JP2012078528A - Photosensitive composition, photosensitive resin transfer film, resin pattern and production method of resin pattern, substrate for liquid crystal display device, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having good developability and showing excellent insulating property, transparency, alkali resistance and adhesiveness to a substrate of a cured film of the composition, and to provide a photosensitive resin transfer film, a resin pattern, a production method of a resin pattern, a substrate for a liquid crystal display device and a liquid crystal display device using the composition.SOLUTION: The photosensitive composition contains (A) a resin having an acidic group in a side chain, (B) dipentaerythritol (meth)acrylate (b1) and a polymerizable compound expressed by general formula (b2), and (C) a photopolymerization initiator. When the content of (b1) and the content of the compound expressed by general formula (b2) are denoted by W1 and W2, respectively, with respect to the whole content of polymerizable compounds, W1 and W2 satisfy the relationship represented by expressions (1): 0.6≤W2/W1≤3.0 and (2): 63 mass%≤W1+W2≤100 mass%. The ratio of the content of the (C) photopolymerization initiator to the whole content of the polymerizable compounds is 0.6 or more and less than 5.

Description

  The present invention provides a photosensitive composition, a photosensitive resin transfer film, a resin pattern, and an insulating layer and an overcoat layer for use in a touch panel element having excellent resistance such as insulation, transparency, developability, and alkali resistance. The present invention relates to a resin pattern manufacturing method, a liquid crystal display device substrate, and a liquid crystal display device.

  Conventionally, liquid crystal display devices are widely used in display devices that display high-quality images. The liquid crystal display device is formed by disposing a liquid crystal layer capable of displaying an image with a predetermined orientation between a color filter substrate and a TFT substrate. The black matrix, pixels, overcoat layer, liquid crystal alignment control protrusions, and spacers used in the color filter are patterned exposure of the photosensitive resin layer formed using the photosensitive composition and the photosensitive resin transfer film, It consists of a resin pattern formed on the substrate by patterning with alkali development and further baking.

  In recent years, the demand for liquid crystal display devices equipped with a touch panel as seen in bank ATMs, ticket issuing machines, and portable terminals has been increasing. As a touch panel system, an ultrasonic system, a resistive film system, a capacitive system, and the like are known. From the viewpoint of durability, a demand for a capacitive touch panel is expected to further increase.

  The capacitive touch panel element is manufactured by sandwiching an insulating layer between transparent electrode patterns to form a capacitor, and further covering with an overcoat layer or the like. During the process, the display element is immersed in a solvent, acid or alkali solution, and the surface is locally exposed to a high temperature when sputtering for forming the wiring electrode layer is performed. Therefore, in order to prevent the device from being deteriorated or damaged by such treatment, a transparent insulating layer resistant to these treatments and an overcoat layer laminated thereon are required.

  Such an insulating layer and an overcoat layer have high adhesion to a substrate on which they are to be formed or an adjacent layer such as a conductive layer, the film itself is smooth and tough, and has transparency. It has high heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, and has excellent water resistance, solvent resistance, acid resistance, and alkali resistance. Some performance is required.

  As a transparent photosensitive resin composition, for example, a thermosetting composition containing a polymer having a glycidyl group is known as a protective film for a color filter or the like (see, for example, Patent Document 1 and Patent Document 2). )

  Moreover, the photosensitive resin composition for producing simultaneously an overcoat layer and the columnar spacer arrange | positioned on it is known (for example, patent document 3).

  Usually, the protective film, the overcoat layer, and the columnar spacer are formed through a thermal baking process of 60 minutes or more at a temperature of 200 ° C. or higher. From the viewpoint of responding to a certain substrate, lowering or shortening of the thermal baking process has been studied, and not only high temperature but also a photosensitive resin composition having the same performance as the conventional thermal baking process at low temperature or short time. It is strongly desired.

  However, the thermosetting composition as described above does not have sufficient storage stability at room temperature, and when applied to a transfer material, the thermosetting composition has a drawback that curing proceeds more and developability deteriorates.

On the other hand, the resin composition used for the spacer is characterized by containing a mixture of dipentaerythritol, tripentaerythritol and tetrapentaerythritol, and a (meth) acrylic acid ester mixture which is a reaction product of (meth) acrylic acid. A resin composition is disclosed (for example, see Patent Document 4).
However, the resin composition is mainly intended to improve heat-resistant dimensional stability against heat and rubbing resistance, and when applied to a dot-shaped photospacer with a small area, it can ensure close contact with the lower layer. When applied to a protective film having a large area, it was difficult to say that the adhesion to the lower layer was sufficient. In particular, in the case of a thin film or a low baking temperature of 150 ° C. or less, the shrinkage force at the time of exposure cannot be relaxed, so that the adhesiveness has not reached the practical level.

JP-A-5-78453 JP 2001-91732 A JP 2009-109725 A JP 2002-212235 A

The present invention has been made on the basis of the circumstances as described above, and its purpose is that the developability is good, and the formed cured film is insulated even by a thermal baking step in a temperature range of 150 ° C. or lower. Provided is a photosensitive composition that is excellent in adhesion, transparency, alkali resistance, and the like, and has good adhesion to a substrate and is useful for forming an insulating layer and an overcoat layer, and a photosensitive resin transfer film using the same. There is.
A further object of the present invention is to provide a resin pattern production method using the photosensitive composition of the present invention, a resin pattern obtained thereby, having excellent transparency and adhesion to a substrate, and the resin pattern. The object is to provide a substrate for a liquid crystal display device and a liquid crystal display device.

The above object is achieved by the present invention described below.
That is, the configuration of the present invention is as follows.
<1> (A) a resin having an acidic group in the side chain, (B) a polymerizable compound represented by the following general formula (b1) and a polymerizable compound represented by the general formula (b2), and (C) A photopolymerization initiator,
The content of the polymerizable compound represented by the general formula (b1) with respect to the total content of the polymerizable compound is W1 (mass%), and the content of the polymerizable compound represented by the general formula (b2) is W2. When (mass%), W1 and W2 satisfy the relationship shown in the following formulas (1) and (2),
And the photosensitivity whose content ratio [content of (C) / total content of polymeric compound] of this (C) photoinitiator with respect to the total content of a polymeric compound is 0.6 or more and less than 5 Composition.
0.6 ≦ W2 / W1 ≦ 3.0 Formula (1)
63% by mass ≦ W1 + W2 ≦ 100% by mass (2)

(In the general formula (b1), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same as or different from each other, provided that in the molecule. At least 4 of X in the formulas represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

(In the general formula (b2), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same or different from each other, provided that in the molecule. At least 6 of X's represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
<2> The photosensitive composition according to <1>, further including a polymerizable compound having a structure different from that of the polymerizable compound (B).
<3> The mass ratio [(total content of polymerizable compound) / (A) content] of the total content of the polymerizable compound contained to the content of the resin (A) is 0.45 to 1. The photosensitive composition as described in <1> or <2> which is .6.
<4> A photosensitive resin transfer film having at least a photosensitive resin layer made of the photosensitive composition according to any one of <1> to <3> on a temporary support.
<5> The photosensitive resin transfer film according to <4>, wherein at least one of an oxygen blocking layer and a thermoplastic resin layer is provided between the photosensitive resin layer and the temporary support.

<6> A photosensitive resin layer forming step of providing a photosensitive resin layer on the substrate using the photosensitive composition according to any one of <1> to <3>, and pattern exposure of the photosensitive resin layer. A resin pattern comprising: an exposing step for developing; a developing step for developing the exposed photosensitive resin layer to form a patterned resin layer; and a heating step for heating the patterned resin layer obtained by development Is the method.
<7> The method for producing a resin pattern according to <6>, wherein the photosensitive resin layer forming step is a step of applying and drying the photosensitive composition on a substrate.
<8> A photosensitive resin layer forming step in which a photosensitive resin layer is provided on the substrate using the photosensitive resin transfer film according to <4> or <5>, and an exposure step in which the photosensitive resin layer is subjected to pattern exposure. The method for producing a resin pattern includes: a developing step of developing the exposed photosensitive resin layer to form a patterned resin layer; and a heating step of heating the patterned resin layer obtained by development.
<9> In the photosensitive resin layer forming step, the photosensitive resin layer included in the photosensitive resin transfer film is brought into contact with the substrate, and at least one of heating and pressurization is performed on the substrate from the temporary support. It is a manufacturing method of the resin pattern as described in <8> which is the process of transferring the photosensitive resin layer.

<10> The method for producing a resin pattern according to any one of <6> to <9>, wherein a thickness of the photosensitive resin layer provided on the substrate is in a range of 0.7 μm to 3.0 μm. .
<11> A resin pattern obtained by the method for producing a resin pattern according to any one of <6> to <10>.
<12> A substrate for a liquid crystal display device comprising the resin pattern according to <11>.
<13> A liquid crystal display device comprising the liquid crystal display device substrate according to <12>.
Since the present invention is configured as described above, it has excellent resistance to insulation, transparency, alkali resistance, etc. not only by the conventional high temperature but also by baking in a relatively low temperature region of 150 ° C. or less, and an insulating layer or overcoat for touch panel elements. It is possible to provide a photosensitive composition and a photosensitive resin transfer film, which are useful for producing a layer.

According to the present invention, the developability is good, and the resistance of the formed cured film, such as insulation, transparency, alkali resistance, and the like, as well as with the substrate, even by a thermal baking process in a temperature range of 150 ° C. or lower. A photosensitive composition having excellent adhesion and useful for forming an insulating layer and an overcoat layer, and a photosensitive resin transfer film using the same can be provided.
Further, according to the present invention, by using the photosensitive composition of the present invention, a resin pattern manufacturing method, a resin pattern obtained thereby, having excellent transparency and adhesion to a substrate, the resin pattern It is possible to provide a liquid crystal display device substrate and a liquid crystal display device including

  Hereinafter, the photosensitive composition, photosensitive resin transfer film, resin pattern and resin pattern manufacturing method, liquid crystal display substrate and liquid crystal display device of the present invention will be described in detail.

<Photosensitive composition>
The photosensitive composition of the present invention comprises (A) a resin having an acidic group in the side chain, (B) a polymerizable compound represented by the following general formula (b1), and a polymerizable compound represented by the general formula (b2). And (D) a photopolymerization initiator, and, if desired, a polymerizable compound having a structure different from that of the polymerizable compound (B) (hereinafter referred to as other polymerizable compound as appropriate). You may go out.
In the present invention, two kinds of (B) polymerizable compounds having specific structures described in detail below are included in a specific ratio, and other polymerizable compounds included as desired and the total content of the (B) polymerizable compounds are included. It contains the photopolymerization initiator (C) in a specific ratio with respect to the amount.
Hereinafter, each component which the photosensitive composition of this invention contains is demonstrated one by one.
-(A) Resin having an acidic group in the side chain-
The photosensitive composition of this invention contains (A) resin which has an acidic group in a side chain [Hereinafter, it is suitably called (A) specific resin.].
(A) The specific resin is not particularly limited as long as it has an acidic group in the side chain. In addition to the group having an acidic group: Y (y mol%), the side chain is further branched and / or alicyclic. It preferably contains a group having a structure: X (x mol%) and a group having an ethylenically unsaturated group: Z (z mol%), and if necessary, other groups (L) (1 mol%) You may have. (A) A plurality of X, Y, and Z may be combined in one group in the specific resin.

