CN100475920C - Ink for spacer controller formation - Google Patents
Ink for spacer controller formation Download PDFInfo
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- CN100475920C CN100475920C CNB2004800190782A CN200480019078A CN100475920C CN 100475920 C CN100475920 C CN 100475920C CN B2004800190782 A CNB2004800190782 A CN B2004800190782A CN 200480019078 A CN200480019078 A CN 200480019078A CN 100475920 C CN100475920 C CN 100475920C
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- printing ink
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Abstract
In the method of spacer formation using a printing system, it is intended to improve the adherence between spacer particles and a binder resin. There is provided an ink for spacer formation that can be employed in the printing method. This ink contains a resin composition comprising spacer particles (A) and a thermosetting or active energy ray curable resin for spacer particle dispersion (C).
Description
Technical field
The present invention relates to spacer (spacer) formation printing ink.
Background technology
Open the Japanese Patent spy and to have disclosed the method for utilizing intaglio offset to form spacer in the 2000-35582 communique.In the Japanese Patent spy opens the claim 2 and 3 of 2000-35582 communique, put down in writing the technology of using the printing ink of the spherical spacer that in the resin of viscosity 2000～25000cps, has mixed 20～60 weight %, disclosed resin clearance control pearl (spacer beads) and the polyester based resin of 5 μ in an embodiment.
Japanese patent laid-open 11-323220 communique, spy open flat 9-111170 communique, spy and open flat 7-110404 communique and put down in writing in intaglio offset as being applicable to the heat-curing type printing ink that forms color filter layer or black matrix, have used the technology of polyester-melamine resin, epoxy melamine resin etc.
In addition, open the Japanese Patent spy and disclosed the method for utilizing the ink jet type print process to form spacer in the 2000-347191 communique.In the Japanese Patent spy opens the claim 1 of 2000-347191 communique, put down in writing and comprised the solia particle that forms spacer and the technology contents of adhesive resin.
The announcement of invention
Open in the 2000-35582 communique the Japanese Patent spy, only stipulated its viscosity about resin.Disclosed vibrin among the embodiment, also only stipulated its particle diameter for resin clearance control pearl.
Japanese patent laid-open 11-323220 communique, spy open flat 9-111170 communique, the spy opens in the flat 7-110404 communique, as the adhesive resin of printing ink used in the gravure offset of color filter layer, use polyester-melamine resin, cyanurotriamide modified vibrin, epoxy melamine resin, cyanurotriamide modified Resins, epoxy etc.But, consider that from printing adaptability except these resins, using higher alcohols, ethene is that glycol ethers, propylene are high boiling point series solvents such as ketone such as glycol ethers, pimelinketone, isophorone.Therefore, must at high temperature carry out long drying after the printing,, cause liquid crystal contaminated because it is remaining to have solvent under the inadequate situation of heating.In addition, solidify under the bonding not good situation of post gap control thing, printing ink, oriented film, when oriented film rubs or when vibration, since cause between spacer and adhesive resin interface peel, be moved with the bonding bad spacer that causes of oriented film, so there are problems such as delustring, gap inequality, oriented film be impaired.
Opening the Japanese Patent spy does not all have in 2000-35582 communique and the Te Kai 2000-347191 communique to put down in writing to some extent form chemical bond at the interface of adhesive resin and spacer particle.But, if the interface at adhesive resin and spacer particle does not form chemical bond, then under the situation that has applied external force such as vibration, interface peel appears in meeting of spacer particle and adhesive resin, the spacer particle of peeling off is moved, can cause detrimentally affect to oriented film, occur problems such as delustring after therefore existence is impacted.
Problem of the present invention is to form in the method for spacer by mode of printing, the binding property of spacer particle and adhesive resin is increased.
The present invention relates to be used to the spacer formation printing ink of print process, the feature of this printing ink is to contain A: spacer particle and C: the thermoset or the active energy line curing resin composition (resin composition) that disperse aforementioned gap control thing particle.
Among the present invention, because the spacer particle is dispersed among thermoset or the active energy line curing resin composition C, resin combination C has and comprises the composition that can carry out the functional group of chemical reaction with the spacer particle, so between spacer particle and adhesive resin, generate new chemical bond, binding property is improved.In addition, in the better embodiment, between adhesive resin and oriented film, also generate new chemical bond, consequently, the binding property of spacer and oriented film is improved.
Accompanying drawing simple declaration
Fig. 1 (a) and Fig. 1 (b) are respectively the mode chart in conjunction with the sample attitude of expression spacer particle A, resin B and oriented film.
Fig. 2 (a) and Fig. 2 (b) are the mode chart in conjunction with the sample attitude of expression spacer particle A, resin B, F, G, monomer and oriented film.
The best mode that carries out an invention
Below, illustrate in greater detail each important document of the present invention.
(mode of printing)
Mode of printing comprises the format mode of printing and does not have the version mode of printing.
The format mode of printing is meant the mode of printing that has used version, but the following method of illustration.
(1) letterpress (directly brushing mode, offset printing mode)
(2) intaglio printing or photogravure (transfer printing mode, offset printing mode, intaglio plate bat printing mode)
(3) lithography or offset printing
(4) porous printing or silk screen printing
Do not have the version mode of printing so long as do not use the mode of printing of version to get final product, it is not particularly limited, comprise ink jet printing mode and laser printing mode.Representative ink jet printing mode is as described below.
(1) bubble type (bubble jet)
(2) piezoelectric type
In the better embodiment, resin combination C comprises at least a kind and contains the composition that can carry out the functional group of chemical reaction with particle A.This composition can be Thermocurable, active energy ray-curable resin B, also can be composition arbitrarily such as other resin, monomer or thinner, oligopolymer, optical free radical initiator, solvent.
For example, in the better embodiment, comprise the composition that can carry out the functional group of chemical reaction and be the resin B more than a kind or 2 kinds with particle A.In this case, shown in the pattern of Fig. 1 (a), a of functional group, a ', a of spacer particle A " with the b of functional group, b ', the b of resin B " reaction bonded.
In the better embodiment, comprise the composition that can carry out the functional group of chemical reaction and be the resin B more than a kind or 2 kinds with particle A, and resin B can with the functional group reactions of oriented film.In this case, shown in the pattern of Fig. 1 (b), a of functional group, a1, a of spacer particle A ", a1 " and the b1 of functional group, the b1 of resin B " reaction bonded.Meanwhile, resin B combines with the functional group reactions of oriented film.
