TW200534014A - Plate printing ink, spacer and display device - Google Patents

Abstract

An ink for spacer formation for use in plate printing process, in which the influence of binder on the physical properties of spacer is inhibited. There is provided an ink for spacer formation for use in plate printing process, comprising spacer particles and a thermosetting resin composition for spacer particle dispersion, characterized in that the thermosetting resin composition contains a component having polycaprolactone structure.

Description

200534014 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a printing ink, a spacer and a display element. 5 [Prior art] Japanese Laid-Open Patent Publication No. 2000-35582 discloses a method for forming a spacer between lithographic printing by a concave plate. JP-A-2000-35582 describes the scope of patent application in items 2 and 3, and uses an ink in which a spherical spacer having a weight of 20 to 60 weight 0 / 〇 is mixed in a resin having a viscosity of 2000 to 25000 cps, and the implementation is performed. In the example, 5 10 β resin spacer balls and polyester resins are indicated. Japanese Unexamined Patent Publication No. 11-323220, Japanese Unexamined Patent Publication No. 9-111170, and Japanese Unexamined Patent Publication No. 7-110404 borrow the use of polyester-melamine resin, epoxy melamine resin, and the like as suitable for forming a color in gravure offset printing. Heat-curable ink for filter layer or black matrix. [Summary of the Invention] In Japanese Patent Application Laid-Open No. 2000-35582, only the concentration of resin is specified. In the examples, 'the polyg resin was not peeled', and the resin spacer ball also specified only the particle size. However, in this spacer, the physical properties of the ink at the time of A-print printing are affected by the adhesive resin ', and most of them have physical properties different from those of the spherical spacer itself. Especially the damage strength of the spacer,

