JP2006284738A - Negative energy-sensitive resin composition for forming gap in display device, and method for forming spacer on display element substrate using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative energy-sensitive resin composition for forming a gap in a display device, which imparts excellent display quality without any display unevenness and with which a spacer is manufactured with a high yield. <P>SOLUTION: The negative energy-sensitive resin composition for forming the gap in the display device contains a component formed by formulating (a1) 30-80 wt.% tricyclo (5, 2, 1, 02, 6) deca-8-yl-methacrylate represented by general formula (I), (a2) 2-20 wt.% cross-linking polyfunctional monomer represented by general formula (II), and (a3) 0-68 wt.% another copolymerizable vinyl monomer so as to form a total of 100 wt.%, and (b) a polymerization initiator to generate a free radical via irradiation with an active energy ray, provided that in general formula (II), R represents a divalent to tetravalent aliphatic hydrocarbon group or an oxyalkylene group, A represents an acryloyl group or a methacryloyl group, and n is an integer of 2-4 representing the number of bonds of A. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an energy-sensitive negative resin composition for forming a display device gap used for a liquid crystal spacer disposed in order to keep the thickness of a liquid crystal layer constant in a liquid crystal display device and the like, and a display element substrate using the same The present invention relates to a method for forming a spacer.

  In recent years, liquid crystal color televisions, liquid crystal color display computers, and the like have been put into practical use. These liquid crystal display devices have a gap of about 1 to 10 μm between transparent substrates such as glass provided with transparent electrodes. The liquid crystal material is sealed in the gap, and the liquid crystal material is aligned by the voltage applied between the electrodes, thereby displaying an image. In such a liquid crystal display device, when the gap of the liquid crystal layer changes, display unevenness and contrast abnormalities occur, so spherical glass beads or resin beads having a uniform particle size distribution are arranged in the liquid crystal layer, and the gap of the liquid crystal layer is increased. There is a need for a spacer to keep it constant.

  However, such spherical glass beads and resin bead spacers are generally only dispersed in the liquid crystal layer between the opposing substrates, and are not fixed to the substrates, resulting in variations in spacer distribution. Thus, there are problems such as display unevenness, the spacer moving due to the vibration of the liquid crystal display device, and the abnormal alignment region becomes large, or the alignment film surface is damaged. In addition, since such spherical glass beads or resin bead spacers are also dispersed in the display portion of the liquid crystal display device, there are problems such as lowering the contrast and lowering the display quality.

  As a method for improving these problems, a method of forming a spacer by applying an ultraviolet curable resin on one substrate, drying, and then exposing and developing is disclosed (for example, see Patent Documents 1 to 4). .

  Also disclosed is a method of forming a spacer by using a film previously coated with a photocurable resin coating liquid, transferring the film, and then patterning by exposure / development (see, for example, Patent Document 5).

  The spacers formed by these methods are called columnar spacers or photosensitive spacers, and have problems such as display unevenness, alignment anomalies, and contrast reduction that occur when the spherical glass beads or resin beads are used. It has been proposed as a means for solving the problem.

JP-A-1-134336 JP-A-3-89320 Japanese Patent Laid-Open No. 10-168134 Japanese Patent Laid-Open No. 11-133600 JP-A-11-174461

  If the spacer beads are not uniformly distributed, the distribution density is low, or the particles are aggregated, there is a problem that the cell gap is not uniform. In addition, if the amount of spacer beads spread is large, the spacer beads spread over the openings with a certain probability do not perform the liquid crystal function, so the light control area on the openings is reduced, and the contrast of the liquid crystal display device is reduced. Causes a drop.

  These problems can be formed with a uniform distribution density in a region other than the opening by a method of forming the columnar spacer disclosed in Patent Document 1 at a desired position by photolithography. However, along with the increase in the area of liquid crystal display devices, it is difficult to form columnar spacers with a desired film thickness uniformly over the front surface of the display area, and the height of columnar spacers during production varies greatly from one liquid crystal display device to another. Inferior defective liquid crystal display devices tend to occur. There is also a problem in stability during driving of the cell gap.

  The present invention prevents the contrast of the display device from being lowered due to the dispersion of the spacer beads in the opening, obtains a uniform cell gap over the entire display area of the display device, and has the same cell gap stability as that of the spacer beads even during production. An energy-sensitive negative type for forming a display device gap that can guarantee the display unevenness caused by plastic deformation and maintain the hardness, and can produce a display device with good display quality and high yield without display unevenness. The present invention provides a method of forming a spacer on a substrate for a display element that can produce a resin composition and a spacer using the resin composition with a high yield and is excellent in workability.