In other better embodiment, resin combination C contains various kinds of resin B.Resin B and spacer particle A carry out chemical reaction, and other resin F and resin B are carried out chemical reaction, and with the functional group reactions of oriented film.For example in the example shown in the pattern of Fig. 2 (a), the b ' of functional group of resin B and a ' of functional group of spacer particle A react, resin F and resin B reaction, resin F and resin G reaction.Meanwhile, the functional group reactions of resin F and oriented film.Consequently, by the macromolecular compound that generates, spacer particle A and oriented film are by Chemical bond.
In other better embodiment, the composition beyond the resin in the resin combination with the resin B reaction in the functional group reactions of oriented film.For example in the example shown in the pattern of Fig. 2 (b), the b ' of functional group of resin B and a ' of functional group of spacer particle A react, monomer or thinner and resin B and particle A reaction, the functional group reactions of monomer and oriented film.Consequently, by the macromolecular compound that generates, spacer particle A and oriented film are by Chemical bond.
In the better embodiment, resin B has by the heating b of functional group that can react, particle A have can with a of functional group of the b of functional group reaction.Like this, the reaction between the functional group that is had by spacer particle and adhesive resin makes spacer particle and adhesive resin integrated, and the disengaging of spacer particle can not take place.
As the b of functional group of this resin B, but illustration hydroxyl, epoxy group(ing), carboxyl, water-disintegrable silyl, silanol group, isocyanate group, methylol, alkylation methylol, imino-, acid anhydrides, unsaturated group.The reactivity of a of functional group that these functional groups can be had based on itself and particle A is selected.
Can contain multiple and particle A among the resin combination C has reactive resin B or can mix solidifying agent or coupling agent.Its example can exemplify vibrin and melamine resin, Resins, epoxy and melamine resin, Resins, epoxy and amine are the combination of solidifying agent etc.
As particle A had can with the functional group of composition in resin combination reaction, but illustration silanol group, carboxyl, epoxy group(ing), water-disintegrable silyl, isocyanate group, unsaturated group, methylol, alkylation methylol, imino-, acid anhydrides, amino.
In the better embodiment, resin B had pass through the b of functional group that heating can react for can with the b1 of functional group of the functional group reactions that remains in oriented film.
Like this, the b1 of functional group by adhesive resin and remain in reaction between the functional group of oriented film can improve the binding property of adhesive resin and oriented film.
As the functional group that remains in oriented film, but illustration carboxyl, amide group is considered from reactivity, particularly preferably carboxyl.
As can with the b1 of functional group of the functional group reactions that remains in oriented film, but illustration epoxy group(ing), hydroxyl, amino are considered from reactivity, particularly preferably epoxy group(ing).
In the better embodiment, the b1 of functional group of resin B is an epoxy group(ing), the aforementioned functional groups a of particle A be can with the a1 of functional group of epoxy reaction.The a1 of this functional group can exemplify epoxy group(ing), hydroxyl, silanol group.
In the better embodiment, resin B has the b ' of functional group that utilizes active energy ray to react, particle A have can with a ' of functional group of the b ' of functional group reaction.The b ' of this functional group but unsaturated groups such as illustration acryl, methacryloyl.
The a ' of functional group of particle A but unsaturated groups such as illustration acryl, methacryloyl.
In the better embodiment, resin combination C comprise contain can with the composition of the b1 ' of functional group of the functional group reactions that remains in oriented film.This composition can be a resin B, also can be the resin different with resin B, can be other compositions such as monomer, oligopolymer, thinner, light trigger.The b1 ' of functional group but the illustration epoxy group(ing).
In the better embodiment, printing ink comprise have can with the thinner D and/or the optical free radical initiator E of the functional group of a ' of functional group that can react or the b ' of functional group reaction by active energy ray.
In the better embodiment, resin B has by heating and/or energy line can carry out the b of functional group of cationoid polymerisation ", particle A have can with the b of functional group " a of functional group of reaction ".
As the b of functional group ", but illustration epoxy group(ing), hydroxyl.In addition, as a of functional group of particle A ", but illustration epoxy group(ing), hydroxyl.
In the better embodiment, the b of functional group of resin B " be can with the b1 of functional group of the functional group reactions that remains in oriented film ".The b1 of this functional group " but illustration epoxy group(ing), hydroxyl.
In the better embodiment, the b1 of functional group of resin B " be epoxy group(ing), a of functional group of particle A " be can with the a1 of functional group of epoxy reaction ".The a1 of this functional group " but illustration epoxy group(ing), hydroxyl.
Resin is carried out in the embodiment of cationoid polymerisation, resin combination comprise have can with a of functional group " or the b of functional group " the thinner H and/or the light cationic initiator I of functional group of reaction.
Because printing ink of the present invention is the printing ink that is applicable to corresponding mode of printing, so can determine quantity of solvent and solvent species among the resin combination C according to suitable practical experience.Solvent among the resin combination C can be other composition dissolved solvent that makes among the resin combination C, also can be to make other composition dispersive solvent.
Being used to solvent in the printing ink of format print process of the present invention to be advisable less, specifically better is below the 30 weight %, is more preferably below the 10 weight %.In the special good embodiment, the printing ink that is used to format print process of the present invention does not contain solvent in fact.Solvent composition is not added in this expression consciously energetically in printing ink, except the solvent or unavoidable impurities of trace.
Do not contain solvent in the printing ink in fact by making, can avoid residual solvent after spacer forms, can further realize stable printing the pollution of liquid crystal.Particularly, can omit heating steps thereafter by using the active energy ray-curable resin.
In addition, as the solvent in the printing ink that is used to ink jet type print process of the present invention, but illustration alcohol is, glycol is, propylene glycol is, water isopolarity solvent.
Below, each composition of printing ink of the present invention is described.
(spacer particle)
Be not particularly limited being used for spacer particle of the present invention.Be by separating out the particle that polymerization or seeding polymerization method obtain in the better embodiment.Separate out that polymerization is meant in monomer dissolving but this monomer of polymerization in not dissolving based on the solvent of this polymer of monomers, polymerization that polymer particle is separated out.The seeding polymerization method is meant utilizes monomer to make by above-mentionedly separating out polymer particle swelling that polymerization obtains, making this monomer polymerization obtain the method for after polymerization thing particle by the free radical that is built in this polymer particle again.
