CN101546119B - Radiation sensitive resin composition, division article, preparation method and liquid crystal display element - Google Patents

Radiation sensitive resin composition, division article, preparation method and liquid crystal display element Download PDF

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CN101546119B
CN101546119B CN 200910127064 CN200910127064A CN101546119B CN 101546119 B CN101546119 B CN 101546119B CN 200910127064 CN200910127064 CN 200910127064 CN 200910127064 A CN200910127064 A CN 200910127064A CN 101546119 B CN101546119 B CN 101546119B
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radiation sensitive
resin composition
sensitive linear
compound
methyl
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CN101546119A (en
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杉龙司
一户大吾
内池千浩
花村政晓
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JSR Corp
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Abstract

The present invention relates to a radiation sensitive resin composition, a division matter, a preparation method and a liquid crystal display element. The radiation sensitive resin composition is provided to generate little volume of volatile component when division matter is generated, and to deal with high-coating based on slit die coating method. The radiation sensitive resin composition contains: (A) a group having at least a group selected from a group composed of carboxyl and carboxylic acid anhydride base, and specific multi-mercaptide composition with pentaerythritol 4-(3- mercaptopropionic acid ester) as representation, and a polymer with proportion (M2/Mn) of weight average molar mass (Mw) measured by gel permeation chromatograph and number average molecular weight (Mn) conversed by polystyrene is 1.0 to 2.8; (B) polymeric unsaturated compound; and (C) radiation sensitive polymerization initiator.

