JP5147362B2 - Photosensitive transfer material and method for producing the same, color filter and method for producing the same, and display device - Google Patents

Description

  The present invention relates to a photosensitive transfer material and a manufacturing method thereof, a color filter and a manufacturing method thereof, and a display device.

  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 photosensitive transfer material having a photosensitive resin layer provided using a photosensitive resin composition on a temporary support is used, and the photosensitive resin layer is applied to a substrate by a laminator. There is a method of forming a pattern image by pasting, exposure and development. The photosensitive resin transfer material used in the above method generally has a temporary support, a photosensitive resin layer, and a cover film, and is transferred while peeling the cover film.

An invention relating to a photosensitive element using a predetermined cover film for the purpose of improving laminating properties and the like is disclosed (for example, see Patent Document 1).
JP 2000-330291 A

  However, a pinhole failure may occur in a color filter manufactured using a photosensitive 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 when viewed from the substrate side, but a pinhole failure (hereinafter also referred to as “white spot”) may occur after development.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a photosensitive transfer material capable of suppressing the occurrence of white spots when a transferred photosensitive resin layer is developed, and a method for producing the same.
Another object of the present invention is to provide a color filter in which the occurrence of white spots is suppressed, a method for manufacturing the same, and a display device having a good display appearance.

As a result of intensive research, the present inventors have found that the degree of white spots when developing a photosensitive resin layer transferred using a photosensitive transfer material and the maximum haze of the cover film of the photosensitive transfer material are as follows. The present invention was completed by finding that there is a close relationship between the value and the range of the maximum value capable of suppressing the occurrence of white spots.
That is, specific means for solving the above-described problems are as follows.

<1> A photosensitive transfer material used in the production of a color filter , wherein a temporary support having a thickness of 85 μm to 200 μm , a photosensitive resin layer provided on the temporary support, and a maximum haze value and 3.0% or less, and the cover film covering the photosensitive resin layer, Ru having at least photosensitive transfer material der a.

< 2 > The photosensitive transfer material according to <1 >, wherein the photosensitive resin layer has a total thickness of 2 μm to 25 μm.
< 3 > The ratio of the total thickness of the photosensitive resin layer to the thickness of the temporary support [the total thickness of the photosensitive resin layer / the thickness of the temporary support] is 0.10 or more and 0.22 or less. < 2 > The photosensitive transfer material according to < 2 >.
<4> The thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and the cover film are provided in this order on the temporary support, according to any one of <1> to <3>. It is a photosensitive transfer material.
<5> The photosensitive transfer material according to any one of <1> to <4>, which is used for producing a color filter including a step of transferring the photosensitive resin layer onto a substrate having an area of 0.6 m ² or more. It is.

<6> A production method for producing a photosensitive transfer material used for producing a color filter, wherein a photosensitive resin composition is applied on a temporary support having a thickness of 85 μm or more and 200 μm or less , and dried to obtain a photosensitive resin layer And a step of covering the formed photosensitive resin layer with a cover film having a maximum haze value of 3.0% or less.

<7> The photosensitive transfer material according to any one of <1> to <5> or the photosensitive transfer material manufactured by the method for manufacturing a photosensitive transfer material according to <6> is used. This is a color filter characterized by being manufactured.
<8> The color filter according to <7>, which is manufactured through a step of transferring the photosensitive resin layer onto a substrate having an area of 0.6 m ² or more.

< 9 > The cover film is formed from the photosensitive transfer material according to any one of <1> to <5> or the photosensitive transfer material manufactured by the method for manufacturing a photosensitive transfer material according to <6>. A cover film removing step to be removed; a transfer step of transferring the photosensitive resin layer of the photosensitive transfer material from which the cover film has been removed onto the substrate; and exposing the photosensitive resin layer transferred onto the substrate. It is a manufacturing method of the color filter which has an exposure process and the image development process which develops the exposed said photosensitive resin layer.
<10> The method for producing a color filter according to <9>, wherein the area of the substrate is 0.6 m ² or more.

< 11 > A display device having the color filter according to <7> or <8> or the color filter manufactured by the method for manufacturing a color filter according to <9> or <10> .