  The present invention includes (a1) 30 to 80% by weight of tricyclo (5,2,1,02,6) dec-8-ylmetatalylate represented by the following general formula (I), and (a2) the following general formula ( II) a component in which 2 to 20% by weight of the crosslinkable polyfunctional monomer represented by formula (a3) and another copolymerizable vinyl monomer of 0 to 68% by weight are blended so that the total amount becomes 100% by weight; b) It relates to an energy-sensitive negative resin composition for forming a display device gap, which contains a polymerization initiator that generates free radicals upon irradiation with active energy rays.

（ただし、一般式（ＩＩ）中、Ｒは２〜４価の脂肪族炭化水素基又はオキシアルキレン基、Ａはアクリロイル基又はメタクリロイル基、ｎはＡの結合数で２〜４の整数を示す）

(In the general formula (II), R represents a divalent to tetravalent aliphatic hydrocarbon group or oxyalkylene group, A represents an acryloyl group or methacryloyl group, and n represents an integer of 2 to 4 as the number of bonds of A)

The present invention also includes (I) a step of forming the energy sensitive negative resin composition for forming a display device gap described above on a substrate of a display element in a predetermined position and shape by an inkjet method. II) A method of forming a spacer on a display element substrate, comprising irradiating an active energy ray to form an image forming gap forming spacer on the display element substrate.
The present invention further relates to a method for forming a spacer on the display element substrate as described above, further comprising (III) a step of heating the energy-sensitive negative resin composition having a pattern formed thereon.

  The present invention prevents a reduction in the contrast of the display device, obtains a uniform cell gap in the surface, guarantees the same cell gap stability as the spacer beads even during production, and suppresses display unevenness caused by plastic deformation. An energy-sensitive negative resin composition for forming a gap in a display device capable of producing a liquid crystal display device with good display quality and good yield, which can maintain both hardness and yield, and a spacer using the same. A method for forming a spacer on a display element substrate with good workability is provided. Furthermore, because of ink jet printing, a liquid crystal display device can be produced at low cost.

  Hereinafter, the present invention will be described in detail. The energy-sensitive negative resin composition for forming a gap in a display device according to the present invention is a liquid crystal display device in which liquid crystal is sealed between substrates disposed to face each other, in order to keep the thickness of the liquid crystal layer constant. It is an energy sensitive negative resin composition used for the arranged spacer. FIG. 1 shows an example of a liquid crystal display device. The energy-sensitive negative resin composition for forming a display device gap according to the present invention is a liquid crystal display device in which liquid crystals are sealed between substrates 3 arranged to face each other. The spacer 16 is preferably used in order to keep the thickness of the liquid crystal layer 15 constant.

  The energy-sensitive negative resin composition of the present invention comprises (a1) 30 to 80% by weight of tricyclo (5,2,1,02,6) dec-8-ylmetatalylate represented by the general formula (I): (A2) 2 to 20% by weight of the crosslinkable polyfunctional monomer represented by the general formula (II) and (a3) 0 to 68% by weight of other copolymerizable vinyl monomers are 100% by weight as a whole. And (b) a polymerization initiator that generates free radicals upon irradiation with active energy rays. The liquid crystal spacer is a liquid crystal display device in which liquid crystal is sealed between substrates disposed to face each other, and is a spacer disposed in order to keep the thickness of the liquid crystal layer constant.

  In the present invention, (a1) tricyclo (5,2,1,02,6) dec-8-yl methacrylate (hereinafter abbreviated as TCD-MA) represented by the general formula (I) is represented by the following general formula (I ) And is used in the composition in an amount of 30 to 80% by weight. TCD-MA requires 30% by weight or more in terms of shape stability as a spacer, that is, suppression of display unevenness due to plastic deformation and maintenance of hardness, and heat resistance and low hygroscopicity. If it exceeds 100%, the spacer becomes brittle in strength and is not practical.

  In addition, (a2) the crosslinkable polyfunctional monomer represented by the following general formula (II) is required to be 2% by weight or more in the composition in terms of strength of the molded article, and is strong even if it exceeds 20% by weight. The improvement effect is small. (A3) When the copolymerizable vinyl monomer exceeds 68% by weight in the composition, there are problems in any of optical properties, low hygroscopicity and high heat resistance, and it is not practically used.

