JP2008096981A - Negative photosensitive composition for projection for liquid crystal alignment control and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive composition which is excellent in display qualities such as burn-in and voltage retention rate, electrical reliability, sensitivity and patterning characteristics in the formation of a projection for liquid crystal alignment control in an MVA-LCD, while having a transmittance sufficient to block light from a backlight. <P>SOLUTION: The negative photosensitive composition for a projection for liquid crystal alignment control contains (a) an alkali-soluble resin, (b) a photopolymerization initiator and (c) an ethylenically unsaturated compound, wherein the alkali-soluble resin (a) contains a compound having a phenolic hydroxy group and the photopolymerization initiator (b) contains an oxime ester compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid crystal alignment control projection negative type used in a vertical alignment (VA) type liquid crystal display (LCD, liquid crystal display), and in particular, an alignment division vertical alignment (MVA) type multi-domain vertical alignment (LCD) type LCD. The present invention relates to a photosensitive composition. The present invention also relates to a liquid crystal display device including a liquid crystal alignment control protrusion formed using the negative photosensitive composition for liquid crystal alignment control protrusion.

  In recent years, a technology of a liquid crystal television using a thin liquid crystal display device with low power consumption for a large screen television has been put into practical use, and the market is about to rise rapidly. Accordingly, there is a strong demand for improvement in the low viewing angle of a liquid crystal television, which is inferior to a television using a conventional cathode ray tube.

  In an attempt to improve the viewing angle of liquid crystal display devices, conventionally, a liquid crystal alignment control protrusion was formed on the transparent electrode, and the liquid crystal was locally tilted using the slope of this protrusion to divide the liquid crystal in multiple directions within one pixel. MVA (Multi-Domain Vertical Alignment) to be oriented has been developed (for example, Patent Document 1 and Non-Patent Document 1).

  The liquid crystal alignment control protrusions used here are usually formed by a photolithography method, and a negative acrylic resin is used (Patent Document 2), or a positive resist made of quinonediazide and novolac resin is used ( Patent Document 3). Various photopolymerizable negative resists have also been proposed in consideration of batch formation with a photospacer (Patent Document 4).

  Negative resists using acrylic resin are excellent in plate making characteristics such as sensitivity and resolving power, but are arched and difficult to be rounded at the top as required by the cross-sectional shape, and tend to produce flat portions at the top. In addition, burn-in and display unevenness are likely to occur, and there is a problem that the display quality is deteriorated. On the other hand, positive resists are not only burn-in but also superior in terms of voltage holding ratio, which is one of the indicators of electrical reliability, but they have disadvantages that are inferior to negative ones due to common defects and plate making characteristics.

  In order to solve the above problems, some proposals using an alkali-soluble resin containing a phenol compound instead of an acrylic resin in a negative resist have been made (Patent Documents 5, 6, 7, 8, 9, 10). However, the phenolic hydroxyl group has a problem that the sensitivity is remarkably lowered because it promotes radical polymerization inhibition reaction.

  Further, a technique using a specific oxime ester compound as a photopolymerization initiator is known (see Patent Documents 11 and 12). However, by simply replacing the photopolymerization initiator with an oxime compound, the liquid crystal alignment control protrusions are used. Therefore, image sticking and display unevenness are likely to occur, and the problem of the negative resist that deteriorates the display quality cannot be solved.

  By the way, in the MVA type LCD, when the liquid crystal alignment control protrusion is formed, the transmitted light is disturbed due to the difference in the refractive index between the liquid crystal and the liquid crystal alignment control protrusion. The reduction in contrast due to the perturbation of transmitted light is not preferable in a television in which high contrast is sought. Therefore, in order to prevent this, it has been required to make the liquid crystal alignment control protrusions light-shielding.

In order to make the liquid crystal alignment control protrusions light-shielding, it is conceivable to add carbon black, titanium black, etc., which are usually used for black matrixes, to the liquid crystal alignment control protrusion photosensitive composition. In terms of electrical resistance, and in terms of dielectric constant, titanium black may be used for liquid crystal alignment control protrusions that are in direct contact with the liquid crystal, which may cause display unevenness and may impair the reliability of the liquid crystal display. There is.
Japanese Patent No. 2947350 Japanese Patent No. 3255107 JP 2004-333963 A JP 2002-236371 A JP-A-2005-221930 JP 2005-221947 A JP 2005-266642 A JP 2005-292199 A Japanese Patent Laying-Open No. 2005-300724 JP 2006-098673 A JP 2000-80068 A JP 2006-36750 A “Liquid Crystal” Vol. 3, No. 2, p. 117 (1999)

  The present invention has been made to solve the above-described problems, and in forming a liquid crystal alignment control protrusion in an MVA type LCD, image quality such as image sticking, voltage holding ratio and electrical reliability, and sensitivity, It is an object of the present invention to provide a negative photosensitive composition capable of forming a liquid crystal alignment control protrusion that has excellent patterning characteristics and can also have sufficient transmittance to shield light from a backlight. To do.

  As a result of intensive studies on the above problems, the present inventors have found that the above object can be achieved by using a negative photosensitive composition shown below as a liquid crystal alignment control protrusion forming material. It came to complete.

  The negative photosensitive composition for liquid crystal alignment control protrusions of the present invention (Invention 1) is a liquid crystal alignment containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound. The negative photosensitive composition for control projections is characterized in that (a) the alkali-soluble resin contains a compound having a phenolic hydroxyl group, and (b) the photopolymerization initiator contains an oxime ester compound.

The negative photosensitive composition for liquid crystal alignment control protrusions of the present invention (invention 2) is a liquid crystal alignment containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound. In the negative photosensitive composition for the control protrusion,
The sensitivity of the photosensitive composition is 150 mj / cm ² or less,
The VHR of the liquid crystal alignment control protrusion obtained by exposing the photosensitive composition is 90% or more.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 3 is characterized in that, in claim 2, (a) the alkali-soluble resin contains a compound having a phenolic hydroxyl group.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 4 is characterized in that, in claim 2 or 3, (b) the photopolymerization initiator contains an oxime ester compound.

（（１）式中、Ｒ^２は、それぞれ置換されていてもよい、炭素数２〜１２のアルカノイル基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリールオキシキシカルボニルアルカノイル基、炭素数２〜１０のアミノカルボニル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示す。） The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 5 is characterized in that, in claim 1 or 4, the oxime ester compound has a structure represented by the following general formula (1).

(In the formula (1), R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 carbon atoms alkoxycarbonylalkanoyl group, 8 to 20 carbon atoms phenoxycarbonylalkanoyl group, 3 to 20 carbon atoms heteroaryloxyxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminocarbonyl group, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms.)

（（２）式中、Ｒ^１ａは、それぞれ置換されていてもよい、炭素数１〜１０のアルキル基、炭素数２〜２５のアルケニル基、炭素数１〜２０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、炭素数１〜２０のアミノアルキル基、炭素数２〜１２のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基、又は炭素数７〜２０のフェノキシカルボニル基を示す。
Ｒ^１ｂは、置換されていてもよい芳香環基を示す。
なお、Ｒ^１ａは、Ｒ^１ｂとともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい、炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_ｎ−、−（Ｃ≡Ｃ）_ｎ−、あるいはこれらを組み合わせてなる基が挙げられる（なお、ｎは０〜３の整数）。
Ｒ^２ａは、それぞれ置換されていてもよい、炭素数２〜１２のアルカノイル基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリールオキシキシカルボニルアルカノイル基、炭素数２〜１０のアミノカルボニル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示す。） The negative photosensitive composition for liquid crystal alignment control protrusions of claim 6 is characterized in that, in claim 5, the oxime ester compound has a structure represented by the following general formula (2).

