JP2008009030A - Photosensitive transfer material, laminate and method for producing the same, substrate for liquid crystal display device, liquid crystal display element, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer material which has good conveyability particularly under a hot condition and suppresses the occurrence of density unevenness and distortion of a transferred image due to faulty conveyance, a laminate produced using the photosensitive transfer material and a method for producing the same, a substrate for a liquid crystal display device capable of displaying a high-quality image, a liquid crystal display element and a liquid crystal display device. <P>SOLUTION: The photosensitive transfer material has at least a photosensitive resin layer and a thermoplastic resin layer on one surface of a temporary support, wherein the other surface of the temporary support has a surface roughness (Spa) of 0.015-0.090 μm and expression (1): (d1/η1)/(d2/η2)>0.8 is satisfied. In the formula (1), η1 is the melt viscosity of the thermoplastic resin at 110°C; η2 is the melt viscosity of the photosensitive resin layer at 110°C; d1 is the thickness of the thermoplastic resin layer; and d2 is the thickness of the photosensitive resin layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a photosensitive transfer suitable for forming pixels (for example, R, G, B, etc.), a black matrix, and a structure (for example, a spacer that is disposed on a substrate and holds a predetermined gap) constituting a liquid crystal display device. The present invention relates to a material, and a laminate, a substrate for a liquid crystal display device, and a liquid crystal display device manufactured with the photosensitive transfer material, and particularly suitable for an ODF (One Drop Fill) method that is becoming a mainstream method for manufacturing a liquid crystal display device in recent years. The present invention relates to a photosensitive transfer material, a substrate for a liquid crystal display device and a liquid crystal display device which are made of the photosensitive transfer material and enable high-quality image display.

  Conventionally, liquid crystal display devices are widely used for display devices that display high-quality images. In general, a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a color filter substrate having R, G, B pixels and a black matrix and a TFT substrate. That is, since maintaining the thickness of the liquid crystal layer uniformly determines the image quality, a spacer for keeping the thickness of the liquid crystal layer constant is provided.

  A transfer material useful for the production of various recording elements such as a color filter has a transfer layer on a temporary support, and is used as a transfer medium by being transported to a substrate as a transfer medium. In general, a method of transferring the transfer layer from the temporary support to the substrate is generally used after the substrate is adhered to the substrate.

However, the transfer properties of the conventional transfer material are not sufficient, and the accuracy of the pixels, the black matrix, and the structure is not sufficient, and density unevenness and distortion of the transferred image occur.
Also, from the viewpoint of the process, when a transfer material is poorly conveyed, uniform contact with the transfer medium cannot be obtained, and the same trouble occurs.
In particular, in order to complete the lamination, it is necessary to heat the transfer material in advance and transport the transfer material at a high temperature. Degradation is likely to occur.

In order to improve the transportability of the transfer material, a technique for defining the moisture content and dry weight of the transfer layer has been proposed (see, for example, Patent Document 1). As another method, a method of adding a silicone compound to the transfer layer is described (for example, see Patent Document 2). By these methods, the surface properties of the transfer layer are improved, and a certain degree of improvement in transportability is observed. However, these methods are made by paying attention to the characteristics of the transfer surface, and a sufficient effect cannot be obtained when the back surface is conveyed in contact with the roller. In particular, in the former case, when transported at a high temperature, there is a concern that the moisture content in the transfer layer changes due to heat and a desired effect cannot be obtained.
JP 2001-80224 A Japanese Patent Laid-Open No. 11-58999

The object of the present invention, which was made in consideration of the above-mentioned problems, is a photosensitivity in which the conveyance property, particularly the conveyance property under high temperature conditions, is good, and the density unevenness and distortion of the transferred image due to the conveyance failure are suppressed. It is an object of the present invention to provide a transfer material, a laminate produced using the photosensitive transfer material, and a method for producing the same, and to achieve the object.
Another object of the present invention is to provide a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal display device capable of displaying a high-quality image.

Means for solving the above-mentioned problems are as follows.
<1> A photosensitive transfer material having at least a photosensitive resin layer and a thermoplastic resin layer for assisting transfer of the photosensitive resin layer on one surface of a temporary support,
The surface of the surface opposite to the side having the photosensitive resin layer of the temporary support (Spa) is 0.015 to 0.090 μm, the layer thickness of the thermoplastic resin layer, and the photosensitive property The photosensitive transfer material characterized in that the layer thickness of the resin layer, the melt viscosity η1 of the thermoplastic resin layer at 110 ° C., and the melt viscosity η2 of the photosensitive resin layer at 110 ° C. satisfy the following formula (1): It is.
(D1 / η1) / (d2 / η2)> 0.8 Formula (1)
[In the formula (1), η1: melt viscosity at 110 ° C. of the thermoplastic resin layer, η2: melt viscosity at 110 ° C. of the photosensitive resin layer, d1: layer thickness of the thermoplastic resin layer, d2: of the photosensitive resin layer Layer thickness. ]

<2> The melt viscosity η1 at 110 ° C. of the thermoplastic resin layer is 200 to 3000 Pa · s, and the melt viscosity η2 at 110 ° C. of the photosensitive resin layer is 350 Pa · s to 180000 Pa · s, and The photosensitive transfer material according to <1>, wherein the thermoplastic resin layer has a thickness of 2 to 50 μm.

<3> The photosensitive transfer material according to <1> or <2>, wherein the photosensitive resin layer contains a filler.

<4> The photosensitive transfer material according to <3>, wherein the filler is an extender pigment or a pigment.

<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the photosensitive resin layer has a thickness of 1 μm to 10 μm.

<6> The photosensitive transfer material according to any one of <1> to <5>, wherein the thermoplastic resin layer includes a polymer and a plasticizer.

<7> The photosensitive transfer material according to any one of <1> to <6> is transferred to a substrate, and is formed by performing at least one exposure, one development, and at least one baking. It is the manufacturing method of the laminated body characterized by the above-mentioned.

<8> The method for producing a laminate according to <7>, wherein the laminate is provided with a spacer on a substrate.

<9> The method for producing a laminate according to <7>, wherein the laminate is provided with a pixel on a substrate.

<10> A laminate produced by the laminate production method according to <7>.

<11> A substrate for a liquid crystal display device comprising the laminate according to <10>.

<12> A liquid crystal display element comprising the substrate for a liquid crystal display device according to <11>.

<13> A liquid crystal display device comprising the liquid crystal display element according to <12>.

According to the present invention, there is provided a photosensitive transfer material that has good transportability, particularly transportability under high-temperature conditions, and that suppresses density unevenness and distortion of a transferred image due to poor transport, and the photosensitive transfer material. The laminated body produced using it and its manufacturing method can be provided.
In addition, according to the present invention, it is possible to provide a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal display device that can display a high-quality image.

<Photosensitive transfer material>
The photosensitive transfer material of the present invention is a photosensitive transfer material having at least a photosensitive resin layer and a thermoplastic resin layer for assisting transfer of the photosensitive resin layer on one surface of a temporary support, The surface roughness (Spa) of the surface opposite to the side having the photosensitive resin layer of the support is 0.015 to 0.090 μm, the layer thickness of the thermoplastic resin layer, and the photosensitive resin layer The melt viscosity η1 of the thermoplastic resin layer at 110 ° C. and the melt viscosity η2 of the photosensitive resin layer at 110 ° C. satisfy the following formula (1).
(D1 / η1) / (d2 / η2)> 0.8 Formula (1)
[In the formula (1), η1: melt viscosity at 110 ° C. of the thermoplastic resin layer, η2: melt viscosity at 110 ° C. of the photosensitive resin layer, d1: layer thickness of the thermoplastic resin layer, d2: of the photosensitive resin layer Layer thickness. ]
Moreover, you may have other layers, such as an intermediate | middle layer, between a thermoplastic resin layer and the photosensitive resin layer as needed.
First, (1) the surface roughness (Spa) of the back surface and (2) formula (1) in the photosensitive transfer material of the present invention will be described.