（ただし、一般式（ＩＩ）中、Ｒは２〜４価の脂肪族炭化水素基又はオキシアルキレン基、Ａはアクリロイル基又はメタクリロイル基、ｎはＡの結合数で２〜４の整数を示す）

(In the general formula (II), R represents a divalent to tetravalent aliphatic hydrocarbon group or oxyalkylene group, A represents an acryloyl group or methacryloyl group, and n represents an integer of 2 to 4 as the number of bonds of A)

The crosslinkable polyfunctional monomer used in the present invention is not particularly limited as long as it does not impair inkjet suitability. For example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5 penta down Diacrylates such as diol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, oligoester diacrylate, polybutadiene diacrylate, and similar dimethacrylates Bifunctional crosslinkable monomer, trimethylolethane triacrylate, trimethylolpropane Trifunctional crosslinkable monomers such as triacrylates such as reacrylate and pentaerythritol triacrylate, and trimethacrylates similar to these, or tetrafunctional crosslinkable properties such as pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate And monomers. Diacrylate or dimethacrylate having a relatively high molecular weight main chain can also be used.

  Of these, particularly preferred are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and the like, and dimethacrylates similar to these, Examples include trimethacrylate.

  Other copolymerizable vinyl monomers (monomers) used in the present invention are not particularly limited as long as they basically do not impair ink jet printability. For example, unsaturated fatty acid esters, aromatics Examples include vinyl compounds, vinyl cyanide compounds, unsaturated dibasic acids and their derivatives, unsaturated fatty acids and their derivatives.

  Examples of the unsaturated fatty acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, octadecyl acrylate, etc., cyclohexyl acrylate, acrylic acid Acrylic acid cycloalkyl esters such as methylcyclohexyl, acrylic acid (iso) bornyl, adamantyl acrylate, etc., acrylic acid aromatic esters such as phenyl acrylate, benzyl acrylate, naphthyl acrylate, fluorophenyl acrylate, chlorophenyl acrylate, acrylic Acrylic acid-substituted aromatic esters such as bromophenyl acrylate, fluorobenzyl acrylate, chlorobenzyl acrylate, bromobenzyl acrylate, fluoromethyl acrylate, Halogenated alkyl esters such as fluoroethyl acrylate, chloroethyl acrylate, bromoethyl acrylate, 2-hydroxyethyl acrylate, hydroxyalkyl acrylates such as polyethylene glycol acrylate, glycidyl acrylate, alkylaminoalkyl acrylate Esters, acrylic esters such as cyanoalkyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, etc. Such as cyclohexyl acid, methyl cyclohexyl methacrylate, (iso) bornyl methacrylate, adamantyl methacrylate, etc. Aromatic cycloalkyl ester, phenyl methacrylate, benzyl methacrylate, methacrylic aromatic ester such as naphthyl methacrylate, fluorophenyl methacrylate, chlorophenyl methacrylate, bromophenyl methacrylate, fluorobenzyl methacrylate, chlorobenzyl methacrylate, methacrylic acid Methacrylic acid substituted aromatic esters such as bromobenzyl acid, methacrylic acid halogenated alkyl esters such as fluoromethyl methacrylate, fluoroethyl methacrylate, chloroethyl methacrylate, bromoethyl methacrylate, polyethylene glycol ester methacrylate, 2-hydroxyethyl methacrylate Methacrylic acid hydroxyalkyl ester, glycidyl methacrylate, alkylaminoalkyl methacrylate And methacrylic acid esters such as methacrylic acid cyanoalkyl esters, α-fluoroacrylic acid esters, α-chloroacrylic acid esters, α-substituted acrylic acid esters such as α-cyanoacrylic acid esters, and the like.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α-fluorostyrene, α-substituted styrene such as α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, There are nuclear substituted styrenes such as butyl styrene and methoxy styrene. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

  The unsaturated dibasic acid and its derivatives include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, There are N-substituted maleimides such as N-chlorophenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, maleic acid, maleic anhydride, fumaric acid and the like.