(In formula (2), R ^1a is an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 3-20 alkoxycarbonylalkyl group, C8-20 phenoxycarbonylalkyl group, C1-20 heteroaryloxycarbonylalkyl group, C1-20 heteroarylthioalkyl group, C0-20 An aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a benzoyl group having 7 to 20 carbon atoms. , A heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms. Show.
R ^1b represents an ^optionally substituted aromatic ring group.
R ^1a may form a ring with R ^1b , and the linking group may have a substituent, each having 1 to 10 carbon atoms, — (CH═CH) _n —. ,-(C≡C) _n- , or a group formed by a combination thereof (where n is an integer of 0 to 3).
R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. , An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, and 7 carbon atoms -20 benzoyl group, C1-C20 hetero aryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 phenoxycarbonyl group. )

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 7 is characterized in that in any one of claims 1 to 6, the OD value is 0.5 / μm or more.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 8 is characterized in that it contains at least two kinds of organic pigments in any one of claims 1 to 7.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 9 is the negative photosensitive composition according to claim 8, wherein the maximum absorption wavelength in the wavelength range of 400 to 800 nm is in the wavelength range of 500 to 600 nm as at least two kinds of organic pigments. An organic pigment (hereinafter referred to as “organic pigment (500 to 600)”) and an organic pigment having a wavelength of 600 to 800 nm (hereinafter referred to as “organic pigment (600 to 800)”). The difference between the maximum absorption wavelength of the pigment (500 to 600) and the maximum absorption wavelength of the organic pigment (600 to 800) is 10 nm or more.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 10 is characterized in that, in claim 8 or 9, at least three kinds of organic pigments are contained.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 11 has the maximum absorption wavelength in the wavelength range of 400 to 800 nm as the at least three organic pigments in claim 10 in the wavelength range of 400 to 500 nm. An organic pigment (hereinafter referred to as “organic pigment (400 to 500)”), an organic pigment in the wavelength region of 500 to 600 nm (hereinafter referred to as “organic pigment (500 to 600)”), and a wavelength of 600 to 800 nm. Organic pigments (hereinafter referred to as “organic pigments (600 to 800)”) in the range of the maximum absorption wavelength of the organic pigments (400 to 500) and the maximum absorption wavelength of the organic pigments (500 to 600) And the difference between the maximum absorption wavelength of the organic pigment (500 to 600) and the maximum absorption wavelength of the organic pigment (600 to 800) is 10 nm or more, respectively.

  The liquid crystal display device of the present invention (Claim 12) includes a liquid crystal alignment control protrusion formed by using the negative photosensitive composition for liquid crystal alignment control protrusion according to any one of claims 1 to 11. It is characterized by.

According to the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention, there is no problem of burn-in even when directly in contact with liquid crystal, excellent display quality such as voltage holding ratio and electrical reliability, and from the backlight. An excellent liquid crystal alignment control protrusion capable of sufficiently blocking light can be formed with good sensitivity and patterning characteristics.
Therefore, a high-contrast liquid crystal display device can be realized by the liquid crystal alignment control protrusion formed from the negative photosensitive composition of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. These contents are not specified.

[Negative photosensitive composition for liquid crystal alignment control protrusion]
First, the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention (hereinafter sometimes simply referred to as “photosensitive composition”) will be described in detail.

The negative photosensitive composition for liquid crystal alignment control protrusions of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound.
Moreover, the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention usually contains an organic pigment, and further contains solid components such as a surfactant, a thermal polymerization inhibitor, and a plasticizer as necessary. Can do.

  The negative photosensitive composition for liquid crystal alignment control protrusions according to the first aspect of the present invention includes (a) a compound in which an alkali-soluble resin has a phenolic hydroxyl group, and (b) a photopolymerization initiator based on an oxime ester. It is characterized by containing a compound.

The negative photosensitive composition for liquid crystal alignment control protrusions according to the second aspect of the present invention has a sensitivity of the photosensitive composition of 150 mj / cm ² or less, and a liquid crystal obtained by exposing the photosensitive composition. The VHR of the orientation control protrusion is 90% or more.
Also in the negative photosensitive composition for liquid crystal alignment control protrusions according to the second aspect, (a) a compound having a phenolic hydroxyl group may be used as the alkali-soluble resin, and (b) a photopolymerization initiator. As such, an oxime ester compound may be used, but is not limited thereto.
As a device for achieving the above sensitivity and VHR, the negative photosensitive composition for liquid crystal alignment control protrusions according to the second aspect,
(1) An oxime ester compound is used as a photopolymerization initiator.
Even if the oxime ester compound is not used as a photopolymerization initiator,
(2) Increase the content of photopolymerization initiator.
(3) Increase the content of ethylenically unsaturated compounds.
The above-mentioned sensitivity and VHR can be achieved by such a method.

  The photosensitive composition of the present invention is used to form liquid crystal alignment control protrusions in the procedure of image formation such as application to a substrate, drying, exposure, and development in accordance with a method for forming liquid crystal alignment control protrusions described later.

In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and (meth) acrylic, (meth) acrylate, (meth) acryloyl groups, and the like have the same meaning. And “(co) polymer” means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “(acid) anhydride”, “(anhydrous) ... acid”. "Is meant to include both acids and anhydrides. In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
In the present invention, the term “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense.

  Hereinafter, each component which comprises the photosensitive composition of this invention is demonstrated.

[1] Organic pigment and pigment dispersion [1-1] Organic pigment As the organic pigment contained in the photosensitive composition of the present invention, a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, brown Various color pigments such as pigments can be used. The structure includes organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 2, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
The maximum absorption wavelength of these red pigments is generally 500 to 600 nm.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.
The maximum absorption wavelength of these blue pigments is generally 600 to 800 nm.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. Pigment Green 7 and 36.
The maximum absorption wavelength of these green pigments at a wavelength of 400 to 800 nm is generally 600 to 800 nm.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
The maximum absorption wavelength of these yellow pigments at a wavelength of 400 to 800 nm is generally 400 to 500 nm.

Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, preferably C.I. I. Pigment oranges 38 and 71.
The maximum absorption wavelength of these orange pigments at a wavelength of 400 to 800 nm is generally 450 to 550 nm.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, preferably C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.
The maximum absorption wavelength of these purple pigments at a wavelength of 400 to 800 nm is generally 500 to 600 nm.

  The photosensitive composition of the present invention preferably contains at least two kinds of organic pigments as described above, and the maximum absorption wavelength in the wavelength range of 400 to 800 nm is in the wavelength range of 500 to 600 nm. Organic pigments selected from organic pigments (hereinafter referred to as “organic pigments (500 to 600)”) and organic pigments in the wavelength region of 600 to 800 nm (hereinafter referred to as “organic pigments (600 to 800)”). It is preferable to include a pigment. In this case, the difference between the maximum absorption wavelength of the organic pigment (500 to 600) and the maximum absorption wavelength of the organic pigment (600 to 800) is preferably 10 nm or more, particularly preferably 20 nm or more.

  Furthermore, the maximum absorption wavelength in the wavelength range of 400 to 800 nm is an organic pigment (organic pigment (400 to 500)) in the wavelength range of 400 to 500 nm, and an organic pigment in the wavelength range of 500 to 600 nm (hereinafter “organic pigment”). (500 to 600) ”) and an organic pigment in the wavelength region of 600 to 800 nm (hereinafter referred to as“ organic pigment (600 to 800) ”). Even more preferred. In this case, the difference between the maximum absorption wavelength of the organic pigment (400 to 500) and the maximum absorption wavelength of the organic pigment (500 to 600), and the maximum absorption wavelength of the organic pigment (500 to 600) and the organic pigment (600 to 800) The difference from the maximum absorption wavelength is preferably 10 nm or more, particularly preferably 20 nm or more.

  If the combination of the organic pigments contained falls outside the above conditions, the light from the backlight that passes through the liquid crystal alignment control protrusions cannot be sufficiently shielded depending on the wavelength, which adversely affects the contrast of the liquid crystal display device. give.

  The total ratio of the organic pigment to the total solid content in the photosensitive composition of the present invention is usually 1 to 70% by weight, preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. If the proportion of the organic pigment is too small, the liquid crystal alignment control projections cannot be sufficiently shielded from light, adversely affecting the contrast. Conversely, if the proportion of the organic pigment is too large, it is difficult to form a good shape as the liquid crystal alignment control projections. In the present invention, the “total solid content” means all components other than the solvent component described later among the components contained in the negative photosensitive composition for liquid crystal alignment control protrusions.

[1-2] Solvent The organic pigment used in the present invention is usually dispersed in a liquid together with a solvent, a dispersant, and other components as necessary, and a negative dispersion composition for liquid crystal alignment control projections as a pigment dispersion. Use in the preparation is advantageous in handling.

  Examples of the solvent (dispersion medium) used in the pigment dispersion include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n -Octane, Valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl pionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used alone or in combination of two or more.

  When the organic pigment of the present invention is used as a pigment dispersion, the content of the solvent in the entire pigment dispersion is not particularly limited, but the upper limit is usually 99% by weight. When the solvent exceeds 99% by weight, the amount of the pigment, the dispersing agent, etc. becomes too small, which is inappropriate for forming a dispersion. On the other hand, the lower limit of the solvent content of the pigment dispersion is usually 50% by weight, preferably 60% by weight, and more preferably 70% by weight in consideration of viscosity and the like.

[1-3] Dispersant As the dispersant, a polymer dispersant and / or a pigment derivative is preferably used.

  Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. A dispersing agent etc. can be mentioned. Specific examples of such dispersants are EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENECA). ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These polymer dispersants can be used alone or in combination of two or more.