  There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

There is no restriction | limiting in particular as a monomer (monomer which has an acidic group) used in order to introduce | transduce an acidic group into the side chain of the said (A) specific resin, Styrenes, (meth) acrylates, vinyl ethers , Vinyl esters, (meth) acrylamides and the like introduced with acidic groups such as the above carboxyl groups, (meth) acrylates, vinyl esters, (meth) acrylamides introduced with acidic groups Preferably, an acidic group is introduced into (meth) acrylates.
In this specification, when referring to both or one of “acrylic” and “methacrylic”, when referring to “(meth) acrylic” and either or both of “acrylate” and “methacrylate” ) Acrylate ".

  Specific examples of the monomer having an acidic group can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, Itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate Etc. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

  (A) As for the introduction amount of the monomer which has an acidic group in the side chain in specific resin, 5-70 mol% is preferable, 10-60 mol% is further more preferable, and 20-50 mol% is especially preferable. When the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.

  Further, the preferred range of the acid value suitable for (A) the specific resin varies depending on the molecular structure that can be taken, but it is generally preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 -130 mg KOH / g is particularly preferred. When the acid value is within the preferable range, an insulating layer and an overcoat layer excellent in good insulation, transparency, water resistance, alkali resistance and acid resistance can be obtained. For this reason, what is necessary is just to determine the usage-amount of the monomer which has an acidic group in a side chain so that an acid value may become the said range.

In addition, as described above, (A) the specific resin may further have a “group having a branched and / or alicyclic structure” or an “ethylenically unsaturated group” in the side chain.
That is, the specific resin (A) in the present invention comprises a group having a branched and / or alicyclic structure in the side chain: X (x mol%), a group having an acidic group: Y (y mol%), ethylene Insulating property and transparency of the resin pattern to be formed should be a copolymer of at least terpolymer having a group having a polymerizable unsaturated group: Z (z mol%) in different copolymer units. From the viewpoint of water resistance, alkali resistance, reduction of acid-resistant development residue, and reticulation. Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.

Hereinafter, the “group having a branched and / or alicyclic structure in the side chain” will be described.
Examples of the branched group include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. , 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are more preferable.

  The group having an alicyclic structure represents an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group. , Tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, and tricyclopentanyl group. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, a tricyclopentenyl group, and the like. Is preferred.

  Examples of the monomer containing a group having a branched and / or alicyclic structure in the side chain include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like ( (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth ) T-butyl acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic acid 3-octyl, t-octyl (meth) acrylate, and the like, among which (meth)
I-propyl acrylate, i-butyl (meth) acrylate, t-butyl methacrylate and the like are preferable, and i-propyl methacrylate and t-butyl methacrylate are more preferable.

Next, a specific example of the monomer containing a group having an alicyclic structure in the side chain is (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2- Methyl-2-adamantyl, (meth) acrylic acid 2-ethyl-2-adamantyl, (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid o Tahydro-4,7-mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, (meth) acrylate-1-menthyl, tricyclo (meth) acrylate Decyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [ 4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, (meth) And cyclohexyl acrylate.
Among these (meth) acrylates, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylate, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 1-menthyl, (meth) acrylic acid tricyclodecyl, etc. are preferred, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

  The copolymer composition ratio of the respective components of the specific resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally stated, but “has a branched and / or alicyclic structure in the side chain. The “group” is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. When the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the developer resistance of the image area is also good.

  The “ethylenically unsaturated group” is not particularly limited, but a (meth) acryloyl group is preferable. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group. The method for introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known ones. For example, a compound having an acidic group (for example, acrylic acid, methacrylic acid, vinylbenzoic acid, maleic acid, maleic acid) A method of adding a (meth) acrylate having an epoxy group to a monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, etc., a group having a hydroxyl group (for example, 2- Examples thereof include a method of adding (meth) acrylate having an isocyanate group to hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, etc., and a method of adding (meth) acrylate having a hydroxy group to a group having an isocyanate group.

Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.
The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these.

  The content of the repeating unit having an “ethylenically unsaturated group in the side chain” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 70 mol%. When the group having an ethylenically unsaturated group in the side chain is within the above range, developability and curability are also good.

  (A) The specific resin may include a repeating unit derived from another monomer in addition to the three types of repeating units. Such other monomer is not particularly limited, for example, (meth) acrylic acid ester having no branched and / or alicyclic structure, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, And monomers having a hydrocarbon alkenyl group.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.
The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in said (A) specific resin, it is preferable that molar composition ratio is 0-30 mol%, and it is more preferable that it is 0-20 mol%.

  Specific examples of (A) specific resin include compounds represented by compounds P-1 to P-35 described in paragraph numbers [0057] to [0063] of JP-A-2008-146018.

  Said (A) specific resin is made from the process of two steps, the process of the (co) polymerization reaction of a monomer, and the process of introduce | transducing an ethylenically unsaturated group. First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

  (A) The weight average molecular weight of the copolymer suitable as the specific resin is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is less than 10,000, the strength of the resin decreases, the insulating layer and the overcoat layer tend to cohesively break, and the development speed becomes too fast, so that the resin pattern easily drops off the substrate. Become. When the weight average molecular weight exceeds 100,000, the development residue increases, which is not preferable.

  (A) The glass transition temperature (Tg) suitable as the specific resin is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, an insulating layer and an overcoat layer excellent in good insulation, transparency, water resistance, alkali resistance and acid resistance can be obtained.

The (A) specific resin has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000. Good insulation, transparency, water resistance, and alkali resistance The insulating layer and the overcoat layer excellent in acid resistance are preferable.
Furthermore, a preferable example of the (A) specific resin is more preferably a resin in which all of the preferable molecular weight, glass transition temperature (Tg), and acid value are in the preferable range.

As content of the said (A) specific resin, 5-70 mass% is preferable with respect to the said photosensitive composition total solid, and 10-50 mass% is more preferable.
In addition, solid content means the total amount of the other component except a solvent in the photosensitive composition here.
The photosensitive composition of the present invention may contain, in addition to the specific resin (A), a resin other than the resin having an acidic group in the side chain (other resin) as long as the effects of the present invention are not impaired. . When other resins are contained, the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass of the (A) specific resin. The aspect containing only is more preferable.

-(B) Polymerizable compound represented by general formula (b1) and Polymerizable compound represented by general formula (b2)-
The photosensitive composition of the present invention contains at least one of two kinds of specific polymerizable compounds each having the structure shown below, and further contains (B-2) another polymerizable compound having a structure different from these. May be.

(In the general formula (b1), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same as or different from each other, provided that in the molecule. At least 4 of X in the formulas represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

(In the general formula (b2), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same or different from each other, provided that in the molecule. At least 6 of X's represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

Here, the content of the polymerizable compound represented by the general formula (b1) with respect to the total amount of the polymerizable compound contained in the photosensitive composition is represented by W1 (mass%) and the general formula (b2). When the content rate of a polymeric compound is set to W2 (mass%), it is required that W1 and W2 satisfy | fill the relationship shown to following formula (1) and Formula (2). When the contents W1 and W2 satisfy the relationship shown in the following formulas (1) and (2), the insulating layer and overcoat for a touch panel element excellent in insulation, transparency, water resistance, alkali resistance, and acid resistance A resin pattern such as a layer can be provided.
0.6 ≦ W2 / W1 ≦ 3.0 Formula (1)
63% by mass ≦ W1 + W2 ≦ 100% by mass (2)

[Polymerizable compound represented by formula (b1)]
In the polymerizable compound represented by the general formula (b1), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —, and H ₂ C═C contained in one molecule of the polymerizable compound. (R) -C (O)-is 4 or more. More preferably, the number is 5 or more, and the most preferable are 5.5 and 6. In addition, this number may be shown by an average value. For example, an equivalent mixture of 5 and 2 containing H ₂ C═C (R) —C (O) — per molecule H ₂ C═C (R) —C (O) — is contained in one molecule at 5.5.
R is a hydrogen atom or a lower hydrocarbon group having 4 or less carbon atoms such as a methyl group, more preferably a lower hydrocarbon group having 2 or less carbon atoms such as a hydrogen atom or a methyl group, most preferably. Is a hydrogen atom or a methyl group. Rs in H ₂ C═C (R) —C (O) — contained in one molecule may be the same or different from each other, but are preferably the same in terms of synthesis suitability.
Specific examples of the polymerizable compound represented by the general formula (b1) include dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta Mention may be made of erythritol hexaacrylate and mixtures thereof.
Of these, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are more preferred.

[Polymerizable compound represented by formula (b2)]
In the polymerizable compound represented by the general formula (b2), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —, and H ₂ C═C contained in one molecule of the polymerizable compound. (R) -C (O)-is 6 or more. More preferably, the number is 7 or more, and the most preferable are 7.5 and 8. In addition, this number may be shown by an average value. For example, an equivalent mixture of 7 and 8 containing H ₂ C═C (R) —C (O) — in one molecule, H ₂ C═C (R) —C (O) — is assumed to be contained in 7.5 in one molecule.
R is a hydrogen atom or a lower hydrocarbon group having 4 or less carbon atoms such as a methyl group, more preferably a lower hydrocarbon group having 2 or less carbon atoms such as a hydrogen atom or a methyl group, most preferably. Is a hydrogen atom or a methyl group. Rs in H ₂ C═C (R) —C (O) — contained in one molecule may be the same or different from each other, but are preferably the same in terms of synthesis suitability.
Specific examples of the polymerizable compound represented by the general formula (b2) include tripentaerythritol hexamethacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripenta Mention may be made of erythritol octaacrylate and mixtures thereof.
Of these, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and mixtures thereof are more preferred.