  The unsaturated fatty acids and derivatives thereof include (meth) acrylamides such as acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylmethacrylamide, N-diethylmethacrylamide, calcium acrylate, (Meth) acrylic acid metal salts such as calcium methacrylate, barium acrylate, barium methacrylate, lead acrylate, lead methacrylate, tin acrylate, tin methacrylate, zinc acrylate, zinc methacrylate, acrylic acid, methacrylic acid and so on.

  Examples of the polymerization initiator (b) that generates free radicals upon irradiation with active energy rays in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N ′. -Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369, Ciba Specialty Chemicals Co., Ltd. trade name), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (Irgacure-907, Ciba Specialty Chemicals Co., Ltd. trade name) Aromatic ketones such as 2-ethylanthraquinone, phenanthrenequinone 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4 -Quinones such as naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o- Lorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl 2,4,5-triarylimidazole dimer such as imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl) heptane and the like, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like.

  In the 2,4,5-triarylimidazole dimer, the substituents substituted with two 2,4,5-triarylimidazoles may be the same or different. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. Further, 2,4,5-triarylimidazole dimer is preferable from the viewpoint of adhesion and sensitivity in the photolithography process, and 2-methyl-1- [4 from the viewpoint of visible light transmittance when a liquid crystal spacer is used. More preferred is-(methylthio) phenyl] -2-morpholino-propan-1-one. These can be used alone or in combination of two or more.

  In the present invention, the amount of the polymerization initiator (b) that generates free radicals upon irradiation with active energy rays is preferably 0.05 to 20 parts by weight with respect to the total solid content, and preferably 0.1 to 15 parts by weight. It is more preferable to set it as a weight part, and it is especially preferable to set it as 0.15-10 weight part. If the amount used is less than 0.05 parts by weight, the photocuring tends to be insufficient, and if it exceeds 20 parts by weight, a display device gap formed in a predetermined position and shape by (II) inkjet method described later. In the step of irradiating the forming energy-sensitive negative resin composition with active energy rays, the absorption of the active energy rays on the active energy ray-irradiated surface of the energy-sensitive negative resin composition is increased, and the internal curing is increased. There is a tendency to become insufficient.

  In addition, the energy-sensitive negative resin composition of the present invention contains an inorganic filler and carbon composed of titanium oxide, zinc oxide, alumina, or silicon oxide as necessary for the purpose of coloring or improving ink jet printing suitability. About 0.01 to 50 parts by weight can be contained per 100 parts by weight of the total composition. These are used alone or in combination of two or more.

  In addition, the energy-sensitive negative resin composition of the present invention includes, if necessary, an adhesion imparting agent such as a diluent solvent, a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, and a flame retardant. , Stabilizers, antioxidants, fragrances, thermal crosslinking agents, polymerization inhibitors and the like can be contained in an amount of about 0.01 to 50 parts by weight with respect to 100 parts by weight of the total amount of the composition. These are used alone or in combination of two or more.

The viscosity of the energy-sensitive negative resin composition in the present invention is not particularly limited, but in order to obtain 1 to 10 μm of ink jet printing suitability and a gap width as a spacer, at 22 ° C., 1 × 10 ^{−3 to} 100 X10 ⁻³ Pa · sec is preferable, 2 × 10 ^{−3 to} 90 × 10 ⁻³ Pa · sec is more preferable, and 3 × 10 ⁻³ to 80 × 10 ⁻³ Pa · sec is preferable. It is particularly preferred.

  Further, the contact angle on the substrate of the energy-sensitive negative resin composition in the present invention is not particularly limited, but in order to obtain 1 to 10 μm of ink jet printability and a gap width as a spacer, 20 to 90 at 22 ° C. Preferably.

Hereinafter, an example of a method for forming a spacer in a liquid crystal display device will be described using the display device gap forming energy-sensitive resin composition of the present invention.
[(I) Step of Forming Energy-Sensitive Negative Resin Composition at Predetermined Position and Shape by Inkjet Method on Substrate]
There is no restriction | limiting in particular in the board | substrate used by this invention, For example, a ceramic plate, a plastic plate, a glass plate etc. are mentioned. On this substrate, an insulating layer, a black matrix layer, a color filter layer, an electrode such as ITO, a TFT, or the like may be provided.

  Next, it coats in the predetermined position on a board | substrate by the inkjet method. As an ink jet apparatus, there are a piezo conversion method and a heat conversion method depending on a difference in ink discharge method, and a piezo conversion method is particularly preferable. An apparatus in which the ink particle frequency is about 5 to 100 KHz and the nozzle diameter is about 1 μm to 80 μm, and 1 to 1,000 nozzles are incorporated in one head is preferable.