According to the present invention, it is possible to provide a photosensitive transfer material that can suppress the occurrence of white spots when the transferred photosensitive resin layer is developed, and a method for manufacturing the same.
In addition, according to the present invention, it is possible to provide a color filter in which occurrence of white spots is suppressed, a method for manufacturing the same, and a display device having a good display appearance.

Hereinafter, the photosensitive transfer material and the manufacturing method thereof, the color filter and the manufacturing method thereof, and the display device of the present invention will be described in detail.
<Photosensitive transfer material>
The photosensitive transfer material of the present invention includes a temporary support, a photosensitive resin layer provided on the temporary support, and a cover film having a maximum haze value of 3.0% or less. And a cover film covering the layer.

When the photosensitive transfer material of the present invention has the above configuration, it is possible to suppress the occurrence of white spots when the transferred photosensitive resin layer is developed.
When the photosensitive resin layer of the photosensitive transfer material having a cover film having a maximum haze value exceeding 3.0% is transferred onto a substrate and developed, white spots increase rapidly.
The cause of this is not clear, but the cover film having a maximum haze value exceeding 3.0% has large surface unevenness, and the surface unevenness of the photosensitive resin layer covered with the cover film is large. Considered as one. When the photosensitive resin layer is laminated on the substrate, voids or the like are generated between the substrate and the photosensitive resin layer, and it is estimated that white spots are generated when the photosensitive resin layer is developed. .

In the present invention, the “haze degree” is an amount representing the turbidity (cloudiness) of the cover film, and refers to an amount represented by a ratio (%) of diffuse transmitted light to total light transmitted light.
The “haze degree” in the present invention refers to a value measured using an optical haze meter (“HGM-2DP”, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136: 2000.
In the present invention, the “maximum value of the haze degree” means the maximum value of the haze degree measured at 10 measurement points located at the intersection of a straight line that bisects the longitudinal direction and a straight line that divides the width direction into 11 equal parts. Point to.

  Hereafter, each element which comprises the photosensitive transfer material of this invention is demonstrated in detail.

(Temporary support)
The photosensitive transfer material of the present invention has a temporary support.
The temporary support is preferably flexible and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heating. 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.
Although there is no limitation in particular in the thickness of a temporary support body, 5-300 micrometers is preferable and 20-200 micrometers is more preferable.

(Thermoplastic resin layer)
The photosensitive transfer material of the present invention may have at least one thermoplastic resin layer. The thermoplastic resin layer is preferably provided between the temporary support and the photosensitive resin layer.
The component used for the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and polymer softening by the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by point measuring method is selected from organic polymer substances having a temperature of about 80 ° C. or less.

  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.

  The thickness of the thermoplastic resin layer is preferably 6 to 100 μm, and more preferably 6 to 50 μm. When the thickness of the thermoplastic resin layer is in the range of 6 to 100 μm, the unevenness can be completely absorbed even if the substrate has unevenness.

(Middle layer)
The photosensitive transfer material of the present invention may have at least one intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. The intermediate layer is preferably provided between the temporary support and the photosensitive resin layer (in the case where the thermoplastic resin layer is provided, between the thermoplastic resin layer and the photosensitive resin layer).
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. Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  The thickness of the intermediate layer is preferably 0.1 to 5.0 μm, and more preferably 0.5 to 2.0 μm. In the range of 0.1 to 5.0 μm, the oxygen blocking ability does not decrease, and it does not take too much time during development or removal of the intermediate layer.

(Photosensitive resin layer)
The photosensitive transfer material of the present invention has at least one photosensitive resin layer.
When the photosensitive resin layer is used for forming a light-shielding portion such as a black matrix, a layer made of a photosensitive black resin layer disclosed in JP-A-2005-3861 or a colored composition disclosed in JP-A-2004-240039. In the same manner as described above, a photosensitive resin layer can 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.

  The thickness of the photosensitive resin layer is preferably 0.4 to 15 μm, and more preferably 0.7 to 8 μm. If it is the range of 0.4-15 micrometers, it can have sufficient coloring performance and patterning performance.

(Cover film)
The photosensitive transfer material of the present invention is provided with a 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.

  As described above, the maximum haze value of the cover film in the present invention is 3.0% or less, but from the viewpoint of more effectively suppressing the occurrence of white spots after development, 2.5% or less is preferable, 2.0% or less is more preferable, and 1.0% or less is particularly preferable.

