JP4579022B2 - LAMINATE MANUFACTURING METHOD, LAMINATE, LIQUID CRYSTAL DISPLAY DEVICE SUBSTRATE, LIQUID CRYSTAL DISPLAY ELEMENT, LIQUID CRYSTAL DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a photosensitive transfer material suitable for forming a structure constituting a liquid crystal display device (for example, a spacer disposed on a substrate and holding a predetermined gap), and a liquid crystal display including the photosensitive transfer material. The present invention relates to a device substrate and a liquid crystal display device, and in particular, a photosensitive transfer material suitable for an ODF (One Drop Fill) method, which is becoming a mainstream method for manufacturing a liquid crystal display device in recent years, and a high quality composed of the photosensitive transfer material. The present invention relates to a liquid crystal display device substrate and a liquid crystal display device that enable image display.

  Conventionally, liquid crystal display devices have been 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 pair of substrates, and maintaining the distance between the substrates, that is, the thickness of the liquid crystal layer, determines the image quality. A spacer for keeping the thickness of the liquid crystal layer constant is provided.

When forming a spacer using a resin composition, there is a method using a transfer material having a photosensitive resin layer made of the resin composition on a temporary support. In addition to the photosensitive resin layer, this transfer material is composed of a temporary support and a photosensitive resin that have a cushioning thermoplastic resin layer to avoid improper transfer due to unevenness present on the transfer surface of the transfer material. It is provided between the layers.
In recent years, in order to reduce costs, it is desired to develop the photosensitive resin layer and the thermoplastic resin layer in one development process. However, if the thermoplastic resin layer is thick, it takes a long time in one development step, and uniform development is difficult. In order to solve this problem, it is desired to reduce the thickness of the thermoplastic resin layer.

In the method of reducing the thickness of the thermoplastic resin layer, since the thermoplastic resin layer does not have sufficient cushioning properties, a new problem arises that the thickness of the photosensitive resin layer varies due to transfer failure.
The present invention provides a photosensitive transfer material that does not cause transfer failure even in a thin thermoplastic resin layer that can be removed in a single development step, and that does not vary in the layer thickness of the photosensitive resin layer. An object of the present invention is to provide a color filter and a liquid crystal display device having a spacer produced using a photosensitive transfer material and having a uniform distance between a pair of substrates on which a liquid crystal layer exists. This is the subject of the present invention.

Specific means for achieving the above object are as follows.
<1> A photosensitive transfer material having at least a thermoplastic resin layer and a photosensitive resin layer in order from the temporary support side on the temporary support, wherein the melt viscosity η at 110 ° C. of the thermoplastic resin layer is a 200PaS～3000PaS, and the melt viscosity η at 110 ° C. of the photosensitive resin layer is 350PaS～180000PaS, and the layer thickness of the thermoplastic resin layer is a 2~14μm der Ru sensitive optical transfer material, at least one The laminate is transferred to a substrate having irregularities on its surface, exposed at least once, subjected to at least one development step and baked at least once to form a laminate composed of spacers provided on the substrate. It is a manufacturing method .
<2> The photosensitive transfer material is an optical transfer material feeling that having a least intermediate layer, stacked according to, wherein the thickness of the intermediate layer is 1.6μm or less <1> It is a manufacturing method of a body .
<3> The photosensitive transfer material according to <1> or <2>, wherein the photosensitive resin layer contains a filler.
<4> The method for producing a laminate according to <3>, wherein the filler is an extender pigment or a pigment.
<5> The method for producing a laminate according to any one of <1> to <4>, wherein the photosensitive resin layer has a thickness of 1 μm to 10 μm.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein the thermoplastic resin layer includes a polymer and a plasticizer.
< 7 > A laminate produced by the method according to < 6 >.
< 8 > A substrate for a liquid crystal display device comprising the laminate according to < 7 >.
< 9 > A liquid crystal display device comprising the liquid crystal display device substrate according to < 8 >.
< 10 > A liquid crystal display device comprising the liquid crystal display element according to < 9 >.

  The laminate produced using the photosensitive resin transfer material of the present invention has no variation in film thickness, and a liquid crystal display device provided with a substrate for a liquid crystal display device using the laminate provides high quality image quality. be able to.