Above-mentioned separating out in polymerization and the seeding polymerization as a monomeric part, is preferably the cross-linking polymer particle that has used multivalence vinyl compounds such as Vinylstyrene, Phthalic acid, diallyl ester, tetraene propoxy-ethane.The solvent resistance and the thermotolerance of cross-linking polymer particle are good.Above-mentioned separating out in polymerization and the seeding polymerization, as the liquid crystal spacer, the particle that acquisition is the ideal spherical shape and has the size-grade distribution of homogeneous, special good is to obtain the bigger spherical shape particle of particle diameter in seeding polymerization.
Among the present invention, except above-mentioned particle, also can use the polymer particle, glass particle, ceramic particle, the metallics that get by other polymerization polymerization, but as the liquid crystal spacer, as mentioned above, this particle is preferably spherical shape and the particle size-grade distribution homogeneous.
By on this particle, adhesion layer being set, can import functional group described later at particle surface.
But material exemplified by acrylic methyl esters as this adhesion layer use, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, 2-EHA, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid 2-ethylhexyl, stearyl methacrylate, lauryl methacrylate(LMA), methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, IVE, vinylbenzene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, vinyl acetate, vinylchlorid, 1, the 1-Ethylene Dichloride, ethylene fluoride, vinylidene fluoride, ethene, propylene, isoprene, chloroprene, polymerisable monomeric homopolymer such as divinyl or the above-mentioned monomeric multipolymer more than 2 kinds etc. have thermoplastic material.
Above-mentioned thermoplastic polymer or multipolymer are by thermoplastic, and para-directing group plate surface manifests good tack.Material as adhesion layer, also can use epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester, glycidyl allyl ether, the acrylate that contains the ester ring type epoxy group(ing) or methacrylic ester etc. to contain the monomeric homopolymer of epoxy group(ing) or the above-mentioned monomeric multipolymer that contains epoxy group(ing) more than 2 kinds, or contain the polymkeric substance that the monomer of epoxy group(ing) and the monomeric multipolymer beyond the above-mentioned monomer that contains epoxy group(ing) etc. contain epoxy group(ing), or polyvinyl alcohol etc. comprises the polymkeric substance that glass surface or the glass surface that scribbles polyimide coating is had the functional group of affinity.Polyvinyl alcohol obtains by vinyl acetate polymerization posthydrolysis.
In the better embodiment, the polymkeric substance that makes particle surface and formation adhesion layer in the spacer particle is with covalent bonds.But this method illustration graft polymerization method and high molecular weight reactive method.The graft polymerization method be included in particle surface import the polymeric vinyl can take place, be the above-mentioned monomer methods of starting point polymerization with this vinyl, and import polymerization starter, utilize these 2 kinds of the above-mentioned monomer methods of this initiator polymerization at particle surface.
(1) in the vinyl introductory technique, make particle surface have functional groups such as hydroxyl, carboxyl, epoxy group(ing), silyl, silanol group, isocyanate group, have the monomer reaction that can form the functional group of covalent linkage and import vinyl with above-mentioned functional group reactions by making.
(2) in the initiator introductory technique, make above-mentioned functional group be present in particle surface, by make have with above-mentioned functional group can form the functional group of covalent linkage superoxide, cross initiator for reaction such as oxyhydroxide, azo-compound and import initiator.
(3) make functional group be present in the method on surface
Separating out under the situation that polymerization or seeding polymerization make particle by above-mentioned, use alcohol such as methyl alcohol, ethanol, Virahol, secondary propyl alcohol, the trimethyl carbinol as solvent, ketone such as acetone, ethyl methyl ketone isopolarity solvent makes to comprise the monomeric monomer mixture polymerization with above-mentioned functional group.The particle that makes by this polymerization is in the surface functional group orientation.Monomer with above-mentioned functional group is as described below.Carboxylic monomer comprises vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, toxilic acid, maleic anhydride, citraconic acid etc.The monomer of hydroxyl comprises vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinyl carbinol etc.The monomer that contains epoxy group(ing) comprises epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester, glycidyl allyl ether etc.The monomer that contains methylol comprises N hydroxymethyl acrylamide, N-methylol methacrylamide etc.Contain amino monomer and comprise vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate etc.The monomer of amide-containing comprises acrylamide, methacrylic acid acid amides etc.The monomer that contains silyl comprises γ-metacryloxy propyl trimethoxy silicane, vinyltriacetoxy silane, to trimethoxysilyl vinylbenzene, to triethoxysilyl vinylbenzene, to trimethoxysilyl-alpha-methyl styrene, to triethoxysilyl-alpha-methyl styrene, γ-propenyloxy group propyl trimethoxy silicane, vinyltrimethoxy silane, N-β-(N-vinyl benzene methylamino ethyl-gamma-amino propyl group) Trimethoxy silane hydrochloride etc.
In addition, as the method that imports silyl, also can adopt to make the surface have silanol group, hydroxyl, carboxyl etc. to contain the method that particle and the silane coupling agent of the functional group of active hydrogen react.
Beyond the above-mentioned polymer particle, during inanimate matter particles such as employing glass, pottery, metal, for example, can import silyl on the surface by with γ-(2-amino-ethyl) aminopropyl methyl disilane, γ-(2-amino-ethyl) TSL 8330, γ-glycidoxy tripropyl methoxy silane, γ-Qiu Jibingjisanjiayangjiguiwan, methyltrimethoxy silane, silane coupling agents such as trimethoxysilyl vinylbenzene, METHYL TRICHLORO SILANE are handled.
Above-mentioned surface has imported the polymer particle of silyl or inanimate matter particle by with alkali or acid treatment silyl being hydrolyzed, and forms the particle that the surface has silanol group.
As the active energy ray-curable resin, can exemplify the urethane acrylate oligomer that oligopolymer with polyurethane structural forms with acrylate-based the combination, oligopolymer and the acrylate-based polyester acrylic ester oligomer that forms that combines with polyester construction, oligopolymer and the acrylate-based epoxy acrylate oligomer that forms that combines with epoxy group(ing), oligopolymer and the methacrylate based urethane methacrylate oligopolymer that forms that combines with polyurethane structural, oligopolymer and the methacrylate based polyester methacrylate oligopolymer that forms that combines with polyester construction, oligopolymer and the methacrylate based epoxy methacrylates oligopolymer that forms that combines with epoxy group(ing), has acrylate-based urethane acrylate, has acrylate-based polyester acrylate, has acrylate-based Epocryl, has methacrylate based urethane methacrylate, has methacrylate based polyester methacrylate, has methacrylate based epoxy methacrylates resin etc.