A film having a good haze degree can be produced by selecting a material, optimizing a kneading method, filtering after melting the material, and the like.
Specific methods for adjusting the maximum haze value of the cover film to 3.0 or less include the methods shown in the following (1) and / or (2).
(1) The haze degree is adjusted by setting the conditions for forming a film from a molten state to rapid cooling and low stretching.
(2) When the polymer is formed from a molten state and then stretched to a predetermined thickness, the degree of haze is adjusted by controlling the heating temperature and the degree of stretching.

  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. When 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.
The photosensitive transfer material can be produced, for example, by the steps described in paragraphs [0064] to [0066] of JP-A-2005-3861.

<Method for producing photosensitive transfer material>
The method for producing the photosensitive transfer material of the present invention described above is not particularly limited. For example, it can be produced by the steps described in paragraphs [0064] to [0066] of JP-A-2005-3861. it can.
As an example of the method for producing a photosensitive transfer material of the present invention, a step of applying a photosensitive resin composition on a temporary support and drying to form a photosensitive resin layer, and the formed photosensitive resin layer And a step of covering with a cover film having a maximum haze value of 3.0% or less.

Here, two or more photosensitive resin layers may be formed. Further, a thermoplastic resin layer and / or an intermediate layer (oxygen barrier layer) may be applied and formed before the formation of the photosensitive resin layer.
As a method of applying the photosensitive resin layer composition, the thermoplastic resin layer forming coating solution, and the intermediate layer forming coating solution on the temporary support, a known coating method can be used. For example, it can be formed by applying and drying these coating liquids using a coating machine such as a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, a wire bar coater, or an extruder.

The method of covering the photosensitive resin layer with the cover film is not particularly limited, but a method of overlaying the cover film on the photosensitive resin layer on the temporary support and press-bonding it can be used. For the pressure bonding, a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator capable of further improving productivity can be used.
As the pressure bonding conditions, an atmospheric temperature of 20 to 45 ° C. and a linear pressure of 1000 to 10,000 N / m are preferable.
As the cover film, a cover film having a maximum haze degree of 3.0 or less selected by the above-described haze measurement method may be used, or produced by the above-described method for adjusting the haze degree, A cover film having a maximum value of 3.0 or less may be used.

As described above, the photosensitive transfer material and the manufacturing method thereof of the present invention have been described. When the size of the substrate to which the photosensitive resin layer is transferred is large (for example, the area is 0.6 m ² or more, more preferably the area is 1.0 m ² or more. In the case of (2), the following forms are preferable from the viewpoint of more suitably maintaining the tension balance during transfer and further reducing white spots after development.
The thickness of the temporary support is preferably 85 μm or more and 200 μm or less, and more preferably 90 μm or more and 150 μm or less.
The total thickness of the transfer layer is preferably 2 μm or more and 25 μm or less, and more preferably 5 μm or more and 22 μm or less.
Here, the transfer layer refers to a layer obtained by removing the temporary support and the cover film from the photosensitive transfer material, and includes at least one photosensitive resin layer. For example, in the case where the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and the cover film are provided in this order on the temporary support, the thickness of the thermoplastic resin layer and the intermediate layer The sum of the thickness and the thickness of the photosensitive resin layer is the total thickness of the transfer layer.
The ratio of the total thickness of the transfer layer to the thickness of the temporary support [total thickness of transfer layer / thickness of the temporary support] is preferably 0.10 or more and 0.25 or less. It is more preferably 10 or more and 0.22 or less, and particularly preferably 0.12 or more and 0.22 or less.

  The photosensitive transfer material of the present invention is suitably used for producing a color filter. A method for manufacturing the color filter will be described later.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced using at least one kind of the photosensitive transfer material of the present invention. Specifically, the structure which provided the structure (pattern image) on the board | substrate using the said photosensitive transfer material is mentioned.
Since the color filter is produced using a photosensitive transfer material that is less likely to cause white spots after development, occurrence of white spots is suppressed.
Examples of the structure include 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.
In the color filter of the present invention, at least one of the structures is formed of the photosensitive transfer material of the present invention.