  The predetermined position is not particularly limited, but a position that overlaps the black matrix, preferably a position that is not visible when displayed, or a position that does not overlap the outer peripheral portion or the pixel electrode is displayed on the display element. It is preferable in that the quality is not lowered. Thereby, the light leakage concerning a spacer can be suppressed. When the arrangement interval overlaps the black matrix, it is naturally determined that the arrangement interval is an integral multiple of the black matrix arrangement interval.

  The shape of the spacer is not particularly limited, but a cylindrical shape or a conical shape is preferable in terms of easy production by ink jet printing. As for the cylinder and the cone, as shown in FIGS. 2 (a) to 2 (d), a rounded chamfered shape is easy in manufacturing. Although there is no restriction | limiting in particular as a diameter of the bottom face of a cylinder or a cone, 2-50 micrometers is preferable. If it is less than 2 μm, the pillar may fall down due to the aspect ratio, and a predetermined gap may not be provided. If it exceeds 50 μm, the area occupied by the spacers increases in the display area that can be seen, and the display quality of the display element may be degraded. The height of the cylinder or cone is adjusted as appropriate according to the requirements of the display element. In general, in the case of a liquid crystal display device application, it is 2 to 10 μm although it varies depending on the application and method.

  Prior to coating on the substrate by the ink jet method, an undercoat layer combined with a resin, a solvent, or the like of the coating liquid may be provided in advance in order to adjust the acceptability and wettability of the ink. A polyimide resin, a PVA derivative resin, an acrylic resin, an epoxy resin composition, or the like can be used for the underfill layer.

[(II) Step of irradiating active energy ray to energy-sensitive negative resin composition]
In the present invention, as a method of irradiating an energy-sensitive negative resin composition formed by coating by an inkjet method with active energy rays, the energy-sensitive negative resin composition laminated on a substrate is known. And a method of irradiating the active energy ray.
Moreover, as an active energy ray in this invention, although a well-known active energy source can be used and what radiates | emits an ultraviolet-ray effectively from a viewpoint which simplifies a production process, it is not restrict | limited in particular. For example, a carbon arc lamp, an ultra high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. are mentioned.

[(III) Step of heating the energy-sensitive resin composition layer on which the pattern is formed]
In the present invention, as shown in FIGS. 2A to 2D, a spacer is formed in a predetermined position and shape by an inkjet method, irradiated with active energy rays, and a gap forming spacer is imaged on the display element substrate. It is preferable to heat the energy-sensitive negative resin composition thus formed. Examples of the heating method include known methods such as hot air radiation and infrared irradiation heating, and are not particularly limited as long as the energy-sensitive negative resin composition having a pattern formed on the substrate is effectively heated. .
The temperature during heating is preferably 100 to 180 ° C, more preferably 100 to 150 ° C, and particularly preferably 100 to 130 ° C. If this heating temperature is less than 100 ° C, the effect of thermosetting may be insufficient. If it exceeds 180 ° C, the constituent components of the energy-sensitive negative resin composition tend to thermally decompose.

