JP2008129431A - Photosensitive transfer material, color filter and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer material which is low in production cost and substantially avoids occurrence of defects such as a pinhole and pattern fall-out, a color filter produced using this photosensitive transfer material, and a display device with this color filter. <P>SOLUTION: The photosensitive transfer material includes a temporary support, at least one photosensitive resin layer formed on the temporary support, and a cover film covering the photosensitive resin layer, wherein the photosensitive resin layer contains ≥10% of a pigment based on a solid content and the cover film has ring dots having a diameter of ≥10 μm in a number of 50-500 dots/m<SP>2</SP>and ring dots having a diameter of ≥300 μm in a number of ≤3 dots/m<SP>2</SP>. The color filter produced using this photosensitive transfer material and the display device with this color filter are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a color filter that is preferably used in a large-screen display device such as a photosensitive transfer material, a notebook computer, and a television monitor that are preferably used for manufacturing a color filter, and a display device having the color filter.

  The color filter is an indispensable component for a liquid crystal display (hereinafter also referred to as “liquid crystal display device”). As a method for easily producing this color filter, a resin transfer material in which a resin layer of a photosensitive resin composition is provided on a temporary support is used, the resin layer is attached to a substrate by a laminator, and a pattern is formed by exposure and development. There is a way to do it. The resin transfer material used in the above method generally has a temporary support, at least one photosensitive resin layer, and a cover film, and is transferred while peeling the cover film.

  A pinhole failure may occur in a color filter manufactured using a resin transfer material. In particular, this tendency has become prominent in resin transfer materials used for forming black images containing a large amount of pigment and RGB images having dark colors. Before development, no bubbles or the like are found in the resin layer as viewed from the substrate side, but a pinhole failure may occur after development.

In addition, the invention regarding the photosensitive element which uses a predetermined cover film for the purpose of improving laminating property etc. is disclosed (for example, refer patent document 1).
JP 2000-330291 A

  The present invention has been made in view of the above-mentioned conventional problems, and has been manufactured using a photosensitive transfer material that is low in production cost and has few occurrences of defects such as pinholes and pattern dropout, and this photosensitive transfer material. An object is to provide a color filter and a display device having the color filter.

In view of such circumstances, the present inventor has conducted extensive research, and as a result, has been able to find the number range of ring points that can achieve both the number of defects such as pinholes and pattern dropouts and the productivity of the cover film. completed.
That is, the present invention
<1> A photosensitive transfer material having at least a temporary support, at least one photosensitive resin layer formed on the temporary support, and a cover film covering the photosensitive resin layer, The photosensitive resin layer contains a pigment having a solid content ratio of 10% or more, the number of ring points having a diameter of 10 μm or more of the cover film is 50 to 500 pieces / m ² , and the number of ring points having a diameter of 300 μm or more. It is a photosensitive transfer material characterized in that it is 3 pieces / m ² or less.

  <2> The photosensitive transfer material according to <1>, which is used for producing a color filter.

  <3> A color filter produced using at least one photosensitive transfer material according to <1> or <2>.

  <4> A display device having the color filter according to <3>.

  According to the present invention, a photosensitive transfer material that is low in manufacturing cost and has few defects such as pinholes and pattern dropouts, a color filter manufactured using the photosensitive transfer material, and a display device having the color filter are provided. Can be provided.

Hereinafter, the photosensitive transfer material, the color filter, and the display device of the present invention will be described in detail.
<Photosensitive transfer material>
The photosensitive transfer material of the present invention has at least a temporary support, a photosensitive resin layer formed on the temporary support, and a cover film covering the photosensitive resin layer, and the photosensitive resin layer. Includes a pigment having a solid content ratio of 10% or more, and the cover film has 50 to 500 / m ² ring points having a diameter of 10 μm or more, and 3 / m ² ring points having a diameter of 300 μm or more. It is characterized by being ² or less.
The photosensitive transfer material of the present invention is suitably used for producing a color filter.