(substrate)
In the color filter of the present invention, as the substrate on which the structure is provided, for example, a transparent substrate is used, and a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate and the like are known. Glass plate or plastic film.
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, 500-1200 micrometers is generally preferable and 700-1100 micrometers is especially preferable.

  As an example of a method for producing a color filter using the photosensitive transfer material of the present invention, a cover film removing step for removing the cover film from the photosensitive transfer material of the present invention, and the photosensitivity from which the cover film has been removed. A transfer step of transferring the photosensitive resin layer of the transfer material onto the substrate, an exposure step of exposing the photosensitive resin layer transferred onto the substrate, and developing the exposed photosensitive resin layer to form a pattern image And a development process obtained.

(Transfer process)
The transfer step is a step of transferring the photosensitive resin layer of the photosensitive transfer material from which the cover film has been removed onto a substrate.
In this case, it is preferable to perform the method by removing the temporary support after laminating the photosensitive resin layer of the photosensitive transfer material on the substrate.
The transfer (bonding) of the photosensitive resin layer to the substrate surface is performed by stacking the photosensitive resin layer on the substrate surface, pressurizing 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 process, development process, and other processes)
As examples of the exposure step, the development step, and other steps, the methods described in paragraph numbers [0035] to [0051] of JP-A-2006-23696 can be suitably used in the present invention.

The exposure step is a step of exposing the photosensitive resin layer transferred onto the substrate.
Specifically, there is a method in which a predetermined mask is disposed above the photosensitive resin layer formed on the substrate and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer. .
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

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

The development method may be any of paddle development, shower development, shower & spin development, dip development, and the like.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower.
When a thermoplastic resin layer or an intermediate layer is provided, an alkaline solution having a low solubility of the photosensitive resin layer is sprayed by a shower before development, and the thermoplastic resin layer, the intermediate layer, etc. are removed. It is preferable to keep. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

  The manufacturing method of the color filter of this invention may have other processes, such as a post exposure process and a post-baking process.

<Display device>
The display device of the present invention includes the color filter.
Since the display device of the present invention includes the color filter with few defects in the structure that is a component, the display device is excellent in appearance.
The display device is not particularly limited, and examples thereof include liquid crystal display devices, plasma display display devices, EL display devices, display devices such as CRT display devices, and the like. 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), OCB (OpticBandNitRic). 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”.

<Selection of cover film>
About each of a plurality of cover films (Oji Paper Co., Ltd. Alphan E-501), 10 measurement points located at the intersection of a straight line that bisects the longitudinal direction and a straight line that divides the width direction into 11 equal parts The haze degree was measured.
Here, the haze degree at each measurement point was measured using an optical haze meter (“HGM-2DP”, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136: 2000.
Next, the following cover films A to D were selected from the plurality of cover films whose haze degree was measured.

-Cover film A-
The maximum haze value is 0.5%.
-Cover film B-
The maximum haze value is 1.5%.
-Cover film C-
The cover film has a maximum haze value of 2.9%.
-Cover film D-
This is a cover film having a maximum haze value of 3.2%.

[ Reference Example 1]
<Production of photosensitive resin transfer material>
On the 75-micrometer-thick polyethylene terephthalate film temporary support body, the coating liquid for thermoplastic resin layers which consists of prescription H1 shown in following Table 1 was apply | coated and dried using the slit-shaped nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the following colored photosensitive resin composition K1 was 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 1.5 μm, and a dry layer were dried on the temporary support. A photosensitive resin layer having a film thickness of 2.3 μm was provided, and the cover film A was pressure-bonded onto the photosensitive resin layer.
The pressure bonding of the cover film A was performed under the condition of 5000 N / m in a 25 ° C. atmosphere using a lamination roll.

  In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the black (K) photosensitive resin layer, and the cover film are integrated is prepared, and the sample name is photosensitive. Resin transfer material K1 was obtained.

(Prescription H1 of coating solution for thermoplastic resin layer)

  In Table 1, as the plasticizer 1, Shin-Nakamura Chemical Co., Ltd. product name: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane) was used. The composition of other components is as follows.