  By the methods described above, a liquid crystal spacer suitable for a liquid crystal display device can be formed. In addition, the energy-sensitive negative resin composition for forming a display device gap in the present invention and the method for forming a spacer on a display element substrate using the same are not limited to the use of a liquid crystal display device. It can also be suitably used for spacer applications such as a display device in which a fluid layer is formed between opposing substrates, such as an electrophoretic display and electronic paper.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Examples 1-14 and Comparative Examples 1-4
As a polymerization initiator that generates free radicals upon irradiation with active energy rays (radical polymerization initiator), 0.5 parts by weight of lauroyl peroxide is added to the mixed liquid having the composition shown in Table 1, and 1,1-bis ( t-Butylperoxy) 3,3,5-trimethylcyclohexane 0.2 part by weight was added and sufficiently stirred.
Using the energy-sensitive negative resin composition shown in Table 1, a piezo-conversion-type inkjet printer, and an ultrahigh pressure mercury lamp exposure device, printing of a dot pattern with a diameter of 30 μm and exposure at 500 mJ / cm ² were performed on the substrate. In Table 1, TCD-MA is (a1) tricyclo (5,2,1,02,6) dec-8-ylmetatalylate (tricyclo [5.2.1.02,6] dec-8 methacrylate). -Yl), 1.6 HDDA is 1,6-hexanediol diacrylate which is a crosslinkable polyfunctional monomer of (a2), ST is styrene, MMA is methyl methacrylate, these are a3) other copolymerizable Vinyl monomer.
Table 2 summarizes the results of printing suitability, spacer shape, and comprehensive evaluation. Examples 1 to 14 were confirmed by an electron microscope to have a good spacer shape. On the other hand, in Comparative Example 1, the reproducibility of the print pattern was low. In Comparative Examples 2 to 4, there was a spacer shape defect. (A1) tricyclo (5,2,1,02,6) dec-8-ylmetatalylate 30 to 80% by weight, (a2) crosslinkable polyfunctional monomer 2 to 20% by weight, (a3) other co-polymers Examples 1 to 14, which are compositions in which 0 to 68% by weight of a polymerizable vinyl-based monomer is blended so that the total amount becomes 100% by weight, have good printing suitability, spacer shape, and comprehensive evaluation. On the other hand, in Comparative Examples 1 to 4 that deviate from the composition ratios of (a1), (a2), and (a3), the print pattern reproducibility is low and the spacer shape is poor as described above.

Examples 15-24
Next, the sample of each Example 1-9 was heated with the hot air circulation oven, and the Example which changed the heating temperature and time shown in Table 3 as Example 15-24 was made into each spacer shape and comprehensive evaluation. The results are summarized. Examples 15 to 24 were confirmed by an electron microscope to have a good spacer shape. On the other hand, Reference Example 1 had a defective shape of the spacer. The heating temperature is preferably 100 to 180 ° C. in the case of heating for 10 minutes.

In the present invention, print suitability was evaluated by evaluating the reproducibility of the shape and the size of the diameter, and evaluating good for ◯ and poor print for poor.
The spacer shape was measured by measuring the height and diameter of the spacer using an electron microscope.
Comprehensive evaluation comprehensively evaluated printing suitability and spacer shape. Both of them showed good evaluations with “good” and bad evaluations with “poor”.

  As described above, according to the present invention, the contrast of the display device can be prevented, a uniform cell gap can be obtained in the plane, and the cell gap stability equivalent to that of the spacer beads can be ensured even during production, and plastic deformation can be achieved. It is possible to provide an energy-sensitive negative resin composition for forming a gap in a display device capable of producing a liquid crystal display device having good display quality and high yield without causing display unevenness, and capable of suppressing the resulting display unevenness and maintaining the hardness. At the same time, the spacer can be manufactured with good yield, low cost and good workability, and an excellent display element substrate spacer can be formed.

An example of a liquid crystal display device illustrating the present invention. (A)-(d) is sectional shape explaining the shape of the spacer regarding this invention.

Explanation of symbols

3 Glass substrate 10 Color filter 11 Black matrix 12 Transparent electrode 13 Flattening film 14 Alignment film 15 Liquid crystal layer 16 Spacer 17 Phase difference film 18 Polarizing plate 19 Reflective film 20 Reflective underlayer

Claims (3)

(A1) 30 to 80% by weight of tricyclo (5,2,1,02,6) dec-8-ylmetatalylate represented by the following general formula (I), and (a2) represented by the following general formula (II) A component containing 2 to 20% by weight of a crosslinkable polyfunctional monomer and (a3) 0 to 68% by weight of another copolymerizable vinyl monomer so that the total is 100% by weight, (b) active energy An energy-sensitive negative resin composition for forming a gap in a display device, comprising a polymerization initiator that generates free radicals upon irradiation with rays.

(In the general formula (II), R represents a divalent to tetravalent aliphatic hydrocarbon group or oxyalkylene group, A represents an acryloyl group or methacryloyl group, and n represents an integer of 2 to 4 as the number of bonds of A) (I) A step of forming the energy-sensitive negative resin composition for forming a display device gap according to claim 1 on a substrate of a display element in a predetermined position and shape by an inkjet method, (II) active energy A method of forming a spacer on a display element substrate, comprising: irradiating a line to form an image of a gap forming spacer on the display element substrate. The method for forming a spacer on the display element substrate according to claim 2, further comprising (III) a step of heating the energy-sensitive negative resin composition having a pattern formed thereon.

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