  More preferable combinations of these include (b1) dipentaerythritol hexa (meth) acrylate and (b2) tripentaerythritol octa (meth) acrylate, (b1) dipentaerythritol hexa (meth) acrylate and (b2) tri Pentaerythritol hepta (meth) acrylate, (b1) dipentaerythritol penta (meth) acrylate and (b2) tripentaerythritol octa (meth) acrylate, (b1) dipentaerythritol penta (meth) acrylate and (b2) tripentaerythritol Hepta (meth) acrylate, (b1) dipentaerythritol hexa (meth) acrylate and (b2) tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (Meth) acrylate mixture, (b1) dipentaerythritol penta (meth) acrylate (b2) tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate mixture, (b1) dipentaerythritol penta (meth) acrylate Mixture of dipentaerythritol hexa (meth) acrylate and (b2) tripentaerythritol octa (meth) acrylate, (b1) Mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate and (b2) tri A pentaerythritol hepta (meth) acrylate mixture is raised.

  More preferably, (b1) dipentaerythritol hexaacrylate and (b2) tripentaerythritol octaacrylate, (b1) dipentaerythritol hexaacrylate and (b2) tripentaerythritol heptaacrylate, (b1) dipentaerythritol pentaacrylate and (b2) ) Tripentaerythritol octaacrylate, (b1) dipentaerythritol pentaacrylate and (b2) tripentaerythritol heptaacrylate, (b1) dipentaerythritol hexaacrylate and (b2) a mixture of tripentaerythritol heptaacrylate and tripentaerythritol octaacrylate, (B1) Dipentaerythritol pentaacrylate (b2) Tripentaerythritol heptaac And (b1) a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate and (b2) a tripentaerythritol octaacrylate, (b1) a dipentaerythritol pentaacrylate and a dipentaerythritol hexaacrylate A mixture and (b2) tripentaerythritol heptaacrylate mixture are mentioned.

The content of the polymerizable compound represented by the general formula (b1) and the polymerizable compound represented by the general formula (b2) with respect to the content of all polymerizable compounds contained in the photosensitive composition of the present invention, When W1 (mass%) and W2 (mass%) are used, it is necessary to satisfy the relationships shown in the following formulas (1) 1 and (2).
0.6 ≦ W2 / W1 ≦ 3.0 Formula (1)
63% by mass ≦ W1 + W2 ≦ 100% by mass (2)

As shown in the formula (2), the polymerizable compound represented by the general formula (b1) and the polymerizable compound represented by the general formula (b2), the respective contents W1 (mass%) and W2 (mass%). ) Is required to be 63% by mass or more and 100% by mass or less from the viewpoint of adhesion to the substrate, preferably 65% by mass or more and 95% by mass, and more preferably 70% by mass or more and 90% by mass or less. is there.
When the total content is less than 63% by mass, the adhesion with the substrate is lowered, which is not preferable. From the viewpoint of developability, the total content is preferably 60% by mass or more. More preferably, it is 63 mass% or more, More preferably, it is 70 mass% or more. If it is less than 60% by mass, the residue during development deteriorates, which is not preferable. That is, in order to satisfy the above two performances, it is necessary that the content is 63% by mass or more and 100% by mass or less, preferably 65% by mass or more and 95% by mass, and more preferably 70% by mass or more and 90% by mass. It is as follows.

  On the other hand, the preferable ratio [W2 / W1] of the content ratios W1 (mass%) and W2 (mass%) is 0.6 or more and 3.0 or less. Preferably they are 0.62 or more and 2.95 or less, More preferably, they are 0.7 or more and 2.6 or less. If it is less than 0.6, the substrate adhesion of the resin pattern immediately after exposure and during development is lowered, and the adhesion of the substrate is similarly reduced even in baking at 150 ° C. or lower. If it exceeds 3.0, the development residue is undesirably deteriorated.

-(B-2) Other polymerizable compounds-
The photosensitive composition of the present invention may contain another polymerizable compound having a structure different from that of the polymerizable compound represented by the general formula (b1) and the general formula (b2). Other polymerizable compounds that can be used together here are the components described in paragraph [0011] of JP-A-2006-23696, and the paragraphs [0040] to [0049] of JP-A-2006-64921. Which are not included in the polymerizable compounds represented by the general formula (b1) and the general formula (b2).
Examples of such a monomer include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
Specific examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, hexanediol di (meth) acrylate , Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanate Rate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; polyfunctional acrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated Examples include functional methacrylate.
Commercially available products may also be used. For example, as urethane (meth) acrylate, U-6HA, U-6LPA, UA-1100H, UA-53H, UA-33H, U-200PA manufactured by Shin-Nakamura Chemical Co., Ltd. UA-4200, UA-7100, UA-32P, UA-7200 (above, trade name).

In the relationship with the specific resin (A), the mass ratio of the total amount of polymerizable compounds contained in the photosensitive composition to the content of the specific resin (A) ((total content of polymerizable compounds)) / (A ) Content] is preferably 0.45 to 1.6.
Further, if desired, the content when (B-2) another polymerizable compound is used in combination is 30% by mass or less with respect to the total content of the polymerizable compound contained in the photosensitive composition of the present invention. It is preferable that it is within a range of 20% by mass or less.
When a photosensitive composition is applied to a final substrate such as a glass substrate to form a pattern, [(total content of polymerizable compound: (B) + (B-2)) / (A) content ] Is more preferably 0.5 to 1.2, and particularly preferably 0.55 to 0.9. When the ratio of [(total content of polymerizable compound) / (A)] is within the above range, the development speed is appropriately maintained, the increase in development residue is suppressed, and pattern chipping or pattern dropout occurs. Even when baked at 150 ° C. or less, adhesion between the formed resin pattern and the substrate is good.

-(C) Photopolymerization initiator-
The photosensitive composition of the present invention contains (C) a photopolymerization initiator. (C) As the photopolymerization initiator, known compounds can be suitably used. For example, triazine derivatives, oxadiazole derivatives, oxime initiators, acetophenone initiators, titanocene initiators, acylphosphine oxides. Preferred examples include system initiators.
Specifically, for example, the components described in paragraph numbers [0012] to [0020] of JP-A-2006-23696, and the paragraph numbers [0050] to [0053] of JP-A-2006-64921 are described. Ingredients.

  Examples of preferable (C) photopolymerization initiator that can be used in the present invention include 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4-bis (trichloro). Methyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine, 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino ] Triazinylamino] -3-phenylcoumarin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- -{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( [eta] 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titani , 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester And the like.

  Among them, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) ) -3-Bromophenyl] -s-triazine, 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin, 2,2-dimethoxy -1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) ) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, A mixture of 2- (2-hydroxyethoxy) ethyl ester is particularly preferred, but not limited thereto.

  The content of the (C) photopolymerization initiator is a ratio [(C) / ((B) + (B-2)) to the total content [(B) + (B-2)] of the polymerizable compound. ] Is preferably 0.6 or more and less than 5, and more preferably 0.75 or more and 3 or less. When the ratio [(C) / (B) + (B-2))] is within the above range, dropping of the resin pattern, reduction of alkali resistance at the time of lift-off of the conductive layer is suppressed, and deterioration of the development residue or pattern The deterioration of the adhesion immediately after exposure is suppressed, and the adhesion between the resin pattern and the substrate is well maintained even when baked at 150 ° C. or lower.

-Other ingredients-
In addition to the components (A) to (D), the photosensitive composition of the present invention can use known additives as other components depending on the purpose as long as the effects of the present invention are not impaired. Examples of such compounds include the components described in paragraph numbers [0012] to [0020] of JP-A-2006-23696, and paragraph numbers [0050] to [0053] of JP-A-2006-64921. The components described are mentioned.

Since the photosensitive composition of the present invention has the above-described configuration, the developability is good, and the formed resin pattern is excellent in adhesion to the substrate and transparency.
Examples of the method of using the resin composition include a support for forming a resin pattern, or a method for forming a photosensitive composition layer by applying the photosensitive composition of the present invention to a substrate. You may form the photosensitive resin transfer film formed by applying the photosensitive composition of this invention on a body, and forming a photosensitive composition layer.
<Photosensitive resin transfer film>
The photosensitive resin transfer film of the present invention is characterized by having at least a photosensitive resin layer made of the photosensitive composition of the present invention on a temporary support.
Although the film thickness of the photosensitive resin layer is appropriately selected according to the purpose, it is generally preferably in the range of 0.7 μm to 3.0 μm as described later.

  In the case of producing a photosensitive resin transfer film, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. . Thereby, the exposure sensitivity can be increased. Moreover, in order to improve transferability, you may provide the thermoplastic resin layer which has cushioning properties.

  Regarding the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, the other layers, and the method for producing the photosensitive transfer film constituting the photosensitive transfer film, paragraph numbers [0024] to JP-A-2006-23696. [0030], the constitution and the method for producing a photosensitive resin transfer film described herein are applied to the production of the photosensitive resin transfer film of the present invention.

<Method for producing resin pattern>
Next, the manufacturing method of the resin pattern of this invention is demonstrated.
The method for producing a resin pattern of the present invention includes a photosensitive resin layer forming step of providing a photosensitive resin layer on a substrate using the photosensitive composition of the present invention, and an exposure step of pattern exposing the photosensitive resin layer. The development process which develops the exposed photosensitive resin layer and forms a patterned resin layer, and the heating process which heats the patterned resin layer obtained by image development are included.

  According to the method for producing a resin pattern of the present invention, a resin pattern such as an insulating layer and an overcoat layer used for a touch panel element having excellent resistance such as insulation, transparency, developability, and alkali resistance can be easily produced.

[Photosensitive resin layer forming step]
The photosensitive resin layer forming step in the production method of the present invention includes a photosensitive resin layer containing the photosensitive composition of the present invention on a substrate serving as a support (hereinafter also simply referred to as “photosensitive resin composition layer”). Is a step of forming.

  This photosensitive resin layer constitutes a resin pattern such as an insulating layer and an overcoat layer through a manufacturing process described later. By using the resin pattern, resistance such as insulation, transparency, developability, and alkali resistance is improved.

  As a method of forming a photosensitive resin layer on a support, (a) a method of applying a solution containing a photosensitive composition by a known coating method, and (b) a transfer method using a photosensitive resin transfer film. A method of laminating is preferable. Each will be described below.

(A) Coating method The photosensitive composition is coated by a known coating method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, It can be carried out by a gravure coating method or an extrusion coating method using a popper described in US Pat. No. 2,681,294.
Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, among others. A method using a slit nozzle or a slit coater described in JP-A-2001-310147 is suitable.

(B) Transfer method In the case of transfer, using a photosensitive resin transfer film, a photosensitive resin layer formed in a film shape on a temporary support is pressure-bonded with a roller or flat plate heated and / or pressurized on the support surface. After bonding by thermocompression bonding, the photosensitive resin composition layer is transferred onto the support by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

  When the photosensitive resin layer is applied and formed by both (a) the coating method and (b) the transfer method, the layer thickness is preferably 0.7 μm to 3.0 μm, and more preferably 0.9 μm to 2 μm. When the layer thickness is in the above range, generation of pinholes when forming the photosensitive resin layer, decrease in adhesion after baking, and increase in development residue are suppressed, and a good resin pattern is formed under appropriate development conditions.