Hereinafter, the present invention will be described in detail.
<Photosensitive transfer material>
The photosensitive transfer material of the present invention is formed by providing at least an alkali-soluble thermoplastic resin layer and a photosensitive resin layer in order from the temporary support side on the temporary support, and the alkali-soluble material. The melt viscosity η at 110 ° C. of the thermoplastic resin layer is 200 PaS to 3000 PaS, the melt viscosity η at 110 ° C. of the photosensitive resin layer is 350 PaS to 180000 PaS or more, and the layer thickness of the thermoplastic resin layer is 2 to 2 It is characterized by being 14 μm.
Moreover, you may have other layers, such as an intermediate | middle layer, between a thermoplastic resin layer and the photosensitive resin layer as needed.

-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 2 to 14 μm. When the layer thickness is less than 2 μm, the peelability from the temporary support at the time of transfer is deteriorated and the peeled surface is damaged, and it becomes difficult to form a fine pattern due to exposure failure due to thickness fluctuation. On the other hand, if it exceeds 14 μm, uniform development is not performed in one development step, which is not preferable.
Moreover, Preferably it is 2-10 micrometers, More preferably, it is 2-8 micrometers, Most preferably, it is 2-6 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-64-15555, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340 And resins 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-mentioned patent specifications. Particularly preferred are styrenes 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 fluorosurfactant 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 Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) or the like, or silicon There may be mentioned system 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.

  The melt viscosity η of the thermoplastic resin layer of the present invention is 200 PaS to 3000 PaS at 110 ° C., preferably 300 PaS to 2500 PaS, more preferably 500 PaS to 2000 PaS. If the melt viscosity η of the thermoplastic resin layer is less than 200 PaS at 110 ° C., the thermoplastic resin layer may protrude during transfer, and the heat roll of the laminate may be soiled. There is a possibility that it is difficult to follow the unevenness on the substrate.

  As a means for adjusting the melt viscosity η of the thermoplastic resin layer to the above range, a method of adjusting the content of the low molecular weight polymer in the polymer constituting the thermoplastic resin layer, 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 at least a polymer substance, a polymerizable monomer, and a photopolymerization initiator. Depending on the case, it can be constituted using a colorant or other components. 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> or 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 = 2~90: 10~98] and, (meth) terpolymer resin with acrylic acid (M ³⁾ and 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 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.

The melt viscosity η at 110 ° C. of the photosensitive resin layer of the present invention is 350 PaS to 18000 PaS, preferably 500 PaS to 150,000 PaS, more preferably 1000 PaS to 120,000 PaS.
When the melt viscosity η at 110 ° C. of the photosensitive resin layer is less than 350 PaS, the height variation of the photosensitive resin layer and the spacer becomes large.

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 η at 110 ° C. of the photosensitive resin layer of the present invention is adjusted to 350 PaS to 180,000 PaS, the ratio B / A is in the range of 0.4 to less than 0.9, preferably 0.6 to less than 0.8. It is preferable to adjust to the range.
Further, as another means for achieving the preferable range of the melt viscosity, it is preferable that the photosensitive resin layer contains an extender pigment or a color pigment. 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 color pigment include pigments described in JP-A No. 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.

  As a layer thickness of the photosensitive resin layer, 1-14 micrometers is preferable and 1-6 micrometers is more preferable. If the layer thickness is less than 1 μm, pinholes may occur during coating formation during production, and if it exceeds 14 μm, it may take a long time to remove unexposed portions during development, which is not preferable. .

-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, Amogen 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, or a polypropylene sheet or film is 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 having irregularities on at least one surface, perform at least one exposure, perform one development step, and perform at least one baking. In this case, the transfer target, which is a substrate having irregularities on at least one surface, is formed by a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with wiring, a light shielding film, or the like that constitutes a liquid crystal display device. And a substrate with a frame, a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter, and a driving substrate with a driving element (for example, a thin film transistor [TFT]).

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 Laid-Open Patent Publication No. 2004-333647), “Method of producing color filter for large liquid crystal by Transer system” (“Challenge to the limit-1:“ Challenge to nano size, macro size ””, 2004 8
See 27th May; sponsored by Chemical Society of Japan)

  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 part or the non-exposed part.