  In the present invention, the “ring point” refers to a point that appears as a Newton ring when the cover film is observed with a microscope.

  The softness | flexibility of this photosensitive resin layer falls that the solid content ratio of the pigment contained in the photosensitive resin layer is 10% or more. Since the portion where the ring point of the cover film exists is uneven, when the photosensitive resin layer is in contact with this portion, the film thickness of the photosensitive resin layer may be non-uniform. When a photosensitive resin layer with a non-uniform film thickness and low flexibility is laminated to a substrate, voids or the like are generated between the substrate and the photosensitive resin layer, which may cause a pinhole failure after development. is there.

  As a result of analysis, the present inventor has found that the occurrence of pinholes correlates with the lot difference of the cover film, particularly the size and number of ring points. The number of ring points decreases and the diameter decreases as the mesh size of the filter at the time of manufacturing the cover film is reduced, but there is a problem that the productivity of the cover film decreases and the cost increases as the mesh size is reduced. The present inventor has found an allowable range in which a ring point may exist in consideration of a balance between the manufacturing cost of the cover film and the frequency of occurrence of pinholes.

  In the photosensitive transfer material of the present invention, it is sufficient that at least one photosensitive resin layer is formed on the temporary support, and a plurality of photosensitive resin layers may be formed. Other resin layers may be formed. More preferably, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are formed in this order on the temporary support. The photosensitive transfer material can be produced, for example, by the steps described in paragraphs [0064] to [0066] of JP-A-2005-3861.

  Hereinafter, each element constituting the photosensitive transfer material will be described in detail.

(Temporary support)
The temporary support used for the photosensitive transfer material of the present invention is preferably flexible and does not cause significant deformation, shrinkage or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As a component used for the thermoplastic resin layer in the photosensitive transfer material, an organic polymer substance described in JP-A-5-72724 is preferable, and the Viker Vicat method (specifically, American Material Testing Method ASM It is particularly preferred that the polymer be selected from organic polymer materials having a softening point of about 80 ° C. or less as determined by ASTM D1235.

  Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
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.

(Photosensitive resin layer)
When the photosensitive resin layer in the present invention is used for forming a light-shielding portion such as a black matrix, the photosensitive black resin layer disclosed in JP-A-2005-3861 or the colored composition disclosed in JP-A-2004-240039 is used. The photosensitive resin layer can be formed in the same manner as the layer to be formed. In the case of being used for the formation of colored pixels such as RGB, the photosensitive resin layer is formed in the same manner as the layer made of the colored photosensitive resin composition described in JP-A-2006-23696 and JP-A-2006-276818. In the case of forming a structure such as a spacer, a photosensitive resin can be formed in the same manner as the layer made of the photosensitive resin composition described in JP-A-2006-276696 and JP-A-2006-64921. A layer can be formed.

(Cover film)
The photosensitive transfer material of the present invention is provided with a thin cover film so as to cover the photosensitive resin layer in order to protect it from contamination and damage during storage. The cover 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. As the cover film material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable.

The number of ring points having a diameter of 10 μm or more of the cover film in the present invention is 50 to 500 pieces / m ² , and the number of ring points having a diameter of 300 μm or more is 3 pieces / m ² or less, preferably 10 μm or more in diameter. The ring point is 50 to 400 pieces / m ² , the ring point having a diameter of 300 μm or more is 2 pieces / m ² or less, the ring point having a diameter of 10 μm or more is 50 to 300 pieces / m ² , and the diameter is 300 μm or more. The ring point is particularly preferably 1 piece / m ² or less.

  A film having a good ring point level in which the diameter and number of ring points satisfy the above range can be produced by selecting materials, optimizing a kneading method, filtering after melting the material, and the like. Here, the ring point size can be measured using, for example, an optical microscope. In the present invention, the diameter of the ring point means the maximum diameter of the ring point.