-Board-
Examples of the support (substrate) for forming the photosensitive resin layer include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (both a color filter substrate). And a driving substrate with a driving element (for example, a thin film transistor [TFT]). The thickness of the support is generally preferably 700 to 1200 μm.

[Patterning process]
The patterning step in the present invention includes an exposure step for pattern exposure of the photosensitive resin layer formed on the support, and a development step for developing the exposed photosensitive resin layer to form a resin pattern. Specific examples of the patterning process include the formation examples described in paragraphs [0071] to [0077] of Japanese Patent Application Laid-Open No. 2006-64921 and the paragraph numbers [0040] to [0051] of Japanese Patent Application Laid-Open No. 2006-23696. The described steps and the like are also preferable examples in the present invention.

[Heating process]
In the manufacturing method of the resin pattern of this invention, the heating process which heats the pattern-shaped resin layer obtained by image development is implemented following the said patterning process.
Usually, the heating conditions in the heating step performed for improving the strength of the resin pattern and the adhesion to the substrate are in the range of 200 to 250 ° C. In the method for producing a resin pattern of the present invention, Since the photosensitive resin composition is used, when the heating condition in the heating step is 150 ° C. or lower, more specifically, even when the heating condition is in the range of 100 to 150 ° C., discoloration of the resin pattern due to heating is suppressed, and the substrate It is possible to form a resin pattern having excellent adhesion to the resin.
Moreover

<Touch panel element>
The insulating layer used in the touch panel element and the overcoat layer laminated thereon are formed on the transparent substrate for touch panel (for example, a glass substrate, a plastic substrate, a substrate provided with a thin film transistor [TFT] on the back), and a first conductive layer pattern (Metal, ITO, etc.) are formed, an insulating layer pattern is formed, a second conductive pattern is further formed, and a capacitor is formed. Subsequently, a patterned overcoat layer is formed.
Specifically, it is formed sequentially as follows.

~ First conductive layer pattern ~
The following two types are mentioned as the first conductive layer pattern forming method.
One is a method of forming a conductive layer pattern by etching. After uniformly forming a metal layer or ITO layer on the substrate by vapor deposition or the like, the resist layer was laminated using a resist solution or a transfer material having a resist layer. The resist layer was exposed and developed to form a pattern. Furthermore, the pattern of a 1st electroconductive layer can be formed by etching with an acid.

  The other is a method for forming a conductive layer pattern by lift-off. A resist layer is laminated on a substrate using a transfer material having a resist solution or a resist layer, and the resist layer is exposed and developed to form a pattern. The shape of this pattern is preferably on a reverse taper. From this, a metal layer or ITO layer is uniformly formed by vapor deposition or the like, and then the metal layer or ITO layer deposited on the resist layer is peeled off together with the resist layer with a stripping solution to form a similar pattern. .

~ Insulating layer pattern ~
The insulating layer is directly applied to the substrate on which the first conductive layer pattern is formed, or a photosensitive transfer material is heated and pressure-bonded to form a photosensitive resin layer, followed by exposure, development and baking. An insulating layer pattern is formed.

~ Second conductive layer pattern ~
The second conductive layer pattern can be formed on the substrate on which the insulating layer pattern is formed in the same manner as the first conductive layer pattern forming method.

~ Overcoat layer ~
The overcoat layer can be formed on the substrate on which the second conductive layer pattern has been formed in the same manner as the method for forming the insulating layer pattern.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention comprises a black shielding part, a coloring part, and a photo spacer. The photospacer is preferably formed on a black light-shielding portion such as a black matrix formed on the support or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a black light shielding portion such as a black matrix, a driving element such as a TFT, and a photo spacer.

  For example, when the photo spacer is provided on the display light-shielding part or the driving element, the display light-shielding part (black matrix or the like) or the TFT driving element previously disposed on the support is covered, for example, photosensitive. By laminating the photosensitive resin layer of the resin transfer film on the support surface and peeling and transferring to form a photosensitive resin layer, the photosensitive resin layer is subjected to exposure, development, heat treatment and the like to form a photo spacer, thereby forming the present invention. A substrate for a liquid crystal display device can be produced.

<Liquid crystal display element>
A liquid crystal display element can be formed by providing the substrate for a liquid crystal display device of the present invention. As one of the liquid crystal display elements, a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) are provided between a pair of supports (including the substrate for a liquid crystal display device of the present invention), at least one of which is transparent. Including at least).

  In this case, the substrate for a liquid crystal display device of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a photo spacer having a uniform height and excellent deformation recovery property, a liquid crystal display element equipped with the color filter substrate has a cell gap unevenness between the color filter substrate and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

  As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving unit between a pair of light transmissive supports (including the liquid crystal display device substrate of the present invention), and the liquid crystal The driving means has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates and excellent deformation recovery.

  Also in this case, the substrate for a liquid crystal display device of the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.

  Examples of liquid crystals that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.

  In addition, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, a black matrix may be formed as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
The liquid crystal display device of the present invention is configured by providing a touch panel element on the liquid crystal display device substrate. That is, as described above, the cell gap is regulated to a predetermined width by the photo spacer and the liquid crystal material is enclosed in the regulated gap between the TFT drive substrate and the color filter substrate that are arranged to face each other. The liquid crystal display device is configured by providing a touch panel element on the TFT drive substrate side of the liquid crystal display element in which the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness.

  A touch panel element in which a first conductive layer pattern, an insulating layer pattern, a second conductive layer pattern, and an overcoat layer are sequentially laminated directly on the surface of the TFT drive substrate opposite to the surface on which the TFT is provided may be used. In this case, it is necessary to fabricate the liquid crystal display device substrate before sealing the liquid crystal between the TFT drive substrate and the color filter substrate at a temperature lower than the heat resistant temperature of the sealing material or the like.

  The liquid crystal display mode in the liquid crystal display device includes STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Preferably mentioned. Among them, in the liquid crystal display device of the present invention, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode that easily causes display unevenness due to fluctuations in the cell thickness of the liquid crystal cell is desirable, and the cell thickness is 2 to 4 μm. The VA display mode, the IPS display mode, and the OCB display mode are preferably configured.

  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; and a counter electrode (conductive layer). And (b) a driving substrate and a counter substrate provided with a counter electrode (conductive layer); and a counter substrate provided with a counter electrode (conductive layer). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, and the like. .

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display element of the present invention. For example, the liquid crystal display device can be configured as various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. . In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

  The liquid crystal display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and the like except that the liquid crystal display device of the present invention described above is provided. It can generally be configured using various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “%” and “part” are based on mass.

Examples 1 to 28 and Comparative Examples 1 to 13 (Insulating layer pattern and overcoat layer: transfer method, three types of sequential developer systems)
Example 1
-Production of photosensitive transfer film for insulating layer and overcoat layer-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A1 was applied, dried at 100 ° C. for 2 minutes, and further at 120 ° C. for 1 minute. It was dried to form a thermoplastic resin layer having a dry layer thickness of 15 μm. Here, the temperatures “100 ° C.” and “120 ° C.” in the drying conditions are both temperatures of the drying air. The same applies to the temperature under the following drying conditions.

[Formulation A1 of coating solution for thermoplastic resin layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55 / 11.7 / 4.5 / 28.8 [mol ratio], weight average molecular weight 90,000) 4 parts · Styrene / acrylic acid copolymer (= 63/37 [mol ratio], weight average molecular weight 8,000) ··· 136 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl 〕propane
··· 90.7 parts · Surfactant 1 (Structure 1 below) · · · 5.4 parts · Methanol ··· 111 parts · 1-methoxy-2-propanol ··· 63 4 parts methyl ethyl ketone 534 parts

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

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution composed of the following formulation B is applied, dried at 80 ° C. for 1 minute, and then further dried at 120 ° C. for 1 minute to obtain a dry layer thickness of 1.6 μm. An intermediate layer was laminated.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol (PVA-205, saponification degree 88%, manufactured by Kuraray Co., Ltd.)
・ ・ ・ ・ 3.22 parts ・ Polyvinylpyrrolidone (PVP K-30, manufactured by IS Japan Co., Ltd.)
・ ・ ・ ・ 1.49 parts ・ Methanol ・ ・ ・ ・ 42.9 parts ・ Distilled water ・ ・ ・ ・ 52.4 parts

  Next, a photosensitive resin layer coating solution having the following formulation 1 was further applied onto the formed intermediate layer, and each was dried at 100 ° C. for 2 minutes, and further dried at 120 ° C. for 1 minute (drying). Condition A), a transparent photosensitive resin layer having a dry layer thickness of 1.38 μm was laminated.

<Coating liquid formulation 1 for photosensitive resin layer>
1-methoxy-2-propyl acetate 599 parts Methyl ethyl ketone 238 parts Solsperse 20000 (Lubrizol) 1.88 parts Polymer 45% solution (JP 2008- Structural formula P-25 described in paragraph No. [0058] of the 146018 publication:
Weight average molecular weight = 35,000, solid content 45%, 1-methoxy-2-propyl acetate 15%, 1-methoxy-2-propanol 40%) [(A) specific resin] 114 parts Mixture of polymerizable compounds: DPHA solution (dipentaerythritol hexaacrylate: 48%, dipentaerythritol pentaacrylate: 28%, 1-methoxy-2-propyl acetate: 24%) [(B) represented by the general formula (b1) 16.3 parts. Mixture of the following polymerizable compounds (n = 1: tripentaerythritol octaacrylate content: 85%, n = 2 and n = 3 as impurities are 15% in total) 20.5 parts [(B) polymerizable compound represented by formula (b2)]
-Urethane monomer (NK Oligo UA-32P, Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, 1-methoxy-2-propyl acetate: 25%) ... 7.72 parts [(B-2) Others Polymerizable compound]
2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine, ... 1.27 parts [(C) Photopolymerization initiator]
2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole [(C) photopolymerization initiator] 0.635 parts Hydroquinone monomethyl ether [solvent] 0.072 parts ・ Megafac F-784-F (manufactured by DIC Corporation) ・ ・ ・ ・ 0.51 part [Surfactant]

  In the above formula, all Xs are acryloyl groups and are a mixture of n = 1-3.

  As described above, after forming a laminated structure of a PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin composition layer, the surface of the photosensitive resin composition layer is further covered with a 12 μm thick cover film. A polypropylene film was applied by heating and pressing to obtain an insulating material and a photosensitive transfer film for overcoat (1). The sample was wound around a 3 inch core of ABS resin, wrapped with a black polyethylene film and a transparent polyethylene film, and stored at 25 ° C. for 7 days.