The subject of the present invention, the characteristics of milk ancestors, vary greatly. In the ink for forming spacers used in the lithography method, the influence of the adhesive on the physical characteristics of the spacer can be suppressed. The present invention is a kind of ink for lithographic printing, which is 200534014 spacer forming ink used in the lithographic printing method. The right door, ^ 3 has spacer particles and a thermosetting resin composition in which the spacer particles are dispersed. The thermosetting resin composition contains a component having a polycaprolactone structure. In addition, the present invention relates to a method for forming a spacer, which is a method in which the aforementioned printing ink for printing is printed on a substrate, and is heat-treated to harden to form a spacer. The present invention also relates to a spacer formed by this method, and a display element having the spacer. By printing and curing the ink for lithographic printing of the present invention, the influence of the adhesive resin can be suppressed, and a spacer having the same or almost unchanged physical properties as the spherical spacer itself can be formed. For example, in the liquid crystal display element shown schematically in FIG. 1, spherical spacer particles 2 are present between a pair of substrates 4, and liquid crystal 1 is filled between the pair of substrates 4. In contrast, in the case of the present invention, as shown schematically in Fig. 2, the spacer particles 2 are fixed to the surface of the substrate by the hardened material 3 constituting the thermosetting resin composition of the ink. According to the present invention, when the spacer particles 2 are fixed to the surface of the substrate 4 by the resin 15 3, the same physical characteristics as those of the spacer particles 2 shown in FIG. 1 can be obtained. Brief Description of Drawings Fig. 1 is a sectional view schematically showing an example of a liquid crystal display element obtained by a conventional method. Fig. 2 is a cross-sectional view schematically showing an example of a liquid crystal display element obtained using the lithographic printing ink of the present invention. Fig. 3 is a test force-displacement chart showing the results of a separate compression test of the spherical spacer. Fig. 4 is a diagram showing the test force-displacement 200534014 of the compression test result in Example 1. Fig. 5 is a test force-displacement graph showing the results of a compression test in Comparative Example 1. Fig. 6 is a graph showing the load-separation test results of the spherical spacer alone. Le / circle shows the displacement map of the embodiment. Fig. 8 is a graph showing a test force-displacement result of a load-unload test result in Comparative Example i. 10 [Embodiment] The printing ink of the present invention includes spacer particles and a thermosetting resin composition in which the spacer particles are dispersed, and the thermosetting resin composition includes a component having a polycaprolactone structure. . In addition, if necessary, it further contains a solvent, a viscosity modifier, and other additives. These materials are explained in order. 15 (Typographic printing method) The typographic printing method refers to the printing method of Hunan version. The following methods can be exemplified. It does not include plateless methods such as inkjet or laser. (1) Letterpress printing (straight brush method, offset printing method) (2) Gravure printing or photogravure printing (transfer side 20 pad printing method), (3) lithography or offset printing (4) stencil printing or screen printing Printing [spacer particles] The combination of spacer particles is limited to 200534014 substances, inorganic substances, compounds or mixtures of these. The above-mentioned resin is not particularly limited, and examples thereof include polyethylene, polypropylene, polyisohexene, polygasified ethylene, polytetrafluoroethylene, polystyrene, polymethylmethacrylate, polyethylene terephthalate, Polybutene terephthalate, polyamidoamine, polyamidoimide, polymill, polydiphenyl ether, 5 polyformaldehyde and other linear or crosslinked polymer; epoxy resin, benzene resin, Melamine resin, guanamine resin, unsaturated polystyrene resin, diethylene benzene polymer, diethyl benzene styrene copolymer The organic-inorganic composite 10 particles can be selected as a spacer from the viewpoint of physical properties, such as a resin having a cross-linked structure, such as a propylphthalate polymer and a tripropyl isocyanate polymer. The coating material of the spacer is not particularly limited, and examples thereof include a resin and a low-melting-point metal. The resin is not particularly limited, and examples thereof include polyolefins such as polyethylene, ethylene / vinyl acetate copolymer, and ethylene / acrylate copolymer; polymethyl (meth) acrylate, polyethyl (meth) acrylate (Meth) acrylate polymers or copolymers such as polybutyl (meth) 15 acrylate; polystyrene, styrene / acrylate copolymer, SB type styrene / butadiene block copolymer, SBS Block polymers such as styrene / butadiene block copolymers, water additives, etc .; thermoplastic resins such as vinyl-based polymers or copolymers, epoxy resins, benzene and fluorene, etc. Thermosetting resins such as cyanamide resins, mixtures of these, and the like are not simply bonded physically and chemically. First, in Shida's shell; in the spacer particles, the surface of the particles can be combined with the polymer constituting the adhesion layer by covalent bonds. This method can be exemplified by a graft polymerization method 2 and a polymer reaction method. In the graft polymerization method, it is possible to consider the method of polymerizing the ethylenic group on the surface of the particle and using the ethylene as the starting point to polymerize the aforementioned monomer 200534014 method, and introducing a polymerization initiator on the surface of the particle, and Both methods of polymerizing the aforementioned monomers by this initiator. The thermosetting resin composition of the present invention contains at least a component having a polycaprolactone structure. The composition contains at least two types of 5 components that can be hardened by heat treatment, and either of these components contains a polycaprolactone structure. It is preferable that the resin serving as the main agent contains a polycaprolactone structure, and the resin is reacted with a hardening agent which can cause a crosslinking reaction. [Thermosetting resin containing a polycaprolactone structure] ^ The thermosetting resin containing a polycaprolactone structure may include a polyS resin, an acrylic resin, an epoxy resin, and a polycaprolactone structure. Reactant of polyester resin and acid anhydride. (Polyester resin with a polycaprolactone structure) The polyester resin with a polycaprolactone structure may be a single or two or more kinds of polycaprolactone polyols, and polycaprolactone polyols may be exemplified by JP 11- It is described in 15 (0016) of 228905. Examples of the polycaprolactone polyol include the following two functional polycaprolactone glycols:

m + n is an integer from 4 to 35 r: c2h4, c2h4oc2h4, c (ch3) 2 (ch2) 2 200534014 and the following:

〇 ^ (CH2) 5O ^ H

R—〇-EC (CH2) 5Ofe Η 〇, 〇1 (CH2) 50 ^ Η 〇 1 + m + n is an integer from 3 to 30_ R: CH2CHCH2, CH3C (CH2) 3, CH3CH2C (CH2) 3 3 Polycaprolactone triols, 4-functional polycaprolactone polyols, and the like. With respect to the aforementioned polycaprolactone polyol, a polyvinyl alcohol, such as polyvinyl alcohol, polypropanol, 5 polycarbonate diol, or polyether polyol, which has not been modified with polycaprolactone, may be used in combination. Further, polycondensates of polycaprolactone polyalcohol with the following dicarboxylic acids and polyalcohols can be mentioned. Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and the like, such as lower alkyl esters, acid anhydrides, and the like. These can be used alone or in combination of two kinds. the above. ® 10 The fatty acid dicarboxylic acid component can be adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, Himic acid, etc. Lower alkyl esters, acid anhydrides, etc. can be used alone or in combination of two or more. Examples of the polyol component include glycols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, diethylene glycol, neopentyl alcohol, 1,4-cyclohexanediethanol, 3-methylpentane-1,5-diol, 1,4-bicyclohexane Methanol, benzenediol, ethylene oxide or propylene oxide additives of bisphenol A, aliphatic or aromatic diols such as hydrogenated bisphenol A, etc. These can be used alone 10 200534014 or two or more. Examples of the trivalent or higher alcohols include trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol. These may be used alone or in combination of two or more. Using these raw materials, polyester resins with a polycaprolactone structure can be obtained by a known polycondensation method (Reference to Introduction to Coatings and Synthetic Resins, Kitaoka Sho, New Polymer Library, 7 Polymer Journal). (Acrylic resin with polycaprolactone structure) The (meth) acrylic acid ester (and other ethylene monomers as required) with polycaprolactone structure can be obtained by radical polymerization to obtain acrylic resin with polycaprolactone structure. 10 Dilute acid resin. Examples of the polycaprolactone-modified hydroxyethyl (meth) acrylate are compounds not shown in the following general formula.