  In the present invention, the thickness of the cover film is preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 10 to 30 μm. If the thickness is 1 μm or more, the strength of the cover film is sufficient, so that the cover film is not easily broken when the cover film is bonded to the photosensitive resin layer. If the thickness is 100 μm or less, the price of the cover film does not increase, and wrinkles are unlikely to occur when the cover film is laminated.

  Such cover films are commercially available, for example, polypropylene films such as Alfan MA-410, E-200C, E-501, Shin-Etsu Film Co., Ltd. manufactured by Oji Paper Co., Ltd., PS manufactured by Teijin Limited. Examples thereof include polyethylene terephthalate films such as PS series such as −25, but are not limited thereto. Moreover, it can be easily manufactured by sandblasting a commercially available film.

  In the present invention, a polyolefin film such as a polyethylene film can be used as the cover film. A polyolefin film usually used as a cover film is produced by heat-melting raw materials, kneading, extrusion, biaxial stretching, casting, or inflation.

<Color filter>
The color filter of the present invention is produced using at least one kind of the photosensitive transfer material of the present invention. The color filter of this invention has the structure formed with the resin composition which comprises the photosensitive resin layer which concerns on this photosensitive transfer material. As a general structure, a light shielding portion such as a black matrix (hereinafter also referred to as a K image), a colored image (pixel) such as red (R), green (G), and blue (B), an overcoat layer, a resin spacer, Examples thereof include a rib material for liquid crystal alignment.

  Below, the manufacturing method of the structure which comprises the color filter using the photosensitive transfer material of this invention is described. The structure can be formed by transferring the photosensitive resin layer onto the substrate and then exposing and developing the photosensitive resin layer.

(Transfer process)
In the present invention, as a method for transferring the photosensitive resin layer onto the substrate, a photosensitive transfer material having the photosensitive resin layer on the temporary support is used, and the photosensitive resin layer is laminated on the substrate, and then the temporary support. A method of removing by removing is preferable.
Transfer (bonding) of the photosensitive resin layer to the substrate surface is generally performed by removing the cover film of the photosensitive transfer material, and then overlaying the photosensitive resin layer on the substrate surface, and applying pressure and heating. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used.

(Exposure, development process, and other processes)
After transferring the photosensitive resin layer, a pattern can be formed by exposure, development, and other processes. As an example of this step, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 can be suitably used in the present invention.

(substrate)
In the present invention, as a substrate constituting the color filter, 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 close_contact | adherence with the photosensitive resin layer favorable 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 and 500-1100 micrometers is especially preferable.

<Display device>
The display device of the present invention is not particularly limited as long as it includes the color filter of the present invention described above, and a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, etc. Is mentioned. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).

  Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  The display device of the present invention includes ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), and OCB (OpticBandNyStic). Various display modes such as (Vertical Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted. It is characterized by using the color filter as described above, and it has no display unevenness when mounted on a TV or monitor, and can have a wide color reproduction range and a high contrast ratio. It can be suitably used for a large-screen display device or the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts”, “%”, and “molecular weight” below represent “parts by mass”, “mass%”, and “weight average molecular weight”.

(Example of cover film production)
Oji Paper Co., Ltd. Alphan E-501 was observed with a microscope, and a portion of the cover film that meets the ring point conditions of the cover films A to F was selected, cut, and used.

-Cover film A-
50 / m ² ring points with a diameter of 10 μm or more, 0 / m ² ring points with a diameter of 300 μm or more
-Cover film B-
More rings point diameter 10μm is 500 / ^{m 2,} 3 or ring points or more in diameter 300 [mu] m / ^{m 2}
-Cover film C-
More rings point diameter 10μm is 400 / ^{m 2,} the ring points or more in diameter 300μm Two / ^{m 2}
-Cover film D-
300 / m ² ring points with a diameter of 10 μm or more, 1 / m ² ring points with a diameter of 300 μm or more
-Cover film E (comparative example)-
30 / m ² ring points with a diameter of 10 μm or more, 0 / m ² ring points with a diameter of 300 μm or more
-Cover film F (comparative example)-
Ring points with a diameter of 10 μm or more are 600 pieces / m ² , ring points with a diameter of 300 μm or more are 4 pieces / m ²

