Following the exposure, development is performed. The developer can be appropriately selected according to the purpose without any particular limitation. For example, all known developers that are usually used for developing a photosensitive layer and the like are preferably used.

[0044] For the development, a colored image pattern of a cured film corresponding to an image can be obtained by removing the unexposed portion by a method of spraying a developer or immersing in a developer. In order to harden the colored image pattern more strongly after the image formation, it is preferable to further perform post exposure and post beta. As the post-beta temperature, a heating time in which a temperature of 60 to 280 ° C is preferable is more preferably about 1 to 60 minutes.

[0045] Cleaning process

In the washing treatment step, the washing treatment solution of the present invention is used, and preferably the substrate, the photosensitive layer, the colored image, etc. are washed under pressure. As a result, the dirt can be easily removed and removed. In addition, when the object to be processed has a configuration in which a photosensitive layer is provided on a substrate, particularly in a configuration in which a photosensitive layer and an oxygen blocking layer are sequentially laminated on the substrate, the substrate or photosensitive layer is formed. Development residue or the like is likely to occur on the surface of the layer. Therefore, the cleaning treatment liquid of the present invention is used in the cleaning treatment step, preferably under pressurized conditions. Thus, it is possible to efficiently remove development residues and the like in the substrate and the photosensitive layer, and it is possible to form a colored image with good surface smoothness and edge shape and high resolution.

[0046] The pressurizing conditions, pressurizing means, and the like are the same as those described in the section "Cleaning treatment liquid" of the present invention.

[0047] (Method for manufacturing color filter)

The method for producing a color filter of the present invention includes a photosensitive layer forming step, an exposure and image forming step, and further includes a cleaning treatment step. The formation of the photosensitive layer, exposure 'development, and washing treatment are the same as in the colored image forming method of the present invention.

In the method for producing a color filter of the present invention, in particular, it is preferable to repeat the formation of the colored image by using different colored images of 3 to 4 colors!

[0048] For example, a method for forming red, green, and blue colored images on a black matrix formed by chromium vapor deposition or the like in the same manner as the colored image forming method of the present invention, and a black colored image forming material After forming a black matrix using, a method for forming red, green, and blue colored images in the same manner as the colored image forming method of the present invention, as in the colored image forming method of the present invention. Examples thereof include a method of forming a black matrix using a black image forming material in the gap between these colored images after forming red, green and blue colored images. The order in which the colored images of red, green and blue are formed is not particularly limited. Further, it may be used for manufacturing a color filter having transparent pixels W in addition to colored pixels such as RGB.

[0049] (Method for manufacturing array substrate with color filter)

The method for producing an array substrate with a color filter of the present invention comprises a photosensitive layer forming step of forming a predetermined photosensitive layer on a TFT (thin film transistor) active matrix substrate (TFT array substrate), and an exposure and development step. In addition, it has a cleaning process. The formation, exposure and development, and washing treatment of the photosensitive layer are the same as the colored image forming method of the present invention. As the TFT active matrix substrate, a conventional one without particular limitation can be used without limitation. For example, a gate signal line and an additional capacitance electrode are formed on an active matrix substrate (array substrate), and gate insulation is formed thereon. After forming the film, a semiconductor layer and a channel protective layer are formed, and an n + Si layer that becomes a TFT source and drain is formed, and then a metal layer and an ITO film are formed by a sputtering method. By patterning, a drain signal line and a source signal line can be formed.

The method for producing an array substrate with a color filter of the present invention can be preferably carried out according to, for example, the description in JP-A-10-206888.

[0050] In the method for producing an array substrate with a color filter of the present invention, the TFT active matrix substrate is formed of an amorphous silicon, a low-temperature polysilicon substrate, or a continuous-grain silicon substrate. I like it.