R CH2 ~ CC0CH2CH20 — [C (CH2) 5〇] ^-η 0 ο or CH3 η: an integer from 1 to 25. Specifically, polycaprolactone can be used to modify hydroxyethyl (meth) acrylate (General 15 Lakshear FM), "Praxil FA" (Daisher Chemical)), carboxy-terminal flexible (meth) acrylate ("Plaxil FMA" (Daisher Chemical)), • m ethyl ethyl ir and flexible (meth) propanoic acid vinegar ("Prachel FD" (Daier Chemical)), etc. In addition, other vinyl monomers that can be used in combination include methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate 200534014, octyl acrylate, cyclohexyl propylene triester, and tetrahydrofuran acrylic acid. Ester, methmethacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octadecyl methacrylate, lauryl methyl Acrylate, methyl vinyl ether, ethyl vinyl ether, 5 n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile , Vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, acrylic acid, methacrylic acid, itaconic acid, pagonic acid , Maleic acid, maleic anhydride, maleic acid, acrylamide, allylamine, methacrylamide, N-carboxymethacrylamide, N, N • dimethylpropene醢, Ν, Ν-monomethyl Methyl-propionic acid ethyl Chang purpose g, ν, Ν- diethylamino ethyl acetate methylpropanesulfonic baked, dipropylene g women with propan-acyl amine. In addition, it is also possible to use 2 · Ethyl Acrylic Acid S, 2-Ethyl Ethyl Methyl Acrylate, 2-Ethyl Ethyl Acrylate, 2-Ethyl Ethyl Acrylate, Allyl An ethylene monomer having an 0H group such as an alcohol. Furthermore, it is also possible to use a reactant of a radical initiator E with acrylic acid, amidyl acrylic acid, itaconic acid, crotonic acid, maleic acid and the like. The above-mentioned illustrations do not limit the present invention. Using these materials, polyester resins with a polycaprolactone structure can be obtained by a known free-radical polymerization method (Refer to Introduction to Coatings and Synthetic Resins, Kitaoka Co., Ltd., Shinichi Molecular Library 7, Molecular Publication Association). A commercially available product of the 20 acrylic resin having a polycaprolactone structure is the "Plakcol DC" series. [Reactant of polyester resin with polycaprolactone structure and acid anhydride] The reactant can be easily synthesized by reacting various acid anhydrides on the 0H group of the polyester resin having polycaprolactone structure as exemplified above. . Examples of the acid anhydrides that can be used here include phthalic anhydride, trimellitic anhydride, all 12 200534014 5 10 15 20 pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol benefit ... Aromatic carboxylic anhydrides such as pyromellitic anhydride, anhydrides of azelaic acid, fatty acids such as ~, acid, lauric acid, tetrahydrophthalic anhydride, 0 inch, oxymethylene dicarboxylic anhydride Alicyclic citric anhydride such as tetrahydrophthalic anhydride (Nadic anhydride), gas stick > anhydride (Himic Anhydride). (Epoxy resin with a polycaprolactone structure) Epoxy resin with a polycaprolactone structure can be modified with epoxy resin (such as "Prakert G" series), flexible Grease, Γ e J clothing gas resin (cases D some Roche Said 2080 "series), polyfunctional alicyclic clothing milk resin (" Izhuo Liude ΘΤ300 "," Ibolite GT4〇〇 ") Wait, this is the best— "Early use or use more than two kinds, or use with the epoxy resin exemplified below. Specific examples of the epoxy compound that can be used in this way include, for example, hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl = mystery, phenyl diglycidyl, benzene Switch to mystic resin epoxy resin, mystic resin epoxy resin for nail paint, pour phenyl methane epoxy resin, dicyclopentadiene dimethanol epoxy resin, Shuangpan A epoxy resin , Double W-type epoxy resin, double 3-point S-type epoxy resin, 2, 2-bis (4-Cyclophenylphenyl H, l 15 3, 3, 3_ Epoxy compound of fluoropropane, hydrogenated double age A Type epoxy resin, hydrogenated biszefen F-type epoxy resin, hydrogenated double-pan S-type epoxy resin, hydrogenated 2, 2 · bis (4_meridylphenylgan \-soil ,, 丨, 3, 3, 3_ Hexafluoropropane epoxy compound, brominated bisphenol A type epoxy resin, desertified bisg fraction_F type epoxy resin, cyclohexanedimethanol diglycidyl etherification 4A, 1 6 ρ 'hexane Glycidyl Ether, 1,4-Butanediol Diglycidyl Ether, One-Ethyl-Ceco-1 ^ -J-Glycidyl Ether, Polysulfide Glycidyl Ether, Biphenyl Type Epoxy Resin® 7 A Lacquer Use g to separate acid resin ring Resin, epoxy resin with naphthalene skeleton, acid 13 200534014, heterocyclic epoxy resin, etc. (Other resins with polycaprolactone structure) Other resins that can be used in the present invention, can be modified with caprolactone Base resin, caprolactone modified butyral, etc. 5