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>
In the present invention, the laminate is appropriately selected from spacers formed on the substrate, colored pixels formed on the substrate, black matrix formed on the substrate, etc., obtained using the photosensitive transfer material of the present invention. The

《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 a 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 drive element, the liquid crystal display device substrate of the present invention has the photosensitive property of the present invention so as to cover the display light-shielding portion and the drive 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 enclosed in the gap (an encapsulated portion is referred to as a liquid crystal layer). The spacer disposed on the substrate in order 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, and (b) the color filter is directly formed on the driving side substrate. Examples include a color filter integrated drive substrate and a counter substrate provided with a counter electrode (conductive layer) arranged to face each other with a spacer interposed therebetween, and a liquid crystal material 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.
<Coating liquid for thermoplastic resin layer>
The thermoplastic resin layer coating liquid is prepared by mixing the components shown in Table 1 at the blending ratios shown in Table 2, and using the thermoplastic resin layer coating liquids of Examples 1 to 11 and Comparative Examples 1 to 3, respectively. It was adjusted.

Example 1
A thermoplastic resin layer coating solution having the composition of Example 1 in Table 2 is applied onto a temporary support made of a polyethylene terephthalate film having a width of 1610 mm and a thickness of 75 μm, and then dried, whereby a heat of 3 μm in thickness is obtained. A plastic resin layer was formed.

Next, an intermediate layer having a thickness of 0.8 μm was formed on the thermoplastic resin layer by applying and drying an intermediate layer coating solution 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 GAF Corporation)
・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 44 parts ・ Distilled water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 53 parts

  Furthermore, the photosensitive resin layer whose thickness is 4.0 micrometers was formed by apply | coating and drying the coating liquid for photosensitive resin layers of the following composition. The content of colloidal silica contained in the photosensitive resin layer was 20% by mass. On this photosensitive resin layer, a cover film made of polypropylene (thickness: 12 μm) was provided by pressure bonding to prepare a photosensitive transfer material.

<Coating liquid P1 for photosensitive resin layer>
・ Colloidal silica dispersion (colloidal silica: 30 parts, methyl ethyl ketone: 70 parts) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 12 parts ・ 1-methoxy-2 -Propyl acetate-45 parts-Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80
(Mass average molecular weight = 40,000) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8 parts ・ DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2-propyl Acetate: 24 parts) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8 parts ・ Hydroquinone monomethyl ether ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.003 parts ・ 2,4-bis- (trichloromethyl) ) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine 0.2 part Victoria pure blue BOHM (Hodogaya Chemical Co., Ltd.) 1 .7 parts Megafak F-780-F (Dainippon Ink Chemical Co., Ltd.)
0.087 parts Methyl ethyl ketone 24.3 parts Methanol ... 1.6 parts

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 Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp through a predetermined photomask,
KOH-based developer (KOH, with nonionic surfactant, trade name: CDK-1, manufactured by Fuji Film Electronics Material Co., Ltd.) diluted to 71 times with pure water at 25 ° C., flat nozzle pressure 0. Shower develop at 15 MPa until the unexposed areas are completely developed,
Unexposed portions of the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer were dissolved and removed. Table 3 shows the evaluation relating to the development time.

  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 3.7 μm on the liquid crystal display substrate.

<Method for Manufacturing Liquid Crystal Display Device>
A polyimide alignment film is formed on the obtained color filter on which the spacer pixel pattern is formed, and rubbed with a roll wrapped with a nylon cloth, and then the electrode substrate facing the substrate for the liquid crystal display device at 180 ° C. Sealed with a sealing material, liquid crystal was injected, and a liquid crystal display device was manufactured.

(Example 2)
In Example 1, a liquid crystal display device was produced in the same manner as in Example 1 except that the thickness of the thermoplastic resin layer was changed from 3 μm to 6 μm.

(Example 3)
In Example 2, liquid crystal was produced in the same manner as in Example 2 except that the amount of colloidal silica added was changed so that the content of colloidal silica contained in the photosensitive resin layer was 20% by mass to 10% by mass. A display device was produced.