-Composition of polymer 1-
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. ) ··· 21 parts · Methyl ethyl ketone · · · 26 parts · Propylene glycol monomethyl ether · · · 13 parts · Methanol · · · 40 parts

-Composition of polymer 2-
・ Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.) 42 parts methyl ethyl ketone 49.5 parts propylene glycol monomethyl Ether: 8.5 parts

-Composition of surfactant 1-
・ The following structure 1 ・ ・ ・ 30 parts ・ Methyl ethyl ketone ・ ・ ・ 70 parts

(Prescription P1 of coating solution for intermediate layer)
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)... 32.2 parts ・ Polyvinylpyrrolidone (manufactured by IPS Japan Co., Ltd., K-30)
・ ・ ・ 14.9 parts ・ Distilled water ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ 429 parts

(Preparation of colored photosensitive resin composition K1)
The colored photosensitive resin composition K1 is first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3' in the amounts shown in Table 2 -Bromophenyl] -s-triazine and phenothiazine were weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. The amount of the surfactant 1 described in 1) is weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200. It was obtained by

  Of the photosensitive resin composition K1 shown in Table 2, the K pigment dispersion 1 used was trade name “FDK-001” manufactured by Tokyo Ink Co., Ltd. The composition of the K pigment dispersion 1 is as follows.

-Composition of K pigment dispersion 1-
・ 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 other components in Table 2 is as follows.
-Composition of binder 1-
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts propylene glycol monomethyl ether acetate 73 parts

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

<Production of substrate with black matrix>
A 300 mm x 400 mm (0.12 m ² ) non-alkali glass substrate was washed with a rotating brush having nylon hair 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 K1 is peeled off, a laminator (manufactured by Hitachi Industries (Lamic II type)) is used, and the upper rubber roller temperature is 95 ° C. and the lower rubber is heated to 120 ° C. Lamination was performed at a roller temperature of 120 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.5 m / min.
After the temporary support is peeled off at the interface with the thermoplastic resin layer, the distance between the substrate and the mask is set to 100 μm using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. Pattern exposure was performed at an amount of 95 mJ / cm ² .

Next, triethanolamine developer (trade name: T-PD2, manufactured by FUJIFILM Corporation) 12 times with pure water (1 part by weight of T-PD2 and 11 parts by weight of pure water are mixed) The liquid was diluted with shower at 30 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the substrate, 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 Film Co., Ltd., diluted 5 times with pure water) and shower developed at 32 ° C. for 60 seconds (cone nozzle pressure 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-SD3 manufactured by FUJIFILM Corporation) diluted 10 times with pure water and used at 35 ° C. It was sprayed with a shower at a cone type nozzle pressure of 0.02 MPa for 50 seconds, and further, a residue was removed by rubbing the formed image using a rotating brush having nylon bristles.
Then, it washed with 10.0MPa with the high-pressure jet water washing apparatus by Asahi Sunac Co., Ltd., and obtained the black matrix (BM) pattern.
Thereafter, the substrate was post-exposed with an ultrahigh pressure mercury lamp at an exposure amount of 2000 mJ / cm ² from both sides and then heat treated at 240 ° C. for 100 minutes.
This obtained the board | substrate with a black matrix.

<Evaluation>
The following evaluation was performed on the substrate with the black matrix. The evaluation results are shown in Table 3.
~ Evaluation of white spots ~
The black matrix was observed with an optical microscope (magnification 200 times), and the number of white spots after development per unit area was measured. If it is 8.0 pieces / cm ² or less, it is within a practically allowable range.

-Evaluation of bubbles during lamination-
After laminating the photosensitive resin transfer material on the substrate and before peeling off the temporary support, a transmission surface inspection was performed with a planar light source having an illuminance of 15000 cd / cm ² .
The substrate was divided into virtual areas of 30 mm × 40 mm × 100 squares, and the way of entering bubbles was determined by ranking as follows.
~Judgment criteria~
A ... Bubble area 5/100 or less B ... Bubble area 6/100 to 20/100
C ... Bubble area 21 / 100-40 / 100
D: Bubble area 41/100 to 60/100
E ... Bubble area 61/100 or more

[ Reference Examples 2-3, Comparative Example 1]
Reference Example 1, the cover film A, the cover film B, except for changing the cover film C, or the cover film D, in the same manner as in Reference Example 1 to prepare a photosensitive resin transfer material, in the same manner as in Reference Example 1 A black matrix (BM) pattern was formed to obtain a substrate with a black matrix. The obtained black matrix was evaluated in the same manner as in Reference Example 1. The evaluation results are shown in Table 3.