-Production of photosensitive transfer film for spacers-
On the 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution comprising the above formulation A1 was applied, dried at 100 ° C. for 2 minutes, and further at 120 ° C. It was dried for a minute to form a thermoplastic resin layer having a dry layer thickness of 18 μm.
Next, on the formed thermoplastic resin layer, an intermediate layer coating solution composed of the above-mentioned formulation B is applied, dried at 80 ° C. for 1 minute, and then further dried at 120 ° C. for 1 minute to obtain a dry layer thickness of 1.6 μm. An intermediate layer was laminated.

  Next, a photosensitive resin layer coating solution having the following formulation 2 was further applied onto the formed intermediate layer, dried at 100 ° C. for 2 minutes, and further dried at 120 ° C. for 1 minute (drying). Condition A), a photosensitive resin layer having a dry layer thickness of 4.5 μm was laminated.

<Coating solution for photosensitive resin layer for spacer>
· 1-methoxy-2-propyl acetate ··· 450 parts · methyl ethyl ketone ··· 233 parts · Solsperse 20000 (manufactured by Lubrizol) ··· 3.13 parts · 45% polymer solution (Japanese Patent Laid-Open No. 2008-146018) Structural formula P-25 described in paragraph [0058]: weight average molecular weight = 35,000, solid content 45%, 1-methoxy-2-propyl acetate 15%, 1-methoxy-2-propanol 40%) ... 184 parts [(A) Specific resin]
Mixture of polymerizable compounds B1-1: DPHA liquid (dipentaerythritol hexaacrylate: 38%, dipentaerythritol pentaacrylate: 38%, 1-methoxy-2-propyl acetate: 24%) 26.1 parts [(B) Polymerizable compound represented by formula (b1)]
Mixture B2-1 of the above-described polymerizable compounds (n = 1: tripentaerythritol octaacrylate content 85%, the total of n = 2 and n = 3 as impurities is 15%) ... 32.9 parts [(B ) Polymerizable compound represented by general formula (b2)]
-Urethane monomer (NK Oligo UA-32P Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, 1-methoxy-2-propyl acetate: 25%) ... 12.4 parts [(B-2) other Polymerizable compound]
2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine ... 2.03 parts [(C) light Polymerization initiator]
2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole [(C) photopolymerization initiator] 1.02 parts Hydroquinone monomethyl ether [solvent] 117 parts Megafac F-784-F (manufactured by DIC Corporation) 0.85 parts [surfactant]

  As described above, after forming a laminated structure of a PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin composition layer, the surface of the photosensitive resin composition layer is further covered with a 12 μm thick cover film. A polypropylene film was applied by heating and pressing to obtain a photosensitive transfer film for spacer (1). The sample was wound around a 3 inch core of ABS resin, wrapped with a black polyethylene film and a transparent polyethylene film, and stored at 25 ° C. for 7 days.

≪Preparation of color filter substrate≫
<1. Preparation of photosensitive dark color composition>
-Preparation of carbon black dispersion (K-1)-
A carbon black dispersion (K-1) was prepared according to the following formulation.
・ Carbon black (Color Black FW2 manufactured by Degussa) ・ ・ ・ 26.7 parts ・ Dispersant (Dispalon DA7500 manufactured by Enomoto Kasei Co., Ltd. Acid value 26 Amine value 40)
... 3.3 parts Benzyl methacrylate / methacrylic acid (= 72/28 [mol ratio]) copolymer (molecular weight 30,000, 50% by mass solution of propylene glycol monomethyl ether acetate)
・ ・ ・ ・ 10 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ ・ 60 parts

  The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion (K-1). It was.

  Using the obtained carbon black dispersion liquid (K-1), a photosensitive dark color composition coating liquid CK-1 was prepared according to the formulation shown in Table 1 below. Numerical values in Table 1 indicate mass ratios.

Details of each component in Table 1 are as follows.
Resin solution C-2: benzyl methacrylate / methacrylic acid (= 85/15 mol ratio) copolymer (Mw 10,000, 50 wt% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-3: trade name Cyclomer P ACA-250 manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate Solution (solid content: 50% by mass)]
Polymerizable compound C-5: trade name TO-1382 manufactured by Toagosei Co., Ltd. (The main component is a monomer having a pentafunctional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group. )
・ Initiator C-7: Trade name “OXE-02” Ciba Specialty Chemicals Co., Ltd. ・ Surfactant C-8: Trade name “Megafac R30” DIC Corporation ・ Solvent: PGMEA = propylene glycol monomethyl Ether acetate EEP = 3-Ethoxyethyl propionate

<2. Formation of black matrix by coating>
-Photosensitive dark color composition layer forming step-
The film after post-baking using the slit coater (model number HC8000, made by Hirata Kiko Co., Ltd.) to the glass substrate (Corning Millennium 0.7mm thickness) which washed the photosensitive dark color composition CK-1 obtained. Coating was performed at a coating speed of 120 mm / second by adjusting the interval between the slit and the glass substrate and the discharge amount so that the thickness was 1.2 μm.

-Pre-bake process, exposure process-
Next, after heating (prebaking treatment) at 90 ° C. for 120 seconds using a hot plate, exposure is performed at 100 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.). did.

-Development process-
Then, it developed with the inclination conveyance type developing device (model number SK-2200G, Dainippon Screen Mfg. Co., Ltd., inclination angle 5 °). That is, a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (a diluted solution of 1 part by weight of CDK-1 and 99 parts by weight of pure water), 25 ), The shower pressure was set to 0.20 MPa, development was performed for 60 seconds, and washed with pure water to obtain a developed black matrix.

-Baking process-
Next, post baking was performed in a clean oven at 220 ° C. for 40 minutes, and a black pixel provided with a black matrix having a grid pattern in which a color pixel formation region had an opening of 90 μm × 200 μm, a thickness of 1.2 μm, and a line width of about 25 μm. A matrix substrate was formed.
When the optical density (OD) of the completed black matrix was measured using X-Rite 361T (V) (manufactured by Sakata Inx Engineering Co., Ltd.), it was 4.2.

<3. Preparation of photosensitive coloring composition>
-3-1. Preparation of photosensitive coloring composition coating liquid CR-1 for red (R) −
A red (R) dispersion (R-1) was prepared according to the following formulation.
Pigment Red 254 (average particle size 43 nm in SEM observation) 11 parts Pigment Red 177 (average particle size 58 nm in SEM observation) 4 parts Solution of dispersion resin A-3 below・ ・ 5 parts ・ Dispersant (Brand name: Disperbyk-161, manufactured by Big Chemie)
(30% solution of propylene glycol monomethyl ether acetate) 3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mol ratio] copolymer, molecular weight 30,000, propylene glycol Monomethyl ether acetate solution (solid content: 50% by mass)) ... 9 parts Solvent B: Propylene glycol monomethyl ether acetate 68 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a red (R) dispersion (R-1). Got. When the dispersed particles in the obtained red (R) dispersion (R-1) were observed with an SEM, the average particle size was 36 nm.

Using the obtained red (R) dispersion liquid (R-1), a photosensitive coloring composition coating liquid CR-1 for red (R) was prepared according to the following formulation.
-Red (R) dispersion (R-1)-100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries, Ltd.-2 parts-Polymerizable compound: DPHA liquid (dipenta Erythritol hexaacrylate: 63%, dipentaerythritol pentaacrylate: 37%) ... 8 parts Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino- Phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part Polymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-molforinophenyl) -butanone -1 ... 1 part-Polymerization initiator: Diethylthioxanthone-0.5 part-Polymerization inhibitor: p-methoxyphenol-0.001 part-Fluorosurfactant ( Product name: Megafac made by R30 DIC Corporation)
・ ・ ・ 0.01 part ・ Nonionic surfactant (trade name: Tetronic R150, manufactured by ADEKA)
··· 0.2 parts · Solvent: Propylene glycol n-butyl ether acetate ··· 30 parts · Solvent: Propylene glycol monomethyl ether acetate ··· 100 parts Mixing and stirring the above ingredients for red (R) The photosensitive coloring composition coating liquid CR-1 was obtained.

-3-2. Preparation of photosensitive coloring composition coating solution CG-1 for green (G) −
A green (G) dispersion (G-1) was prepared according to the following formulation.
Pigment Green 36 (average particle diameter 47 nm in SEM observation) 11 parts Pigment Yellow 150 (average particle diameter 39 nm in SEM observation) 7 parts Solution of dispersion resin A-3 below 5 parts, dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 85/15 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 (% By mass)) ··· 11 parts · Solvent: Propylene glycol monomethyl ether acetate ··· 70 parts

  The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a green (G) dispersion (G-1 ) When the dispersed particles in the obtained green (G) dispersion liquid (G-1) were observed with an SEM, the average particle diameter was 32 nm.

Using the obtained green (G) dispersion liquid (G-1), a photosensitive coloring composition coating liquid CG-1 for green (G) was prepared according to the following formulation.
-Green (G) dispersion (G-1) ... 100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries) ... 2 parts-Polymerizable compound: DPHA liquid Pentaerythritol hexaacrylate: 63%, dipentaerythritol pentaacrylate: 37%) ··· 8 parts Polymerizable compound: Tetra (ethoxy acrylate) of pentaerythritol ··· 2 parts · Polymerization initiator: 1 , 3-Bistrihalomethyl-5-benzooxolantolyazine
2 parts polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-molforinophenyl) -butanone 1 part polymerization initiator: diethyl Thioxanthone-0.5 part-Polymerization inhibitor: p-methoxyphenol-0.001 part-Fluorosurfactant (trade name: Megafac R08 manufactured by DIC)-0.02 part-Nonionic interface Activator (trade name: Emulgen A-60, manufactured by Kao Corporation) 0.5 parts Solvent: propylene glycol monomethyl ether acetate 120 parts Solvent: propylene glycol n-propyl ether acetate -30 parts The said composition was mixed and stirred and the photosensitive coloring composition coating liquid CG-1 for green (G) was obtained.

− 3-3. Preparation of photosensitive coloring composition coating solution CB-1 for blue (B) −
A blue (B) dispersion (B-1) was prepared according to the following formulation.
Pigment Blue 15: 6 (average particle diameter 55 nm by SEM observation)
14 parts Pigment Violet 23 (average particle diameter 61 nm by SEM observation) 1 part Solution A-3 in the following dispersion resin 5 parts Dispersant (trade name: Disperbyk) -161, 30% solution manufactured by Big Chemie)
3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 (% By mass)) ··· 4 parts · Solvent: propylene glycol monomethyl ether acetate ··· 73 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a blue (B) dispersion (B-1 ) When the dispersed particles in the obtained blue (B) dispersion liquid (B-1) were observed with an SEM, the average particle diameter was 39 nm.