  The ratio of the polymer dispersant to the total solid content of the pigment dispersion is usually 10 to 90% by weight, preferably 10 to 70% by weight, and more preferably 10 to 50% by weight. If the ratio of the polymer dispersant in the pigment dispersion is too large, the ratio of the pigment is relatively reduced, so that the coloring power is lowered and the film thickness tends to be too thick with respect to the color density. If the proportion of the dispersing agent is too small, there is a risk that dispersion stability deteriorates and problems such as reaggregation and thickening occur.

  On the other hand, as pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoidolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, In the present invention, anthraquinone pigments and azo pigment derivatives are preferably used as derivatives of the same type as the pigment to be used. These pigment derivatives can be used individually by 1 type or in mixture of 2 or more types.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, and the like. They are bonded directly or via a linking group such as an alkyl group, aryl group, heterocyclic group or the like. The substituent of the pigment derivative is preferably a sulfonamide group, a quaternary salt thereof, or a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.

  Specific examples of suitable pigment derivatives include sulfonic acid derivatives of azo pigments and sulfonic acid derivatives of anthraquinone pigments.

  The ratio of the pigment derivative to the total solid content of the pigment dispersion is usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight. If the ratio of the pigment derivative in the pigment dispersion is too small, the dispersion stability deteriorates, and there is a risk of problems such as re-aggregation and thickening. Conversely, if it is too large, the contribution to dispersion stability is saturated. On the other hand, the color purity may be lowered, which is not preferable.

  In the present invention, the above-described polymer dispersant and pigment derivative may be used in combination as the dispersant.

[1-4] Other components Although there is no restriction | limiting in particular as another component mix | blended with the pigment dispersion which concerns on this invention as needed, The pigment dispersion of this invention is the below-mentioned (a ) A part of the alkali-soluble resin may be included, and by including such a binder resin, the dispersion stability in producing the pigment dispersion according to the present invention can be enhanced.

  In this case, the addition amount of the binder resin is preferably 5 to 100% by weight, particularly 10 to 80% by weight, based on the total organic pigment in the pigment dispersion. If the added amount of the binder resin is less than 5% by weight with respect to the total organic pigment in the pigment dispersion, the effect of increasing the dispersion stability is insufficient, and if it exceeds 100% by weight, the pigment concentration is lowered. Color density cannot be obtained.

[1-5] Particle Size Distribution of Organic Pigment In the pigment dispersion according to the present invention, the particle size of the pigment is usually 30 nm or more, preferably 50 nm or more, more preferably 80 nm or more, and usually 500 nm or less, preferably 350 nm or less. More preferably, it is 250 nm or less. The half-value width of the particle size distribution is preferably 250 nm or less, particularly 150 nm or less, particularly 100 nm or less.
Here, the particle size of the pigment refers to the value of the average particle size obtained by a particle size distribution analyzer using a laser diffraction / scattering method or the like. Further, the half-value width of the particle size distribution refers to the inside of the horizontal axis where the half value of the maximum value in the particle size distribution is half.

[1-6] Method for Producing Pigment Dispersion Various methods can be adopted as a method for producing the pigment dispersion according to the present invention in order to realize the above particle size distribution, but hard spheres (beads) are used. A bead mill method in which the pigment is dispersed by collision is particularly preferably used.
The beads used in the bead mill method include those made of glass, zirconia (ZrO ₂ ), chrome, etc. Among them, zirconia beads having a high specific gravity and less contamination such as wear powder are preferable. The average particle size of the beads used is usually 30 to 500 μm, preferably 30 to 300 μm. When the average particle size of the beads is less than 30 μm, the weight of the beads is light, the collision energy is reduced, and the dispersion ability is lowered. When the average particle diameter of the beads is larger than 500 μm, the void volume between the beads is large and it is difficult to make the pigment fine particles. Further, the bead weight is heavy, excessive collision energy is applied to the pigment, and it is difficult to make the particle size of the pigment within the range of 30 to 500 nm.

  The disperser used in the dispersion treatment may be any disperser that can use the above beads, and is not particularly limited. For example, “TORUSMILL” manufactured by Getzmann in a batch type, “Agitator mill” manufactured by Ashizawa in a continuous type, for example. "Picomill" manufactured by Asada Tekko Co., Ltd., "Apex Mega" manufactured by Kotobuki Giken Kogyo Co., Ltd. and the like.

  The method for preparing the pigment dispersion is not particularly limited, but the dispersion using the dispersion equipment is performed during the manufacturing process of the pigment dispersion. For example, first, the above-described pigment, dispersant, solvent, and binder resin as necessary are mixed in advance as a dispersion composition to form a liquid. This blended solution is dispersed with beads using the above-mentioned disperser to obtain a desired pigment dispersion.

  In addition, although there is no restriction | limiting in particular in the usage-amount of bead, It is preferable to set it as about 50-90 volume% of the vessel volume of the disperser used for a dispersion process. If the bead filling amount is too small, it takes time to obtain a pigment dispersion having a desired particle size distribution by the dispersion treatment. If the bead filling amount is too large, the mechanical load increases and the beads are damaged. spread.

  In addition, as a pre-process of the dispersion process using beads having an average particle diameter of 30 to 500 μm, a pre-process such as a roll mill, a kneader, or a dispersion process using large-diameter beads exceeding the average particle diameter of 500 μm may be performed. . Further, the prepared pigment dispersion may be further post-treated. As the post-treatment method, for example, treatment by “K.F.

[2] Alkali-soluble resin (a) The alkali-soluble resin used in the first embodiment of the present invention is not particularly limited as long as it is a resin containing a compound having a phenolic hydroxyl group, but a novolac resin or a hydroxystyrene resin. Resin etc. are mentioned.
A novolac resin and a hydroxystyrene resin may be used in combination.
In addition, a copolymer resin of an acrylic acid derivative having a phenolic hydroxyl group, a polyvinyl acetal resin having a phenolic hydroxyl group, an acid anhydride-modified resin of a novolak epoxy acrylate, or the like can also be used as the alkali-soluble resin. .
Furthermore, a resin other than a compound having a phenolic hydroxyl group such as an acrylic resin or a resin having another phenolic hydroxyl group can be mixed with an alkali-soluble resin as long as the effects of the present invention are not impaired. (A) The alkali-soluble resin preferably contains at least 10% by weight of a resin containing a phenolic hydroxyl group, particularly 30% by weight or more.

  The (a) alkali-soluble resin used in the second aspect of the present invention is not particularly limited, but a resin containing a compound having a phenolic hydroxyl group is preferably used.

[2-1] Novolak-based resin The novolak-based resin used in the present invention includes, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, At least one of phenols such as 1,2,4-benzenetriol, benzoic acid, 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol and the like is reacted with an acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraalkaline. Hydrate, propionaldehyde, benzaldehyde, salicylaldehyde, aldehydes such as furfural, or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, at least one resin obtained by polycondensation of.

  The reaction between phenols and aldehydes is carried out without solvent or in a solvent. A resole resin that has been polycondensed in the same manner can be used except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “MW”) of the novolak resin by gel permeation chromatography (GPC) is usually 1,000 to 20,000, preferably 1,000 to 10,000. More preferably, it is 1,000 to 8,000. If the MW is less than 1,000, the electrical reliability is lowered, and if it exceeds 10,000, the developability is lowered.

  In order to improve alkali solubility, the novolac resin is obtained by reacting a resin in which a carboxylic acid is added to a part of the phenolic hydroxyl group, a part of the hydroxyl group of the novolak resin and an unsaturated group-containing epoxy compound. A so-called novolac type epoxy acrylate resin to which a carboxylic acid is added can also be preferably used.

  Here, examples of the carboxylic acid directly added to the phenolic hydroxyl group include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, and 3-ethyl. Tetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and the like The anhydride of these is mentioned.

The so-called novolak epoxy acrylate resin in which a carboxylic acid is added after reacting a part of the hydroxyl group of the novolak resin with the unsaturated group-containing epoxy compound includes glycidyl acrylate, glycidyl. Examples thereof include methacrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) acrylate, methyl glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) vinyl, and the like. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.
Of these, glycidyl methacrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

  A known method can be used for the reaction of the novolac resin and the unsaturated group-containing epoxy compound. For example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc., in an organic solvent. By reacting at a reaction temperature of 50 to 150 ° C. for several to several tens of hours, an unsaturated group-containing epoxy compound can be added to the novolak resin. The proportion of the unsaturated group-containing epoxy compound added to the hydroxyl group of the novolak resin is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.