Further, the color filter of the array substrate with a color filter may have transparent pixels W in addition to colored pixels such as RGB, or only black or only one spacer may be formed. Further, a transparent interlayer insulating film having a contact hole may be formed. When an array substrate is used, it is preferable not to use a brush in the cleaning process from the viewpoint of not scratching the TFT, but in that case, a residue may be a problem even with a transparent resin not containing a pigment. The present invention is also preferably used in that case.

Example

[0051] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

[0052] Preparation of monochromatic photosensitive resin composition

(Colored photosensitive resin composition K1)

[table 1]

Colored photosensitive resin composition K1

K pigment dispersion 1

twenty five

(Rikiichi Bon Black)

Propylene glycol monomethyl ester

8.0

Ruacetate

Methyl ethyl ketone 37

Binder 2 9.1

DPHA; ¾ 4.2

2, 4-bis (trichloromethyl) -6

[4'— (N, N-bisethoxy carbonate

0.1 60

Rumethyl) amino 1'-bromo

Le] —s—triazine

Hydroquinone monomethyl ether 0.002

Surfactant 1 0.044

Parts by mass

Note) The unit of numerical values in the table is parts by mass, and the same applies to Tables 2 to 7 below. Remove ether acetate, mix at a temperature of 24 ° C (± 2 ° C) and stir at 150 RPM for 10 minutes, then the amounts of methyl ethyl ketone, Ninder 2, hydroquinone monomethyl ether, DPHA solution listed in Table 1 , 2, 4 Bis (trichloromethyl) 6— [4,-(N, N bisethoxycarboromethylmethylamino) -3, bromophenol] — s Triazine, Surfactant 1 is weighed, temperature 25 ° C (± 2 ° C) was added in this order, and the mixture was stirred at 150 ° C for 30 minutes at a temperature of 40 ° C (± 2 ° C).

[0053] Of the compositions described in Table 1,

The composition of K pigment dispersion 1 was as follows.

• Carbon black (trade name: Nipex35, manufactured by Degussa Japan Co., Ltd.) 13.1 parts, dispersant (compound 1 below) 0.65 parts

'Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

Random copolymer, molecular weight 37,000) 6. 72 parts

'Propylene glycol monomethyl ether acetate 79. 53 parts

[0054] [Chemical 8]

Compound 1

[0055] The composition of the binder 2 was as follows.

'Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio

Random copolymer, molecular weight 38,000) 27 parts' Propylene glycol monomethyl ether acetate 73 parts

The composition of DPHA solution is

'Dipentaerythritol hexaatalylate (containing polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts

'Propylene glycol monomethyl ether acetate 24 parts The composition of surfactant 1 was as follows.

• The following compound 2 30 parts

• 70 parts methyl ethyl ketone

[0056] [Chemical 9] Compound 2

Kide)

(Colored photosensitive resin composition R101)

[Table 2] Colored photosensitive resin composition

R101

R pigment dispersion 1

40

(C.I.P..254)

R Pigment dispersion 2

4.5

(C.I.P..177)

Propylene gel monome

7.6

Tyl ether acetate

Methyl ethyl ketone 37

Binder 1 0.8

DPHA solution 4.4

2_Trichloromethyl 5-

(P-styrylstyryl) 1, 0.14

3, 4_oxadiasol

2, 4_bis (trichloromethyl)

) _6_ [4 '_ (N, N-bisethoxycarbonylmethyl 0.06

Le) Amino 1'-Bromohue

Dill] —s—triazine

Phenothiazine 0.010

Additive 1 0.52

Surfactant 1 0.07 Colored photosensitive resin composition R101 is the first to remove the amount of R pigment dispersion 1, R pigment dispersion 2, propylene glycol monomethyl ether acetate in the amounts shown in Table 2, and the temperature is 24 °. Mix at C (± 2 ° C) and stir at 150 RPM for 10 minutes, then the amount of methyl ethyl ketone, binder 1, DPHA solution, 2 trichloromethyl-5- (p-styrylstyryl) -1, 3 , 4-Oxadiazole, 2, 4 Bis (trichloromethyl) 6— [4,1 (N, N-bisethoxycarboromethylamino) -3, -bromophenol] — s Triazine and phenolothiazine are weighed and Add in this order at 24 ° C (± 2 ° C) and stir at 150 RPM for 30 minutes.Further remove the amount of Surfactant 1 listed in Table 2 to a temperature of 24 ° C (± 2 ° C). And stirred at 30 RPM for 5 minutes and filtered through nylon mesh # 200.