The optical free radical initiator (Photoepolymerizationinitiater initiater) that can sneak into active energy line curing resin composition is the composition that can produce free radical by light.It preferably causes the composition of the polymkeric substance, simple function or the multi-functional monomeric radical polymerization that contain unsaturated group, can use in the known in the past free radical reaction type Photoepolymerizationinitiater initiater in photoresist field any, is not particularly limited.For example, benzophenone, methyl phenyl ketone, bitter almond oil camphor, bitter almond oil camphor ethyl isobutyl ether, benzoin iso-propylether, ethoxybenzoin, 2,4-dimethyl thioxanthone, 2-clopenthixal ketone, EAQ, 4,4 '-two dimethylamino benzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal etc.These Photoepolymerizationinitiater initiaters can use separately or be used in combination more than 2 kinds according to the type of used solidifying agent (linking agent) and thinner.
Consumption to Photoepolymerizationinitiater initiater is not particularly limited, and usually crosslinked active energy ray-curable resin uses with the ratio about 0.01～10 weight part corresponding to ionization ray such as the utilization ultraviolet ray of 100 weight parts or electron rays.
The thinner D that can sneak into active energy line curing resin composition can adopt the compound with at least 1 polymerisable carbon-to-carbon unsaturated bond.Specifically; can use in the following monomer more than a kind or 2 kinds; allyl acrylate; the vinylformic acid benzene methyl; vinylformic acid butoxy ethyl ester; vinylformic acid butoxy glycol ester; cyclohexyl acrylate; vinylformic acid two pentamethylene esters; 2-EHA; the vinylformic acid glycerine ester; epihydric alcohol acrylic ester; vinylformic acid 2-hydroxy methacrylate; vinylformic acid 2-hydroxy propyl ester; isobornyl acrylate; isodecyl acrylate; Isooctyl acrylate monomer; lauryl acrylate; vinylformic acid 2-methoxyl group ethyl ester; vinylformic acid methoxyl group glycol ester; the vinylformic acid phenoxy ethyl; the stearyl acrylate alcohol ester; ethylene glycol diacrylate; diacrylate glycol ether ester; diacrylate 1; the 4-butanediol ester; diacrylate 1; the 5-pentadiol ester; diacrylate 1; 6-hexylene glycol ester; vinylformic acid 1; the ammediol ester; diacrylate 1; 4-cyclohexanediol ester; 2; 2-dihydroxy methylpropane diacrylate; the diacrylate glycerine ester; diacrylate tripropylene glycol ester; three vinylformic acid glycerine esters; Viscoat 295; the polyoxyethylene Viscoat 295; pentaerythritol triacrylate; tetramethylol methane tetraacrylate; the diacrylate triethyleneglycol ester; the polyoxypropylene Viscoat 295; the diacrylate butanediol ester; three vinylformic acid 1; 2; 4-trihydroxybutane ester; diacrylate 2; 2; 4-trimethylammonium-1; the 3-pentadiol ester; diallyl fumarate; dimethacrylate 1; 10-decanediol ester; esters of acrylic acids such as dipentaerythritol acrylate; and with the methyl acrylic ester of methacrylate based replacement aforesaid propylene perester radical; γ-metacryloxy propyl trimethoxy silicane; l-vinyl-2-pyrrolidone; 2-hydroxyethyl acryl phosphoric acid ester; tetrahydrofurfuryl acrylate; vinylformic acid two cyclopentenes esters; vinylformic acid two cyclopentenes oxygen base ethyl esters; diacrylate 3-butanediol ester; diacrylic acid pentyl diol ester; polyethyleneglycol diacrylate; hydroxyl trimethylacetic acid ester neopentylglycol diacrylate; phenol-oxyethane modification acrylate; phenol-epoxy pronane modification acrylate; N-vinyl-2-Pyrrolidone; dihydroxyphenyl propane-oxyethane modification diacrylate; the pentaerythritol diacrylate monostearate; diacrylate Tetraglycol 99 ester; polypropyleneglycol diacrylate; TriMethylolPropane(TMP) epoxy pronane modification triacrylate; isocyanuric acid oxyethane modification triacrylate; TriMethylolPropane(TMP) oxyethane modification triacrylate; tetramethylolmethane five acrylate; tetramethylolmethane six acrylate; acrylate monomers such as tetramethylol methane tetraacrylate, and these acrylate-basedly are substituted by methacrylate based and methacrylic ester that obtain.
In addition, from considering that with the binding property of oriented film thinner D is preferably the reagent with epoxy group(ing).Its example can exemplify (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, 4-hydroxybutyl acrylate glycidyl ether, Racemic glycidol (methyl) acrylate etc.
Consumption to thinner is not particularly limited, and corresponding to the active energy ray-curable resin of 100 weight parts, uses with the ratio of 1～200 weight part usually.
(being heating and curing property resin)
As being heating and curing property resin, can exemplify Resins, epoxy (solidifying agent of amine, polymeric amide, acid anhydrides etc.), vibrin and melamine resin, Resins, epoxy and melamine resin etc.
Concrete example as Resins, epoxy, can exemplify the quinhydrones diglycidylether, DGEC, resorcinol diglycidyl ether, the phenyl diglycidylether, phenol-novolac epoxy resin, cresol-novolac epoxy resin, trihydroxybenzene methylmethane type Resins, epoxy, Dicyclopentadiene (DCPD) dimethanol type Resins, epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3, the epoxy compounds of 3-HFC-236fa, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type Resins, epoxy, A Hydrogenated Bisphenol A S type Resins, epoxy, hydrogenation 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3, the epoxy compounds of 3-HFC-236fa, brominated bisphenol a type epoxy resin, brominated bisphenol F type Resins, epoxy, the cyclohexanedimethanodiglycidyl diglycidyl ether compound, 1, the 6-hexanediol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, the glycol ether diglycidylether, poly-sulphur diglycidylether, bisphenol-type epoxy resin, the dihydroxyphenyl propane novolac epoxy resin, the Resins, epoxy that contains the naphthalene skeleton, hetero ring type Resins, epoxy etc.