The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the total of the novolak resin and the unsaturated group-containing epoxy compound). .
In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, dibutylhydroxytoluene, phenothiazine, etc.) The amount used is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

  The carboxylic acid anhydride to be further added to the resin obtained above includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, anhydrous Trimellitic acid, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. , Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, particularly preferred The compound is anhydrous tetrahydro Tal acid and biphenyl tetracarboxylic acid dianhydride.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be obtained by continuing the reaction under the same conditions as in the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, and more preferably 20 to 140 mg-KOH / g. It is particularly preferable that the amount is small. When the resin acid value is less than the above range, alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.

  In the present invention, these novolac resins can be used singly or in combination of two or more.

[2-2] Hydroxystyrene resin Examples of the hydroxystyrene resin used in the present invention include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, and pentahydroxy. Styrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2 -Hydroxystyrenes such as-(p-hydroxyphenyl) propylene (note that these have a halogen atom such as chlorine, bromine, iodine or fluorine or an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring. 1 type or 2 types or more) Or, further, styrenes such as styrene and α-methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, tricyclo [5 .2.1.0] One or more of comonomers such as acrylic acid derivatives such as decan-8-yl (meth) acrylate, glycidyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, Examples thereof include homopolymers or copolymers of hydroxystyrenes polymerized in the presence of a radical polymerization initiator or a cationic polymerization initiator.

  The MW of the hydroxystyrene resin is usually 2,000 to 50,000, preferably 2,000 to 20,000. When the MW is less than 2,000, the electrical reliability is lowered, and when it exceeds 20,000, the developability is lowered.

  In order to increase the alkali solubility in the hydroxystyrene resin, a carboxylic acid may be added to a part of the phenolic hydroxyl group. Examples of the carboxylic acid in this case include oxalic acid, maleic acid, itaconic acid, Phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4- Examples include methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and anhydrides thereof.

  In this invention, a hydroxy styrene resin can be used individually by 1 type or in mixture of 2 or more types.

[2-3] Acrylic Resin In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group. means.

  The acrylic resin needs to contain a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain in order to ensure alkali solubility. Among them, an acrylic resin having a carboxyl group that can be developed with a highly alkaline solution, for example, an acrylic acid (co) polymer, a styrene-maleic anhydride resin, and a novolac epoxy acrylate anhydride-modified resin. Etc. Of these, particularly preferred are (co) polymers containing (meth) acrylic acid, (co) polymers containing (meth) acrylic acid esters having a carboxyl group, and novolak epoxy acrylate anhydride-modified resins. These acrylic resins are excellent in developability, transparency, and the like, and have advantages in that copolymers having different performances can be obtained in combination with various monomers, and the production method can be easily controlled.

  The novolak-type epoxy acrylate acid anhydride-modified resin mentioned here includes a resin in which all of the hydroxyl groups of the novolac resin are substituted, unlike a resin in which a part of the hydroxyl groups of the novolak resin is substituted. Specifically, this novolak-type epoxy acrylate anhydride-modified resin adds an α, β-unsaturated monocarboxylic acid to the epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. Furthermore, it is obtained by a method of imparting alkali solubility by reacting with a polybasic acid anhydride.

  As an epoxy resin used as a raw material, (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, the following formula (I Biphenyl novolak type epoxy resin, naphthalene novolak type epoxy resin, epoxy resin represented by the following formula (II), and the like can be suitably used (see Japanese Patent No. 2878486).

  The (co) polymer containing (meth) acrylic acid or the (co) polymer containing a (meth) acrylic acid ester having a carboxyl group is, for example, a (co) weight mainly composed of the following monomers: It is a coalescence.

That is, examples of the monomer include a compound obtained by adding an acid (anhydride) to hydroxyalkyl (meth) acrylate.
Examples of the hydroxyalkyl (meth) acrylate include (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- ( (Meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acrylic) Leuoxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ) Ester, maleic acid (2- (meth) acryloyloxypropyl) ester Succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid ( Examples include 2- (meth) acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, and the acid (anhydride) includes (anhydrous) succinic acid and (anhydrous) phthalic acid. , (Anhydrous) maleic acid and the like.
Any of these hydroxyalkyl (meth) acrylates and acids (anhydrides) may be used alone or in combination of two or more.

  Monomers that can be copolymerized with the above monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itacone. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl Esters of (meth) acrylic acid such as (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, and (meth) acrylic acid Caprolactone, β-propiolac , Γ-butyrolactone, δ-valerolactone and other lactones added compounds, acrylonitrile, methacrylonitrile and other acrylonitriles, (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloyl Acrylamides such as morpholine, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethylacrylamide, vinyl acids such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate Etc. These may be used alone or in combination of two or more.

  In particular, as a preferred acrylic resin for improving the strength of the coating film on the substrate, at least one of the following monomers (i) and at least one of the following monomers (ii) are used in combination. A polymerized acrylic resin is exemplified.

Monomer (i): styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) acrylsulfamide, etc. Monomer (ii): (meth) acrylic acid (2- (meth) acryloyloxyethyl) ester or succinic acid (2- (meth) acryloyloxyethyl) ester, Adipic acid (2- (meth) acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid ( Has a carboxyl group such as 2- (meth) acryloyloxyethyl) ester (Meth) acrylic acid ester In the production of the acrylic resin, the monomer (i) is usually 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, ii) is usually used in a proportion of 2 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%.

  The acrylic resin preferably includes an acrylic resin having an ethylenic double bond in the side chain. By using such an acrylic resin, the photocurability of the photosensitive composition of the present invention is improved, so that the resolution of the liquid crystal alignment control protrusion and the adhesion to the substrate can be further improved.

As a method for introducing an ethylenic double bond into the side chain of an acrylic resin, for example, the method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, etc.,
(1) A method of reacting a carboxyl group of an acrylic resin with a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group
(2) A method of reacting acrylic acid chloride or the like with the hydroxyl group of the acrylic resin may be mentioned.

  Specifically, an acrylic resin having a carboxyl group or a hydroxyl group is added to glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride, (meth) allyl chloride, etc., by reacting one or more compounds, it has an ethylenic double bond group in the side chain. An acrylic resin can be obtained. Especially, what made the alicyclic epoxy compound like (3,4-epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group and a hydroxyl group is preferable.

  As described above, the method of introducing an ethylenic double bond into an acrylic resin having a carboxyl group or a hydroxyl group in advance is usually 2 to 50 with respect to the carboxyl group or hydroxyl group of the acrylic resin having a carboxyl group or a hydroxyl group. A method of bonding a compound having an ethylenic double bond of 5 mol%, preferably 5 to 40 mol% is preferable. The carboxyl group content is preferably in the range of 5 to 200 mg-KOH / g as the acid value. When the acid value is less than 5 mg-KOH / g, it becomes insoluble in an alkaline developer, and when it exceeds 200 mg-KOH / g, the development sensitivity may be lowered.

  In the present invention, as the alkali-soluble resin, a vinyl monomer having an aromatic hydroxyl group in the side chain, specifically, o, m, p-hydroxyphenylmethacrylamide, o, m, p-hydroxystyrene, It is also effective to use an acrylic resin using o, m, p-hydroxyphenylmaleimide or the like as a part of the copolymerization component. Although the resin containing such a component is disadvantageous in terms of sensitivity as a photopolymerizable composition, it is characterized by developability, substrate adhesion, chemical resistance, etc., so that light during exposure is blocked. In addition, the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention, which tends to have a low polymerization rate on the substrate surface, is very effective depending on the formulation.

  The weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of the acrylic resin is preferably in the range of 1,000 to 100,000 in terms of polystyrene. When the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease.

  The ratio of the (a) alkali-soluble resin to the total solid content in the photosensitive composition of the present invention is usually 10 to 80% by weight, preferably 15 to 70% by weight. If the proportion of (a) the alkali-soluble resin is too much within this range, sufficient sensitivity for forming the liquid crystal alignment control protrusions is not ensured, and if it is too small, the preferred shape of the liquid crystal alignment control protrusions is not formed.

[3] Ethylenically unsaturated compound The photosensitive composition of the present invention is a photopolymerizable photosensitive composition containing (a) an alkali-soluble resin and (c) an ethylenically unsaturated compound and (b) a photopolymerization initiator. is there.

  The (c) ethylenically unsaturated compound used in the photopolymerizable photosensitive composition of the present invention is not particularly limited as long as it is a low molecular weight compound that can be polymerized, but addition polymerization having at least one ethylenic double bond is possible. (Hereinafter abbreviated as “ethylenic compound”) is preferable. Such an ethylenic compound is cured by addition polymerization by the action of a photopolymerization initiator system described later when the photosensitive composition of the present invention is irradiated with actinic rays.