Using the obtained blue (B) dispersion liquid (B-1), a blue (B) photosensitive coloring composition coating liquid CB-1 was prepared according to the following formulation.
-Blue (B) dispersion (B-1) ... 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [mol ratio] copolymer, molecular weight 30,000) , Propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)) ... 7 parts Epoxy resin: (trade name Celoxide 2080 manufactured by Daicel Chemical Industries) ... 2 parts UV curable resin : (Trade name Cyclomer P ACA-250, manufactured by Daicel Chemical Industries, Ltd.)
(Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ... 4 parts Polymerizable compound: DPHA solution ( Dipentaerythritol hexaacrylate: 63%, dipentaerythritol pentaacrylate: 37%) ... 12 parts-Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl) -1- (o-acetyloxime) ethanone ··· 3 parts · Polymerization inhibitor: p-methoxyphenol · · 0.001 part · Fluorosurfactant (trade name: Megafac R08 DIC・ 0.02 part ・ Nonionic surfactant (trade name: Emulgen A-60, Kao Corporation) ・ ・ ・ ・ 1.0 part ・ Solvent: -Ethyl ethoxypropionate 20 parts · Solvent: Propylene glycol monomethyl ether acetate 150 parts The above components are mixed and stirred to obtain a photosensitive coloring composition coating solution CB-1 for blue (B). It was.

<4. Synthesis of Dispersing Resin A-3>
(1. Synthesis of chain transfer agent A3)
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] (the following compound (33)) 7.83 parts, and having an adsorption site, and a carbon-carbon double bond The following compound (m-6) (4.55 parts) having a thiophene was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of the mercaptan compound (chain transfer agent A3) shown below was obtained.

(2. Synthesis of dispersion resin A-3)
A mixed solution of 4.99 parts of a 30% solution of chain transfer agent A3 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether, It heated at 90 degreeC under nitrogen stream. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. To the reaction solution, 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added and cooled to room temperature, whereby a solution of dispersion resin A-3 (polystyrene equivalent weight average molecular weight 24000) (dispersion resin 30) was obtained. Mass%, propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate 49 mass%).
The acid value of this dispersion resin A-3 was 48 mg / g. The structure of dispersion resin A-3 is shown below.

<Production of color filter>
-Photosensitive coloring composition layer formation process-
The obtained red (R) photosensitive coloring composition coating liquid CR-1 was applied to the black matrix forming surface side of the black matrix substrate. Specifically, as in the case of forming the photosensitive dark color composition layer, the interval between the slit and the black matrix substrate so that the layer thickness of the photosensitive coloring composition layer after post-baking is about 2.1 μm, Coating was performed at a coating speed of 120 mm / sec by adjusting the discharge amount.

-Colored layer pre-baking step, colored layer exposure step-
Next, after heating (prebaking treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 90 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.). .

  Further, the mask pattern and the exposure machine were set so that the overlap (exposure overlap amount) between the exposure pattern and the black matrix was 9.0 μm.

-Colored layer development process, colored layer baking process-
Then, it developed with the inclination conveyance type developing device (model number SK-2200G, Dainippon Screen Mfg. Co., Ltd., inclination angle 5 °). That is, a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (a diluted solution of 1 part by weight of CDK-1 and 99 parts by weight of pure water), 25 The shower pressure was set to 0.2 MPa at 45 ° C., and development was performed for 45 seconds, followed by washing with pure water. Next, post baking was performed for 30 minutes in a 220 ° C. clean oven to form heat-treated red pixels.

  Subsequently, in the said photosensitive coloring composition layer formation process, colored layer prebaking process, colored layer exposure process, colored layer development process, and colored layer baking process, the photosensitive coloring composition coating liquid CR-1 for red (R) is used. A green pixel was formed in the same manner except that the photosensitive coloring composition coating solution CG-1 for green (G) was used. Thereafter, a blue pixel was formed in the same manner except that the photosensitive coloring composition coating liquid CR-1 for red (R) was replaced with the photosensitive coloring composition coating liquid CB-1 for blue (B). A color filter was obtained.

  An ITO (Indium Tin Oxide) transparent electrode was further formed by sputtering on the R pixel, G pixel, B pixel, and black matrix of the color filter obtained above.

-Production of photo spacer-
Remove the black polyethylene film and the transparent polyethylene film, take out the photosensitive transfer film (1) for spacers, and use the rotary cutter on the cover film to reach a part of the temporary support from the cover film surface. A depth cut was made.
Next, it peeled at the interface of a cover film and a photosensitive resin layer using the tape, and removed the cover film.

  The exposed photosensitive resin layer is sputter-formed with the ITO film prepared above and overlaid on the ITO film of the color filter substrate that has been heated to a surface temperature of 90 ° C. in advance to form a laminator Lamic II type [Hitachi Indust Were used, and bonded at a conveying speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm, an upper roll of 90 ° C., and a lower roll of 120 ° C.

  Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask for preparing a spacer pattern (quartz exposure mask having an image pattern), the mask and a thermoplastic resin layer With the color filter substrate placed so as to face each other in a substantially vertical state, the distance between the mask surface and the surface on the side in contact with the intermediate layer of the photosensitive resin layer is 100 μm, Proximity exposure was performed from the thermoplastic resin layer side with an exposure amount of i-line of 50 mJ / cm ² .

  Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 10 times with pure water (1 part of T-PD2 and 9 parts of pure water). The liquid diluted to a ratio of 2) was developed with shower at 30 ° C. for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Subsequently, a sodium carbonate developer (containing 0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer; Product name: T-CD1 (manufactured by Fujifilm Co., Ltd.) diluted 10 times with pure water) and shower developed at 27 ° C. for 45 seconds with a cone type nozzle pressure of 0.15 MPa, and a spacer pattern image Got.

  Subsequently, a solution obtained by diluting a cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.)) 10 times with pure water Used, and sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa, the residue around the formed pattern image was removed to obtain a desired spacer pattern.

  Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 60 minutes (heat treatment step) to produce a photospacer.

Thus, a color filter substrate with a photospacer was obtained.
The obtained spacer pattern was a cylindrical shape having a diameter of 20 μm and an average height of 4.2 μm. The average height of each of the 200 spacers obtained was measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), and the highest position of the spacer from the ITO transparent electrode forming surface. The height was measured and calculated by calculating the arithmetic average of 200 values.

<Production of touch panel element (insulating layer pattern and overcoat layer: transfer method, three sequential developer systems)>
~ Preparation of first conductive layer pattern ~
The cleaned glass substrate (Corning Millennium 0.7 mm thickness) was cleaned with a rotating brush having nylon hair while spraying a glass cleaner solution adjusted to 25 ° C. for 20 seconds with a shower. A ring solution (0.3% by mass aqueous solution of N-β (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

  From the surface of the cover film, using a rotary cutter on the polypropylene cover film of the photosensitive resin transfer material K1 described in paragraph No. [0121] of JP-A-2006-301122, on the obtained silane coupling treated glass substrate. A cut having a depth up to a part of the temporary support was made.

Next, it peeled at the interface of a cover film and a photosensitive resin layer using the tape, and removed the cover film. The surface of the black photosensitive layer exposed after the removal and the surface of the silane coupling-treated glass substrate are brought into contact with each other, and a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) is used for 2 at 100 ° C. Lamination was performed on a substrate heated for minutes at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, the substrate and the first conductive layer pattern production mask (quartz exposure mask with image pattern) are vertically aligned with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. Then, the distance between the exposure mask surface and the black photosensitive resin composition layer was set to 100 μm, and pattern exposure was performed with an exposure dose of i line 70 mJ / cm ² .

  Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 10 times with pure water (1 part of T-PD2 and 9 parts of pure water). The liquid diluted to a ratio of 2) was developed with shower at 30 ° C. for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Subsequently, a sodium carbonate developer (containing 0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer; Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, shower-developed at 29 ° C. for 30 seconds with a cone-type nozzle pressure of 0.15 MPa, and a spacer pattern image Got.

  Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water was used. Sprayed at 33 ° C for 20 seconds with a cone-type nozzle pressure of 0.02 MPa, showered to remove the residue around the pattern image, and sprayed with pure water for 10 seconds to obtain a reverse-tapered black pattern. It was.

Next, using a sputtering apparatus (SIVAC 3030 manufactured by ULVAC, ITO sputtering having a thickness of 360 mm (main current; 2A, prespter current; 1A, preheating temperature 100 ° C., sputtering temperature 100 ° C., preheating time 30 minutes, Ar flow rate 80 sccm, O ₂ The flow rate was 6 ccm, the pre-sputtering time was 2 minutes, the speed was 850 mm / min, and the substrate temperature was 100 ° C.).

  After leaving it at room temperature for 30 minutes, it was immersed for 5 minutes in a 40 ° C. heated stripping solution (2.38% TMAH aqueous solution) while applying ultrasonic waves of 40 kz, and the entire black pattern on which ITO was deposited was peeled off. Water is sprayed for 10 seconds by showering, and after washing with pure water shower, the silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

~ Preparation of insulating layer pattern ~
An insulating layer pattern was formed by laminating, exposing, developing, and baking the photosensitive transfer film (1) for an insulating layer on the obtained substrate having the second conductive layer pattern in the same manner as the photospacer preparation method. However, the mask used was an insulating layer pattern preparation mask, the proximity exposure was changed to 40 mJ / cm ² i-line, development using a sodium carbonate-based developer at 25 ° C. for 50 seconds, and baking conditions changed to 100 ° C. for 15 minutes. It was done.

~ Preparation of second conductive layer pattern ~
A second conductive layer pattern was formed on the substrate having the insulating layer pattern in the same manner as the first conductive layer pattern. However, the mask was changed to a mask for preparing the second conductive layer pattern.

-Production of overcoat layer-
The overcoat photosensitive transfer film (1) was laminated, exposed, developed and baked on the obtained glass substrate with the second conductive layer pattern in the same manner as the method for producing the insulating layer to form an insulating layer pattern. However, the mask was changed to use an insulating layer pattern preparation mask.

<Production of liquid crystal display device>
Separately, a TFT substrate in which TFTs are arranged on a glass substrate is prepared as a counter substrate, and the transparent electrode forming surface side of the color filter substrate with a photo spacer obtained above and the TFT forming surface side of the counter substrate are respectively provided. Patterning was performed for the PVA mode, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. A polarizing plate HLC2-2518 (manufactured by Sanlitz Co., Ltd.) was attached to the side of the liquid crystal cell obtained as described above on the back side of the liquid crystal cell.

  Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate. Next, the touch panel element was placed on the front surface of the liquid crystal cell, and the polarizing plate HLC2-2518 was attached to obtain a liquid crystal display device.