Except aforementioned epoxy resins, be preferably alicyclic epoxy resin, oxetane resin.Alicyclic epoxy resin be peracetic acid is acted on have the unsaturated group more than 2 the annular aliphatic unsaturated compound and have the oxide-based of oxirane ring, representative is with the Resins, epoxy of the type of the double bond epoxidation of cyclohexene ring, in addition, be preferably the resin that has the epoxy group(ing) more than 2 in 1 molecule.Specifically, for example better can use 3,4-epoxycyclohexyl methyl carboxylic acids ester, 3 ', 4 '-epoxycyclohexane carboxylate (UCC corporate system trade(brand)name UVR6110 and UVR6105, the system trade(brand)name CELLOXIDE of Dai Saier KCC 2021 etc.), two (3,4-epoxycyclohexyl methyl) adipic acid ester (UCC corporate system trade(brand)name UVR6128 etc.), 6-caprolactone modification 3,4-epoxycyclohexyl methyl carboxylic acids ester and 3 ', 4 '-epoxycyclohexane carboxylate (the system trade(brand)name CELLOXIDE of Dai Saier KCC 2081 etc.), 1-methyl-4-(2-methyl oxirane base)-7-oxabicyclo [4.4.0] heptane (the system trade(brand)name CELLOXIDE of Dai Saier KCC 3000 etc.).They can use separately also and can be used in combination more than 2 kinds.
Oxetane compound is the compound that intramolecularly has the trimethylene oxide ring more than 1.Specifically, better can use 3-ethyl-3-hydroxymethyl trimethylene oxide (the system trade(brand)name OXT101 of Toagosei Co., Ltd etc.), 1, two [(3-ethyl-3-oxetanyl) methoxymethyl] benzene of 4-(the system trade(brand)name OXT121 of Toagosei Co., Ltd etc.), 3-ethyl-3-(phenoxymethyl) trimethylene oxide (the system trade(brand)name OXT211 of Toagosei Co., Ltd etc.), two (1-ethyl-3-oxetanyl) methyl ether (the system trade(brand)name OXT221 of Toagosei Co., Ltd etc.), 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (Toagosei Co., Ltd system trade(brand)name OXT212 etc.), the good especially 3-ethyl-3-hydroxymethyl trimethylene oxide that is to use, 3-ethyl-3-(phenoxymethyl) trimethylene oxide, two (1-ethyl-3-oxetanyl) methyl ether.They can use separately also and can be used in combination more than 2 kinds.
Polymer polyatomic alcohol is not particularly limited, for example being preferably at least a kind of polyethers that is selected from polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol etc. is polyvalent alcohol, the at least a kind of polyester that is selected from the ester of polyvalent alcohol and polyprotonic acid formation is a polyvalent alcohol, be selected from carbonic acid 1,6-hexylidene ester and carbonic acid 1, at least a kind of polycarbonate-based polyvalent alcohol of 5-pentylidene ester, at least a kind of polylactone that is selected from polycaprolactone polyol and poly-butyrolactone polyvalent alcohol is a polyvalent alcohol.
Can select these polyethers is that polyvalent alcohol, polyester are that polyvalent alcohol, polycarbonate-based polyvalent alcohol and polylactone are a kind in the polyvalent alcohol or make up multiple.
Melamine resin can exemplify aminoresin such as methyl-etherified melamine resin, butyl ether melamine resin, isobutyl etherify melamine resin, butyl ether benzo guanamine resin etc., can use the mixture more than a kind or 2 kinds wherein.Can exemplify three and ニ カ ラ ッ Network MS-21, MS-11, MW-24, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, the MX-410 of chemistry as the commercially available product of the aminoresin among the present invention, the サ イ メ Le 370,771,325,327,703,712,715,701,202,207 of Mitsui サ イ テ ッ Network etc.
Can add solidifying agent or acid catalyst in the being heating and curing property resin.But this solidifying agent illustration acid anhydrides, amine are that solidifying agent, positively charged ion are solidifying agent.
Acid anhydrides is that the object lesson of solidifying agent can exemplify aromatic carboxylic acid acid anhydrides such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, the anhydrous trimellitic acid 1,2-anhydride of ethylene glycol, biphenyltetracarboxyacid acid acid anhydride, the acid anhydrides of aliphatic carboxylic acids such as nonane diacid, sebacic acid, dodecanedioic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, 3, methylene radical 1 in the 6-, 2,3, ester ring type carboxylic acid anhydride such as 6-tetrahydronaphthalic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, Ha イ ミ ッ Network acid anhydrides.
Amine is that the object lesson of solidifying agent can exemplify diaminodiphenyl-methane, diamino diphenyl sulfone, diamino-diphenyl ether, Ursol D, mphenylenediamine, O-Phenylene Diamine, 1, arylamine such as 5-diaminonaphthalene, MXDP, fatty amines such as quadrol, two quadrols, isophorone diamine, two (4-amino-3-methyl bicyclic hexyl) methane, polyether diamine, guanidine classes such as Dyhard RU 100,1-(o-tolyl) biguanides.
As catalyzer, possess representational have tertiary amines (three (dimethylaminomethyl) phenol, dimethyl benzene methylamine, 1,8-diazabicylo (5,4,0) undecane (DBU)), imidazoles etc.
As acid catalyst, be preferably acid such as tosic acid, lauryl Phenylsulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, butyl phosphoric acid, octyl group phosphoric acid, the amine corrective that these are sour etc.
(cationically polymerizable resin)
As the cationoid polymerisation resin, can exemplify epoxy compounds, oxetane compound, tetrahydrofuran compound, cyclic acetal compound, annular lactone compound, cured ethylene compound, Thietane compound, Vinyl Ether compound, spiro orthoester compound, ethene unsaturated compound, cyclic ether compound, cyclic thioether compound, vinyl compound etc. as the resultant of reaction of epoxy compounds and lactone.
Be preferably mixed diluent H and/or light cationic initiator I in the cationoid polymerisation resin.
As light cationic polymerization initiators I, can exemplify aryl diazonium salts type compound, triaryl matte salt type compound, diaryl group iodized salt type compound etc.
As thinner H, but exemplified by alkyl groups phenol monoglycidyl ether, alkyl monoglycidyl ether, dipropylene glycol diglycidylether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 1,6-hexylene glycol glycidyl ether etc.
Consumption to the light cationic polymerization initiators is not particularly limited, and the active energy ray-curable resin corresponding to 100 weight parts uses with the ratio of 0.1～10 weight part usually.
Consumption to thinner also is not particularly limited, and the active energy ray-curable resin corresponding to 100 weight parts uses with the ratio of 1～40 weight part usually.
Embodiment
(embodiment 1)
Mix spacer particle A, resinous principle B and ultraviolet radical initiator, make printing ink.The functional group of particle A is a hydroxyl, and resinous principle B is the urethane acrylate that contains isocyanate group, and initiator is 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone [ダ ロ キ ュ ア 1173 (チ バ ガ イ ギ-corporate system)].Utilize the Japanese Patent spy to open the gravure offset of 2000-35582 record, ink printing on filter sheet base plate, is made its curing, spacer is disposed on the BM.Specifically be exactly in 80 ℃ of preheatings of carrying out 10 minutes, then with the 1000mj/cm irradiation ultraviolet radiation.Assessment result to the gained spacer is shown in table 1 and table 2.