Of the compositions shown in Table 2, additive 1 was a phosphate ester special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152).

The composition of R pigment dispersion 1 was as follows.

• C. I. P. R. 254 (Product name: Irgaphor Red B—CF,

Ciba Specialty Chemicals Co., Ltd.) 8 parts

, Dispersant (compound 4) 0.8 parts 'Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

Random copolymer, molecular weight 30,000) 8 parts

'83 parts of propylene glycol monomethyl ether acetate

The composition of R pigment dispersion 2 was as follows.

• C. I. P. R. 177 (Product name: Cromophtal Red A2B,

Ciba Specialty Specialty Chemicals Co., Ltd.) 18 copies

'Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

Random copolymer, molecular weight 30,000) 12 parts

'Propylene glycol monomethyl ether acetate 70 parts

Polymer (benzyl metatalylate Z methacrylic acid Z methyl metatalylate

= Random copolymer with a molar ratio of 38Z25Z37, molecular weight 40,000) 27 parts' Propylene glycol monomethyl ether acetate 73 parts (Colored photosensitive resin composition G101)

[Table 3]

Colored photosensitive resin composition G101 is prepared by first removing G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 3 at a temperature of 24. Mix at ° C (± 2 ° C) and stir at 150 RPM for 10 minutes, then the amount of methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, 2 trichloromethyl mono 5- (p-styryl styryl) listed in Table 3 ) -1, 3, 4 Oxadiazole, 2, 4 Bis (trichloromethyl) 6 — [4, — (N, N bisethoxycarboromethylamino) —3, -bromophenol] — s— Triazine and phenothiazine Then, add it in this order at a temperature of 24 ° C (± 2 ° C), stir for 150R PM for 30 minutes, and then force off the amount of surfactant 1 listed in Table 4 to a temperature of 24 ° C. This was obtained by adding the solution at (2 ° C), stirring at 30 RPM for 5 minutes, and filtering through nylon mesh # 200.

[0060] Of the compositions listed in Table 3,

As the G pigment dispersion 1, “trade name: GT 2” manufactured by Fuji Film Elect Kokuku Materials Co., Ltd. was used.

As Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

[0061] (Colored photosensitive resin composition B101)

[Table 4]

Colored photosensitive resin composition B101 is prepared by first removing B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 4 at a temperature of 24 ° C ( ± 2 ° C) and stirred at 150 RPM for 10 minutes, then the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2 trichloromethyl-5- (p-styrylstyryl)-1, 3, 4 —Oxadiazole, 2, 4 Bis (trichloromethyl) 6— [4,1- (N, N-bisethoxycarboromethylamino) -3, -bromophenol] — s Triazine and phenothiazine, temperature 25 ° C (± 2 ° C) was added in this order, and stirred at a temperature of 40 ° C (± 2 ° C) for 1 50 RPM for 30 minutes, and then the amount of surfactant 1 listed in Table 4 was applied. It is obtained by adding at a temperature of 24 ° C (2 ° C), stirring at 30 RPM for 5 minutes, and filtering through nylon mesh # 200.