10 [Hardener] The curing system for imparting thermosetting property in the thermosetting resin composition is not particularly limited. For example, a melamine resin may be added, and a hardener and an acid catalyst may be added. Examples of such a hardener include acid anhydrides, amine-based hardeners, and cationic hardeners. In the present invention, in the step of disposing the spacer under the alignment film, the spacer needs heat resistance. Therefore, from the viewpoint of the heat resistance of the spacer, the following combinations are particularly preferred. Polyester resin and melamine resin with polycaprolactone structure (Example 1) Acrylic resin and melamine resin with polycaprolactone structure (Example 15 3) Polyester resin and epoxy resin with polycaprolactone structure

20 Acrylic resins and epoxy resins having a polycaprolactone structure and reactants of polycaprolactone polyols and anhydrides and epoxy resins (Example 2) Especially, when a polyester resin having a polycaprolactone structure and When the melamine resin is combined, the thermosetting property can be improved. Therefore, by causing the acid anhydride to locally react with the OH group of the polyester polyol having a polycaprolactone structure, and introducing a COOH group, the polyester resin and the melamine resin are introduced. Pre-condensation. In the case of an acrylic resin, fluorenyl acrylic acid, acrylic acid, etc. can be introduced by using a vinyl monomer and a monomer having a COOH group. 14 200534014 (melamine resin)