Example 4
In Example 2, a liquid crystal display device was produced in the same manner as in Example 2 except that the photosensitive resin layer coating liquid P2 was changed to the photosensitive resin layer coating liquid P2 described below instead of the photosensitive resin layer coating liquid P1.

<Coating liquid P2 for photosensitive resin layer>
Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80
(Mass average molecular weight = 40,000) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10 parts DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2 -Propyl acetate: 24 parts) ............ 9.9 parts ・ Hydroquinone monomethyl ether ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.004 parts ・ 2,4- Bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine 0.25 part Victoria pure blue BOHM (Hodogaya Chemical Co., Ltd.)・ 1.7 parts ・ Megafac F-780-F (Dainippon Ink Chemical Co., Ltd.)
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.087 parts ・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 32.7 parts ・ Methanol・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.6 parts

(Example 5)
In Example 4, a liquid crystal display device was produced in the same manner as in Example 4 except that the thickness of the intermediate layer was changed from 0.8 μm to 1.6 μm.

(Example 6)
In Example 5, a liquid crystal display device was produced in the same manner as in Example 5 except that the composition of the coating solution for the thermoplastic resin layer was changed to the composition of Example 6 in Table 2.

(Example 7)
In Example 2, a liquid crystal display device was produced in the same manner as in Example 2 except that the film thickness of the photosensitive resin layer was changed from 3.7 μm to 5.2 μm.

(Example 8)
In Example 2, a liquid crystal display device was produced in the same manner as in Example 2 except that the film thickness of the photosensitive resin layer was changed from 3.7 μm to 2.5 μm.

Example 9
In Example 1, a liquid crystal display device was produced in the same manner as in Example 1 except that the film thickness of the thermoplastic resin layer was changed from 3 μm to 10 μm.

(Example 10)
In Example 1, the composition of the thermoplastic resin layer coating solution was changed to the composition of Example 10 in Table 2, and the film thickness of the thermoplastic resin layer was changed from 3 μm to 6 μm in the same manner as in Example 1. A liquid crystal display device was produced.

(Example 11)
In Example 1, the composition of the thermoplastic resin layer coating solution was changed to the composition of Example 11 in Table 2, and the film thickness of the thermoplastic resin layer was changed from 3 μm to 6 μm in the same manner as in Example 1. A liquid crystal display device was produced.

(Comparative Example 1)
In Example 6, a liquid crystal display device was produced in the same manner as in Example 6 except that the formulation P2 of the photosensitive resin layer coating solution was changed to the following formulation P3.
<Coating liquid P3 for photosensitive resin layer>
Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80
(Mass average molecular weight = 40,000) ............ 9.3 parts DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2- Propyl acetate: 24 parts) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 11 parts ・ Phenothiazine ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.0043 parts ・ 2 , 4-Bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine, 0.27 part Victoria pure blue BOHM ... ················································· 1.7 ... 33 parts, 1-methoxy- - propyl acetate ............. 45 parts Methanol ........................... 1.6 parts

(Comparative Example 2)
In Comparative Example 1, the composition of the thermoplastic resin layer coating solution was changed to Comparative Example 2 in Table 2, and the formulation P3 of the photosensitive resin layer coating solution was changed to the above formulation P2, and Comparative Example 1 and A liquid crystal display device was produced in the same manner.

(Comparative Example 3)
In Comparative Example 1, the composition of the thermoplastic resin layer coating solution was changed to Comparative Example 3 in Table 2, the formulation P3 of the photosensitive resin layer coating solution was changed to the following formulation P4, and the film thicknesses were A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the plastic resin layer was changed to 14.6 μm and the photosensitive resin layer was changed to 5.2 μm.

<Coating liquid P4 for photosensitive resin layer>
Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80
(Mass average molecular weight = 40,000) ················ 3.0 parts DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2- Propyl acetate: 24 parts) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.8 parts Silica sol 30 mass% methyl isobutyl ketone dispersion ・ 7.1 parts (MIBK-ST, manufactured by Nissan Chemical Co., Ltd.) )
・ Phenothiazine ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.001 part ・ 2,4-Bis- (trichloromethyl) -6- [4- (N, N- Diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine ..0.19 part Victoria Pure Blue BOHM .............. 0.02 part. Mega Fax F-780-F (Dainippon Ink Chemical Co., Ltd.) ・ ・ ・ 0.01 part ・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7.4 1-Methoxy-2-propyl acetate 8.6 parts Methanol ... 0.5 parts

[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.