[0062] Of the compositions described in Table 4,

As the B pigment dispersion 1, “trade name: CF Blue EX3357” manufactured by Mikuni Color Co., Ltd. was used. As the B pigment dispersion 2, “trade name: CF Blue EX3383” manufactured by Mikuni Color Co., Ltd. was used. The composition of binder 3 is

• Polymer (benzyl metatalylate Z methacrylic acid Z methyl metatalylate

= 36Z22Z42 molar ratio random copolymer, molecular weight 38,000) 27 parts' Propylene glycol monomethyl ether acetate 73 parts

[0063] (Photosensitive resin composition S)

[Table 5]

The photosensitive resin composition s is a transparent material for forming an interlayer insulating film on an active matrix substrate.

(Cleaning treatment liquid of the present invention)

[Table 6] Liquid 1 Liquid 2 Liquid 3 Liquid 4 Liquid 5 Liquid 6 Liquid 7 Liquid 8 Liquid 9 Liquid 10 Liquid 1 1

PO 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0 0 0.3

AG 0 0 0 0 0 0 0 0 0.3 0 0

AE 0 0 0 0 0 0 0 0 0 0.3 0

NB (35 mass ⁰ / o liquid) 1.4 1.4 0.6 1.4 2.9 1.4 1.4 1.4 1.4 1.4 0

B4SN 0 0.3 0.1 0.3 0.3 0.3 0 0 0 0 0.3 Sodium carbonate 'monohydrate 0.7 0.7 0.7 0.3 0.7 0.7 0.7 5.8 0.7 0.7 0.7 Sodium bicarbonate 0.3 0.3 0.3 0.2 0.3 0.3 0 3.2 0.3 0.3 0.3 Water 97.3 97.0 98.0 97.5 95.5 97.0 97.6 89.3 97.3 97.3 98.4 cleaning solution, _c which was prepared by the formulation described in table 6

[0065] where PO in the table is:

[Chemical 10]

Ph—0 ~ (rCH _z ¼2 ~ ^CH ₃ Compound 3

OH

AG:

Surfinol 485 manufactured by Nissin Chemical Industry Co., Ltd.

AE:

C H -0- (CH CH -0) H

10 21 2 2 7

NBU

Kao Corporation Perex NBL

Sodium dibutylnaphthalenesulfonate (35% by weight aqueous solution)

B4SN:

Nippon Co., Ltd. New Coal B4-SN (CAS. No81503-86-8) Polyoxyethylene j8-Naphthyl ether Sulfate

[0066] (Cleaning treatment liquid of comparative example)

[Table 7]

Comparison liquid 1 Comparison liquid 2 Comparison liquid 3 Comparison liquid 4 Comparison liquid 5 Comparison liquid 6

PO 0.3 0.3 0 0 0 0.3

AG 0 0 0 0 0 0

AE 0 0 0 0 0 0

NBL (35% by mass solution) 1.4 0 1.4 0 1.4 0

B4SN 0 0 0 0 0 0 Sodium carbonate Monohydrate 0 0.7 0.7 0.7 0 0 Sodium bicarbonate 0 0 0 0 0 0 Water 98.3 99.0 97.9 99.3 98.6 99.7 The cleaning solution of the comparative example was prepared according to the formulation shown in Table 7 above.

[0067] Preparation of photosensitive resin transfer material

On a 75 μm-thick polyethylene terephthalate film temporary support, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation HI was applied and dried. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14. on the temporary support, an intermediate layer having a dry film thickness of 1. and a dry layer are dried. A photosensitive resin layer with a thickness of 2. was provided and a protective film (12 m thick polypropylene film) was pressure-bonded.

In this way, a photosensitive resin transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a photosensitive resin layer of black (K) is produced, and the sample name is photosensitive. It was named as a natural oil transfer material K1.