(Example 1)
-Production of photosensitive resin transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the following colored photosensitive resin composition B1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.2 μm was provided, and the cover film A was pressure-bonded on the photosensitive resin layer.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the blue (B) photosensitive resin layer, and the cover film are integrated is prepared, and the sample name is photosensitive. Resin transfer material B1 was obtained.

Coating liquid for thermoplastic resin layer: Formulation H1
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 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 = 90,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, 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 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: 2, 2-
Bis [4- (methacryloxypolyethoxy) phenyl] propane) 9.1 parts. 0.54 parts of the following surfactant 1

Intermediate layer coating solution: Formulation P1
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd., K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts

  The colored photosensitive resin composition B1 is first weighed in the amounts of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate listed in Table 1 and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 RPM for 10 minutes, then weigh out the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, phenothiazine as shown in Table 1. , Added in this order at a temperature of 25 ° C. (± 2 ° C.), stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM, and weighed out the surfactant 1 in the amount shown in Table 1 to a temperature of 24 ° C. (± 2 ° C.) and added at 30 RPM for 5 minutes and filtered through nylon mesh # 200.

  Of the compositions shown in Table 1, B Pigment Dispersion 1 uses “trade name: CF Blue EX3357” manufactured by Mikuni Dye Co., Ltd., and B Pigment Dispersion 2 is manufactured by Gokoku Dye Co., Ltd. “Trade name: CF Blue EX3383” was used.

Moreover, the composition of the binder 3 was as follows.
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate)
= Random copolymer with a molar ratio of 36/22/42, molecular weight 38,000) 27 parts, 73 parts propylene glycol monomethyl ether acetate

The composition of the DPHA solution was as follows.
・ Dipentaerythritol hexaacrylate (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 structure 1 30 parts ・ Methyl ethyl ketone 70 parts

-Formation of blue (B) pixels-
A 300 × 400 mm (0.12 m ² ) non-alkali glass substrate was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. After washing with pure water, a silane cup A ring solution (0.3% by mass aqueous solution of N-β (aminoethyl) 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 with a substrate preheating device and sent to the next laminator.
After the cover film of the photosensitive resin transfer material B1 is peeled off, a rubber roller temperature of 130 ° C. and a linear pressure of 100 N are applied to the substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II type)). / Cm, laminating at a conveyance speed of 2.2 m / min.
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 Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In a state where is vertically set, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, a triethanolamine developer (trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) is 12 times with pure water (1 part by weight of T-PD2 and 11 parts by weight of pure water are mixed) ) Was subjected to shower development 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. Subsequently, air was blown onto the upper surface of the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Subsequently, Na carbonate-based developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , 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 a cone type nozzle pressure of 0.15 MPa to form a photosensitive resin layer. Development was performed to obtain a patterning image.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 10 times with pure water was used. Sprayed with a shower with a cone type nozzle pressure of 0.02 MPa at 20 ° C., and further removed the residue by rubbing the image formed with a rotating brush having nylon bristles to obtain a blue (B) pixel. Thereafter, the substrate was post-exposed with an ultrahigh pressure mercury lamp at an exposure amount of 500 mJ / cm ² from both sides and then heat-treated at 220 ° C. for 15 minutes. As a result, a color filter substrate was obtained.
The shape of the obtained pattern was 300 μm in length, 100 μm in width, and 2.0 μm in height, and 1000 substrates on which similar patterns were formed were produced. The total area of the pattern portion at this time was 0.3 m ² (assuming RGB pixels).