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

(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. C and above are practical levels.
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.
The obtained 10,000 spacers were observed with a microscope, and the area of the missing part (indicated by C in the figure) in which nine or more missing spacers (indicated by B in the figure) are continuous from side to side. Asked.
The area (%) of the part where the spacer was removed was calculated by the number of spacers (shown as A in the figure) in which the removal was recognized × the substrate area of the display unit 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.

In Table 3,
* Polymer ratio: High molecular weight polymer / Low molecular weight polymer ** Plasticizer content: Solid content of plasticizer / thermoplastic resin layer formulation

In Examples 1 to 11, which are the present invention, even if the thickness of the thermoplastic resin layer was made thinner than before, it had sufficient cushioning properties and there was little variation in the thickness of the spacer due to poor transfer. The spacers of Comparative Examples 1 to 3 had variations in film thickness, and the liquid crystal display devices using the spacers were not of high quality.
Example 12
The transfer material is changed to a photosensitive transfer material in the form of a roll 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 two photosensitive transfer materials are wound in a roll shape. First and second transfer material feeding mechanisms that house two rotated photosensitive transfer material rolls and feed the photosensitive transfer material from each photosensitive transfer material roll synchronously, and each sent photosensitive transfer First and second processing mechanisms that form half-cut parts (processed parts) that are boundary positions that can be cut in the width direction on the protective film of the material, and adhesive labels that partially have non-adhesive parts are bonded to each protective film. A spacer is formed in the same manner as in Example 1 except that the laminator is provided with the first and second label adhering mechanisms, and a liquid crystal display device including the spacer is manufactured. It was.

(Example 13)
The liquid crystal display device was changed in the same manner as in Example 10 except that the transfer material was changed to a photosensitive transfer material in the form of a roll 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). Produced.

  In the case of Example 12 and Example 13, the height variation of the spacer is as good as in Examples 1 to 11, and is more preferable in that it can be transferred to a large substrate using a conventional transfer material.

These are explanatory drawings for showing a calculation method of the remaining ratio of the spacer.

Explanation of symbols

10 Substrate A Spacer B Spacer missing part (Non-calculated part)
C Spacer missing area (calculated area)

Claims (10)

A photosensitive transfer material having at least a thermoplastic resin layer and a photosensitive resin layer in order from the temporary support side on the temporary support, and the melt viscosity η at 110 ° C. of the thermoplastic resin layer is 200 to 3000 PaS. , and the and the melt viscosity η at 110 ° C. of the photosensitive resin layer is 350PaS～180000PaS, and a thermoplastic layer thickness of the resin layer is 2~14μm der Ru sensitive optical transfer material, on at least one surface A method for producing a laminate, which is transferred to a substrate having irregularities, exposed at least once, subjected to at least one development step and baked at least once to form a laminate composed of spacers provided on the substrate . The photosensitive transfer material is an optical transfer material feeling that having a least intermediate layer, The method according to claim 1 laminate according to the thickness of the intermediate layer is equal to or is 1.6μm or less . The method for producing a laminate according to claim 1 or 2, wherein the photosensitive resin layer contains a filler. The said filler is an extender or a pigment, The manufacturing method of the laminated body of Claim 3 characterized by the above-mentioned. The method for producing a laminate according to any one of claims 1 to 4, wherein the photosensitive resin layer has a thickness of 1 µm to 10 µm. The method for producing a laminate according to any one of claims 1 to 5, wherein the thermoplastic resin layer includes a polymer and a plasticizer. A laminate produced by the method according to claim 6 . A substrate for a liquid crystal display device comprising the laminate according to claim 7 . The liquid crystal display element provided with the board | substrate for liquid crystal display devices of Claim 8 . A liquid crystal display device comprising the liquid crystal display element according to claim 9 .

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