  Examples of the ethylenic compound include (A) an unsaturated carboxylic acid, (B) an ester of an unsaturated carboxylic acid and a monohydroxy compound, and (C) an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. (D) Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, (E) Unsaturated carboxylic acids and polyvalent carboxylic acids, and polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples thereof include esters obtained by an esterification reaction with a compound, and (F) an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl-containing hydroxy compound.

  (A) As unsaturated carboxylic acid, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Examples include loxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl succinic acid, and the like.

  (B) As esters of unsaturated carboxylic acid and monohydroxy compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, benzyl (meth) acrylate, methoxyphenyl (meth) acrylate, and the like.

  (C) Esters of aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol Acrylic esters such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. may be mentioned. Furthermore, the acrylic acid part of these acrylates is a methacrylic acid ester substituted for a methacrylic acid part, an itaconic acid ester substituted for an itaconic acid part, a crotonic acid ester substituted for a crotonic acid part, or a maleic acid substituted for a maleic acid part Examples include esters.

  Examples of (D) esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.

  (E) The esters obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyvalent hydroxy compound are not necessarily a single substance, and may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  (F) Ethylene compounds having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate. And polyisocyanate compounds such as aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyl) (Meth) acryloyl such as oxymethyl) propane, 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products of group-containing hydroxy compound.

Examples of ethylenic compounds other than those described above include acrylamides such as ethylene bisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate.
These ethylenic compounds may be used individually by 1 type, respectively, and may use 2 or more types together.

  When using an oxime ester compound as a photopolymerization initiator, the proportion of the ethylenic compound is usually 5 to 50% by weight, preferably 10 to 40% by weight, based on the total solid content of the photosensitive composition of the present invention. When the ratio of the ethylenic compound is less than this, sufficient image formation and substrate adhesion cannot be maintained, while when it exceeds the ratio, it becomes difficult to form a good shape as the liquid crystal alignment control protrusion.

  When using other than the oxime ester compound as the photopolymerization initiator, the proportion of the ethylenic compound is usually 5 to 70% by weight, preferably 10 to 70% by weight, based on the total solid content of the photosensitive composition of the present invention. More preferably, it is 40 to 70% by weight. When the ratio of the ethylenic compound is less than this, sufficient image formation and substrate adhesion cannot be maintained, and the sensitivity is also deteriorated. That is, when using other than the oxime ester compound as the photopolymerization initiator, the sensitivity tends to deteriorate. Therefore, in order to increase the sensitivity, the ethylenic compound is used in comparison with the case where the oxime ester compound is used as the photopolymerization initiator. It is preferable to increase the ratio. On the other hand, when the ratio of the ethylenic compound is larger than this, it becomes difficult to form a good shape as the liquid crystal alignment control protrusion.

[4] Photopolymerization initiator system component The negative photosensitive composition for liquid crystal alignment control protrusions of the present invention, together with the above-mentioned ethylenic compound, directly absorbs light or is photosensitized to undergo a decomposition reaction or a hydrogen abstraction reaction. And a photopolymerization initiator system component having a function of generating a polymerization active radical. In the present invention, the photopolymerization initiator component means a mixture in which (b) an additive such as a photopolymerization initiator, an accelerator, and a sensitizing dye is used in combination.

[4-1] Photopolymerization initiator The photosensitive composition according to the first aspect of the present invention contains an oxime ester-based compound as the (b) photopolymerization initiator.
In the photosensitive composition according to the second aspect of the present invention, an oxime ester compound is not necessarily used as the (b) photopolymerization initiator, but an oxime ester compound is preferably used.

  Specific oxime ester compounds include those having a structure represented by the following general formula (1), preferably the following general formula (2).

（（１）式中、Ｒ^２は、それぞれ置換されていてもよい、炭素数２〜１２のアルカノイル基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリールオキシキシカルボニルアルカノイル基、炭素数２〜１０のアミノカルボニル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示す。）

(In the formula (1), R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 carbon atoms alkoxycarbonylalkanoyl group, 8 to 20 carbon atoms phenoxycarbonylalkanoyl group, 3 to 20 carbon atoms heteroaryloxyxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminocarbonyl group, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms.)

（（２）式中、Ｒ^１ａは、それぞれ置換されていてもよい、炭素数１〜１０のアルキル基、炭素数２〜２５のアルケニル基、炭素数１〜２０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、炭素数１〜２０のアミノアルキル基、炭素数２〜１２のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基、又は炭素数７〜２０のフェノキシカルボニル基を示す。
Ｒ^１ｂは、置換されていてもよい芳香環基を示す。
なお、Ｒ^１ａは、Ｒ^１ｂとともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい、炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_ｎ−、−（Ｃ≡Ｃ）_ｎ−、あるいはこれらを組み合わせてなる基が挙げられる（なお、ｎは０〜３の整数）。
Ｒ^２ａは、それぞれ置換されていてもよい、炭素数２〜１２のアルカノイル基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリールオキシキシカルボニルアルカノイル基、炭素数２〜１０のアミノカルボニル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示す。）

(In formula (2), R ^1a is an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 3-20 alkoxycarbonylalkyl group, C8-20 phenoxycarbonylalkyl group, C1-20 heteroaryloxycarbonylalkyl group, C1-20 heteroarylthioalkyl group, C0-20 An aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a benzoyl group having 7 to 20 carbon atoms. , A heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms. Show.
R ^1b represents an ^optionally substituted aromatic ring group.
R ^1a may form a ring with R ^1b , and the linking group may have a substituent, each having 1 to 10 carbon atoms, — (CH═CH) _n —. ,-(C≡C) _n- , or a group formed by a combination thereof (where n is an integer of 0 to 3).
R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. , An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, and 7 carbon atoms -20 benzoyl group, C1-C20 hetero aryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 phenoxycarbonyl group. )

R ² in the general formula (1) and R ^2a in the general formula (2) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Of the cycloalkanoyl group.

In addition, the aromatic ring group of R ^1b in the general formula (2) is a generic term for an aromatic hydrocarbon ring group and a heteroaromatic ring group, and preferably an optionally substituted carbazoyl group or a substituted Examples thereof include an optionally substituted thioxanthonyl group and an optionally substituted phenyl sulfide group.

  Specific examples of the oxime ester-based compound suitable for the present invention include compounds exemplified below, but are not limited to these compounds.

  These oxime ester compounds are known per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750.

In the first embodiment, as the photopolymerization initiator (b), one or more of the oxime ester compounds can be used, and these oxime ester compounds can be combined with other photopolymerization initiators. It can also be used together, and high sensitivity can be expected by the combined use.
In the second embodiment, (b) one or more of the oxime ester compounds may be used as the photopolymerization initiator, and other than these oxime ester compounds and oxime ester compounds. These photopolymerization initiators may be used in combination, or only a photopolymerization initiator other than the oxime ester compound may be used.

  In the first aspect, as the other photopolymerization initiator that can be used in combination with the oxime ester compound and the photopolymerization initiator other than the oxime ester compound that can be used in the second aspect, for example, the following compounds can be used. Can be mentioned.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4 A halomethylated oxadiazole derivative such as oxadiazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2 ' -Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole 2 An imidazole derivative such as a monomer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzanthrone derivatives;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropyl) Phenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- ( acetophenone derivatives such as p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, bis-cyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophenyl- 1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6-tetrafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,4, 6-trifluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, bis-cyclopentadienyl-Ti-2,4-di-fluoropheny -1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophen-1-yl), bis-methylcyclopentadienyl-Ti-bis- ( , 6-di-fluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl) -phen-1-yl, etc. :

  When the (b) photopolymerization initiator containing the oxime ester compound is used, the blending ratio of the (b) photopolymerization initiator is usually 0.1 to 30% by weight in the total solid content of the photosensitive composition of the present invention, Preferably it is 0.5-20 weight%, More preferably, it is 0.7-10 weight%. If the blending ratio is extremely low, the sensitivity to the exposure light may be lowered. Conversely, if the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure may be induced.

  When (b) a photopolymerization initiator other than the oxime ester compound is used, it is necessary to increase the blending ratio of (b) the photopolymerization initiator as compared with the case where an oxime ester compound is used as the photopolymerization initiator. The total solid content of the photosensitive composition is preferably 3% by weight or more, more preferably 4 to 15% by weight, and particularly preferably 6 to 15% by weight. If it is less than this range, the sensitivity to the exposure light beam may be reduced, and if it is more than this range, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

[4-2] Sensitizing dye In addition to the initiator component, a sensitizing dye may be further added to the photosensitive composition of the present invention. In order to cause a photopolymerization reaction under high light shielding, it is preferable to add a sensitizing dye.
Examples of such a sensitizing dye include a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and a 3-ketocoumarin compound described in JP-A 63-221110. Xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292. (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403, and a julolidyl group described in JP-A-6-295061. Examples thereof include sensitizing dyes and diaminobenzene compounds described in JP-A No. 11-326624.