[Evaluation]
About the touch panel element of the obtained Example and the liquid crystal display device, performance evaluation was performed as follows.
−Insulation−
After the touch panel element obtained in the above example was stored at 50 ° C. and 95% RH for 200 hours, a liquid crystal display device was prepared in the same manner as in the above example, and the number of malfunctions due to poor insulation was evaluated.

<Evaluation criteria>
○: Malfunctions within 1000 inputs were within 2 times.
X: The malfunction was 1000 times or more during 1000 times of input.

-Pencil hardness-
The overcoat layer obtained in the above Example was evaluated for pencil hardness according to JIS K5600-5-4. The practical level is 3H or higher.

-High humidity test surface-
After the touch panel element obtained in the above Example was stored at 60 ° C. under 95% RH, the humidity was adjusted to 23 ° C. and 55% for 30 minutes, and then the overcoat layer was observed with an optical microscope. The practical level is C or higher.

<Evaluation criteria>
A: No defects are found on the entire overcoat layer in both the ITO vapor deposition part and the ITO lift-off part.
B: Slight spot-like defects were observed only at the corners of the rectangular pattern of the ITO vapor deposition portion in the non-display area.
C: Slight spot-like defects were observed only at the corners of the rectangular pattern of the ITO vapor deposition portion in the display area.
D: Spot-like defects were observed on the substrate near the rectangular pattern edges (four sides).
E: Spot-like defects were observed on the entire surface of the substrate.

-Development residue-
In the above-mentioned “-Preparation of insulating layer pattern and overcoat layer-”, after the proximity exposure, development is performed in the same manner as the development conditions of each example, SEM observation of the formed rectangular pattern portion is performed, and there are residues around the periphery. I checked if it remained. The practical level is C or higher.

<Evaluation criteria>
A: No residue is seen at all.
B: A slight residue was observed at the corner of the rectangular pattern.
C: A slight residue was observed on the rectangular pattern edges (4 sides).
D: Residues were observed on the rectangular pattern edges (4 sides) and the substrate in the vicinity of the pattern.
E: Residues were confirmed in some places on the substrate.

-Development pattern adhesion-
In the above-mentioned “-Preparation of insulating layer pattern”, after the proximity exposure, development was performed in the same manner as the development conditions of each example, and 1000 insulating layer patterns formed to form a rectangular pattern were laminated using an optical microscope. Was observed to evaluate development pattern adhesion. The practical level is C or higher.

<Evaluation criteria>
A: None of the 1000 insulating layer patterns dropped out.
B: One to three of 1000 insulating layer patterns were dropped.
C: 4 or 5 pieces were dropped out of 1000 insulating layer patterns.
D: 6 to 10 pieces were dropped out of 1000 insulating layer patterns.
E: 11 or more pieces were dropped out of 1000 insulating layer patterns.

-Alkali resistance-
The substrate having the insulating layer pattern formed as described above was immersed in a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution heated to 40 ° C. for 5 minutes and stored in a water tank in advance. After washing with pure water for 2 seconds, water was removed with an air knife and observed with an optical microscope.

<Evaluation criteria>
A: None of the 1000 insulating layer patterns dropped out.
B: One to three of 1000 insulating layer patterns were dropped.
C: 4 or 5 pieces were dropped out of 1000 insulating layer patterns.
D: 6 to 20 pieces were dropped out of 1000 insulating layer patterns.
E: 20 or more of 1000 insulating layer patterns dropped out.

-Evaluation of adhesion immediately after exposure-
In the method for producing the insulating layer or overcoat layer of the example, adhesion immediately after pattern exposure was evaluated according to the following valence criteria. The practical level is C or higher.

<Evaluation criteria>
A: No peeling part is seen on the entire overcoat layer in both the ITO vapor deposition part and the ITO lift-off part.
B: A slight peeling portion was observed only in a part of the ITO lift-off portion in the non-display area.
C: Slight peeling portions were observed only in a part of the ITO vapor deposition portion and the ITO lift-off portion in the non-display area.
D: A slight peeling portion was observed only in a part of the ITO vapor deposition portion and the ITO lift-off portion in the display area.
E: The entire surface was peeled from the substrate by curing shrinkage.

-Transparency after baking-
A substrate treated with a silane coupling solution was prepared on the cleaned glass substrate (Corning Millennium 0.7 mm thickness) by the method shown in the preparation of the first conductive layer pattern of the example. Subsequently, an overcoat layer was produced according to the method for producing an overcoat layer. A transmittance of 400 to 800 nm was measured with a spectrophotometer UV2100 type (manufactured by Shimadzu Corporation) and evaluated according to the following evaluation criteria. The practical level is C or higher.

<Evaluation criteria>
A: The transmittance of 400 nm is 95% or more and the average transmittance of 400 to 800 nm is 95% or more. B: The transmittance of 400 nm is 90% or more and less than 95% and the average transmittance of 400 to 800 nm is 90% or more. C: The transmittance of 400 nm is 85% or more and less than 90% 400-800 nm average transmittance 85% or more D: 400 nm transmittance is 80% or more and less than 85% E: 400 nm transmittance is less than 80%

[Examples 2 to 6]
In the coating liquid formulation 1 for the photosensitive resin layer of Example 1, photopolymerization was performed while keeping the solvent composition ratio, the solid content concentration, the ratio of the two types of photopolymerization initiators, and the ratio of the three types of polymerizable compounds constant. Initiator (C) / polymerizable compound (B) ratios from 4.92 to 3.48 (Example 2), 2.46 (Example 3), 1.23 (Example 4) and 0.87 (respectively) Example 5), except that the prescription was changed so as to be 0.62 (Example 6) and a liquid crystal display device with a touch panel was prepared, the same results as in Example 1 were evaluated and the results shown in Table 2 were similarly evaluated. Got.

[Comparative Examples 1 and 2]
In the coating liquid formulation 1 for the photosensitive resin layer of Example 1, photopolymerization was performed while keeping the solvent composition ratio, the solid content concentration, the ratio of the two types of photopolymerization initiators, and the ratio of the three types of polymerizable compounds constant. The touch panel mounted liquid crystal was changed by changing the formulation so that the initiator (C) / polymerizable compound (B) ratio was 4.92 to 5.0 (Comparative Example 1) and 0.58% by mass (Comparative Example 2), respectively. Except that the display device was prepared, the same procedure as in Example 2 was performed, and evaluation was performed in the same manner to obtain the results shown in Table 2.

[Examples 7 to 10]
In the coating solution formulation 3 for the photosensitive resin layer of Example 3, the value of W2 / W1 is set to 1 while keeping the polymerizable compound (B) / (A) specific resin ratio, solvent composition ratio, and solid content concentration constant. .41 to 2.76 (Example 7), 2.04 (Example 8), 0.96 (Example 9) and 0.60 (Example 10), respectively, to produce a liquid crystal display device with a touch panel. Except for the above, the same procedure as in Example 3 was performed, and the same evaluation was performed to obtain the results shown in Table 2.

[Comparative Examples 3 and 4]
In the coating solution formulation 3 for the photosensitive resin layer of Example 3, the value of W2 / W1 is set to 1 while keeping the polymerizable compound (B) / (A) specific resin ratio, solvent composition ratio, and solid content concentration constant. .41 was changed to 3.16 (Comparative Example 3) and 0.54 (Comparative Example 4), respectively, except that a liquid crystal display device with a touch panel was prepared, and the results shown in Table 2 were obtained. It was.
In the table below, “crude TPOA” indicates the content of a mixture of polymerizable compounds containing tripentaerythritol octaacrylate, and “TPOA (pure content)” is the polymerizable compound (b2) according to the present invention. The content of tripentaerythritol octaacrylate is shown. “UA-32P” indicates the content of (B-2) a urethane monomer (NK Oligo UA-32P, manufactured by Shin-Nakamura Chemical Co., Ltd.) which is a compound belonging to other polymerizable compounds.

[Examples 11 to 15]
In the coating composition 3 for the photosensitive resin layer of Example 3, the polymerizable compound (B) / (A) specific resin while keeping the solvent composition ratio, the solid content concentration, and the ratio of the three kinds of polymerizable compounds constant. The ratios from 0.75 to 0.48 (Example 11), 0.6 (Example 12), 0.9 (Example 13), 1.2 (Example 14), and 1.6 (Example 15), respectively. ) Was performed in the same manner as Example 3 except that the liquid crystal display device with a touch panel was prepared by changing the formulation so that the results shown in Table 2 were obtained.

[Comparative Examples 5 and 6]
In the coating composition 3 for the photosensitive resin layer of Example 3, the polymerizable compound (B) / (A) specific resin while keeping the solvent composition ratio, the solid content concentration, and the ratio of the three kinds of polymerizable compounds constant. The same procedure as in Example 3 was performed except that the liquid crystal display device with a touch panel was prepared by changing the prescription so that the ratio was changed from 0.75 to 0.44 (Comparative Example 5) and 1.62 (Comparative Example 6), respectively. In the same manner, the results shown in Table 3 were obtained.

Example 16
In the coating solution formulation 3 for the photosensitive resin layer of Example 3, the urethane monomer (NK oligo UA-32P was removed and the purity of the polymerizable compound mixture B2-1 was changed from 85% to 99%, and W2 / The same as Example 3 except that the liquid crystal display device with touch panel was prepared by changing the formulation so that the ratio of W1, the polymerizable compound (B) / (A) specific resin ratio, the solvent composition ratio, and the solid content concentration were constant. The results shown in Table 3 were obtained by evaluating in the same manner.

[Examples 17 to 20]
In Example 3, urethane-based monomer (0% (Example 17), 20% (Example 18) as shown in the table of NK oligo UA-32P content) in the coating solution formulation 3 for photosensitive resin layer The ratio of W2 / W1, the polymerizable compound (B) / (A) specific resin ratio, the solvent composition ratio, and the solid content concentration, except for changing to 25% (Example 19) and 30% (Example 20). The procedure was the same as in Example 3 except that it was constant, and the same evaluation was performed to obtain the results shown in Table 3.

[Comparative Example 7]
In Example 3, the urethane-based monomer used in the coating solution formulation 3 for photosensitive resin layer (except that the content of NK oligo UA-32P was changed to 32% as shown in the table, the ratio of W2 / W1, polymerizability) The same procedure as in Example 3 was carried out except that the compound (B) / (A) specific resin ratio, solvent composition ratio, and solid content concentration were kept constant, and the results shown in Table 3 were obtained in the same manner.

[Examples 21 to 24]
In Example 3, the thickness for the photosensitive resin layer is 1.38 μ to 0.75 μ (Example 21), 2.24 μ (Example 22), 2.6 μ (Example 23), and 3,0 μ (Example). Except for the change to 24), the same operation as in Example 3 was performed, and evaluation was performed in the same manner to obtain the results shown in Table 4.