(evaluation method)
(between tackiness agent and spacer bonding)
After making ink solidification on the sample, obtain the printing ink cross section by the cutting sample, utilize scanning electron microscope observation adhesive resin and spacer interface to have or not and peel off." zero " expression is unstripped, and " △ " expression part is peeled off, and " * " expression is peeled off fully.
(printing ink and directed substrate bonding)
Behind printing-ink on the directed substrate, carry out scotch tape and peel off, have or not peeling off of printed layers with observation by light microscope." zero " expression is unstripped, and " △ " expression part is peeled off, and " * " expression is peeled off fully.
(delustring)
Form the ITO/ polyimide alignment film on the surface, utilize printing press printing-ink on BM, under prescribed condition, carry out heat treated through on the substrate of friction treatment.Then,, utilize ordinary method to make baseplate-laminating, make the stn liquid crystal screen by in box, injecting liquid crystal (メ Le Network corporate system ZLI-2293 (S078W)) in the printing and sealing agent of substrate periphery portion.
Observe the directed abnormal conditions of estimating the liquid crystal spacer periphery of liquid crystal display when connecting power supply that makes.
That is, the liquid crystal display that utilizes aforesaid method to make is applied 50V, 1 second volts DS (DC), the variation to directed unusual (the delustring state) of liquid crystal spacer periphery before and after applying is estimated.
Delustring does not take place in " zero " expression, " △ " but the expression confirmation unit is divided the state that delustring takes place, there is delustring in " * " expression.
In addition, under the same conditions, " the gap inequality " of the screen that is used for the delustring evaluation and makes judged by the screen outward appearance.
This evaluation is the no gap of " zero " expression inequality, " * " expression generation gap inequality.
(liquid crystal pollution)
In sample plasma bottle, inject the ink solidification thing of specified amount and the LC (メ Le Network corporate system ZLI-4792) of specified amount, in moisture eliminator, urge heat treated.Corresponding to liquid crystal, resin cured matter (removing thinner) is 5%.Under following condition, urge heat treated, measure liquid crystal pollution.
Short heating condition: 80 ℃-7hr,
Determination of resistivity: apply DC 20V-5 and measure resistance value second,
Device: liquid electrode (the electric system of peace rattan LE21), the high resistance determinator (ケ ス レ-SR-6517)
Estimate: poor with blank (blank): " zero " expression does not have, and difference is arranged slightly in " △ " expression but in the same order of magnitude, " * " expression differs one more than the order of magnitude.
(shock-resistance)
The screen that makes in " delustring evaluation " is applied surging force, estimate delustring situation thereafter.
Table 1
| Embodiment 1 | 2 | 3-1 | 3-2 | 4 | 5 | 6 | 7 | 8 | |
| Bonding between adhesive resin and spacer | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Bonding between printing ink and directed substrate | △ | △ | ○ | ○ | ○ | △ | ○ | ○ | × |
| Delustring | △ | △ | ○ | ○ | ○ | △ | ○ | ○ | × |
| The gap inequality | △ | △ | ○ | ○ | ○ | △ | ○ | ○ | △ |
| Liquid crystal pollution | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ |
Table 2
| Embodiment 9 | 10 | 11 | 12 | 13 | 14 | Comparative example 1 | Comparative example 2 | |
| Bonding between adhesive resin and spacer | ○ | ○ | ○ | ○ | ○ | ○ | × | × |
| Bonding between printing ink and directed substrate | ○ | ○ | ○ | ○ | △ | △ | × | △ |
| Delustring | ○ | ○ | ○ | ○ | ○ | △ | × | △ |
| The gap inequality | ○ | ○ | ○ | ○ | ○ | △ | × | △ |
| Liquid crystal pollution | △ | △ | △ | ○ | ○ | × | × | △ |
| Shock-resistance | ○ | × |
This result represents that liquid crystal pollution is suppressed among the embodiment 1.
(embodiment 2)
Used spacer particle A similarly to Example 1.The functional group of particle A is a hydroxyl.Use Resins, epoxy as resinous principle B, also mixed methyl tetrahydrophthalic anhydride [エ Port ラ イ ト B-570] (big Japanese ink Co., Ltd. system), as the aromatic uncle amine of catalyzer as anhydride curing agent.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by 200 ℃ of heating 60 minutes, make its curing.
Consequently, the binding property of resin and spacer particle, the binding property of printing ink and oriented film all increases.
(embodiment 3-1)
Used spacer particle A similarly to Example 1.The functional group of particle A is a hydroxyl.Daicel Chemical Industries, Ltd.'s system), " エ ピ コ-ト 1001 " (Resins, epoxy use " プ ラ Network セ Le 410D " (polycaprolactone tetrol: as resinous principle B, japan epoxy resin Co., Ltd. system), " サ イ メ Le 303 " (melamine resin, Mitsui サ イ テ ッ Network Co., Ltd. system), mixed tosic acid as acid catalyst.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by making its curing in 30 minutes 150 ℃ of heating.Consequently, obtained good characteristic.
(embodiment 3-2)
Used same spacer particle A with the embodiment 7 of No. the 3417681st, Japanese Patent (surface has particle synthetic of epoxy group(ing)).The functional group of particle A is an epoxy group(ing).Using " エ ピ コ-ト 828 " (Resins, epoxy of dihydroxyphenyl propane type, japan epoxy resin Co., Ltd. system) as resinous principle B, is that solidifying agent has mixed " H30 " (amine of ketoimine type is solidifying agent, japan epoxy resin Co., Ltd. system) as amine.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by making its curing in 30 minutes 150 ℃ of heating.Consequently, obtained good characteristic.
(embodiment 4)
Used spacer particle A similarly to Example 1.The functional group of particle A is a hydroxyl.Used " エ Port リ-De GT403 " (multifunctional alicyclic epoxy resin, Daicel Chemical Industries, Ltd.'s system) as Resins, epoxy composition B, mixed " サ Application エ イ De SI-100L " (aromatic matte salt type compound) as polymerization starter.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by making its curing in 30 minutes 150 ℃ of heating.Consequently, obtained good characteristic.