Of these sensitizing dyes, amino group-containing sensitizing dyes and xanthene dyes are particularly preferable.
These sensitizing dyes may be used alone or in combination of two or more.

  The blending ratio of the sensitizing dye in the photosensitive composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight in the total solid content of the photosensitive composition. It is.

[5] Other solid content The photosensitive composition of the present invention may contain a solid content other than the above components as necessary. Examples of these components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers, and the like.

[5-1] Surfactant As the surfactant, one or more of anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but they adversely affect various properties. In view of low possibility, it is preferable to use a nonionic surfactant.
The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total solid content in the photosensitive composition. %, Most preferably in the range of 0.03 to 0.3% by weight.

[5-2] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include one or two of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. More than seeds are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content in the photosensitive composition.

[5-3] Plasticizer Examples of the plasticizer include 1 such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Species or two or more are used.
The blending ratio of the plasticizer is preferably 10% by weight or less with respect to the total solid content in the photosensitive composition.

[6] Preparation of photosensitive composition In order to prepare the photosensitive composition of the present invention, the above-mentioned solvent, (a) alkali-soluble resin, (c) ethylenically unsaturated compound, ( b) A predetermined amount of a photopolymerization initiator and other components blended as necessary are mixed to obtain a uniform dispersion. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained photosensitive composition with a filter etc.

  In the photosensitive composition of the present invention, the solvent content is 99% by weight or less, particularly 90% by weight or less, particularly 70% by weight or more, particularly 75% by weight for the same reason as the solvent content in the pigment dispersion described above. % Or more is preferable.

[7] OD Value of Photosensitive Composition The negative photosensitive composition for liquid crystal alignment control protrusions of the present invention preferably has an OD value of 0.5 / μm or more.
The OD value of the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention can be determined by, for example, patterning the negative photosensitive composition of the present invention on a glass substrate and determining the optical density (OD value) of the image area. It can be determined by measuring with a reflection densitometer.

If the OD value is less than 0.5 / μm, the disturbance of the transmitted light from the backlight cannot be sufficiently shielded.
A preferable OD value is 0.5 / μm or more. Note that the upper limit of the OD value is 2.0 / μm or less because mask alignment becomes difficult in the exposure process during patterning.

[8] Sensitivity of photosensitive composition In the first embodiment of the present invention, the sensitivity of the photosensitive composition is 150 mj / cm ² or less.
This sensitivity can be evaluated by the method shown in the Examples section below.
If the sensitivity of the photosensitive composition exceeds 150 mj / cm ² , the object of the present invention to provide a highly sensitive negative photosensitive composition for liquid crystal alignment control protrusions cannot be achieved. The sensitivity of the photosensitive composition is preferably 120 mj / cm ² or less, particularly 100 mj / cm ² or less. Although there is no restriction | limiting in particular in the minimum of the sensitivity of the photosensitive composition, Usually, it is 30 mj / cm < ² > or more.
In addition, it is preferable to satisfy | fill such sensitivity also in the photosensitive composition of a 2nd aspect.

[9] VHR of liquid crystal alignment control protrusion
The VHR of the liquid crystal alignment control protrusion obtained by exposing the photosensitive composition according to the second aspect of the present invention is 90% or more.
The VHR of the liquid crystal alignment control protrusion can be evaluated by the method shown in the section of the example described later.
When the VHR of the liquid crystal alignment control protrusion is less than 90%, the object of the present invention to provide a liquid crystal alignment control protrusion excellent in display quality such as voltage holding ratio and electrical reliability cannot be achieved. The VHR of the liquid crystal alignment control protrusion is preferably 92% or more, particularly 94% or more. The upper limit of VHR of the liquid crystal alignment control protrusion is not particularly limited, but is usually 99% or less.
In addition, it is preferable to satisfy | fill such VHR also in the photosensitive composition of a 2nd aspect.

[Method for forming liquid crystal alignment control protrusions]
Next, a method for forming liquid crystal alignment control protrusions using the negative photosensitive composition for liquid crystal alignment control protrusions of the present invention will be described.

  First, a black matrix obtained by the method described in JP-A-2003-33011 and a color filter of red, blue, and green are provided, and further, for example, ITO (indium tin oxide having a thickness of 150 nm) is used as a transparent electrode. The above-described photosensitive composition for liquid crystal split alignment protrusions of the present invention is applied on a transparent substrate (hereinafter sometimes simply referred to as “substrate”) having a thickness of 0.1 to 2 mm. It is applied by the method, wire bar method, flow coating method, die coating method, roll coating method, spray coating method or the like. In particular, the die coating method significantly reduces the amount of coating solution used; there is no influence of mist adhering to the case of the spin coating method; To preferred.

  The thickness of the coating film depends on the required size of the liquid crystal alignment control protrusions, but is usually 0.2 to 10 μm, preferably 0.5 to 5 μm, more preferably as the film thickness after drying described below. The range is 0.8 to 3 μm.

Drying of the photosensitive composition coating film after coating the photosensitive composition on the substrate is preferably by a drying method using a hot plate, IR oven, or convection oven. Usually, after preliminary drying, it is heated again and dried.
The conditions for the preliminary drying can be appropriately selected according to the type of the solvent in the photosensitive composition, the performance of the dryer to be used, etc., but usually at a temperature of 40 to 80 ° C. for 15 seconds to 5 minutes, preferably It is selected in the range of 30 seconds to 3 minutes at a temperature of 50 to 70 ° C.

The temperature condition of the reheat drying after the preliminary drying is 50 to 200 ° C., preferably 70 to 160 ° C., more preferably 70 to 130 ° C. higher than the preliminary drying temperature. The drying time is usually 10 seconds to 10 minutes, preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion of the coating film to the substrate. However, if the drying temperature is too high, thermal polymerization may be induced to cause development failure.
Note that this drying step may be a vacuum drying method that is performed in a vacuum chamber without increasing the temperature.

  Image exposure is performed by superimposing a matrix pattern on the coating film of the photosensitive composition and irradiating a UV or visible light source through this matrix risk pattern. Examples of the light source used for the above image exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, Examples thereof include laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can be used.

  After the exposure, unexposed uncured portions are removed by development to form pixels. Development can be performed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This developer may contain organic solvents, buffering agents, complexing agents, dyes or pigments.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or Trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Yes And alkali compounds. These alkaline compounds may be used alone or in a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzenes. Examples thereof include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkylbetaines and amino acids. These may be used alone or in combination of two or more.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. These may be used alone or in combination of two or more. The organic solvent can be used by mixing with water.

  The temperature of development processing is 10-50 degreeC normally, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. Further, the developing method may be any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  Usually, an image obtained after development is required to have a fine line reproducibility with a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display.

  The photosensitive composition of the present invention is usually 150 ° C. or higher for the purpose of obtaining a cross-sectional arch shape necessary for the shape of the liquid crystal alignment control protrusion after development and for obtaining sufficient electrical reliability. , Preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 The heat treatment is performed for at least minutes, usually at most 120 minutes, preferably at most 60 minutes, more preferably at most 40 minutes.

  The liquid crystal alignment control protrusion formed as described above has a cross-section arch having a bottom width of usually 0.5 to 20 μm, preferably 3 to 17 μm and a height of usually 0.2 to 5 μm, preferably 0.5 to 3 μm. The angle with which the side surface of the protrusion is the substrate surface is usually 10 to 40 °, preferably 15 to 35 °.

  In addition, the liquid crystal control protrusion thus obtained preferably has a light transmittance at a wavelength of 550 nm of 30% or less per 1 μm of film thickness, and each light at a wavelength of 450 nm, 550 nm, and 610 nm. Is particularly preferably 30% or less in terms of transmittance per 1 μm of film thickness. The transmittance per 1 μm of film thickness can be determined by, for example, applying a photosensitive composition for liquid crystal control protrusions onto a substrate and drying. In the case of negative, the entire exposure is performed with a predetermined exposure amount, and in the case of positive, no exposure is performed. After performing the predetermined development and heat treatment, the transmittance is measured with a spectrophotometer, while the film thickness of the photosensitive composition is separately measured and converted to the transmittance per 1 μm of film thickness. Can be obtained.