The melamine resin used in the present invention may be, for example, a compound that acts on melamine on melamine, or a modified base of the compound. This melamine resin can be specifically described as "Nicolacu 5 MS-2, MS-1, MW-24, MS-0 (U, MX-002, MX · 730, MX-750, MX-708, MX706, MX-042, MX-410 "," Semel 370, 77, 325, 327, 703, 712, 715, 701, 202, Mitsui Symantec Corporation, 207 ", etc. These melamine resins can be used alone or in combination of two or more types. Specific examples of acid anhydride-based hardeners include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid. Anhydrides, aromatic anhydrous anhydrides such as ethylene glycol anhydrous phthalic anhydride, biphenyltetrahydroanhydride, anhydride anhydrides such as azelaic acid, sebacic acid, and lauric acid, tetrahydrophthalic anhydride, Alicyclic carboxylic acid anhydrides such as hexahydrophthalic anhydride, endo-human methyltetrahydromonocarboxylic acid anhydride (Nadic anhydride), chlorobridged anhydride, and 15 meters of mic anhydride (Himic Anhydride). Specifics of amine hardeners Examples include diaminodiphenylphosphonium, diaminodiphenylphosphonium, diaminodiphenyl ether, p-phenylenediamine, m-phenylene Aromatic amines such as methylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-stilbene diamine; ethylene diamine, ethylene diamine, isophorone di Aliphatic amines such as amines, bis ('amino group_3_methylbis 20 5-hexyl) methane and polyetherdiamine; and guanidines such as dicyandiamide and 丨 (o-phenyl) biguanide. Catalysts Based on tertiary amines (gins (dimethylaminomethyl) phenol, difluorenyl T-based amine, 1,8-diazabicyclo (5, 4, 0) undecane (DBU)) and imidazole Acid catalysts are preferably p-toluenesulfonic acid, laurylbenzenesulfonic acid, dinonyldecanesulfonic acid 15 200534014 acid, monononylnaphthalenedisulfonic acid, butyl phosphoric acid, octyl phosphoric acid and the like Acid amine neutralized product. The printing ink of the present invention may contain a solvent. The solvent may be exemplified below. 5 10 (1) Low boiling point solvents such as n-hexane, n-pentane, and volatile oils, etc. Group hydrocarbons; aromatic hydrocarbons such as cyclohexane, toluene, methylcyclohexane; alcohols, ethanol, n-propanol, isopropanol, n-butanol, second butanol, isobutanol and other alcohols; methyl acetate Ester, Acetic acid Vinegar, isopropyl acetate, n-propyl acetate; ketones such as propylene, methyl ethyl, and methyl isopine. (2) aliphatic hydrocarbons such as petroleum solvents with a boiling point of 120 ~ 230 ° C; xylene, Aromatic hydrocarbons such as solvent oil, tetragas, Caishuang, etc. · Alcohols such as cyclohexanol, 2-methylcyclohexanol, etc .; Butyl acetate, etc .; = base ring S 'dipropane, isophorol Dilute alcohol, propylene alcohol 15 y vinyl alcohol early top, alcohol monofluorene, acetol monoethyl acetol mono-t, propylene alcohol mono-3 acrylic acid monoacetate_acetic acid vinegar, etc. _ boiling point 230 ~ 32 ot of high-boiling-point solvents such as aliphatic hydrocarbons such as ink and ink; alcohols such as tridecyl alcohol;-scales such as dimethyl alcohol; diethylene glycol ^, diethyl alcohol, 20 acetic acid acetic acid _. I Ding Zhi special ㈣; Divinyl alcohol butyl 乂 some examples of cereals are described in, for example, the publication of the Printing Society Publishing Department) on page 43 of the table bulletin :: == use ink, used for borrowing Appearance / Compatibility of printed space on the surface substrate for liquid crystal panel 16 200534014. From the viewpoint of cutting the oxygen reflection layer of the printed materials,-with alcohols with 9 or more carbon atoms (for example, Mitsubishi Chemical Co., Ltd .: "Diananaru"), above the fat on the Buddha's peak Family hydrocarbon solvents, glycol ethers, and glycols are preferred (Reference: "Printing Ink Screens (Released by Akihara Soka Printing Society).