(1) Back surface roughness (Spa)
In the photosensitive transfer material of the present invention, as described above, the surface roughness (SPa) of the back surface is defined as 0.015 to 0.090 μm, preferably 0.020 to 0.070 μm. More preferably, it is 0.025-0.040 micrometer. When the surface roughness (SPa) is within a preferable range, high-speed lamination can be performed, and no wrinkles are generated in the heating roller portion, and a good image can be obtained.

In the present invention, examples of the means for controlling the surface roughness (Spa) include a means for adding fine particles such as silica, tin dioxide, zirconium oxide, and titanium oxide to the coating layer serving as the back surface.
As the silica, either natural silica or synthetic silica (dry silica and wet silica) can be used, but synthetic silica is preferred from the viewpoint of uniformity of particle diameter. Also, so-called colloidal silica can be preferably used.
Preferred silicas that can be used in the present invention include, for example, Seahoster KE-E20, KE-E30, KE-P30 (manufactured by Nippon Shokubai Co., Ltd.), Snotex XL, YL, ZL (manufactured by Nissan Chemical Co., Ltd.). The transfer material described in paragraphs [0007] to [0032] of JP-A-2006-48024 can be referred to.

As the tin oxide, tin (IV) oxide having a SnO ₂ composition is preferable. Moreover, what doped antimony etc. has electroconductivity, and since the surface resistivity of a laminated | multilayer film can be reduced and adhesion of refuse can be prevented, it is preferable. Such tin oxide fine particles are commercially available such as FS-10D, SN-38F, SN-88F, SN-100F, TDL-S, and TDL-1 (all antimony-doped tin oxide fine particles manufactured by Ishihara Sangyo Co., Ltd.). Fine particles can also be used.

Zirconium oxide has a composition of ZrO ₂ , and for example, NZS-20A, NZS-30A (both manufactured by Nissan Chemical Co., Ltd.) and the like can be used.
As the titanium oxide, titanium (IV) oxide having a composition of TiO ₂ is preferable. Titanium oxide may be either a rutile type or an anatase type. Moreover, the surface treatment may be performed. As titanium oxide, for example, Idemitsu titania IT-S, IT-O, IT-W (all manufactured by Idemitsu Kosan Co., Ltd.) and the like can be used.

  The surface roughness (Spa) can also be controlled by the shape of fine particles such as silica, tin dioxide, zirconium oxide, and titanium oxide, and the thickness of the coating layer to which the fine particles are added.

  The surface roughness (Spa) can be measured with a known surface roughness meter, for example, using a three-dimensional surface roughness meter Surfcom 575A (manufactured by Tokyo Seimitsu Co., Ltd.). In addition, it is preferable that the surface roughness of the back surface falls within a preferable range of the present invention under the conditions of a measurement magnification of 20000 times and a cutoff wavelength of 0.08 mm using the measuring instrument.

  In addition to the layer having a great influence on the surface roughness, the back surface is provided with a protective layer, a conductive layer, an undercoat layer and the like described in paragraph numbers [0017] to [0022] of JP-A-2006-48024. Also good.

(2) Formula (1) In the present invention, it is essential that the thermoplastic resin layer and the photosensitive resin layer have a layer thickness and a melt viscosity at 110 ° C. satisfy the formula (1). ) Is preferable, and it is more preferable that the following formula (3) is satisfied.
(D1 / η1) / (d2 / η2)> 0.8 Formula (1)
500> (d1 / η1) / (d2 / η2)> 0.9 Formula (2)
300> (d1 / η1) / (d2 / η2)> 1.0 (3)

  The formula (1) is a conditional formula regarding the layer thickness of the thermoplastic resin layer and the photosensitive resin layer and the melt viscosity at 110 ° C., and the thickness of the photosensitive resin layer changes when the formula (1) is satisfied. Without being transferred to the substrate. If the lower limit of the expression (1) is not reached, a portion where the thickness of the photosensitive resin layer to be transferred becomes thinner than a set value is generated due to the unevenness of the substrate, and the height variation of the spacer becomes large. .

  In order to make the layer thicknesses of the thermoplastic resin layer and the photosensitive resin layer within the above preferable ranges, it can be achieved by adjusting the solid content concentration of the thermoplastic resin layer and the photosensitive resin layer coating solution. .

  To bring the melt viscosity at 110 ° C. of the thermoplastic resin layer and the photosensitive resin layer into the above preferred range, the type and content of monomers or plasticizers contained in the thermoplastic resin layer and the photosensitive resin layer, This can be achieved by adjusting the type and molecular weight of the binder, the type and content of the pigment, and the like.

  The layer thickness of the photosensitive resin layer provided in the photosensitive transfer material of the present invention is preferably 1 μm or more and 10 μm or less from the viewpoint of securing transferability and spacer height uniformity. The thickness is more preferably 1.5 μm or more and 8 μm or less, and particularly preferably 2 μm or more and 6 μm or less.

  In the present invention, the melt viscosity η1 at 110 ° C. of the thermoplastic resin layer is 200 to 3000 Pa · s, and the melt viscosity η2 at 110 ° C. of the photosensitive resin layer is 350 Pa · s to 180,000 Pa · s, and The thermoplastic resin layer preferably has a layer thickness of 2 to 50 μm.

  Hereinafter, the photosensitive transfer material of the present invention will be described in detail.

-Alkali-soluble thermoplastic resin layer-
The photosensitive transfer material of the present invention has at least one alkali-soluble thermoplastic resin layer. The alkali-soluble thermoplastic resin layer (hereinafter, also simply referred to as “thermoplastic resin layer”) enables alkali development, and prevents the transferred material from being contaminated by the thermoplastic resin layer itself protruding during transfer. Therefore, it is necessary to be alkali-soluble, and when transferring the photosensitive resin layer, which will be described later, onto the transfer target, transfer defects caused by unevenness on the transfer target are effectively prevented. It is a layer that has a function as a cushioning material that can be deformed in accordance with the unevenness on the transferred material when the photosensitive transfer material is heated and adhered to the transferred material.

  In the present invention, the layer thickness of the alkali-soluble thermoplastic resin layer is set to satisfy the above formula (1) (or formula (2), formula (3)), but is 2 to 50 μm. It is preferable that it is 3-30 micrometers.

  The thermoplastic resin layer can be configured using at least an alkali-soluble thermoplastic resin, and other components can be appropriately used as necessary. The alkali-soluble thermoplastic resin is not particularly limited and may be appropriately selected. However, those having a substantial softening point of 80 ° C. or less are preferable.

  Examples of the resin contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Saponified product such as saponified product with acrylic ester copolymer, poly (meth) acrylic acid ester, and saponified product such as (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. It is preferable that there is at least one. In addition, use organic polymers soluble in alkaline aqueous solutions from the "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). You can also. These may be used individually by 1 type and may use 2 or more types together. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. In the present invention, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.

  Among the resins contained in the alkali-soluble thermoplastic resin layer, the weight average molecular weight is in the range of 50,000 to 500,000 (Tg = 0 to 140 ° C.), more preferably the weight average molecular weight is 60,000 to 200,000 (Tg = 30 to 110 ° C.). Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-1444615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64- No. 5551, JP-A-64-155550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340 Examples of the resin soluble in the alkaline aqueous solution described in 1). Particularly preferred is a methacrylic acid / 2 monoethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

  Of the various resins described above, the weight average molecular weight is preferably in the range of 3,000 to 30,000 (Tg = 30 to 170 ° C.), and more preferably the weight average molecular weight is 4,000 to 20,000 (Tg = 60 to 140). In the range of ° C.). These preferred specific examples can be selected from those described in the above patent specifications, and particularly preferably, styrene described in JP-B-55-38961 and JP-A-5-241340. / (Meth) acrylic acid copolymer.