[ Reference Example 4]
In Reference Example 1, a photosensitive resin transfer material was prepared in the same manner as in Reference Example 1 except that the thermoplastic resin layer was not provided, and a black matrix (BM) pattern was formed in the same manner as in Reference Example 1 to obtain a black matrix. An attached substrate was obtained. The obtained black matrix was evaluated in the same manner as in Reference Example 1. The evaluation results are shown in Table 3.

As shown in Table 3, in Reference Examples 1 to 3 using cover films having a haze degree of 3.0% or less, the number of white spots was greatly reduced. Moreover, in these reference examples 1-3, the bubble at the time of lamination was also reduced. In addition, good results were obtained in Reference Example 4 in which the thermoplastic resin layer was not provided.

[ Reference Example 5]
<Production of color filter (Production by lamination of photosensitive resin transfer material)>
(Production of photosensitive resin transfer materials R1, G1, B1, and S1)
In the production of the photosensitive resin transfer material K1 of Reference Example 1, the formulation H1 of the coating solution for the thermoplastic resin layer was changed to the formulation H2 described in Table 4 below, and the colored photosensitive resin composition K1 was changed to Table 5 below. Photosensitive resin transfer materials R1, G1, B1, and S1 were produced in the same manner as in Reference Example 1 except that the colored photosensitive resin compositions R1, G1, B1, and S1 having the described composition were changed.

In Table 5, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used as the G pigment dispersion 1. As the Y pigment dispersion 1, “trade name: CF EX3393” manufactured by Mikuni Color Co., Ltd. was used. 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 EX3387” manufactured by Mikuni Color Co., Ltd. was used. Additive 1 used was a phosphate ester special activator (Enomoto Kasei Co., Ltd., trade name: HIPLAAD ED152). Solsperse 20000 is a dispersant manufactured by Nippon Lubrizol Corporation.
The detailed composition of other components is as follows.

-Composition of R pigment dispersion 1-
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF, manufactured by 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

-Composition of R pigment dispersion 2-
・ C. I. P. R. 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 18 parts-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 30,000)・ 12 parts ・ Propylene glycol monomethyl ether acetate 70 parts

~ Binder 2 composition ~
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, molecular weight 40,000) ・ ・ ・ 27 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ 73 parts

-Composition of binder 3-
・ Polymer (benzyl methacrylate / methacrylic acid / = 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts propylene glycol monomethyl ether acetate 73 parts

-Composition of binder 4-
-Polymer (methacrylic acid / allyl methacrylate = 20/80 molar ratio random copolymer, molecular weight 36,000) ... 100 parts

The product name “MIBKst” manufactured by Nissan Chemical Industries, Ltd. was used as the colloidal silica dispersion. The composition is as follows.
-Composition of colloidal silica dispersion-
・ Colloidal silica: 30 parts ・ Methyl isobutyl ketone: 70 parts

(Formation of red (R) pixels)
The substrate with the black matrix obtained in Reference Example 1 was washed with a brush, further washed with pure water, and then sent to a substrate preheating device without using a silane coupling agent. Furthermore, it heated at 100 degreeC for 2 minute (s) with this board | substrate preheating apparatus, and sent to the above-mentioned laminator.
The conditions for cleaning with a brush and the conditions for pure water shower cleaning are the same as those for the alkali-free glass substrate in Reference Example 1.
Next, in the same process as the photosensitive resin transfer material K1 in Reference Example 1 using the photosensitive resin transfer material R1, heat treated red is applied to the black matrix forming surface side of the substrate with the black matrix after heating. (R) Pixels were formed to obtain a “substrate with black matrix and R pixels”. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 35 ° C. for 35 seconds.
Next, the obtained “substrate with black matrix and R pixel” 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. . Furthermore, it heated at 100 degreeC for 2 minute (s) with this board | substrate preheating apparatus, and sent to the laminator.