[0068] Coating liquid for thermoplastic resin layer: Formulation HI

• methanol

• Propylene glycol monomethyl ether acetate 6.36 parts

• Methyl ethyl ketone 52. 4 parts

'Methylmetatalylate / 2-ethylhexyl talylate / benzyl

Metatalylate Z Methacrylic Acid Copolymer (Copolymerization composition ratio (molar ratio)

= 55/11. 7/4. 5/28. 8, Molecular weight = 90,000, Tg 70. C)

5. 83 咅

• Styrene z acrylic acid copolymer (copolymerization composition ratio (molar ratio))

= 63,37, molecular weight = 10,000, Tg 100. 13. 6 parts

• Bisphenol A with pentaethylene glycol monomethacrylate

2-equivalent dehydration-condensed compound (made by Shin-Nakamura Chemical Co., Ltd., trade name: 2, 2-bis [4 (methacryloxypolyethoxy) phenol] propane)

9. 1 copy

• Surfactant 1 0.54 parts

[0069] Coating solution for intermediate layer: Formulation P1

PVA205 (Polybulol alcohol, manufactured by Kuraray Co., Ltd., (Oxidation degree = 88%, polymerization degree 550) 32.2 parts

• Polybulol pyrrolidone (ISPI'Japan Co., Ltd., K-30)

14. 9 咅

'Distilled water 524 parts

• Methanore 429 咅

[0070] Next, the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is used as the colored photosensitive resin composition R101, G101, B101, and the photosensitive resin. In the same manner as above except that the composition S was changed to the photosensitive resin transfer material R101,

G101, B101, and S were prepared.

[Example 1]

-Black (K) image formation-A glass cleaner solution adjusted to 25 ° C is sprayed onto a non-alkali glass substrate for 20 seconds while showering with a rotating brush with nylon bristles. Coupling solution (N—β (aminoethyl) _{Ύ —aminopropyltrimethoxysilane 0.3} mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and pure Water shower washed. This substrate was heated at 100 ° C for 2 minutes with a substrate preheating device and sent to the next laminator.

After removing the protective film of the photosensitive resin transfer material K1, the substrate heated to 100 ° C using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C, wire Lamination was performed at a pressure of 100 NZcm and a conveyance speed of 2. 2 mZ.

After the temporary support is peeled off at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are used with a proximity type exposure machine (manufactured by Dainippon Kaken Co., Ltd.) with an ultra-high pressure mercury lamp. ) Was set vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mjZcm2.

[0072] Next, triethanol amine developing solution (triethanolamine § Min 30 mass ^_0/0 containing, trade name: T - PD2, manufactured by Fuji Photo Film Co., 12 times with pure water (T-PD2 1 The solution obtained by diluting 11 parts by mass of pure water with 11 parts by mass) was developed with shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Continue to the top of this board The air was blown off to drain the liquid, and then pure water was sprayed for 10 seconds in a shower, washed with a pure water shutter, and air was blown to reduce the liquid pool on the substrate.

Continuing carbonate Na based developer (0.38 mol Z l sodium bicarbonate, sodium carbonate 0.47 mol Z l, dibutyl sodium naphthalene sulfonate 5 wt ^{_0/0, Ύ} two on surfactants, defoamers , Containing stabilizer, trade name: T CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water), shower developed at 29 ° C for 30 seconds, cone type nozzle pressure 0.15 MPa The resin layer was developed to obtain a patterning image.

Subsequently, the cleaning solution of the present invention described in Table 6 was diluted 10-fold with pure water, sprayed in a shower at 33 ° C for 20 seconds and a cone type nozzle pressure of 0.02 MPa, and further formed with a rotating brush having nylon bristles. The image was rubbed to remove the residue, and a black (K) image was obtained. Thereafter, the substrate was subjected to heat treatment at 220 ° C. for 15 minutes after post-exposure with an exposure amount of 500 miZcm ² (1,000 mj / cm ^{2 in} both sides) with an ultra-high pressure mercury lamp. The substrate on which this K image was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

[0073] —Red (R) pixel formation

Using the photosensitive resin transfer material R101, a heat-treated red (R) pixel was obtained in the same process as the photosensitive resin transfer material K1. However, the exposure was 40 mjZcm ² and development with Na carbonate-based image solution was 35 ° C for 35 seconds.