10 15

20 In addition, in the ink of the present invention, in order to adjust the viscosity of the ink suitable for printing, a viscosity adjusting agent may be used. For example, the viscosity adjusting agent can be exemplified by: such as ultra-powder silicon dioxide (for example, Kuroro D'or, manufactured by Ayerelo Gil Co., Ltd., Mizkasir, Mizusawa Chemical Co., Ltd., Fuji Silicia Chemical Co., Ltd.'s trade name Celia, Silo Hobick, Fuso Chemical Industry Co., Ltd., etc.). The spacer formed by the above-mentioned printing ink and lithographic printing can not only maintain physical properties such as the breakage strength of the spacer and the compressive strength of ig% compression strength when the spherical spacer is alone, but also can provide fixation. In the present invention, the adhesive resin that does not inhibit the physical characteristics of the spherical spacer is achieved by having a component having a polycaprolactone structure. From the viewpoint of the physical characteristics of the adhesive resin, it is preferably elastic. The rate is 0.1 to 9.0 GPa (0.2 to 5.0 GPa) and the recovery rate is 60% or more (more preferably 70% to 100%). Within this range, because the adhesive resin has sufficient flexibility and resilience to the spherical spacer, it is possible to print and form a spacer having almost the same breaking strength, compression ratio, and 10% compressive strength as the spherical spacer alone. Pieces. However, 'if the elasticity of the resin for ink exceeds 9.0 Gpa, or when the recovery rate is less than 60%', since the adhesive resin is harder and harder to deform than the spacer particles, 17 200534014 the spacer formed by printing is also subjected to the adhesive resin The effect is hard and difficult to deform, and the resilience is also reduced. Therefore, when the spacer formed by printing is larger than the spherical spacer alone, the breaking strength is large, the compression ratio is small, and the 10% compressive strength becomes large. In this case, the agent for bonding the LCD substrate by the liquid crystal titration method, if the liquid crystal droplet is less than 5 mm, the spacer is not changed, and residual bubbles are likely to occur. In addition, when the LCD is used at a low temperature, the volume of the liquid crystal in the interior shrinks. At this time, by applying external pressure, when the spacer is not deformed in the same manner as described above, low-temperature foaming easily occurs. When the rebound rate is less than O. OIGpa, the physical characteristics of the spacer formed by printing will be close to the individual characteristics of the spherical spacer. However, since the fixing property is not sufficient for 10 minutes, spacers such as subsequent cleaning steps and rubbing steps are likely to fall off the substrate, and cracks may be generated in the display portion when the LCD substrate is attached to the LCD substrate. On the other hand, because the cross-linked structure k is not filled with a knife, the coating film for the facing film will penetrate into the spacer printed during printing, and ‘there is no Yang Chengding, which is the cause of poor liquid crystal alignment. Example 1 Example 1 (Polymer Resin + Trimeric Ammonium Resin)) Mixed with "Prachyl Side" (Polycaprolactone tetraol, Dai Chier Chemical Co., Ltd. Duyi) 45 replacement parts , 20 parts by weight of polycaprolactone triol (polycaprolactone and tetrahydrophthalic anhydride) & 1 mole ratio, "Saimei 3" (melamine Resin, Nitsui 20 — Kaifu Tieke Co., Ltd.) 35 weight "Yanaru 135" (solvent ·· carbon number 13 > Tochi 15 alcohol grade blend, manufactured by Sanka Chemical Co., Ltd.) 25 weight Faces u, +, 1+, U0 ~ 125 C react for 6 ~ 7 hours. 1 part of the above resin solution (total amount) was added, "Aiello Gil 300CF i degree adjuster: porous sulphur dioxide, F" (manufactured by Yelloro Inc.); [2 1 part by weight, 25 parts by weight of "Dianaru 13 ^" and also cereals) were pre-mixed and dispersed by roll 18 200534014 to obtain a resin composition for ink. The obtained resin composition was coated on a glass plate with "Dakuta 4MIL", and was cured at 220 ° C for 1 hour to form a film. The physical properties of this film have an elastic modulus of 0.56 GPa (universal hardness of 22.4 N / mm2) and a recovery rate of 90%. Measurement of recovery rate 5 Methods are summarized below. Fisher Instrument Co., Ltd. H100V film thickness 20 // 1T1 or more (glass plate) using indenter Vickers maximum load 10mN 0 load speed 10mN / 8sec maximum creep time 60sec load removal speed 10mN / 8sec minimum load Creep time 60 sec On the other hand, prepare a particle diameter of 4 // m, breaking strength of 774 MPa, 10% 15 compressive strength of 52 MPa, compression rate of 33.2%, and recovery rate of 18.9% (Measuring Device, Shimadzu Corporation Micro Compression Tester MCTM- 201) of spherical spacer particles. The test conditions are as follows. Figure 3 is a test force ~ displacement diagram showing the results of a compression test, and Figure 6 is a test force-displacement diagram showing the results of a load-unload test. 20 Shimadzu Corporation Micro Compression Tester MCTM-201 Compression test using FLAT50 indenter (Figure 3) Load speed 0.888mN / sec Load-relief test (Figure 6) 19 200534014 Maximum load 9.8mN Load speed .28mN / sec

Holding time Osec Minimum load 0.98mN

65 parts by weight of the spacer particles were mixed and dispersed in 35 parts by weight of "Dianaru 135", and the spacer dispersion was adjusted. 100 parts of the resin composition for the ink was mixed, and 65 parts by weight of the spacer dispersion liquid was mixed and dispersed to prepare a printing ink (including a spacer ratio of 25%). The printing system is based on the Japanese Patent Office No. 10-15 of 2000-35582. The method already printed is printed on a glass substrate. . Allow it to harden for hours. The breakage strength of the spacer 形成 formed on the glass plate is 756 MPa, 100/0 compressive strength 60.3 MPa, and the compression ratio 32.3% α ^ L exhibits almost the same physical property values as when the spacer particles are alone. The fourth figure is _ ^ ^ The test force-displacement diagram of the results of the compression test. Figure 7 shows the test force-displacement diagrams showing the results of load division, one, and type test. They are similar to the graphs in Figures 3 and 6, respectively. (Comparative Example 1)