[Comparative Examples 8 and 9]
In the same manner as in Example 3, except that the thickness for the photosensitive resin layer in Example 3 was changed from 1.38 μ to 0.68 μ (Comparative Example 8) and 3.2 μ (Comparative Example 9), respectively. The results shown in Table 4 were obtained by evaluation.

[Examples 25-27]
In Example 3, instead of the compound represented by Structural Formula P-25 used as the polymer solution of the coating solution formulation 3 for photosensitive resin layer, paragraph numbers of JP 2008-146018 A, respectively. The compound represented by the structural formula P-10 described in [0061] (Example 25), the following structure 2 (Example 26), and the following structure 3 (Example 27) are equal in polymer solid content. The results shown in Table 4 are the same as in Example 3, except that the amount of 1-methoxy-2-propyl acetate added is adjusted so that the solid content of the coating solution is the same. Got.

[Comparative Example 10]
Instead of all the polymerizable compounds used in the coating solution formulation 3 for the photosensitive resin layer in Example 3, the acrylic ester mixture (A-1) (W1 + W2 = 79) of Synthesis Example 1 of JP-A-2002-212235 .8, W2 / W1 = 11.9) was carried out in the same manner as in Example 3, and the results as shown in Table 4 were obtained, such as a decrease in the residue. W1 + W2 and W2 / W1 were 71.9% and 11.9, respectively.

[Comparative Examples 11 to 13]
Instead of the formulation 1 of the photosensitive resin layer coating solution used in Example 1, the coating solution for protective film material (Comparative Example 11) described in Example 1 of JP-A-5-78453, and JP-A-2001-91732 The same as in Example 1 except that the composition V1 described in Example 1 (Comparative Example 12) and the negative photosensitive resin described in Example 1 of JP-A-2009-109725 (Comparative Example 13) were used. The results shown in Table 4 were obtained.

[Examples 28 to 32]
In the formulation 3 of the coating solution for the photosensitive resin layer of Example 3, the total amount of the mixture of photopolymerization initiators was not changed, but 2,4-bis- (trichloromethyl) -6- [4- (N, N -Diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine (Example 28), 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole (Example 29) ), Oxime initiator IRGACURE OXE 01 (Ciba: Example 30), acetophenone initiator IRGACURE 379 (Ciba: Example 31), IRGACURE 907 (Ciba: Example 32) It carried out like Example 3 and evaluated similarly, and obtained the result shown in Table 4.

(Examples 33 to 35, Comparative Examples 14 to 17) (Insulating layer pattern and overcoat layer: one transfer method for each type of transfer method)
Example 33
In the production of the insulating layer pattern and the overcoat layer in Example 1, the developer was changed from a three-type sequential developer system to a one-time developer system using the following developer A, and the development conditions at that time were changed. The procedure was the same as in Example 1 except that the temperature was changed to 30 ° C. for 60 seconds, and the results shown in Table 5 were obtained by evaluating in the same manner.

-Developer A-
Triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation)) 100 parts Na carbonate developer (0.38 mol / liter hydrogen carbonate Contains sodium, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent and stabilizer; trade name: T-CD1 (manufactured by FUJIFILM Corporation)
・ ・ ・ ・ 140 parts ・ Cleaning agent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer included; trade name: T-SD3 (manufactured by FUJIFILM Corporation) ・ ・ ・ ・ 100 parts ・Pure water ··· 660 parts · Potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) ··· 10 parts

Example 34
Coating liquid for photosensitive resin layer used in Example 3 instead of coating liquid formulation 1 for photosensitive resin layer (photopolymerization initiator (C) / polymerizable compound (B) = 4.92%) in Example 33 Similar to Example 33 except that Formulation 3 (photopolymerization initiator (C) / polymerizable compound (B) = (photopolymerization initiator (C) / polymerizable compound (B) = 2.46%) was used. The results shown in Table 5 were obtained by evaluating in the same manner.

Example 35
Example 34 was carried out in the same manner as in Example 34 except that the phantom image solution B in which the potassium hydroxide developer CDK-1 was removed from the developer A in Example 34 was evaluated in the same manner, and the results shown in Table 5 were obtained.

[Comparative Example 14]
Instead of the coating solution formulation 3 for the photosensitive resin layer in Example 34, instead of all the polymerizable compounds used in the coating solution formulation 3 for the photosensitive resin layer, the synthesis example 1 of JP-A-2002-212235 The same procedure as in Example 34 was performed except that the acrylic ester mixture (A-1) (W1 + W2 = 79.8, W2 / W1 = 11.9) was used, and the results shown in Table 5 were obtained in the same manner. .

[Comparative Examples 15-17]
In Example 34, instead of the formulation 1 for the photosensitive resin layer coating solution used in Example 1, the coating solution for protective film material described in Example 1 of JP-A-5-78453 (Comparative Example 15), JP Similar to Example 34 except that the composition V1 described in Example 1 of 2001-91732 (Comparative Example 16) and the negative photosensitive resin described in Example 1 of JP-A 2009-109725 (Comparative Example 17) were used. An experiment was conducted and evaluated in the same manner, and the results shown in Table 5 were obtained.

(Examples 36 to 67, Comparative Examples 18 to 30)
(Insulating layer pattern and overcoat layer: coating method)
Example 36
Photo spacers were produced on the color filter substrate by the same patterning process and heat treatment process as in Example 1.

<Production of touch panel element (insulating layer pattern and overcoat layer: coating method system)>
~ Preparation of first conductive layer pattern ~
It produced similarly to the preparation method of the 1st conductive layer pattern of Example 1.

~ Preparation of insulating layer pattern ~
On the obtained substrate having the first conductive layer pattern, the coating solution formulation 1 for the photosensitive resin layer is applied to a glass substrate coater MH-1600 (manufactured by FAS Asia) having a slit-like nozzle. Was applied. Subsequently, a part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating film, and then pre-baked at 100 ° C. for 3 minutes to obtain a 1.38 μm thick photosensitive film. A functional resin composition layer was formed (layer forming step).
Proximity exposure was 250 mJ / cm ² i-line, and development using a sodium carbonate developer was performed at 25 ° C. for 60 seconds. Thereafter, the processes other than Example 1 were performed in the same manner as the production of the insulating layer pattern.

~ Preparation of second conductive layer pattern ~
It produced similarly to the preparation method of the 2nd conductive layer pattern of Example 1.

-Production of overcoat layer-
The obtained glass substrate with the second conductive layer pattern was coated, pre-baked, developed, and baked in the same manner as the method for producing the insulating layer pattern to form an insulating layer pattern. However, the mask was changed to use an insulating layer pattern preparation mask.

<Production of liquid crystal display device>
A liquid crystal display device was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1 to obtain the results shown in Tables 6 and 7.

[Examples 37 to 67, Comparative Examples 18 to 30]
It implemented except having used the coating liquid for photosensitive resin layers used in Examples 2-27 and Comparative Examples 1-13 shown in Tables 2-4 instead of the formulation 1 of the coating liquid for photosensitive resin layers of Example 36. It carried out similarly to Example 36, evaluated similarly, and obtained the result shown in Table 6 and Table 7.

  From the above results, the photosensitive composition of the present invention has good developability after pattern exposure, no development residue is observed, and the formed resin pattern has various properties such as insulation, transparency, and alkali resistance. It can be seen that it is excellent and useful for producing an insulating layer and an overcoat layer used for a touch panel element.

Claims (13)

(A) a resin having an acidic group in the side chain, (B) a polymerizable compound represented by the following general formula (b1) and a polymerizable compound represented by the general formula (b2), and (C) photopolymerization initiation An agent,
The content of the polymerizable compound represented by the general formula (b1) with respect to the total content of the polymerizable compound is W1 (mass%), and the content of the polymerizable compound represented by the general formula (b2) is W2. When (mass%), W1 and W2 satisfy the relationship shown in the following formulas (1) and (2),
And the photosensitivity whose content ratio [content of (C) / total content of polymeric compound] of this (C) photoinitiator with respect to the total content of a polymeric compound is 0.6 or more and less than 5 Composition.
0.6 ≦ W2 / W1 ≦ 3.0 Formula (1)
63% by mass ≦ W1 + W2 ≦ 100% by mass (2)

(In the general formula (b1), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same as or different from each other, provided that in the molecule. At least 4 of X in the formulas represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

(In the general formula (b2), X represents a hydrogen atom or H ₂ C═C (R) —C (O) —. A plurality of X may be the same or different from each other, provided that in the molecule. At least 6 of X's represent H ₂ C═C (R) —C (O) —, where R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.   The photosensitive composition according to claim 1, further comprising a polymerizable compound having a structure different from that of the polymerizable compound (B).   The mass ratio [(total content of polymerizable compound) / (A) content] of the total content of the polymerizable compounds contained to the content of the resin (A) is 0.45 to 1.6. The photosensitive composition of any one of Claims 1 or 2.   The photosensitive resin transfer film which has at least the photosensitive resin layer which consists of a photosensitive composition of any one of Claims 1-3 on a temporary support body.   The photosensitive resin transfer film of Claim 4 which has at least one of an oxygen interruption | blocking layer and a thermoplastic resin layer between the said photosensitive resin layer and the said temporary support body.   The photosensitive resin layer formation process which provides a photosensitive resin layer using the photosensitive composition of any one of Claims 1-3 on a board | substrate, and the exposure process which carries out pattern exposure of the photosensitive resin layer And a developing process of developing the exposed photosensitive resin layer to form a patterned resin layer, and a heating process of heating the patterned resin layer obtained by development.   The method for producing a resin pattern according to claim 6, wherein the photosensitive resin layer forming step is a step of applying and drying the photosensitive composition on a substrate.   A photosensitive resin layer forming step of providing a photosensitive resin layer on the substrate using the photosensitive resin transfer film according to claim 4 or 5, an exposure step of pattern exposure of the photosensitive resin layer, and exposure. A method for producing a resin pattern, comprising: a developing step of developing the photosensitive resin layer to form a patterned resin layer; and a heating step of heating the patterned resin layer obtained by development.     In the photosensitive resin layer forming step, the photosensitive resin layer of the photosensitive resin transfer film is brought into contact with the substrate, and at least one of heating and pressurization is performed, and the photosensitive resin is formed on the substrate from the temporary support. The method for producing a resin pattern according to claim 8, which is a step of transferring a layer.   The method for producing a resin pattern according to any one of claims 6 to 9, wherein a thickness of the photosensitive resin layer provided on the substrate is in a range of 0.7 µm to 3.0 µm.   The resin pattern obtained by the manufacturing method of the resin pattern of any one of Claims 6-10.   The board | substrate for liquid crystal display devices provided with the resin pattern of Claim 11.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 12.