[Liquid Crystal Display (Panel)]
Next, the liquid crystal display device (panel) of the present invention will be described.
In the liquid crystal display device of the present invention, an alignment film is usually formed on a color filter, and a liquid crystal alignment control protrusion is formed on the alignment film by the spacer and the above-described photosensitive composition of the present invention. A liquid crystal cell is formed together, liquid crystal is injected into the formed liquid crystal cell, and the liquid crystal cell is connected to the counter electrode.
As the alignment film used here, a resin film such as polyimide is suitable. Gravure printing method and / or flexographic printing method is usually adopted for the formation of the alignment film. After printing, after curing treatment by thermal firing, surface treatment is performed by ultraviolet irradiation or rubbing cloth treatment, and liquid crystal The alignment film is formed by processing into a surface state that can adjust the inclination of the film. The alignment film thus formed has a thickness of several tens of nm, for example, 50 to 80 nm.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.

  As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less.

  After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following, “part” means “part by weight”.

<Synthesis of alkali-soluble resin (P-1)>
To the separable flask, m-cresol 332.4 g, p-cresol 142.5 g, 37 wt% formalin aqueous solution 213.9 g, and oxalic acid dihydrate 15.0 g were added, and the internal temperature was 95 with stirring and heating under reflux. The temperature was raised to 0 ° C. and the reaction was carried out for 5 hours. While the internal temperature was raised to 180 ° C. over 1.5 hours, water was distilled out of the system, and then the internal temperature was further raised to 195 ° C., and the pressure was not reduced under a reduced pressure of 15 torr (2.0 kPa). The monomer of the reaction was distilled off to obtain an alkali-soluble resin (P-1) having a phenolic hydroxyl group. The MW of the obtained alkali-soluble resin (P-1) was 3500.

<Synthesis of alkali-soluble resin (P-2)>
In a separable flask, 20 g of propylene glycol monomethyl ether acetate was stirred and purged with nitrogen, and the temperature was raised to 70 ° C. To this, 13.84 g of p-acetoxystyrene, 6.16 g of acrylic acid, 0.3 g of dodecanethiol, and 1.2 g of azobisisobutyronitrile were added dropwise, and stirring was further continued at 70 ° C. for 4 hours. The reaction solution was added dropwise to 300 ml of hexane with stirring, and the precipitated resin was filtered off. A solution prepared by dissolving the obtained solid in 20 g of methanol / 5 g of triethylamine / 1 g of deionized water was dropped into 500 ml of a 1% by weight aqueous hydrochloric acid solution with stirring, and the precipitated resin was filtered off twice. 18 g of an alkali-soluble resin (P-2) having a phenolic hydroxyl group was obtained. The MW of the obtained alkali-soluble resin (P-2) was 17300.

<Synthesis of alkali-soluble resin (P-3)>
In a separable flask, 90 g of propylene glycol monomethyl ether acetate and 6.1 g of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.) were stirred while being purged with nitrogen, and the temperature was raised to 80 ° C. . 20 g of styrene, 57 g of glycidyl methacrylate, and 82 g of a monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 80 ° C. for 4 hours.

  Next, the inside of the reaction vessel was purged with air, 27.0 g of acrylic acid, 0.7 g of trisdimethylaminomethylphenol and 0.12 g of hydroquinone were added, and the reaction was continued at 80 ° C. for 6 hours. Thereafter, 52.0 g of tetrahydrophthalic anhydride (THPA) and 0.7 g of triethylamine were added and reacted at 85 ° C. for 3.5 hours to obtain a polymerization reaction solution. The obtained alkali-soluble resin (P-3) had a MW of about 15,000.

<Synthesis of alkali-soluble resin (P-6)>
284 g of m / p-cresol novolak resin (m / p = 6/4, MW = 3000) and 205.7 g of propylene glycol monomethyl ether acetate were placed in a reaction vessel and dissolved at 100 ° C. in a nitrogen atmosphere. Subsequently, 47.3 g of succinic anhydride and 7.1 g of diethylaniline were added and reacted at 100 ° C. for 10 hours. After confirming that succinic anhydride disappeared by FT-IR, the reaction was completed. To this was added 440 g of propylene glycol monomethyl ether acetate, and the reaction solution was cooled to obtain an alkali-soluble resin (P-6) having a phenolic hydroxyl group. The obtained resin had a MW of 4000.
The m / p-cresol novolak resin (m / p = 6/4, MW = 3000) was the same method as the alkali-soluble resin (P-1) except that 192.5 g of a 37 wt% formalin aqueous solution was used. Manufactured by.

<Synthesis of alkali-soluble resin (P-7)>
120 g of MW4000 metacresol novolak resin and 71 g of glycidyl methacrylate were dissolved in 191 g of propylene glycol monomethyl ether acetate, 0.19 g of paramethoxyphenol and 1.9 g of tetraethylammonium chloride were added, and the mixture was reacted at 90 ° C. for 13 hours. After confirming that glycidyl methacrylate was 1% or less by gas chromatography analysis, 45.6 g of tetrahydrophthalic anhydride and 45.6 g of propylene glycol monomethyl ether acetate were added, and the mixture was further reacted at 95 ° C. for 5 hours. It was confirmed by IR that the acid anhydride disappeared, and an alkali-soluble resin (P-7) solution having a phenolic hydroxyl group was obtained.
The metacresol novolak resin (MW = 4000) was produced in the same manner as the alkali-soluble resin (P-1) except that 474.9 g of metacresol and 315.0 g of a 37 wt% formalin aqueous solution were used.

<Synthesis of Dispersion Resin-1>
A reaction vessel was charged with 35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.). Under an atmosphere, the temperature was raised to 80 ° C., 10.5 parts of benzyl methacrylate, 7.5 parts of methyl methacrylate, and 11.9 parts of methacrylic acid were added dropwise over 2 hours, and further stirred for 4 hours. Obtained. The obtained dispersion resin-1 had a MW of 12,000. Moreover, when the neutralization titration by KOH was performed, the acid value was 120 mg-KOH / g.

<Preparation of pigment dispersion (I-1)>
As a pigment, C.I. I. 2.782 g of C.I. Pigment Violet (C.I.P.V.) 23 (maximum absorption wavelength region in a wavelength range of 400 to 800 nm = 500 to 600 nm) I. CI Pigment Blue (C.I.P.B.) 15: 6 (maximum absorption wavelength region in a wavelength range of 400 to 800 nm = 600 to 800 nm) of 9.538 g and a dispersant “DisperBYK-2001” (manufactured by Big Chemie) 3.640 g, 4.04 g of the aforementioned dispersion resin-1 and 79.4 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were taken and mixed. Here, 3 times the total weight of these zirconia beads (0.5 mm diameter) was mixed, filled in a stainless steel container, and dispersed for 6 hours in a paint shaker to obtain a pigment dispersion (I-1). Was prepared.

<Preparation of pigment dispersion (I-2)>
As a pigment, C.I. I. Pigment Red (C.I.P.R.) 254 (maximum absorption wavelength region in a wavelength range of 400 to 800 nm = 500 to 600 nm) of 14.700 g and a dispersant “DisperBYK-2001” (manufactured by Big Chemie) 3. 230 g of the above-mentioned dispersion resin-1 was used in the same manner as in the pigment dispersion liquid (I-1) except that 2.940 g of the above-mentioned dispersion resin-1 and 78.150 g of propylene glycol monomethyl ether acetate (PGMEA) were used as the solvent. 2) was prepared.

Ｓ−２：チバスペシャリティケミカルズ社製、「イルガキュアー９０７」
Ｓ−３：チバスペシャリティケミカルズ社製、「イルガキュアー３６９」
Ｓ−４：２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール２量体
Ｓ−５：２−メルカプトベンゾチアゾール
Ｐ−４：丸善石油化学社製「マルカリンカー Ｓ−２Ｐ」（ポリ−ｐ−ヒドロキシスチレン）
Ｐ−５：下記構造式の化合物（本州化学工業社製：ＢｉｓＰ−ＬＶ）

Ｐ−８：日本化薬（株）製：ＺＣＲ−１５６９Ｈ（ＭＷ＝４０００〜５０００、酸価＝１００ｍｇ−ＫＯＨ／ｇ）
Ｆ−１：住友３Ｍ社製フッ素系界面活性剤「ＦＣ４３０」
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート <Other materials used>
M-1: Nippon Kayaku Co., Ltd .: Dipentaerythritol hexaacrylate (DPHA)
M-2: Shin-Nakamura Chemical Co., Ltd .: Bifunctional phosphate "PM-21"
S-1: A compound having the following structure was synthesized by the method described in JP-A-2006-036750.