  In addition to the thermoplastic resin, the alkali-soluble thermoplastic resin layer has various components within the range where the softening point does not substantially exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support as other components. A polymer, a supercooling substance, an adhesion improving agent, a surfactant, a release agent, and the like can be added. By these, Tg can be adjusted. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono (meth) Addition reaction product with acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products of bisphenol A and polyethylene glycol mono (meth) acrylate. The amount of the plasticizer in the alkali-soluble thermoplastic resin layer is generally 200% by mass or less and preferably in the range of 20 to 100% by mass with respect to the thermoplastic resin.

  The surfactant can be used as long as it is mixed with the thermoplastic resin of the present invention. Preferred surfactants used in the present invention include JP 2003-337424 A [0015] to [0024], JP 2003-177522 A [0012] to [0017], and JP 2003-177523 A [0012]. ] To [0015], JP2003-177521A [0010] to [0013], JP2003-177519A [0010] to [0013], JP2003-177520A [0012] to [0015] The surfactants disclosed in JP-A-11-133600, [0034] to [0035], and JP-A-6-16684, are preferred. In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorine-based surfactant is most preferable.

  When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. If the number of fluorine atoms is too large, it is not preferable in that the solubility in an ordinary solvent not containing fluorine is lowered. When the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.

  As a particularly preferred surfactant, a monomer represented by the following general formula (a) and general formula (b) is included, and the mass ratio of the general formula (a) / general formula (b) is 20/80 to 60 / The thing containing 40 copolymers is mentioned.

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 18, m represents an integer of 2 to 14. p and q represent integers of 0 to 18 but are not included when p and q are simultaneously 0.)
Specific examples of the surfactant are described in Table 1 of paragraph No. [0068] of JP-A No. 2003-337424.

  Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F-780-F, F171, F173 , F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), or the like, or And silicon-based surfactants. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant.

In the present invention, the melt viscosity η1 of the thermoplastic resin layer is set so as to satisfy the above formula (1) (or formula (2), formula (3)), and is 200 to 3000 Pa · s. Preferably, the pressure is 300 to 2500 Pa · s, more preferably 500 to 2000 Pa · s.
When the melt viscosity η1 of the thermoplastic resin layer is less than 200 Pa · s at 110 ° C., the thermoplastic resin layer may protrude during transfer, and the heat roll of the laminate may be soiled. There is a risk that the cushioning property is insufficient and it is difficult to follow the unevenness on the substrate.

  Means for adjusting the melt viscosity η1 of the thermoplastic resin layer to the above range include a method for adjusting the content of the low molecular weight polymer in the polymer constituting the thermoplastic resin layer and the content of the plasticizer, etc. There is. The content ratio of the high molecular polymer to the low molecular weight polymer in the polymer constituting the thermoplastic resin layer is preferably 10/90 or more and less than 45/55, more preferably 12/88 or more and less than 40/60, and more preferably 15/85 or more and 38 Most preferred is less than / 62. If the content ratio is less than 10/90, the peelability may decrease, and if it is 45/55 or more, the cushioning property may decrease. Here, the low molecular weight polymer means a polymer having a weight average molecular weight of 3,000 or more and less than 10,000.

  The amount of the plasticizer added is preferably 28 to 43%, more preferably 30 to 40%, and particularly preferably 32 to 38% based on the solid content of the binder and the plasticizer contained in the thermoplastic resin layer. If it is less than 28%, the cushioning property may be deteriorated, and if it exceeds 43%, the thermoplastic resin layer may protrude during transfer, and the heat roll of the laminate may be soiled.

-Intermediate layer-
The photosensitive transfer material of the present invention may have at least one intermediate layer. An intermediate | middle layer is provided on the said thermoplastic resin layer provided on the temporary support body, Comprising: Between this thermoplastic resin layer and the photosensitive resin layer mentioned later, it is provided. By disposing the intermediate layer, an organic solvent is used for forming the thermoplastic resin layer and the photosensitive resin layer, which is preferable in that the two layers can be prevented from being mixed with each other.

The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution. As the constituent material of the intermediate layer, known materials can be used. For example, a polyvinyl ether / maleic anhydride polymer described in JP-A No. 46-2121 and JP-B No. 56-40824, a water-soluble carboxyalkyl cellulose solution. Salts, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and their Water soluble salts of the group consisting of similar substances, styrene / maleic acid copolymers, maleate resins, and the like.
These may be used in combination of two or more, in addition to being used alone.

Among these, it is preferable to use a water-soluble resin, that is, a water-soluble polymer material. Among these, it is more preferable to use at least polyvinyl alcohol, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
There is no restriction | limiting in particular as said polyvinyl alcohol, According to the objective, it can select suitably, The thing whose saponification degree is 80 mol% or more is preferable.

  When using the said polyvinyl pyrrolidone, as content, 1-75 volume% is preferable with respect to solid content of an intermediate | middle layer, 1-60 volume% is more preferable, 10-50 volume% is especially preferable. If the content is less than 1% by volume, sufficient adhesion to the thermoplastic resin layer may not be obtained, and if it exceeds 75% by volume, the oxygen barrier ability may be lowered.

  The intermediate layer according to the present invention preferably has a low oxygen permeability. When the oxygen permeability of the intermediate layer is large and the oxygen blocking ability is low, it may be necessary to increase the amount of light at the time of exposure to the photosensitive resin layer, which will be described later, or it may be necessary to lengthen the exposure time, and resolution May fall.

The thickness of the intermediate layer is preferably about 0.1 to 1.6 μm, and more preferably 0.5 to 1 μm. If the thickness is less than 0.1 μm, the oxygen permeability may be too high, and if it exceeds 1.6 μm, it may take a long time to develop or remove the intermediate layer.
The film thickness of the intermediate layer can be adjusted by adjusting the concentration of the intermediate layer coating solution.

-Photosensitive resin layer-
The photosensitive transfer material of the present invention has at least one photosensitive resin layer. The photosensitive resin layer is a layer constituting the resin structure when a resin structure such as a spacer is formed, and includes, for example, a polymer substance, a polymerizable monomer, and a photopolymerization initiator, As needed, it can comprise using a filler, a coloring agent, and another component. In the case of containing a colorant, a colored pixel constituting the color filter can be formed.

<Polymer material>
The polymer substance has a function as a binder component when a laminated body such as a spacer or a colored pixel is formed. The polymer material is a resin described in the above <thermoplastic resin layer>, a carboxylic acid group or a carboxyl group in the side chain. Preferred examples are polymers having polar groups such as acid bases and polymer resins having allyl groups polymerizable by light as described in paragraphs [0031] to [0054] of JP-A No. 2003-131379, which are themselves polymerizable. As mentioned.

The polymer substance may be either a monomer homopolymer appropriately selected according to the purpose, or a copolymer composed of a plurality of monomers. You may make it use together.
Examples of the polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer as described in JP-A-25-25957, JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid, and others. And multi-component copolymers with these monomers.

There is no restriction | limiting in particular as a monomer of the high molecular substance which has an allyl group, According to the objective, it can select suitably, For example, alkyl (meth) acrylate, allyl (meth) acrylate, hydroxyalkyl (meth) acrylate , Vinyl compounds, allyl group-containing (meth) acrylates, and the like. In the present specification, (meth) acrylate represents acrylate or methacrylate.
These monomers may be used in combination of two or more in addition to being used alone.

  Examples of the alkyl (meth) acrylate and allyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate, hydroxypentyl ( And (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and the like, among others, hydroxyethyl (meth) acrylate, hydroxy n-propyl (meth) acrylate, hydroxy n-butyl (meth) acrylate, etc. Is preferred.

  As the vinyl compound, for example, styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like are preferable. Can be mentioned.

  Examples of the allyl group-containing (meth) acrylate include allyl (meth) acrylate, 2-methylallyl acrylate, crotyl acrylate, chloroallyl acrylate, phenylallyl acrylate, and cyanoallyl acrylate. ) Acrylate is particularly preferred.

  Among the above-described polymer substances, a resin having at least allyl group-containing (meth) acrylate as a monomer unit is preferable, and is selected from allyl group-containing (meth) acrylate, (meth) acrylic acid, and allyl group-free (meth) acrylate. A resin having a monomer as a monomer unit is more preferable.