The substrate on which the K image and R pixel were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to the substrate preheating device.

[0074] —Green (G) pixel formation—

Using the photosensitive resin transfer material G101, heat-treated green (G) pixels were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure was 40mi / cm ² and development with a sodium carbonate developer was 34 ° C for 45 seconds.

The substrate on which the K image and R and G pixels were formed was again cleaned with a brush as described above. After pure water shower cleaning, the silane coupling solution was not used and the substrate was sent to the substrate preheating device. [0075] Blue (B) pixel formation

Using the photosensitive resin transfer material B101, heat-treated blue (B) pixels were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure was 30 mj / cm ² , and development with a sodium carbonate developer was 36 ° C for 40 seconds.

[0076] The substrate on which the R, G pixel, and B images were formed was beta-treated at 240 ° C for 50 minutes to obtain the target color filter.

[0077] <Evaluation of development residue>

Among the formation of the color filter, the substrate was extracted before post-exposure when forming the R pixel, and the residue removal property was evaluated. In order to evaluate the degree of deterioration after empty shower operation, the same evaluation was performed after 6 hours of empty shower operation.

The operation time of the empty shower was assumed to be 6 hours, assuming that the color filter line of G5 to G8 size was used, and that it was placed for the longest time due to adjustment.

The equipment used is a 1.2m wide, 2.5m high and 0.8m high development zone with a roller conveyor installed in a developing zone of 4 meters and four arm forces with 15 nozzles. It was of the type that was installed evenly in the length direction and had two rotating brushes between the second and third arms. The cleaning solution showered from the nozzles of the four arms returns to the stock tank (capacity: 200 liters) from the drain port under the zone, and the stock tank force is sent to the nozzles again by the pump. It was.

For evaluation of the residue, the development residue in the unexposed area was observed with a scanning electron microscope for the obtained colored image and evaluated according to the following criteria.

〔Evaluation criteria〕

◎ · · · The development residue was not recognized in the unexposed area.

A slight development residue was observed in the unexposed area.

Δ ···· Slight development residue was observed in the unexposed area.

X · · 'Development residue was clearly observed in the unexposed area.

X X ··· Many development residues were observed in the unexposed areas.

Using the optical microscope, the following criteria were used to determine the pixel edge shape in the resulting colored image. It was evaluated by.

〔Evaluation criteria〕

A pixel edge by exposure with a mask that gives a linear image is a straight line.

O · · Pixel edges due to exposure with a mask that gives a linear image are almost straight.

Δ · · Some pixel edges are distorted by exposure with a mask that gives a linear image.

X · · Pixel edges due to exposure with a mask that gives a linear image are distorted.

[0078] (Comparative example)

Instead of using the cleaning solution of the present invention in Example 1, the same test was performed using the cleaning solutions of Comparative Examples shown in Table 7.

[0079] The results are shown in Tables 8 and 9.

[Table 8]

[Table 9]

[0080] (Example 2)

In Example 1, except that the photosensitive resin transfer material S was used instead of the photosensitive resin transfer material K1, as described in K1 of Example 1, the description in JP-A-10-206888 Therefore, an active matrix substrate with an interlayer insulating film was fabricated. At that time, a mask having a circular contact hole with a diameter of 20 m for each pixel was used, and the cleaning treatment liquid was carried out in the same manner as in Example 1 except that no brush was used.

[0081] With respect to the obtained active matrix substrate with an interlayer insulating film, development residues in the obtained contact hole portions were compared before and after 6 hours of empty shower in the same manner as in Example 1. The results are shown in Table 10.

[Table 10] Solution 1 Comparison solution 1

Development residue o X X

Development residue after empty shower o X X

Judgment o X

Next, as a result of forming an ITO film on the active matrix substrate with an interlayer insulating film and conducting a continuity test of the contact hole portion, the contact failure rate was low and the contact resistance was good.