S-2: “Irgacure 907” manufactured by Ciba Specialty Chemicals
S-3: “Irgacure 369” manufactured by Ciba Specialty Chemicals
S-4: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer S-5: 2-mercaptobenzothiazole P-4: “Marcalinker S-2P” (poly-p) manufactured by Maruzen Petrochemical Co., Ltd. -Hydroxystyrene)
P-5: Compound having the following structural formula (Honshu Chemical Industry Co., Ltd .: BisP-LV)

P-8: Nippon Kayaku Co., Ltd. product: ZCR-1569H (MW = 4000-5000, acid value = 100 mg-KOH / g)
F-1: Fluorosurfactant “FC430” manufactured by Sumitomo 3M
PGMEA: Propylene glycol monomethyl ether acetate

<Examples 1 to 10, Comparative Examples 1 to 7>
(Preparation of resist solution)
A photosensitive composition (resist solution) was prepared by blending various materials in the ratios shown in Tables 1 to 3. At that time, the addition amount of the alkali-soluble resin is in terms of solid content.

(Evaluation of sensitivity, cross-sectional shape, height uniformity)
Each resist solution was applied on a 100 mm square glass substrate (Asahi Glass Co., Ltd. color filter glass plate “AN100”) formed by sputtering a 150 nm thick ITO film, vacuum dried for 1 minute, and then on a hot plate. Prebaking was performed at 80 ° C. for 3 minutes to obtain a coating film having a dry film thickness of 2.2 μm.
Then, image exposure was performed using 3 kW high-pressure mercury through a fine line pattern mask having a width of 10 μm from the coating film side. Next, a developer (development condition A) comprising an aqueous solution containing 0.05% by weight of sodium hydroxide and 0.08% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation), or , Using a developer (development condition B) comprising an aqueous solution containing 0.5% by weight of sodium hydroxide and 0.8% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation), After performing shower development at a water pressure of 0.25 MPa at 23 ° C., the development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was twice the time (break time) for dissolving and removing the photosensitive layer.
The glass substrate thus imaged was post-baked (heat flow) at 230 ° C. for 30 minutes to obtain a glass substrate on which liquid crystal alignment control protrusions were formed.
The sensitivity of each sample at this time was examined with an appropriate exposure amount (mj / cm ² ) that can form a 10 μm-wide mask pattern according to the dimensions. The exposure amount is displayed as an integrated exposure amount obtained from the illuminance measured using UV-SN35M10 at the light receiving portion with an ultraviolet illuminance meter (UV-M03) manufactured by Oak Manufacturing. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.
In addition, the cross-sectional shape with a width of 10 μm at the above exposure amount is observed, and an arch-like shape having no flat portion at the top as shown in FIG. 1A and a flat portion as shown in FIG. Was marked with x.
Further, the height of the resist film at the six points indicated by the circles on the glass substrate 1 shown in FIG. 2 is measured, and the difference between the maximum height and the minimum height is 0.20 μm or less. It was.
The results are shown in Tables 1-3.

(Evaluation of voltage holding ratio (VHR))
An electrode substrate A in which an ITO film is formed on one entire surface of a 2.5 cm square alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) and a 2 mm width at the center of one surface of the 2.5 cm square glass substrate. An electrode substrate B on which a 1 cm square ITO film with a lead-out electrode connected was prepared.
Image formation was performed on the electrode substrate A by the method described in the sensitivity evaluation. However, the entire surface was exposed to light using 3 kW high-pressure mercury without using a mask to obtain a glass substrate whose entire surface was covered with a resist.
After applying an epoxy resin sealant containing silica beads with a diameter of 5 μm on the outer periphery of the resist formation surface of the electrode substrate B using a dispenser, the outer edge of the resist formation surface of the electrode substrate A is shifted by 3 mm. It was heated at 180 ° C. for 2 hours in a hot air circulating furnace while being placed opposite to each other and pressed.
A liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral part was sealed with an ultraviolet curable sealant to complete a voltage holding ratio liquid crystal cell.

  After annealing the liquid crystal cell (heating at 105 ° C. for 2.5 hours in a hot air circulating furnace), a pulse voltage is applied to the electrode substrates A and B at a voltage of 5 V under an application time of 16.67 msec and a span of 500 msec. The voltage holding ratio was measured with “6254 type” manufactured by Toyo Corporation, and the results are shown in Tables 1 to 3.

(Evaluation of light shielding properties)
The optical density (OD value) of the electrode substrate A image-formed by the evaluation of the voltage holding ratio was measured with a Macbeth reflection densitometer (TR927 manufactured by Kolmorgun). The results are shown in Tables 1-3.

  It can be seen from Tables 1 to 3 that according to the present invention, it is possible to form liquid crystal alignment control protrusions with high sensitivity and excellent shape and voltage holding ratio.

It is the schematic diagram of the cross section of the resist film explaining the evaluation criteria of the cross-sectional shape in an Example and a comparative example. It is a schematic plan view of the glass substrate which shows the measurement point for evaluation of the height uniformity in an Example and a comparative example.

Explanation of symbols

1 Glass substrate

Claims (12)

In the negative photosensitive composition for liquid crystal alignment control protrusion containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,
(A) An alkali-soluble resin contains a compound having a phenolic hydroxyl group, and (b) a photopolymerization initiator contains an oxime ester-based compound, a negative photosensitive composition for liquid crystal alignment control protrusions. In the negative photosensitive composition for liquid crystal alignment control protrusion containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,
The sensitivity of the photosensitive composition is 150 mj / cm ² or less,
A negative photosensitive composition for liquid crystal alignment control protrusions, wherein a VHR of a liquid crystal alignment control protrusion obtained by exposing the photosensitive composition is 90% or more.   3. The negative photosensitive composition for liquid crystal alignment control protrusion according to claim 2, wherein (a) the alkali-soluble resin contains a compound having a phenolic hydroxyl group.   4. The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 2, wherein the photopolymerization initiator (b) contains an oxime ester compound. The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 1, wherein the oxime ester compound has a structure represented by the following general formula (1).

(In the formula (1), R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 carbon atoms alkoxycarbonylalkanoyl group, 8 to 20 carbon atoms phenoxycarbonylalkanoyl group, 3 to 20 carbon atoms heteroaryloxyxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminocarbonyl group, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms.) 6. The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 5, wherein the oxime ester compound has a structure represented by the following general formula (2).

(In formula (2), R ^1a is an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 3-20 alkoxycarbonylalkyl group, C8-20 phenoxycarbonylalkyl group, C1-20 heteroaryloxycarbonylalkyl group, C1-20 heteroarylthioalkyl group, C0-20 An aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a benzoyl group having 7 to 20 carbon atoms. , A heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms. Show.
R ^1b represents an ^optionally substituted aromatic ring group.
R ^1a may form a ring with R ^1b , and the linking group may have a substituent, each having 1 to 10 carbon atoms, — (CH═CH) _n —. ,-(C≡C) _n- , or a group formed by a combination thereof (where n is an integer of 0 to 3).
R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. , An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, and 7 carbon atoms -20 benzoyl group, C1-C20 hetero aryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 phenoxycarbonyl group. )   The negative photosensitive composition for liquid crystal alignment control protrusions according to any one of claims 1 to 6, wherein the OD value is 0.5 / µm or more.   The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 1, comprising at least two kinds of organic pigments.   As at least two kinds of organic pigments, an organic pigment having a maximum absorption wavelength in a wavelength range of 400 to 800 nm (hereinafter referred to as “organic pigment (500 to 600)”) and a wavelength of 600 to 600 nm. An organic pigment in the region of 800 nm (hereinafter referred to as “organic pigment (600 to 800)”), the maximum absorption wavelength of the organic pigment (500 to 600) and the maximum absorption of the organic pigment (600 to 800) 9. The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 8, wherein the difference from the wavelength is 10 nm or more.   The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 8 or 9, comprising at least three kinds of organic pigments.   As at least three kinds of organic pigments, an organic pigment having a maximum absorption wavelength in a wavelength range of 400 to 800 nm (hereinafter referred to as “organic pigment (400 to 500)”) and a wavelength of 500 to 500 nm. An organic pigment in the region of 600 nm (hereinafter referred to as “organic pigment (500 to 600)”) and an organic pigment in the region of wavelength of 600 to 800 nm (hereinafter referred to as “organic pigment (600 to 800)”). A difference between a maximum absorption wavelength of the organic pigment (400 to 500) and a maximum absorption wavelength of the organic pigment (500 to 600), and a maximum absorption wavelength of the organic pigment (500 to 600) and the organic pigment The negative photosensitive composition for liquid crystal alignment control protrusions according to claim 10, wherein the difference from the maximum absorption wavelength of (600 to 800) is 10 nm or more.   A liquid crystal display device comprising: a liquid crystal alignment control protrusion formed using the negative photosensitive composition for liquid crystal alignment control protrusion according to claim 1.

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