As a preferred specific example of the polymer substance, a binary copolymer resin of (meth) acrylic acid (M ¹ ) and allyl (meth) acrylate (M ² ) [preferred copolymerization ratio [molar ratio] is M ¹ : M ² = 2 to 90:10 to 98] or a terpolymer resin of (meth) acrylic acid (M ³ ), allyl (meth) acrylate (M ⁴ ) and benzyl (meth) acrylate (M ⁵ ) [suitable copolymerization ratio [molar ratio] is ^{M 3: M 4: M 5} = 5~40: 20~90: 5~70 ] and the like.

  When the polymer substance has an allyl group, the content of the allyl group-containing monomer is preferably 10 mol% or more, preferably 10 to 100 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 20 mol%. 85 mol%.

  The weight average molecular weight of the polymer substance is preferably 5,000 to 100,000, and more preferably 8,000 to 50,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the weight average molecular weight within the range of 5,000 to 100,000, the film strength can be improved.

  As content in the photosensitive resin layer of the said high molecular substance, 15-95 mass% is preferable with respect to the total solid of this layer, 30-85 mass% is more preferable, 40-75 mass% is still more. preferable.

<Polymerizable monomer>
The polymerizable monomer is not particularly limited as long as it has at least one addition-polymerizable ethylenically unsaturated group, and can be appropriately selected according to the purpose. Examples include ester compounds, amide compounds, and other compounds.

  Examples of the ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and other ester compounds. It is done. These may be used individually by 1 type, and may use 2 or more types together, Among these, monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, etc. are preferable.

  Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl mono (meth) acrylate.

  Examples of the polyfunctional (meth) acrylic acid ester include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth). Acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, sorbitol Tri (meth) acrylate, sorbitol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate. Of these, dipentaerythritol poly (meth) acrylate is particularly preferable.

  Other examples of the polyfunctional (meth) acrylic acid ester include those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then (meth) acrylate, Japanese Patent Publication No. 48-41708. Urethane acrylates described in Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490. Polyester acrylates described in the publication, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, (meth) acrylic acid esters and urethane (meth) acrylates described in JP-A-60-258539 And vinyl esters.

  Examples of the “other ester compounds” include trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, Japan Adhesion Association Vol. 20, no. 7, photocurable monomers and oligomers described on pages 300 to 308, and the like.

  Examples of the amide compound include an amide (monomer) of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Specifically, methylene bis- (meth) acrylamide, 1,6-hexa Examples include methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and xylylene bis (meth) acrylamide, and (meth) acrylic acid amide described in JP-A-60-258539. .

  Examples of the “other compounds” include allyl compounds described in JP-A-60-258539.

  The above-mentioned polymerizable monomers may be used in combination of two or more, in addition to being used alone. As content in the photosensitive resin layer of a polymerizable monomer, 10-60 mass% is preferable with respect to the total solid of this layer, and 20-50 mass% is more preferable.

In the present invention, the melt viscosity η2 at 110 ° C. of the photosensitive resin layer is set so as to satisfy the above formula (1) (or formula (2), formula (3)), but is 350 to 180,000 Pa · s. It is preferable that it is 500 to 150,000 Pa · s, more preferably 1000 to 120,000 Pa · s.
If the melt viscosity η2 at 110 ° C. of the photosensitive resin layer is less than 350 Pa · s, the height variation of the photosensitive resin layer and the spacer becomes large, and if it exceeds 180000 Pa · s, there is a possibility that bubbles may be involved during lamination. Absent.

In order to achieve the preferable range of the melt viscosity of the photosensitive resin layer, the content A (mass%) of the polymer and the content (mass%) B of the polymerizable monomer in the photosensitive resin layer A means for adjusting the ratio B / A is preferable.
When the melt viscosity η2 at 110 ° C. of the photosensitive resin layer according to the present invention is adjusted to 350 to 180000 Pa · s, this ratio B / A is in the range of 0.4 or more and less than 0.9, preferably 0.6 or more and 0. It is preferable to adjust to a range of less than .8.

  As another means for achieving the preferable range of the melt viscosity, there is a means for containing a filler in the photosensitive resin layer. Examples of the filler include extender pigments and pigments. There is no restriction | limiting in particular as said extender, Although it can select suitably according to the objective, For example, the extender described in Unexamined-Japanese-Patent No. 2003-302039 [0035]-[0041] is preferable. Examples of the pigment include colored pigments, and examples of the colored pigment include pigments described in JP-A-2003-302039 [0043].

<Photopolymerization initiator>
As the photopolymerization initiator, those containing at least one component having a molecular extinction coefficient of about 50 or more in a wavelength region of about 300 nm to 500 nm are preferable. For example, JP-A-2-48664 and JP-A-1 -152449 and JP-A-2-153353, aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides. Examples thereof include oxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and the like.

  Among them, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 4- [pN, N′-di (ethoxycarbonyl) Methyl) -2,6-di (trichloromethyl) -s-triazine], 2,4-bis- (trichloromethyl) -6- [4- (N, N′-diethoxycarbonylmethylamino) -3-bromo Phenyl] -s-triazine and the like are preferable.

  The above photopolymerization initiators may be used in combination of two or more, in addition to being used alone. As content of a photoinitiator, 0.1-20 mass% is preferable with respect to the quantity of the said polymerizable monomer, and 0.5-10 mass% is more preferable.

  The photosensitive resin layer according to the present invention may contain a colorant such as a dye and a pigment in addition to the above-described polymer substance, polymerizable monomer, and photopolymerization initiator. About the kind, size, etc. of a preferable pigment, it can select suitably from description of Unexamined-Japanese-Patent No. 11-149008, for example. When a colorant such as a pigment is contained, a colored pixel can be formed. Moreover, additives, such as surfactant, can also be added as needed.

  Since the preferable layer thickness of the photosensitive resin layer has already been described, it is omitted here.

-Temporary support-
As the temporary support, those having a peelability from the thermoplastic resin layer to the extent that does not hinder the transfer are preferred, and those having chemical and thermal stability and flexibility are preferred.

  The material for the temporary support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polytetrafluoroethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and polypropylene. .

  There is no restriction | limiting in particular as a structure of a temporary support body, According to the objective, it can select suitably, For example, a single layer structure may be sufficient and a laminated structure may be sufficient. These may be used in combination of two or more, in addition to being used alone.

  The temporary support is preferably not subjected to surface treatment such as glow discharge from the viewpoint of ensuring good releasability with the thermoplastic resin layer, and no undercoat layer such as gelatin is provided. Is preferred. The thickness of the temporary support is preferably about 5 to 300 μm, and preferably 20 to 150 μm.

The temporary support is preferably provided with a conductive layer on at least one surface thereof, or the temporary support itself has conductivity. When the temporary support is configured as described above, the temporary support is used when the temporary support is peeled off after the photosensitive transfer material provided with the temporary support is brought into close contact with the transfer target. And the transferred object is not charged and attracts the surrounding dust, and as a result, even after the temporary support is peeled off, the dust does not adhere to the thermoplastic resin layer, and the subsequent exposure process Thus, the formation of pinholes due to the formation of an extra unexposed portion can be effectively prevented. The surface electric resistance on the surface of the conductive layer on the temporary support or the temporary support having conductivity is preferably 10 ¹³ Ω or less.

  In order to obtain the conductive temporary support, the conductive support may be contained in the temporary support. There is no restriction | limiting in particular as an electroconductive substance, Although it can select suitably according to the objective, For example, a metal oxide, an antistatic agent, etc. are mentioned.

  Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide. These may be used individually by 1 type and may use 2 or more types together. In addition, examples of the form of the metal oxide include crystal fine particles and composite fine particles.