Description

Radiation sensitive linear resin composition, separator and preparation method thereof and liquid crystal display cells
Technical field
The present invention relates to radiation sensitive linear resin composition, separator and preparation method thereof and liquid crystal display cells, more particularly, the radiation sensitive linear resin composition that relates to the material that is suitable as the separator that uses in the display elements such as forming display panels and touch panel, the display element that is formed by said composition is with separator and liquid crystal display cells with this separator.
Background technology
In liquid crystal display cells, in order to make the certain interval (box gap) of maintenance between two substrates, all use the separator particles such as beaded glass with regulation particle diameter, plastic bead all the time.Because these spacer particles randomly are dispersed on the transparency carrier such as glass substrate, in case thereby pixel forms the zone and has spacer particles, spacer particles will occur the reflection phenomenon occurs, and incident light generation scattering, the problem that descends as the contrast of display panels.
Therefore, in order to address these problems, just adopt the method that forms separator by photoetch method.The method is coated in radiation sensitive linear resin composition and forms overlay film on the substrate, by predetermined mask this overlay film is carried out developing behind the ultraviolet exposure, thereby form the separator of point-like or striated, because only the predetermined position beyond pixel forms the zone forms separator, has therefore basically solved the problems referred to above.
In recent years, from the large tracts of land of liquid crystal display cells and the raising equal angles of yield-power, the glass substrate motherboard was maximized to the level of 1500 * 1800mm by former 680 * 880mm level.The production process of liquid crystal display cells usually forms at transparency carrier coating separator and uses radiation sensitive linear resin composition, and after roasting desolventizing on the heating plate, exposes, develops, and forms separator.Yet, along with the maximization of substrate, owing to the problem of calciner and photomask is polluted in volatile ingredient volatilization in the radiation sensitive linear resin composition when the formation of separator, cause the raising of productive temp decline and production cost, thus troubling.
In addition, in the time of on the large substrate after radiation sensitive linear resin composition was coated in for the 5th generation, employing be the slit die coating process, and from shortening the angle of production procedure, require to shorten the coating time.In order to shorten the coating time, the essential coating speed of accelerating, and in case accelerate coating speed, it is irregular then mostly can to produce the striped coating in the situation on the coated surface.Therefore, even can not produce the irregular radiation sensitive linear resin composition of coating in the urgent need to developing the quickening coating speed yet.
In order to address the above problem, the applicant discloses in patent documentation 1 by making it contain the pollution that specific Photoepolymerizationinitiater initiater suppresses the calciner that caused by the Photoepolymerizationinitiater initiater distillation and exposed mask etc.And, in patent documentation 2, disclose by the viscosity of adjustment radiation sensitive linear resin composition and the relation of solids content concn, can in the slit die coating process, obtain the thickness homogeneous, not have irregular filming.But, owing to require in recent years further to improve productive temp, reduce production costs, the amount of the volatile ingredient that therefore produces when forming separator in the urgent need to exploitation is than in the past still less and the radiation sensitive linear resin composition that also can deal with for the high speed coating of slit die coating process.
[patent documentation]
[patent documentation 1] TOHKEMY 2005-234362 communique
[patent documentation 2] TOHKEMY 2006-184841 communique
Summary of the invention
Therefore, the objective of the invention is the considerably less and radiation sensitive linear resin composition that also can deal with for the high speed coating of slit die coating process of the amount of the volatile ingredient that produces when being provided at separator and forming.
Another object of the present invention is, separator of being formed by above-mentioned radiation sensitive linear resin composition and preparation method thereof is provided and shows the good liquid crystal display cells of grade.
Other purposes of the present invention and advantage can be found out by the following description.
According to the present invention, above object and advantages, the first, to be reached by a kind of radiation sensitive linear resin composition, it comprises:
[A] has the n valency group of at least a group selected in the group that is made of carboxyl and acid anhydride and following formula (1) expression, and the ratio (Mw/Mn) of the weight-average molecular weight (Mw) of the polystyrene conversion that is recorded by gel permeation chromatography and the number-average molecular weight (Mn) of polystyrene conversion is 1.0～2.8 polymkeric substance;
[B] polymerizable unsaturated compound; And
[C] radiation sensitive linear polymerization initiator,
Figure G2009101270647D00031
(in the formula (1), R IFor methylene or carbon number are 2～10 alkylidene or alkyl methylene, Y be singly-bound ,-CO-,-O-CO-* is (wherein, with connecting key and the R of " * " IConnect) or-NHCO-* is (wherein, with connecting key and the R of " * " IConnect), n is 2～10 integer and X for optional carbon number with one or more ehter bonds is 2～70 n valency alkyl, perhaps n be 3 and X be 3 valency groups of following formula (2) expression, "+" is expressed as connecting key),
Figure G2009101270647D00032
(in the formula (2), R IIBe that methylene or carbon number are 2～6 alkylidene independently of one another, " * " is expressed as connecting key separately).
According to the present invention, above object and advantages, the second, reached with the manufacture method of separator by display element, it is characterized in that comprising at least in the following order following operation,
(1) operation of the overlay film of the above-mentioned radiation sensitive linear resin composition of formation,
The operation of (2) at least a portion of this overlay film being exposed,
(3) operation of developing of the overlay film after will exposing, and
(4) operation that heats of the overlay film after will developing.
According to the present invention, above object and advantages, the 3rd, reached with separator by the display element of above-mentioned radiation sensitive linear resin composition manufacturing.
According to the present invention, above object and advantages, the 4th, reached by the liquid crystal display cells with above-mentioned separator.
Radiation sensitive linear resin composition of the present invention, the amount of the volatile ingredient that produces when the manufacturing of separator is considerably less, even and when adopting the high speed coating of slit die coating process, it is irregular also can not to produce striped on the overlay film of gained.And radiation sensitive linear resin composition of the present invention has high sensitive, even also can produce the display element separator with enough residual film ratios under low exposure.