(Formation of green (G) pixels)
Next, the photosensitive resin transfer material G1 is used on the “black matrix and R pixel-attached substrate” after the heating, and in the same process as the photosensitive resin transfer material R1, the R pixel formation surface side of the substrate Then, heat-treated green (G) pixels were formed to obtain a “substrate with black matrix, R pixel, and G pixel”. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 34 ° C. and 45 seconds.
Next, the obtained “substrate with black matrix, R pixel, and G pixel” is again cleaned with a brush as described above, and after pure water shower cleaning, the substrate is preheated without using a silane coupling liquid. Sent to the device. Furthermore, it heated at 100 degreeC for 2 minute (s) with this board | substrate preheating apparatus, and sent to the laminator.

(Formation of blue (B) pixels)
Next, on the “substrate with black matrix, R pixel, and G pixel” after the heating, the photosensitive resin transfer material B1 is used, and in the same process as the photosensitive resin transfer material R1, the G of the substrate is changed. Blue (B) pixels that have been heat-treated are formed on the pixel formation surface side to obtain a “substrate with black matrix, R pixel, G pixel, and B pixel”. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate-based developer was 36 ° C. for 40 seconds.

  The obtained “substrate with black matrix, R pixel, G pixel, and B pixel” was baked at 240 ° C. for 50 minutes to obtain a target 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, using the photosensitive resin transfer material S1, a heat-treated spacer is formed in a portion corresponding to the upper part of the partition wall (black matrix) on the ITO film formed in the same process as the photosensitive resin transfer material B1. Thus, a color filter substrate with a spacer was obtained.

<Production of liquid crystal display device>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate with a spacer, 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.

<Evaluation>
(Appearance of display)
For each of the liquid crystal display devices obtained above, as an evaluation of the appearance of the display, the black display when a black test signal is input is visually observed, and the number of bright spot defects is evaluated according to the following evaluation criteria. did. A, B, or C is practically acceptable.
~Evaluation criteria~
A: The number of bright spot defects was less than 2 / m ² .
B: The number of bright spot defects was 2 / m ² or more and less than 4 / m ² .
C: Bright spot defects were 4 / m ² or more and less than 6 / m ² .
D: The number of bright spot defects was 6 / m ² or more and less than 8 / m ² .
E: The number of bright spot defects was 8 / m ² or more.

[ Reference Examples 6-7, Comparative Example 2]
Reference Example 5, the black matrix-bearing substrate obtained in Reference Example 1, Reference Examples 2-3, except for changing the black matrix with the substrate obtained in Comparative Example 1 and color filter in the same manner as in Reference Example 5 A liquid crystal display device was produced and evaluated in the same manner as in Reference Example 5. The evaluation results are shown in Table 6.

As shown in Table 6, in the liquid crystal display devices of Reference Examples 5 to 7 manufactured using a photosensitive transfer material having a cover film having a maximum haze value of 3.0% or less, the appearance of display is Good or practically acceptable.

Example 8
<Manufacture of substrate with image using large substrate>
In the preparation of the black matrix with a substrate of Reference Example 1, to change the size of the non-alkali glass substrate from 300mm × 400mm (0.12m ²⁾ to 1100mm × 1300mm (1.43m ^2), temporary photosensitive resin transfer material K1 A substrate with a black matrix (substrate with an image) was produced in the same manner as in Reference Example 1 except that the thickness of the support was changed to 100 μm.

<Evaluation>
(Evaluation of white spots)
Evaluation similar to the evaluation of white spots in Reference Example 1 was performed.
The formed image (black matrix) was observed with an optical microscope (200 times magnification), the number of white spots per unit area was measured, and evaluated according to the following criteria. A, B, and C are practically acceptable.
~Judgment criteria~
A: White spots after development were less than 2 pieces / cm ² .
B: White spots after development were 2 pieces / cm ² or more and less than 5 pieces / cm ² .
C: White spots after development were 5 pieces / cm ² or more and less than 8 pieces / cm ² .
D: White spots after development were 8 pieces / cm ² or more and less than 11 pieces / cm ² .
E: White spots after development were 11 pieces / cm ² or more.

(Roll dirt)
The stain on the transfer roll after processing 800 sheets in the laminator was visually evaluated. The case where there was no dirt was designated as “A”, the case where dirt was present but within the practically acceptable range was designated as “B”, and the case where the dirt was severely exceeded the practically acceptable range was designated as “C”.