  Examples of the antistatic agent include Electro Stripper A (manufactured by Kao Corporation), Elenon No. 19 (Daiichi Kogyo Seiyaku Co., Ltd.) alkyl phosphate anionic surfactants, Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd.) betaine amphoteric surfactants, Nissan Nonion L (Nippon Yushi Polyoxyethylene fatty acid ester nonionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, 910 (made by Kao Corporation) and Nissan Nonion E (made by Kao Corporation) Polyoxyethylene alkyl ether type nonionic surfactants such as Nippon Oil & Fats Co., Ltd., polyoxyethylene alkylphenol ether type, polyhydric alcohol fatty acid ester type, polyoxyethylene sorbitan fatty acid ester type, polyoxyethylene alkylamine type, etc. Other nonionic surfactants. These may be used individually by 1 type and may use 2 or more types together.

The conductive layer can be formed by appropriately selecting and using a known conductive material. Examples of the conductive material include ZnO, TiO ₂ , SnO ₂ , Al ₂ O _3. In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO _3, etc. are preferable in that a stable conductive effect can be obtained without being affected by the humidity environment. These may be used individually by 1 type and may use 2 or more types together.

The volume resistance value of the metal oxide or the conductive material is preferably 10 ⁷ Ω · cm or less, and more preferably 10 ⁵ Ω · cm or less. The particle diameter of the metal oxide or the conductive substance is preferably 0.01 to 0.7 μm, and more preferably 0.02 to 0.5 μm.

  In the conductive layer, as a binder, for example, cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, vinyl chloride, styrene, acrylonitrile, Homopolymers or copolymers containing vinyl acetate, alkyl acrylates having 1 to 4 carbon atoms, vinyl pyrrolidone, etc., soluble polyesters, polycarbonates, soluble polyamides, etc. can be used.

-Other layers-
In the photosensitive transfer material of the present invention, other layers such as a cover film can be further provided in addition to the above-described layers.

  The cover film has a function of protecting the photosensitive resin layer from dirt, damage, and the like during storage, and can be made of the same or similar material as the temporary support. As a cover film, what can be peeled easily from the said photosensitive resin layer should just be mentioned, For example, a silicone paper, a polyolefin sheet, a polytetrafluoroethylene sheet etc. are mentioned suitably. Among these, a polyethylene sheet or film and a polypropylene sheet or film are preferable. As a thickness of a cover film, about 5-100 micrometers is preferable and 10-30 micrometers is more preferable.

  In the photosensitive transfer material of the present invention, an alkali-soluble thermoplastic resin layer is provided on a temporary support by applying and drying a coating solution for a thermoplastic resin layer that is alkali-soluble. On the resin layer, an intermediate layer coating solution using an aqueous solvent that does not dissolve the thermoplastic resin layer is applied and dried to provide an intermediate layer, and on the intermediate layer, a solvent that does not dissolve the intermediate layer is used. It can manufacture by providing the photosensitive resin layer by apply | coating and drying the coating liquid for photosensitive resin layers. As another method, a cover film provided with a photosensitive resin layer and a temporary support provided with an alkali-soluble thermoplastic resin layer and an intermediate layer in this order from the support side were prepared. The former photosensitive resin layer surface and the latter intermediate layer surface are bonded so that they are in contact with each other, or the cover film is provided with the photosensitive resin layer and the intermediate layer sequentially from the cover film side. It is possible to produce a material having an alkali-soluble thermoplastic resin layer provided on a temporary support and bonding the former intermediate layer surface and the latter thermoplastic resin layer surface so that they are in contact with each other. it can.

  The photosensitive transfer material of the present invention can form a spacer (gap holding member) for holding a pair of substrates constituting a liquid crystal display device in a predetermined gap, or a colored image (colored pixel or the like) when it contains a colorant. ) And the like. As the formation method, it is preferable to transfer the photosensitive transfer material to a substrate and perform at least one exposure, one development, and at least one baking. In this case, as the transfer target as a substrate, a transparent substrate (for example, a glass substrate or a plastics substrate) constituting a liquid crystal display device, a substrate with a wiring, a framed substrate formed of a light shielding film, a transparent conductive film ( For example, a substrate with an ITO film), a substrate with a color filter, a drive substrate with a drive element (for example, a thin film transistor [TFT]), and the like.

Next, an example of forming a constituent member of a liquid crystal display device using the photosensitive transfer material of the present invention will be described.
After removing the cover film from the photosensitive transfer material of the present invention produced as described above, the exposed photosensitive resin layer is bonded onto a desired transfer target body under pressure and heating (laminate). Lamination can be suitably performed using a known laminator, vacuum laminator, etc., and from the viewpoint of increasing productivity, laminators equipped with an auto-cut mechanism and photosensitive transfer material defects are automatically detected. An intelligent laminator that can skip and laminate the normal part, and a large laminator that can laminate a wider roll of photosensitive transfer material can be suitably used.

Since the substrate size has been increased to accommodate large-sized liquid crystal panels and plasma displays, the transfer area of the photosensitive transfer material on the large substrate expands in the width direction (direction intersecting the transport direction), and the There is a need to increase the widthwise dimension of the photosensitive transfer material itself.
In the case of a wide photosensitive transfer material, the handling property in a roll state is deteriorated, and the enlargement of the feeding mechanism for rewinding the photosensitive transfer material from the roll is caused, and the wide photosensitive transfer material is heavy. In addition, there is a problem that the handling becomes complicated, and further, wrinkles or the like are likely to be generated in the surface from the deflection in the width direction of the photosensitive transfer material due to the weight, and air bubbles at the time of laminating are involved to deteriorate the display performance. Therefore, a laminator capable of laminating two or more roll-shaped photosensitive transfer materials on one large substrate can be used particularly suitably.

  As the preferred laminator for a large substrate, two or more web feed mechanisms capable of synchronously feeding a long photosensitive transfer material in which a photosensitive resin layer and a protective film are sequentially laminated on a support, Two or more processing mechanisms for forming a processing portion that can be cut in the width direction corresponding to the boundary position between the peeling portion and the remaining portion in the protective film of each of the long photosensitive transfer materials sent out, and the peeling Two or more peeling mechanisms for peeling a part from each long photosensitive transfer material leaving the remaining part, a substrate transporting mechanism for transporting the substrate to a joining position in a state heated to a predetermined temperature, and A bonding mechanism for disposing each remaining portion between the substrates, and bonding two or more photosensitive material layers exposed by peeling each peeling portion to the substrate integrally and in parallel to obtain a bonded substrate; and Of joint position Two or more detections that are arranged beside and directly detect the boundary position of each long photosensitive web or detect a mark portion provided on each long photosensitive web corresponding to the boundary position And a control mechanism capable of adjusting a relative position between each boundary position and the substrate at the bonding position and a relative position between the boundary positions based on each boundary position information detected by each detection mechanism. Those that are present are preferred. (Japanese Patent Laid-Open No. 2004-333647), “Production Method of Color Filter for Large Liquid Crystal Using Transer System” (“Challenge to the Limit-1:“ Challenge to Nano Size, Challenge to Macro Size ”” August 27, 2004; Refer to the Chemical Engineering Society)

  By using the laminator for large substrates described above, two or more photosensitive transfer materials can be satisfactorily transferred in the width direction on a wide substrate, and a high-quality photosensitive resin layer can be efficiently obtained. Is possible. Further, the long photosensitive transfer material does not need to be configured to be wide, the handling of the long photosensitive transfer material is effectively improved, and the work efficiency and the equipment cost can be easily reduced. This is preferable.

  For example, when forming a transparent spacer, for example, the cover film of the photosensitive transfer material of the present invention is removed, and the exposed photosensitive resin layer is laminated and bonded to the transfer target, and the temporary support is bonded to the thermoplastic resin layer. The film is transferred to the transfer medium by peeling off at the interface. After that, the photosensitive resin layer is exposed through a predetermined mask through the thermoplastic resin layer and the intermediate layer. In the case of the negative type, the non-exposed portion of the photosensitive resin layer is set, and in the case of the positive type, the exposed portion is set. The spacer can be formed by developing and removing using an alkaline aqueous solution and curing only the exposed portion or the non-exposed portion.