(Examples 2-6, Comparative Examples 1-3)
In Example 1, except that the colored photosensitive resin composition B1 was changed to B2 to B4 shown in Table 1, and the cover film was changed to cover films B, C, D, E, and F having ring points shown in Table 3. Blue (B) pixels were formed by the same method as in Example 1 to obtain a color filter substrate.

(Example 7)
-Production of photosensitive transfer material for photospacer formation-
In the production of the photosensitive resin transfer material B1 of Example 1, the colored photosensitive resin composition B1 used was changed to a photospacer-forming resin composition S1 containing colloidal silica as a pigment having the following composition. Produced a photosensitive transfer material S1 for forming a photospacer by the same method as described above. The dry thickness of the photosensitive resin layer was 4.0 μm.

-Formation of photo spacers-
Using the obtained photosensitive transfer material S1 for forming a photospacer, transfer, exposure and development were carried out in the same manner as in Example 1 to produce a photospacer pattern.
Next, the substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step) to produce a substrate with a photo spacer.
The obtained spacer pattern was columnar with a diameter of 20 μm and an average height of 3.4 μm.
Further, the total area of the pattern portion at this time was 0.3 m ² (assuming RGB pixels).

(Examples 8-12, Comparative Examples 4-5)
In Example 7, the same method as in Example 1 except that the photospacer-forming resin composition S1 was changed to S2 to S3 shown in Table 2, and the cover film was changed to a cover film having ring points shown in Table 4. A substrate with a photo spacer was formed.

-Pinhole-
The color filter substrates prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were observed on the entire surface with an optical microscope (differential interference mode, 200 times), and the number of pinholes (size 30 μmφ or more) was observed. The board was judged as good or bad. Table 3 shows the number of non-defective products in 1000 color filter substrates.

Good ... 0 or more and less than 20
Bad ... 20 or more

-Number of omissions-
The substrates with spacers prepared in Examples 7 to 12 and Comparative Examples 4 to 5 were observed on the entire surface with a surface inspection machine (Takano Co., Ltd., CF inspection device LCF-3011XU) to observe the number of dropouts. Judged whether the product is good or bad. Table 4 shows the number of non-defective products in 1000 pieces of substrates with spacers.

Good ... 0 or more and less than 20
Bad ... 20 or more

-Cover film productivity-
The Ofan Paper Co., Ltd. Alphan E-501 was observed with a microscope, and when a portion of the cover film meeting the ring point condition was selected and cut, the usable portion was evaluated.
○: Most were usable.
(Triangle | delta): There was a part which cannot be used a little.
X: There was no usable part.

  The color filter substrate produced in Comparative Example 3 had a lower color purity than the color filter substrate produced in the example, and could not be used as a color filter for display devices.

(Example 13)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
In the production of the photosensitive resin transfer material B1 of Example 1, the same as described above except that the colored photosensitive resin composition B1 used was changed to colored photosensitive resin compositions K1, R1, and G1 having the following compositions. Photosensitive resin transfer materials K1, R1, and G1 were prepared by the above method.

Of the compositions shown in Table 5, the composition of K pigment dispersion 1 is as follows.
・ Carbon black (trade name: Nippon 35, 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

The composition of the binder 2 is 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 the R pigment dispersion 1 is as follows.
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF,
Ciba Specialty Chemicals Co., Ltd.) 8 parts Dispersant (compound 1) 0.8 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 8 parts propylene glycol monomethyl ether acetate 83 parts

The composition of the R pigment dispersion 2 is as follows.
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 12 parts, 70 parts propylene glycol monomethyl ether acetate

The composition of the binder 1 is as follows.
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate)
= Random copolymer with a molar ratio of 38/25/37, molecular weight 40,000) 27 parts · 73 parts propylene glycol monomethyl ether acetate

Additive 1 used was a phosphate ester special activator (Enomoto Kasei Co., Ltd., trade name: HIPLAAD ED152).
As the G pigment dispersion 1, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used.
As the Y pigment dispersion 1, “trade name: CF EX3393” manufactured by Mikuni Color Co., Ltd. was used.