(productivity)
From the viewpoint of white spots and roll stains, “A” is a condition where productivity is particularly excellent, “B” when productivity is inferior to “A” but within a practically acceptable range, and productivity is poor. A case exceeding the allowable range was judged as “C”.
~Judgment criteria~
A: Among white spots and roll dirt, one is rank A and the other is rank B or higher. B: Among white spots and roll dirt, one is rank B or higher and the other is rank C or higher. What is not said A rank C: Other than the above In addition, in the above, "C rank or more" represents A, B, or C, and "B rank or more" represents A or B.

[Examples 9 to 14, Reference Examples 15 to 17]
In Example 8, images were attached in the same manner as in Example 8 except that the thickness of the temporary support and the thickness of the transfer layer (thermoplastic resin layer, intermediate layer, photosensitive resin layer) were changed as shown in Table 7 below. A substrate was prepared and evaluated in the same manner as in Example 8.

[Comparative Example 2]
In Example 8, except that the cover film A was changed to the cover film D, a substrate with an image was produced in the same manner as in Example 8, and the same evaluation as in Example 8 was performed.
The evaluation results of Examples 8 to 14, Reference Examples 15 to 17, and Comparative Example 2 are shown in Table 7.

As shown in Table 7, in the substrates with images of Examples 8 to 14 and Reference Examples 15 to 17 produced using a photosensitive transfer material having a cover film having a maximum haze value of 3.0% or less The transfer white spots were all good or practically acceptable. In particular, in Examples 8 to 14 using the photosensitive transfer material having a temporary support thickness of 85 μm or more and 200 μm or less, white spots were particularly small, and particularly good results were obtained.

Claims (11)

A photosensitive transfer material used in the manufacture of color filters,
A temporary support having a thickness of 85 μm or more and 200 μm or less, a photosensitive resin layer provided on the temporary support, a cover film having a maximum haze value of 3.0% or less and covering the photosensitive resin layer; A photosensitive transfer material having at least The photosensitive transfer material according to claim 1, wherein the total thickness of the transfer layer excluding the temporary support and the cover film is 2 μm or more and 25 μm or less. The ratio of the total thickness of the transfer layer to the thickness of the temporary support (total thickness of transfer layer / thickness of the temporary support) is 0.10 or more and 0.22 or less. 2. The photosensitive transfer material according to 2. The photosensitive transfer according to any one of claims 1 to 3, wherein a thermoplastic resin layer, an intermediate layer, the photosensitive resin layer, and the cover film are provided in this order on the temporary support. material. The photosensitive resin layer has an area of 0.6 m. ² The photosensitive transfer material of any one of Claims 1-4 used for manufacture of the color filter including the process of transferring on the above board | substrate. A manufacturing method for manufacturing a photosensitive transfer material used for manufacturing a color filter,
A step of applying a photosensitive resin composition on a temporary support having a thickness of 85 μm or more and 200 μm or less and drying to form a photosensitive resin layer; and forming the photosensitive resin layer with a maximum haze value of 3 And a step of covering with a cover film that is equal to or less than 0%.   The photosensitive transfer material according to any one of claims 1 to 5 or the photosensitive transfer material manufactured by the method for manufacturing a photosensitive transfer material according to claim 6 is used. A color filter characterized by that. The photosensitive resin layer has an area of 0.6 m. ² The color filter according to claim 7, wherein the color filter is manufactured through a transfer process onto the substrate. The cover which removes the said cover film from the photosensitive transfer material of any one of Claims 1-5, or the photosensitive transfer material manufactured by the manufacturing method of the photosensitive transfer material of Claim 6. A film removal step;
A transfer step of transferring the photosensitive resin layer of the photosensitive transfer material from which the cover film has been removed onto a substrate;
An exposure step of exposing the photosensitive resin layer transferred onto the substrate;
A development step of developing the exposed photosensitive resin layer.   The area of the substrate is 0.6m ² It is the above, The manufacturing method of the color filter of Claim 9. A display device comprising the color filter according to claim 7 or 8 , or the color filter manufactured by the method for manufacturing a color filter according to claim 9 or 10 .