Development can be carried out in accordance with a known alkali development method. For example, a developer or an aqueous developer, particularly an alkaline aqueous solution (alkaline developer) or the like is used to store the developer to be transferred after exposure. Or by spraying the layer on the transfer medium with a spray or the like, and further rub the surface with a rotating brush or wet sponge or irradiate with ultrasonic waves. Can do. The development temperature is usually preferably around room temperature to about 40 ° C. Moreover, it is preferable to perform a water washing process after image development.
In addition, in the process of development after exposure and removal of unnecessary portions, the alkaline aqueous solution used for dissolving the photosensitive resin layer and the thermoplastic resin layer is preferably, for example, a dilute aqueous solution of an alkaline substance, and a water-miscible organic solution. What added the solvent a little is also preferable.

  The alkaline substance is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Salts, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, triethanolamine , Tetraalkylammonium hydroxides such as diethanolamine, monoethanolamine, morpholine, tetramethylammonium hydroxide, or trisodium phosphate. These may be used in combination of two or more, in addition to being used alone.

  As said alkaline aqueous solution, it is preferable that the density | concentration of an alkaline substance is 0.01-30 mass%, and it is preferable that pH is 8-14.

  The organic solvent having water miscibility is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, Examples include ε-caprolactam and N-methylpyrrolidone. The addition amount of the organic solvent having water miscibility is preferably 0.1 to 30% by mass.

  In addition, a well-known various surfactant can be added to the said alkaline aqueous solution, and it is preferable that the addition amount in the case of adding this surfactant is 0.01-10 mass%.

<Laminate>
The laminate of the present invention is obtained by using the photosensitive transfer material of the present invention, and is appropriately selected from spacers formed on the substrate, colored pixels formed on the substrate, black matrix formed on the substrate, and the like. .

《Liquid crystal display device substrate》
The substrate for a liquid crystal display device of the present invention is provided with a laminate formed using the photosensitive transfer material of the present invention. When the laminate is a spacer, the spacer is preferably formed on a display light-shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT, and if necessary, a black matrix or the like. A transparent conductive layer such as ITO or a liquid crystal alignment film such as polyimide may be present between the display light-shielding portion or the driving element such as TFT and the spacer.

  For example, when the spacer is provided on the display light-shielding portion or the driving element, the substrate for the liquid crystal display device of the present invention has the photosensitive property of the present invention so as to cover the display light-shielding portion and the driving element that are arranged in advance. After the transfer material is laminated and peeled and transferred as described above, the spacer can be formed by performing exposure, development and the like.

<Liquid crystal display element>
An element having a liquid crystal layer in which a liquid crystal material is sealed between a pair of opposing substrates, wherein one of the substrates is a liquid crystal display substrate provided with the laminate of the present invention.

<Liquid crystal display device>
The liquid crystal display device of the present invention is a liquid crystal display device in which a pair of substrates arranged opposite to each other is regulated to a predetermined width by a spacer and a liquid crystal material is sealed in the gap (the sealed portion is referred to as a liquid crystal layer). The spacer disposed on the substrate to keep the thickness of the liquid crystal layer constant is formed using the photosensitive transfer material of the present invention described above. That is, the liquid crystal display device substrate of the present invention described above is used as one of the pair of substrates.

  As the liquid crystal in the liquid crystal display device, STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, ASM type, and other various types are preferably mentioned.

  The basic configuration of the liquid crystal display device of the present invention includes (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged, a color filter, and a counter electrode ( A color filter side substrate provided with a conductive layer) is disposed opposite to each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. (B) The color filter is directly formed on the drive side substrate. A color filter integrated drive substrate and a counter substrate provided with a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. . The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” represent “part by mass” and “mass%” in the following.

(Example 1)
Biaxially stretched, heat-fixed at 240 ° C. for 10 minutes, and then a corona discharge-treated polyethylene terephthalate film with a width of 1610 mm and a thickness of 75 μm is used as a temporary support. And dried at 130 ° C. for 2 minutes to form a back surface coating layer having a thickness of 0.08 μm.

[Back surface coating solution 1]
Acrylic resin aqueous dispersion 30.9 parts by mass (Jurimer ET-410, number average molecular weight 9700,
(Weight average molecular weight 17000, solid content concentration 30%, manufactured by Nippon Pure Chemical)
-Carbodiimide crosslinking agent aqueous solution 6.4 parts by mass (carbodilite V-02-L2, solid content concentration 40%; manufactured by Nisshinbo Co., Ltd.)
-Additive 1 Amount described in Table 1-0.73 parts by mass of surfactant (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 1.44 parts by mass (Sandet BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries)
・ Distilled water added so that the total amount becomes 1000 parts by mass

In addition, the detail of the additive 1 used for each said Example and comparative example is as follows.
SN38F: Ishihara Sangyo Co., Ltd. SnO ₂ fine particles (solid content 17%)
R533D: SnO ₂ fine particles (solid content 17%) manufactured by Mitsubishi Materials Corporation
-KE-E20: Nippon Shokubai silica fine particles (trade name: Seahoster KE-E20, solid content 20%)
-KE-E40: Nippon Shokubai silica fine particles (trade name: Seahoster KE-E40, solid content 20%)
In other examples and comparative examples, the back surface coating layer was formed so that the solid content coating amount was the same.

Next, the following back surface protective layer-forming coating solution 1 was applied on the back surface coating layer and dried at 130 ° C. for 2 minutes to form a back surface protective layer having a thickness of 0.05 μm.
[Back surface protective layer forming coating solution 1]
-17.8 parts by mass of polyethylene latex (Chemical S120, solid content concentration 27%, manufactured by Mitsui Chemicals)
・ 11.8 parts by mass of colloidal silica (Snowtex C, solid content 20%, manufactured by Nissan Chemical Co., Ltd.)
-Epoxy curing agent 1.7 parts by mass (Denacol EX-614B, manufactured by Nagase Kasei Co., Ltd.)
・ Surfactant 0.52 parts by mass (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 0.59 parts by mass (Sandet BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries)

  Next, a thermoplastic resin layer having the composition of Example 1 in Table 2 and the film thickness described in Table 6 was formed on the temporary support on the surface opposite to the back surface coating layer forming surface of the temporary support.

  Details of the compositional components described in Table 2 are shown below.

<Binder A>
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (molar ratio) = 55 / 11.7 / 4.5 / 28.8 (trade name: Aromatex FM601, manufactured by Mitsui Chemicals, Ltd., weight (Average molecular weight = 90000, solid content concentration 21% by mass)

<Binder B>
Styrene / acrylic acid copolymer (molar ratio) = 63/37 (trade name: Alloset 7055, manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight = 8000, solid content concentration 41 mass%)

<Plasticizer 1>
・ 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

  Next, an intermediate layer having a thickness of 1.6 μm was formed on the thermoplastic resin layer by applying and drying an intermediate layer coating liquid B1 having the following composition.

<Intermediate layer coating solution B1>
Polyvinyl alcohol ... 2.1 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
Polyvinylpyrrolidone: 0.95 parts (PVP, K-30; manufactured by IS Japan Co., Ltd.)
Methanol ... 44 parts distilled water ...・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 53 copies

  Furthermore, the photosensitive resin layer whose thickness is 2.4 micrometers was formed by apply | coating and drying the dark color composition K1 prepared by the manufacturing method of the following dark color composition.

[Production method of dark color composition]
The dark color composition K1 was first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 3, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 RPM for 10 minutes. 3, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) amino-3-bromophenyl] -S-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C (± 2 ° C), and stirred at a temperature of 40 ° C (± 2 ° C) for 150 RPM for 30 minutes. In addition, the quantity of Table 3 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%

-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

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

  A photosensitive transfer material K1 was produced by providing a cover film made of polypropylene (thickness: 12 μm) by pressure bonding on the formed photosensitive resin layer.

  The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at a substrate temperature of 105 ° C. for 2 minutes with a substrate preheating apparatus.