-Formation of black (K) image-
A glass detergent solution adjusted to 25 ° C. is sprayed on an alkali-free glass substrate with a shower for 20 seconds while being washed with a rotating brush having nylon bristles. 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 with a substrate preheating device and sent to the next laminator.
After the cover film of the photosensitive resin transfer material K1 is peeled off, a rubber roller temperature of 130 ° C. and a linear pressure of 100 N are applied to the substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II type)). / Cm, laminating at a conveyance speed of 2.2 m / min.
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 mounted on a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In the state of being set up vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, a triethanolamine developer (trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) is 12 times with pure water (1 part by weight of T-PD2 and 11 parts by weight of pure water are mixed) ) Was subjected to shower development 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. Subsequently, air was blown onto the upper surface of the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Subsequently, Na carbonate-based developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , 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 a cone type nozzle pressure of 0.15 MPa to form a photosensitive resin layer. Development was performed to obtain a patterning image.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 10 times with pure water was used. Sprayed with a shower with a cone type nozzle pressure of 0.02 MPa at 20 ° C., and further removed the residue by rubbing the image formed with a rotating brush having nylon bristles to obtain a black (K) image. Thereafter, the substrate was post-exposed with an ultrahigh pressure mercury lamp at an exposure amount of 500 mJ / cm ² from both sides and then heat-treated at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the silane coupling solution was not used and was sent to a substrate preheating device.

-Formation of red (R) pixels-
Using the photosensitive resin transfer material R1, heat-treated red (R) pixels were obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 35 ° C. for 35 seconds.
The substrate on which the K image and the R pixel were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating apparatus.

-Formation of green (G) pixels-
Using the photosensitive resin transfer material G1, heat-treated green (G) pixels were obtained in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 34 ° C. and 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, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating apparatus.

-Formation of blue (B) pixels-
Using the photosensitive resin transfer material B1, heat-treated blue (B) pixels were obtained in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate-based developer was 36 ° C. for 40 seconds.

The substrate on which the R, G, B pixel and K images were formed was baked at 240 ° C. for 50 minutes to obtain the desired color filter.

  A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and K image (black matrix) of the color filter substrate obtained above. Next, according to Example 7, spacers were formed in the portion corresponding to the upper part of the partition wall (black matrix) on the ITO film formed above.

-Production of liquid crystal display device-
Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate, thereby producing a liquid crystal display device.

(Examples 14 to 18, Comparative Examples 6 and 7)
In Example 13, except that the photosensitive resin transfer materials K1, R1, G1, B1 and the photosensitive spacer forming photosensitive transfer material S1 used in Example 13 were changed to transfer materials using the cover film described in Table 6. A liquid crystal display device was produced by the same method as in FIG.

[appearance]
For each of the liquid crystal display devices obtained above, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
<Evaluation criteria 1>
○: Display unevenness was not recognized at all, and the appearance was good.
Δ: Display unevenness was slightly observed, but the appearance was good.
X: Display unevenness was noticeable and the appearance was poor.

  In addition, the cover film which comprises the photosensitive resin transfer material used for the comparative example 6 is inferior to the productivity as evident from the said evaluation.

Claims (4)

A photosensitive transfer material having at least a temporary support, at least one photosensitive resin layer formed on the temporary support, and a cover film covering the photosensitive resin layer,
The photosensitive resin layer includes a pigment having a solid content ratio of 10% or more, the number of ring points having a diameter of 10 μm or more of the cover film is 50 to 500 pieces / m ² , and the number of ring points having a diameter of 300 μm or more. Is a photosensitive transfer material characterized in that it is 3 pieces / m ² or less.   The photosensitive transfer material according to claim 1, wherein the photosensitive transfer material is used for producing a color filter.   A color filter produced by using at least one kind of the photosensitive transfer material according to claim 1.   A display device comprising the color filter according to claim 3.