20 Add the stupid to the reactor trough = ~ & 170 parts by weight of anhydride, 16 parts by weight of phthalic anhydride, 16 parts by weight of adipic acid, 270 parts by weight of pentylene glycol and 40 parts by weight of methyl isobutyl fluorenone Servings at 110. 〇,, 140 ° C, 180 ° C for 1 hour, 220 ° C for 2 hours for dehydration and condensation to obtain a resin, and the resin was mixed with "Sémel 303" (melamine resin, = ~ Kaistec) Co., Ltd.) 240 parts by weight. Hereinafter, the same resin as in Example 1 was used to prepare a printing ink. The elasticity of the ink resin for printing is 9.4 g a (universal hardness of 391 N / mm2), and the recovery rate. The physical properties of the spacer formed on the glass plate are 2120 MPa and 60% of breaking strength. 200534014 10% compressive strength of 101.5 MPa and compressibility of 26.1%. By using the ink resin used, it exhibits different physical properties from the spacer particles alone. Fig. 5 is a test force-displacement diagram showing the results of a compression test, and Fig. 8 is a test force-displacement diagram showing the results of a load-unload test. Figures different from those in Figure 5 of Figures 3 and 6 are shown. (Comparative example 2)

65 parts by weight of "Bailun 220" (polyester resin, Toyobo Co., Ltd.), 35 parts by weight of "Semel 303", and 25 parts by weight of "propenyl monoethyl ether acetate" were mixed. Using the same ink resin, 10 inks for printing were prepared. The elasticity of printing ink resin is 10.69GPa (universal hardness 349N / mm2), and the recovery rate is 44%. The breakage strength of the spacer formed on the glass plate is 2297 MPa, 10% compressive strength is 93.6 MPa, and the compression ratio is 25.9%. By using the ink resin used, the physical properties of the spacer particles are different from those of the spacer particles alone. 15 20 (Example 2 (epoxy resin)) 33 parts by weight of "Prachil 410D" and 50 parts by weight of fluorenyltetrahydrophthalic anhydride were reacted at 9 (TC for 5 hours to obtain COOH-group-terminated 40 parts by weight of the reactant, 35 parts by weight of "Albolite GT302" (lactone modified epoxy resin, manufactured by Dairy Chemical Industry Co., Ltd.), and "propenyl monoethyl ether acetate" ( (Solvent) 25 parts by weight are mixed. In the same manner as in Example 1, the ink for printing is used to make printing ink. The elasticity of printing ink resin is 0.58 GPa (universal hardness 391 N / mm2), and the recovery rate is 88.2%. The formed spacer has a breaking strength of 771.9 MPa, a 10% compressive strength of 65.I MPa, and a compression ratio of 32.8%. By using the ink resin used, 21 200534014 exhibits the same physical property values as the spacer particles alone. (Example 3 ( Malonic acid resin + melamine resin))

75 parts by weight of "propenyl monoethyl ether acetate", 5 parts by weight of "Placryst FA-5" (lactone modified acrylate, Daisher Chemical Industry Co., Ltd.), and MMA (Methyl Acrylate) 57 parts by weight of esters, 15 parts by weight of HEMA (hexaethylfluorenyl acrylate), 3 parts by weight of MAA (methacrylic acid), "ABN-E" (Azo Polymerization Initiator, Seatrakin Industries, Japan) ) 3 parts by weight are heated at 80 to 90 ° C for 5 hours, 25 parts by weight of "Swazur 1500" and 0.3 parts by weight of "ABN-E" are added, and polymerized for 3 hours to obtain a resin with a solid content of 60%. 10 75 parts by weight of "Semel 303" was mixed with this resin, and the resin for printing and the printing ink were prepared in the same manner as in Example 1 below. The elasticity of printing ink resin is 3.36 GPa (universal hardness 119.3 N / mm2), and the recovery rate is 75%. 15 20 The breaking strength of the spacer formed on the glass plate is 971.7MPa, 10% compressive strength is 68.3MPa, and the compression ratio is 30.0%. By using the ink resin used, it exhibits the same physical property value as that of the spacer particles alone. (Example 4 (polyester resin + melamine resin)) "Plakcol 410D" in Example 1 was replaced with "Plakcol 303" (polycaprolactone triol, Desir Chemical Industry Co., Ltd. ), The same method. Thus, the obtained film had physical properties of 3.05 GPa (general hardness 79.7 N / mm2) and a recovery rate of 65.7%. Next, the spacers were formed with a breaking strength of 882 MPa, a 10% compressive strength of 68.8 MPa, and a compression rate of 29.7%. (Example 5 (polyester resin + melamine resin)) 22 200534014 Replace "Plakcol 410D" in Example 1 with "Plakcol 308" (Polycaprolactone triol, Daigel chemical Except for Industrial Co., Ltd.), the same method was performed. Thus, the physical properties of the obtained film had an elastic modulus of 21 GPa (common hardness 9.5 N / mm2) and a recovery rate of 88.5%. Next, a break strength of 740.2 MPa, a 10% compressive strength of 52 mpa, and a compression ratio of 35.1% were formed on the glass plate. (Comparative Example 3) 80 parts by weight of "PTMG2000" (polytetramethylene glycol, Mitsubishi Chemical Corporation), 20 parts by weight of "Semel 303", and 10 parts by weight of "Dianaru 135" were mixed Hereinafter, in the same manner as in Example 1, a printing resin and a printing ink were prepared. The elasticity of the printing ink resin is 0.08 GPa (universal hardness 4.9 N / mm2), and the recovery rate is 92.4%. Next, the breakage strength of the spacers formed on the glass plate was 763 MPa, 10% compressive strength 53.5 MPa, and compression ratio 34.5%. The test results of each example and comparative example are summarized in Tables 1 and 2. In Tables i and 15 and Table 2, the fixation and solvent resistance were measured as follows. Fixing property: The same as in Example 1, it was printed on an ITO substrate and dried to make a sample, and a Sello-tape peeling test was performed. The residual rate of the spacers before and after the test was evaluated. "〇": 100% 20 "□": 95 ~ 100% "X": 95% or less Solvent resistance: NMP was used as a solvent on the film obtained by the same method as the film forming method in Example 1, A spot test was performed, and the appearance after the visual test was observed. 23 200534014 "〇": No change in appearance "□": Residual spots "X": Swelling or dissolving