The cover film is removed from the photosensitive transfer material K1 produced by the above manufacturing method on the obtained silane coupling treated glass substrate, and the surface of the photosensitive resin layer exposed after the removal and the silane coupling treated glass substrate 1 was laminated with the laminator shown in FIG. 1 and laminated on the substrate heated at 100 ° C. for 2 minutes, with a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. .
The photosensitive transfer material K1 is sent out from the film original fabric 11, and the cover film, the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and a part of the temporary support are shown in FIG. 2 by the half-cut mechanism 12 shown in FIG. So cut. As shown in FIG. 2, half cutting is performed by using a pair of blades to form two half-cut lines 25 having an interval slightly wider than the interval between the substrates 7 when continuously laminated.

Only the cover film of the area | region affixed on the board | substrate 7 is peeled by the cover film peeling mechanism 13 shown in FIG. That is, it is sent to the laminating roll 14 with the cover film remaining only in a portion corresponding to the interval between adjacent substrates, and is laminated on a glass substrate heated to 100 ° C. with the surface to be laminated facing down.
The substrate is sequentially sent from the previous step with an interval of 30 to 40 mm, and after lamination, the laminated body with a constant interval is cooled to 30 ° C. or less in the cooling zone 16 as shown in FIG. Here, cool air cooled by a cooler or the like is applied. Thereafter, the temporary support is continuously peeled between the upper roll 19 and the peeling roll 17, and the substrate on which the photosensitive resin layer is attached is transferred to the next step.

After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Nihon Hi-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² .

Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The thermoplastic resin layer and the intermediate layer were removed by shower development with a flat nozzle pressure of 0.04 MPa for 50 seconds.
Subsequently, a sodium carbonate-based developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) was used for shower development at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer, thereby obtaining a patterned pixel.

Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film)”, 33 ° C., 20 seconds, cone type nozzle pressure 0 Residue removal was performed with a rotating brush having a shower and nylon hair at 0.02 MPa to obtain a black (K) image.
Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ² from the photosensitive resin layer side from the side of the photosensitive resin layer, and then heat-treated at 220 ° C. for 15 minutes to obtain a black matrix having a height of 2.0 μm. .

[Plasma water repellency treatment]
The substrate on which the black matrix was formed was subjected to plasma water repellency treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

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

Further, C.I. I. Pigment Red 254 instead of C.I. I. A colored ink composition for green (G) pixels was prepared in the same manner as in the red pixel portion colored ink composition except that the same amount of pigment green 36 was used.
Further, C.I. I. Pigment Red 254 instead of C.I. I. A blue (B) pixel colored ink composition was prepared in the same manner as the red pixel colored ink composition except that the same amount of CI Pigment Blue 15: 6 was used.

  Next, using the color inks for R, G, and B pixels described above, an ink jet method is used in the region (the concave portion surrounded by the convex portion) divided by the black matrix of the color filter substrate obtained above. The ink composition was discharged to a desired density using a recording apparatus, and a color filter composed of R, G, and B patterns was produced. The color filter after image coloring was baked in an oven at 230 ° C. for 30 minutes to completely cure the black matrix and each pixel.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap of the black matrix, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found.
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above.

  Next, a photosensitive transfer material T1 having a photosensitive resin layer of 3.7 μm formed by the same method as described above was prepared using the following formulation 1 of the photosensitive resin layer coating solution for spacers, and the color The photosensitive resin layer was formed by transferring onto the ITO of the filter.

The cover film of the produced photosensitive transfer material was peeled off, and this was applied on a glass plate sputtered with ITO using a laminator (manufactured by Hitachi Industries (Lamic II type)), with a linear pressure of 100 N / cm, 130 Bonding was performed at a conveyance speed of 2 m / min. Thereafter, the temporary support made of polyethylene terephthalate film was peeled off from the thermoplastic resin layer and removed. Next, after exposure of 80 mJ / cm ² with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp through a predetermined photomask, KOH developer (KOH, nonionic surfactant) Ingredients, product name: CDK-1, Fuji Film Electronics Material Co., Ltd.) diluted to 71 times with pure water, the unexposed part is completely developed at 25 ° C. and flat nozzle pressure 0.15 MPa. Shower development was performed until the unexposed portions of the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer were dissolved and removed.

  Next, the substrate was baked at 230 ° C. for 30 minutes to form a columnar transparent spacer image pattern (spacer dots) having a side of 16 μm and an average height of about 3.5 μm on the liquid crystal display device substrate.

<Method for Manufacturing Liquid Crystal Display Device>
A polyimide alignment film was formed on the color filter on which the spacer pixel pattern was formed, and then the following steps were performed.

(Formation of liquid crystal alignment control protrusions)
A photosensitive transfer material A1 is prepared by the same method as described above for the coating liquid A for the photosensitive resin layer for liquid crystal alignment control protrusions described below, and transferred onto the polyimide alignment film on the color filter side substrate. A photosensitive resin layer for protrusions for controlling liquid crystal alignment was formed.

[Coating liquid for photosensitive resin layer for liquid crystal alignment control protrusion: Formulation A1]
・ Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 1 0.04 parts

Next, a proximity exposure machine was arranged so that the photomask was at a distance of 100 μm from the surface of the thermoplastic resin layer, and proximity exposure was performed through the photomask with an irradiation energy of 150 mJ / cm ² with an ultrahigh pressure mercury lamp. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying on the substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer for protrusion were developed and removed. . As a result, protrusions made of a photosensitive resin layer patterned in a desired shape were formed on a portion of the color filter side substrate located on the polyimide alignment film and above the R, G, and B pixels. Next, the color filter side substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes to form a liquid crystal alignment control protrusion having a height of 1.5 μm and a vertical cross-sectional shape on the color filter side substrate. We were able to.

  Furthermore, a liquid crystal display element was produced by combining a drive side substrate and a liquid crystal material with the color filter side substrate obtained above. That is, a TFT substrate in which TFTs and pixel electrodes (conductive layers) are arrayed is prepared as a drive side substrate, the surface of the TFT substrate on which the pixel electrodes and the like are provided, and the color filter obtained from the above. The substrate was arranged so as to face the surface on the side where the alignment dividing projections were formed, and fixed with a gap formed by the spacers formed above. A liquid crystal material was sealed in the gap to provide a liquid crystal layer for image display. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the side of the liquid crystal cell on which the polarizing plate was provided to obtain a liquid crystal display device.

(Examples 2-8, Comparative Examples 1-3)
In Example 1, the formulation obtained by replacing the additive 1 in the back surface coating solution 1 with the one described in Table 1, the formulation of the thermoplastic resin layer as described in Table 2, and the coating for the photosensitive resin layer for forming the spacer A color filter, a spacer, a protrusion for controlling liquid crystal alignment, and a liquid crystal display device were prepared in the same manner as in Example 1 except that the liquid formulation T1 was changed to the formulation shown in Table 4.

(Examples 9-11, 14-16, Comparative Examples 4-6)
In Example 1, the formulation obtained by replacing the additive 1 in the back surface coating solution 1 with the one described in Table 1, the formulation of the thermoplastic resin layer as described in Table 2, and the coating for the photosensitive resin layer for forming the spacer Except for changing the liquid formulation T1 to the formulation shown in Table 4 and changing the RGB pixel formation method to the transfer method described below, the color filter, spacer, liquid crystal alignment control protrusion, A liquid crystal display device was produced.

[Formation of RGB pixels]
The color filter red, green, and blue pixel forming coating solutions R1, G1, and B1 shown in Table 5 below were prepared, and the coating solutions were respectively prepared in the same manner as the photosensitive transfer material K1. G1 and B1 were produced. The numbers in Table 5 below indicate “parts by mass”.

In addition, the composition of the binder 2 among the compositions described in Table 5 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 DPHA solution is:
-Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts-Propylene glycol monomethyl ether acetate 24 parts The composition of R pigment dispersion 1 is as follows: It is.
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals) 8 parts Dispersant (compound 1) 0.8 part 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 R pigment dispersion 2 is as follows.
・ C. I. P. R. 177 (trade name: Cromophtal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) 18 parts Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 30,000) 12 parts propylene glycol The composition of 70 parts monomethyl ether acetate 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 ・ Propylene glycol monomethyl ether acetate 73 parts Additive 1 is a phosphate ester-based special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152) was used.
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 Yellow 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 EX3383” manufactured by Mikuni Dye Co., Ltd. was used.
The composition of binder 3 is
・ 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

  Next, using the photosensitive transfer materials R1, G1, and B1, RGB colored pixels are formed in a portion surrounded by the black matrix formed above by the same method as the black matrix manufacturing method, and a color filter It was.