(embodiment 5)
Use utilizes MOI (2-isocyanic ester Jia Jibingxisuanyizhi, Showa Denko K. K's system) and KBM5103 (γ-propenyloxy group propyl trimethoxy silicane, KCC of SHIN-ETSU HANTOTAI system) particle surface carried out surface treatment and imported the spacer particle A of unsaturated group.Used ultraviolet curing resin " M305 " (pentaerythritol triacrylate as resin B, Toagosei Co., Ltd's system), mixed optical free radical polymerization starter (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone " ダ ロ キ ュ ア 1173 " (チ バ ガ イ ギ-corporate system)).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly to make its curing by the ultraviolet ray of shining 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 6)
Used spacer particle A similarly to Example 5.Use the lacquer resins " ENA " contain epoxy group(ing) and unsaturated group (fragrant river KCC system) as resin B, ultraviolet hardening monomer " M210 " (bisphenol A-type EO modification diacrylate, Toagosei Co., Ltd's system) and optical free radical polymerization starter (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone " ダ ロ キ ュ ア 1173 " (チ バ ガ イ ギ-corporate system)) have also been mixed as thinner D.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly to make its curing, made its curing in 30 minutes in 150 ℃ of heating again by the ultraviolet ray of shining 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 7)
Used spacer particle A similarly to Example 5.Use acrylate " M7100 " (polyester acrylate as resin B, Toagosei Co., Ltd's system), ultraviolet hardening monomer " 4HBAGE " (4-hydroxybutyl acrylate glycidyl ether, Nippon Kasei Chemical Company's system) and optical free radical polymerization starter (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone " ダ ロ キ ュ ア 1173 " (チ バ ガ イ ギ-corporate system)) have also been mixed as thinner D.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly to make its curing by the ultraviolet ray of shining 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 8)
Used the spacer particle A same with embodiment 3-2.The functional group of particle A is an epoxy group(ing).Used " エ Port ラ イ ト 828 " (Resins, epoxy as resin B, japan epoxy resin Co., Ltd. system) reaches " OXT-101 " (3-ethyl-3-hydroxymethyl trimethylene oxide, Toagosei Co., Ltd's system), also mixed light cationic polymerization initiators " サ Application エ イ De SI-100L " (aromatic matte salt type compound).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly ultraviolet ray, made its curing in 30 minutes 150 ℃ of heating then by irradiation 1000mj/cm.Consequently, the binding property of resin and spacer particle increases, and liquid crystal pollution also is suppressed.
(embodiment 9)
Used the spacer particle A same with embodiment 3-2.The functional group of particle A is an epoxy group(ing).Use alicyclic epoxy resin " GT301 " (Dai Saier KCC system) as resin B, also mixed light cationic polymerization initiators " サ Application エ イ De SI-100L " (aromatic matte salt type compound).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly ultraviolet ray, made its curing in 15 minutes 120 ℃ of heating then by irradiation 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 10)
Used spacer particle A similarly to Example 2.The functional group of particle A is a hydroxyl.Use " エ ピ コ-ト 806 " (bisphenol f type epoxy resin, japan epoxy resin Co., Ltd. system) as resin B, also mixed light cationic polymerization initiators " サ Application エ イ De SI-100L " (aromatic matte salt type compound).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly ultraviolet ray, made its curing in 15 minutes 120 ℃ of heating then by irradiation 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 11)
Used the spacer particle A same with embodiment 3-2.The functional group of particle A is an epoxy group(ing).Used " エ ピ コ-ト 806 " (bisphenol f type epoxy resin as resin B, japan epoxy resin Co., Ltd. system), thinner (2 functionality Resins, epoxy " エ ピ Network ロ Application 720 " have also been mixed, neopentylglycol diglycidyl ether, big Japanese ink Co., Ltd. system) and light cationic polymerization initiators " サ Application エ イ De SI-100L " (aromatic matte salt type compound).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly ultraviolet ray, made its curing in 15 minutes 120 ℃ of heating then by irradiation 1000mj/cm.Consequently, obtained good characteristic.
(embodiment 12)
Used the spacer particle A same with embodiment 3-2.The functional group of particle A is an epoxy group(ing).Used polycaprolactone tetrol Resins, epoxy with a part of COOH base as resin B.This resin is " プ ラ Network セ Le 410D " (polycaprolactone tetrol: Daicel Chemical Industries, Ltd.'s system) product that gets with methyl tetrahydrophthalic anhydride [エ Port ラ イ ト B-570] (big Japanese ink Co., Ltd. system) reaction.In addition, mixed " Port リ-De GT403 " (multifunctional alicyclic epoxy resin, Daicel Chemical Industries, Ltd.'s system).Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by making its curing in 60 minutes 180 ℃ of heating.Consequently, obtained good characteristic.
(embodiment 13)
Use similarly to Example 5 spacer particle A and optical free radical polymerization starter, used ultraviolet curing resin " M350 " (TriMethylolPropane(TMP) EO modification triacrylate: Toagosei Co., Ltd's system) as resin B.In order to form the viscosity that is suitable for ink-jet, dilute with propylene glycol monomethyl ether, obtain the spacer particle dispersion.
With known ink discharge device the gained dispersion liquid is sprayed on the substrate,, solidifies by make it with the 1000mj/cm irradiation ultraviolet radiation, then 150 ℃ of postheat treatment of carrying out 30 minutes in 120 ℃ after predrying 30 minutes.
(comparative example 1)
Use spacer particle A similarly to Example 1.The functional group of particle A is a hydroxyl.Use polyester acrylate " M7100 " (Toagosei Co., Ltd's system) as resin B, mixed high boiling solvent (propylene-glycol diacetate) and optical free radical polymerization starter.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by after 10 minutes, shining the ultraviolet ray of 1000mj/cm 80 ℃ of heating, making its curing.
Consequently, the binding property of the binding property of spacer particle and resin, printing ink and oriented film descends, and the phenomenon of delustring and gap inequality occurs, also confirms to have taken place liquid crystal pollution.
(embodiment 14)
Use spacer particle A similarly to Example 1.The functional group of particle A is a hydroxyl.Use the trimeric cyanamide vibrin as resin B, mixed the high-boiling point alcohol solvent.Print this mixture similarly to Example 1, make its curing, spacer is disposed on the BM.Specifically be exactly by 210 ℃ of heating 60 minutes, make its curing.
Consequently, the binding property of spacer particle and resin is good, and the binding property of printing ink and oriented film slightly descends, and the phenomenon and the liquid crystal pollution of some delustrings, gap inequality also occurred.
(comparative example 2)
Except spacer particle used among the embodiment 13 being become the used particle of embodiment 1, other operation and embodiment 13 identical experimentizing.Consequently, the binding property of spacer particle and adhesive resin is lower, and shock-resistance is lower.The binding property of printing ink and oriented film slightly descends, and the phenomenon and the liquid crystal pollution of some delustrings, gap inequality also occurred.