Industrial applicability

[0083] The cleaning solution of the present invention is excellent in cleaning and removing dirt such as development residues, and is free from environmental problems. It can form a colored image using the cleaning solution that does not deteriorate even in an empty shower operation. It is. In addition, the color filter obtained by the method for forming a colored image and the method for producing a color filter of the present invention using the cleaning solution is high-quality, and the array with the color filter of the present invention using the color filter. The array substrate with a color filter manufactured by the substrate manufacturing method can be suitably used for a liquid crystal display device, a sensor, a color separation device, and the like.

Claims

The scope of the claims

[1] A basic compound, an acetylene surfactant containing at least one hydroxyl group, an alkyl ether surfactant, and a phenoxyalkylene surfactant. Power selected. At least one surfactant and a naphthalene surfactant A cleaning treatment liquid characterized by containing a surfactant.

[2] The basic compound is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, potassium carbonate, sodium metasilicate and metasilicate. Potassium acid power The cleaning treatment liquid according to claim 1, which is at least one organic alkaline compound selected.

[3] The cleaning liquid according to any one of claims 1 to 2, wherein the content of the basic compound in the cleaning liquid is 0.01 to 50% by mass.

[4] Acetylene surfactant power The cleaning treatment liquid according to claims 1 to 3, which is an acetylenic diol surfactant, any of them.

[5] Phenoxyoxyalkylene surfactant power The cleaning liquid according to any one of claims 1 to 4 represented by the following structural formula (1).

[Chemical 1]

Ph——0— ^ CH CH ₂ — 0 Structural formula (1) In the structural formula (1), Ph represents a fur group. R represents a hydrogen atom or an alkyl group. n represents an integer of 1 or more.

[6] Naphthalene-based surfactant strength The cleaning treatment solution according to claims 1 to 5 represented by the following structural formula (2).

[Chemical 2]

S <¾M Structural formula (2)

1 2

Represents. M represents Na, K or H.

[7] The cleaning treatment liquid according to any one of claims 1 to 6, which is applied to an object to be treated under pressure.

[8] The cleaning treatment liquid according to claim 7, wherein the pressure of pressurization is 0.01 to 100 MPa.

[9] The cleaning treatment liquid according to any one of claims 7 to 8, wherein the pressurization is performed by at least one of brush, sponge and liquid pressure.

[10] The cleaning liquid according to any one of claims 7 to 9, wherein the object to be processed is a transfer material in which at least a photosensitive layer and an oxygen blocking layer are sequentially laminated on a substrate.

[11] The cleaning treatment solution according to any one of claims 1 to 10, which is used by diluting the diluted solution 5 to 1,000 times.

[12] A photosensitive layer forming step of forming a photosensitive layer capable of alkali development on a substrate, an exposure and developing step of exposing and developing the photosensitive layer, and the cleaning treatment according to any one of claims 1 to 11 A colored image forming method comprising at least a cleaning process step of cleaning with a liquid.

[13] As described in claim 12, the photosensitive layer is formed of a transfer material containing at least a resin having an acid value of 20 to 300, a pigment, a monomer containing a photopolymerizable unsaturated bond, and a photopolymerization initiator. Method for forming colored image.

[14] A color that includes at least a photosensitive layer forming step for forming an alkali-developable photosensitive layer on a substrate, and an exposure and developing step for exposing and developing the photosensitive layer to form a plurality of colored images on the same substrate. A method for producing a filter, further comprising a washing treatment step of washing with the washing treatment liquid according to any one of claims 1 to 11.

[15] A photosensitive layer forming step of forming an alkali developable photosensitive layer on the TFT array substrate, and an exposure and developing step of exposing and developing the photosensitive layer, and a plurality of colored images on the same TFT array substrate A method for producing an array substrate with a color filter, comprising: a cleaning process step of cleaning using the cleaning process liquid according to any one of claims 1 to 11. Production method.