Example 12
The photosensitive transfer material is changed to a roll-type photosensitive transfer material having a width of 645 mm and a length of 120 mm, the substrate size is changed to a glass plate (size 1300 mm × 1500 mm), and the laminator is rolled into two photosensitive transfer materials. Two photosensitive transfer material rolls wound around the photosensitive transfer material rolls, and the photosensitive transfer material rolls are synchronously sent out from the respective photosensitive transfer material rolls. First and second processing mechanisms for forming a half-cut portion (processing portion) that is a boundary position that can be cut in the width direction on the protective film of the photosensitive transfer material, and an adhesive label having a non-adhesive part in each protective film A spacer is formed in the same manner as in Example 4 except that the laminator is provided with first and second label adhesion mechanisms to be adhered to the liquid crystal display. To prepare a location.

(Example 13)
A liquid crystal was produced in the same manner as in Example 5 except that the photosensitive transfer material was changed to a roll-type photosensitive transfer material having a width of 1075 mm and a length of 120 mm, and the substrate size was changed to a glass plate (size 2160 mm × 2460 mm). A display device was produced.

(Examples 17 and 18)
In Example 2 and Example 10, except that the substrate was not heated, a color filter, a spacer, a liquid crystal alignment control protrusion, and a liquid crystal display device were produced in the same manner as in Example 2 and Example 10.

[Evaluation]
(Melt viscosity measurement)
The thermoplastic resin layer coating solution and the photosensitive resin layer coating solution were applied to a glass plate and air-dried, followed by vacuum drying at 45 ° C. for 4 hours. A sample was peeled from the glass plate. The measurement was performed using a viscoelasticity measuring apparatus DynAlyser DAS-100 manufactured by Jasco International Co. Ltd. at a measurement temperature of 110 ° C. and a frequency of 1 Hz. Table 6 shows the measurement results.

(Film thickness measurement)
The film thickness was measured using a surface roughness meter P-10 (manufactured by TENCOR). Table 6 shows the measurement results.

(Roll dirt)
After the processing of 10 sheets, the stain on the roll surface on the side in contact with the photosensitive resin transfer material was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 6.
<Evaluation criteria>
A: There is no dirt on the roll.
B: The part of the roll that touches the edge of the transfer material is slightly stained.
C: The part of the roll that comes into contact with the transfer material is slightly stained.
D: The portion of the roll that comes into contact with the transfer material may be severely soiled, resulting in poor conveyance.

(Measurement of spacer height variation)
The height of 1000 spacers obtained was measured with a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), and the percentage of variation with respect to the average value of the maximum value or minimum value of the spacer was evaluated. An evaluation result is shown in Table 6. C or more is a practical use level.
A: The spacer height variation is ± 0.5%, which is very good.
B: Good spacer height variation of ± 1.0%.
C: Normal with a spacer height variation of ± 1.5%.
D: The spacer height variation is bad at ± 2.0%.
E: Spacer height variation is ± 3.0%, which is extremely bad.

<Spacer persistence>
A total of 10000 spacers of 100 vertical and 100 horizontal were formed on the substrate. Using a substrate with a spacer, the remaining property of the spacer was evaluated.
10000 pieces of obtained spacers were observed with a microscope, and the area (shown by C in FIG. 3) where 9 or more spacers (shown by B in FIG. 3) are left and right continuous in the substrate 10 is left and right. .)
The area (%) of the part where the spacer was removed was calculated by the number of spacers (shown as A in FIG. 3) in which the removal was recognized × the substrate area of the display portion supported per unit spacer. However, the substrate area of the display unit in the number of unit spacers is a value obtained by dividing the substrate area corresponding to the screen display unit by the number of spacers.
The substrate area of the display portion was taken as 100%, and the percentage of the missing area was evaluated. It is preferable that the number of missing spacers is as small as possible. When the missing amount is 0.1% or less, there is no transfer defect and it is very good.

From Table 6, in Examples 1-18, since the favorable result was obtained in any evaluation of roll dirt, a spacer missing area, and spacer height variation, the conveyance property in high temperature conditions is favorable. I understand.
On the other hand, it can be seen that in Comparative Examples 1 to 6, the spacer removal area was large, and good transportability was not obtained. In particular, Comparative Examples 3 and 6 in which the surface roughness (Spa) of the back surface exceeded the upper limit was inferior in the evaluation of roll dirt, and in Comparative Examples 2 and 5 outside the range of the formula (1), It was inferior in evaluation of height variation.
In the case of Example 12 and Example 13, the height variation of the spacer is as good as in Examples 1 to 18, and it is more preferable in that it can be transferred to a large substrate using a conventional transfer material.

It is a conceptual diagram which shows the principal part of the apparatus which peels and laminates the photosensitive transfer material. It is a schematic plan view which shows the half cut line of the apparatus shown in FIG. It is explanatory drawing for showing the calculation method of the residual rate of a spacer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive transfer material 7 Transparent substrate 10 Substrate 11 Original film 12 Half cut mechanism 13 Cover film peeling mechanism 14 Laminating roll 16 Cooling zone 17 Peeling roll 19 Upper roll 20 Peeled temporary support 21 Take-up roll 25 Half cut line A Spacer B Spacer missing part (Non-calculated part)
C Spacer missing part area (calculated part area)

Claims (13)

A photosensitive transfer material having at least a photosensitive resin layer and a thermoplastic resin layer for assisting transfer of the photosensitive resin layer on one surface of a temporary support,
The surface of the surface opposite to the side having the photosensitive resin layer of the temporary support (Spa) is 0.015 to 0.090 μm, the layer thickness of the thermoplastic resin layer, and the photosensitive property The photosensitive transfer material characterized in that the layer thickness of the resin layer, the melt viscosity η1 of the thermoplastic resin layer at 110 ° C., and the melt viscosity η2 of the photosensitive resin layer at 110 ° C. satisfy the following formula (1): .
(D1 / η1) / (d2 / η2)> 0.8 Formula (1)
[In the formula (1), η1: melt viscosity at 110 ° C. of the thermoplastic resin layer, η2: melt viscosity at 110 ° C. of the photosensitive resin layer, d1: layer thickness of the thermoplastic resin layer, d2: of the photosensitive resin layer Layer thickness. ]   The thermoplastic resin layer has a melt viscosity η1 at 110 ° C. of 200 to 3000 Pa · s, and the photosensitive resin layer has a melt viscosity η2 at 110 ° C. of 350 Pa · s to 180,000 Pa · s, and the thermoplastic resin. The photosensitive transfer material according to claim 1, wherein the layer has a thickness of 2 to 50 μm.   The photosensitive transfer material according to claim 1 or 2, wherein the photosensitive resin layer contains a filler.   The photosensitive transfer material according to claim 3, wherein the filler is an extender pigment or a pigment.   5. The photosensitive transfer material according to claim 1, wherein the photosensitive resin layer has a thickness of 1 μm to 10 μm.   The photosensitive transfer material according to any one of claims 1 to 5, wherein the thermoplastic resin layer contains a polymer and a plasticizer.   The photosensitive transfer material according to claim 1 is transferred to a substrate, and is formed by performing at least one exposure, one development, and at least one baking. A method for producing a laminate.   The method for manufacturing a laminate according to claim 7, wherein the laminate is provided with a spacer on a substrate.   The method for manufacturing a laminate according to claim 7, wherein the laminate is provided with a pixel on a substrate.   The laminated body manufactured by the manufacturing method of the laminated body of Claim 7.   A substrate for a liquid crystal display device comprising the laminate according to claim 10.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 11.   A liquid crystal display device comprising the liquid crystal display element according to claim 12.

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