As mentioned above, utilize the present invention can improve by the spacer particle in the method for mode of printing formation spacer and the binding property of adhesive resin.
Claims (14)
1. spacer forms and uses printing ink, it is the spacer formation printing ink that is used to print process, contain A: spacer particle and C: the thermoset or the active energy line curing resin composition that disperse aforementioned gap control thing particle, it is characterized in that aforementioned resin C comprises at least a kind and contains the composition that can carry out the functional group of chemical reaction with aforementioned particles A.
2. printing ink as claimed in claim 1, its feature also is, aforementioned composition is the resin B more than a kind or 2 kinds with the b of functional group that can react by heating, and aforementioned particles A has a of functional group that can react with aforementioned functional groups b.
3. printing ink as claimed in claim 2, its feature also is, the aforementioned functional groups b of aforementioned resin B is the b1 of functional group that can react with carboxyl, amide group.
4. printing ink as claimed in claim 3, its feature are that also aforementioned functional groups b1 is an epoxy group(ing), the functional group a1 of the aforementioned functional groups a of aforementioned particles A for reacting with epoxy group(ing).
5. printing ink as claimed in claim 1, its feature also is, aforementioned composition is to have the resin B more than a kind or 2 kinds of utilizing the b ' of functional group that active energy ray can react, and aforementioned particles A has a ' of functional group that can react with aforementioned functional groups b '.
6. printing ink as claimed in claim 5, its feature also is, aforementioned resin C comprises the composition with the b1 ' of functional group that can react with carboxyl, amide group.
7. as claim 5 or 6 described printing ink, its feature also is, aforementioned resin C comprises thinner D and/or the optical free radical initiator E with the functional group that can react with aforementioned functional groups a ', b ' or b1 '.
8. printing ink as claimed in claim 1, its feature also is, aforementioned composition is to have by heating and/or energy line to carry out the b of functional group of cationoid polymerisation " the resin B more than a kind or 2 kinds, aforementioned particles A have can with aforementioned functional groups b " a of functional group that reacts ".
9. printing ink as claimed in claim 8, its feature also are, the aforementioned functional groups b of aforementioned resin B " be the b1 of functional group that can react with carboxyl, amide group ".
10. printing ink as claimed in claim 9, its feature also are, the aforementioned functional groups b1 of aforementioned resin B " be epoxy group(ing), the aforementioned functional groups a of aforementioned particles A " the a1 of functional group for reacting with epoxy group(ing) ".
11. as each described printing ink in the claim 8～10, its feature also is, comprise have can with aforementioned functional groups a " or aforementioned functional groups b " the thinner D and/or the light cationic initiator E of functional group of reaction.
12. as claim 1,2,3,4,5,6,8,9 or 10 described printing ink, its feature also is, does not contain solvent in fact.
13. printing ink as claimed in claim 7, its feature also are, do not contain solvent in fact.
14. printing ink as claimed in claim 11, its feature also are, do not contain solvent in fact.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003209414 | 2003-08-28 | ||
| JP209414/2003 | 2003-08-28 |
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| CNB2004800190782A Expired - Fee Related CN100475920C (en) | 2003-08-28 | 2004-08-25 | Ink for spacer controller formation |
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| JP (1) | JP4847130B2 (en) |
| KR (1) | KR20060041173A (en) |
| CN (1) | CN100475920C (en) |
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| WO2007114145A1 (en) * | 2006-04-06 | 2007-10-11 | Hitachi Chemical Company, Ltd. | Ink for forming liquid crystal spacer and liquid crystal display device using such ink |
| JP2008224849A (en) * | 2007-03-09 | 2008-09-25 | Sekisui Chem Co Ltd | Liquid crystal spacer particle dispersion liquid and method for manufacturing liquid crystal display device |
| JP5245099B2 (en) * | 2008-04-25 | 2013-07-24 | 独立行政法人 国立印刷局 | Authenticity discriminating resin composition, authenticity discriminating ink composition and its authenticity discrimination printed matter |
| TW201020302A (en) * | 2008-09-26 | 2010-06-01 | Natoco Co Ltd | Dispersion for disposing fine particle at predetermined point on substrate by ink-jet printing |
| JP5455818B2 (en) * | 2010-06-29 | 2014-03-26 | 富士フイルム株式会社 | Ink composition, ink set, and image forming method |
| US20140007786A1 (en) * | 2011-04-05 | 2014-01-09 | Lg Chem, Ltd. | Composition for printing and printing method using the same |
| GB201705751D0 (en) * | 2017-04-10 | 2017-05-24 | Rainbow Tech Systems Ltd | Force sensitive resistor |
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| JPH075476A (en) * | 1993-06-15 | 1995-01-10 | Hitachi Ltd | Production of liquid crystal display element |
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| JPH10253966A (en) * | 1997-03-11 | 1998-09-25 | Denso Corp | Liquid crystal display element |
| JP3803510B2 (en) * | 1999-05-25 | 2006-08-02 | 日本電気株式会社 | LCD panel |
| JP3997038B2 (en) * | 1999-09-09 | 2007-10-24 | キヤノン株式会社 | Manufacturing method of color filter with spacer and liquid crystal element |
| JP4603112B2 (en) * | 1999-08-23 | 2010-12-22 | 株式会社日本触媒 | Manufacturing method of liquid crystal display device |
| TW557237B (en) * | 2001-09-14 | 2003-10-11 | Sekisui Chemical Co Ltd | Coated conductive particle, coated conductive particle manufacturing method, anisotropic conductive material, and conductive connection structure |
-
2004
- 2004-08-25 WO PCT/JP2004/012590 patent/WO2005021665A1/en active Application Filing
- 2004-08-25 CN CNB2004800190782A patent/CN100475920C/en not_active Expired - Fee Related
- 2004-08-25 KR KR20057022902A patent/KR20060041173A/en not_active Application Discontinuation
- 2004-08-25 JP JP2005513512A patent/JP4847130B2/en not_active Expired - Fee Related
- 2004-08-27 TW TW093125813A patent/TW200516116A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1816599A (en) | 2006-08-09 |
| KR20060041173A (en) | 2006-05-11 |
| JP4847130B2 (en) | 2011-12-28 |
| WO2005021665A1 (en) | 2005-03-10 |
| JPWO2005021665A1 (en) | 2006-10-26 |
| TW200516116A (en) | 2005-05-16 |
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