Table 1

Physical property example 1 Example 2 Example 3 Example 4 Example 5 Elastic modulus (Gpa) of adhesive resin 0.56 0.58 3.36 3.05 0.21 Recovery rate (%) 90 88.2 75 78.5 88.5 Breaker strength (MPa) 756 771.9 971.7 882 740.2 10% compressive strength (MPa) 60.3 65.1 68.3 68.8 52.8 Compression ratio (%) 32.3 32.8 30.0 29.7 35.1 Fixing properties □□ 〇〇 □ Solvent resistance □ 〇〇〇 □ Table 2 Physical properties Comparative example 1 Comparative example 2 Comparative example 3 Particle adhesion resin only (Gpa) 9.4 10.69 0.08 Recovery rate (%) 55 ~ ^ " 44 92.4 Spacer failure strength (MPa) 2120 2297 763 774 10% compressive strength (MPa) ΤοΓΤ ^ 93.6 53.5 52 Compression ratio (%) 26Λ ^ 25.9 34.5 33.2 Adhesion resistance Solvent resistance 〇〇XU ~ ^ J 〇X, the specific embodiment of the last month this month, but the present invention is not limited to 24 200534014 to these specific embodiments, Various changes or modifications can be implemented without departing from the scope of the patent application. [Brief description of the drawings] Fig. 1 is a cross-sectional view schematically showing one example of a liquid crystal display element obtained by a conventional method. Fig. 2 is a cross-sectional view schematically showing an example of a liquid crystal display element obtained using the lithographic printing ink of the present invention. Fig. 3 is a test force-displacement chart showing the results of a separate compression test of the spherical spacer. 10 FIG. 4 is a test force-displacement diagram showing the results of the compression test in Example 1. FIG. Fig. 5 is a test force-displacement chart showing the results of the compression test in Comparative Example 1. Fig. 6 is a graph showing the test results of the load-relief test of the spherical spacer alone. FIG. 7 is a test force-displacement diagram showing the results of the load-unload test in Example 1. FIG. FIG. 8 is a test force-displacement diagram showing the results of the load-unload test in Comparative Example 1. FIG. 20 [Description of main component symbols] 1 ... Liquid crystal 4 ... Substrate 2 ... Spacer particles 3 ... Resin hardened product 25

Claims (1)

200534014 10. Scope of patent application ·· 1 · A type printing ink is a spacer forming ink used in the type printing method, which includes spacer particles and disperses the spacer particles 5 The thermosetting resin composition of 10, wherein the thermosetting resin composition contains a component having a polycaprolactone structure. 2. As stated in the patent | The printing ink for type j which has been enumerated in item j, further includes one or more solvents selected from the group consisting of higher alcohols, aliphatic smoke and aromatic hydrocarbons. 3. For example, please use the _ item of the patent scope for printing inks, and it also contains a viscosity adjuster made of ^ porous silica. The method for forming the interspecies 1 ^ ox is a method in which the printing ink of any one of items 1 to 3 of the scope of patent application is printed on a substrate, and heat-treated to harden it to form a spacer. 15 5. A kind of spacer ′ is formed by applying the patent scope 6. A display element is formed by the method of the fourth item of the patent application. Partitioner of scope item 5. 26