Embodiment
Below, the present invention is described in detail.
＜radiation sensitive linear resin composition 〉
Radiation sensitive linear resin composition of the present invention comprises that at least [A] has the n valency group of at least a group selected in the group that is made of carboxyl and acid anhydride and above-mentioned formula (1) expression, and the ratio (Mw/Mn) of the weight-average molecular weight (Mw) of the polystyrene conversion that is recorded by gel permeation chromatography and the number-average molecular weight (Mn) of polystyrene conversion is 1.0～2.8 polymkeric substance (hereinafter referred to as " polymkeric substance [A] "); [B] polymerizable unsaturated compound (hereinafter referred to as " polymerizable compound [B] "); And [C] radiation sensitive linear polymerization initiator.
[polymkeric substance [A]]
Contained polymkeric substance [A] has the n valency group of at least a group selected in the group that is made of carboxyl and acid anhydride and above-mentioned formula (1) expression in the radiation sensitive linear resin composition of the present invention.
As R in the above-mentioned formula (1) ICarbon number be 2～10 alkylidene, preferred carbon number is 2～6 alkylidene, more preferably carbon number is 2～6 straight-chain alkyl-sub-or the group of following formula (3) expression.
Figure G2009101270647D00051
(in the formula (3), R IIIFor methylene or carbon number are 2～4 straight-chain alkyl-sub-, the connecting key of band " * " is connected with S).As R ICarbon number be 2～10 alkyl methylene, the group of preferred following formula (4) expression.
Figure G2009101270647D00052
As the Y in the above-mentioned formula (1), preferred-O-CO-* (wherein, with connecting key and the R of " * " IConnect).
N as in the above-mentioned formula (1) is preferably 2～8 integer, 2～6 integer or 8 more preferably, more preferably 2,3,4,6 or 8.
In the above-mentioned formula (1), be 2 o'clock X as n, preferably can enumerate such as carbon number is the alkylidene of 2～10 straight or branched, the divalent group of following formula (5) expression etc.,
(in the formula (5), R IVRespectively do for oneself hydrogen atom or methyl, ml is 1～20 integer, " * " is expressed as connecting key separately); Be 3 o'clock X as n, preferably can enumerate 3 valency groups such as above-mentioned formula (2) expression, 3 valency groups of following formula (6) expression etc.;
Figure G2009101270647D00062
(in the formula (6), " * " is expressed as connecting key separately); Be 4,6 or 8 o'clock X as n, preferably can enumerate such as the group of 4,6 or 8 valencys of following formula (7) expression etc.,
Figure G2009101270647D00063
(in the formula (7), m2 is 0～2 integer, and " * " is expressed as connecting key separately).
The n valency group of at least a group that polymkeric substance [A] is selected and above-mentioned formula (1) expression, can also further have the polymerism unsaturated link on its side chain in the group that is made of carboxyl and acid anhydride.
The content ratio of at least a group of selecting in the group that is made of carboxyl and acid anhydride in the polymkeric substance [A] is preferably 0.1～10 mM/g, more preferably 0.5～5 mM/g.The content ratio of the n valency group of above-mentioned formula (1) expression is preferably 0.005～1 mM/g, more preferably 0.01～0.5 mM/g in the polymkeric substance [A].When having the polymerism unsaturated link on its side chain of polymkeric substance [A], the content ratio of this polymerism unsaturated link is preferably 20 mMs/below the g, more preferably 0.1～15 mM/g, more preferably 0.5～10 mM/g in the polymkeric substance [A].
The weight-average molecular weight of the polystyrene conversion of polymkeric substance [A] (hereinafter referred to as " Mw ") is preferably 2000～100000, and more preferably 5000～50000.When Mw less than 2000, the development of the overlay film that then obtains, residual film ratio etc. are good not, and the situation that the pattern form of the separator of making, thermotolerance etc. can occur suffering damage, on the other hand, if Mw surpasses 100000, it is inadequate then can resolution to occur, and the pattern form of the separator of the making situation that can occur suffering damage.Be 1.0～2.8 with Mw divided by the molecular weight distribution (hereinafter referred to as " Mw/Mn ") of the polymkeric substance [A] of the value of Mn (number-average molecular weight of polystyrene conversion) definition, be preferably 1.0～2.5, more preferably 1.0～2.3.If Mw/Mn surpasses 2.8, then in the high speed coating that adopts the slit die coating process during as coating method, it is irregular to produce striped on the formed overlay film.
Polymkeric substance [A], so long as aforesaid polymkeric substance, what then make by any method all can, be preferably will be at least (a1) contain the polymkeric substance that at least a unsaturated compound (hereinafter referred to as " compound (a1) ") selected in the group that is made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides makes through the free radical polymerization operation in the presence of the compound of following formula (8) expression
Figure G2009101270647D00071
(in the formula (8), X, Y, R IWith n separately with above-mentioned formula (1) in X, Y, R IIdentical with the definition of n).This polymkeric substance can be the polymkeric substance itself that makes through above-mentioned operation, perhaps also can be the polymkeric substance of introducing the polymerism unsaturated link at the side chain of this polymkeric substance.
What the present inventors attentively studied found that, carry out free radical polymerization in the presence of the compound by unsaturated compound being had two above sulfydryls in a part of above-mentioned formula (8) expression, can control the molecular weight distribution of resulting polymers, can improve like this unsaturated compound of supply free radical polymerization to the conversion ratio of polymkeric substance, and find to comprise the polymkeric substance [A] that is made by this method in the radiation sensitive linear resin composition by making, it is considerably less to obtain the volatile ingredient amount that produces when the formation of separator, and can be applicable to the radiation sensitive linear resin composition of the high speed coating of slit die coating process.
As polymkeric substance of the present invention [A], be preferably following polymkeric substance [A1], polymkeric substance [A2-1] or polymkeric substance [A2-2].
Polymer [A1]: by compound (a1) and ethyl group selected from an unsaturated epoxy compound having an oxetanyl group and an unsaturated compound selected from the group consisting of at least one (hereinafter referred to as "Compound (a2-1)"), an unsaturated compound having a hydroxyl group (hereinafter referred to as "compound (a2-2)") and the compound (a1), the compound (a2-1) and the compound (a2-2) other than unsaturated compounds (hereinafter referred to as "compound (a2-3)") consisting of the group consisting of at least one unsaturated compound in the above formula (8) indicates the presence of the compound obtained by radical polymerization of copolymer.Polymkeric substance [A2-1]: make multipolymer (hereinafter referred to as " precursor polymer [A2-1] ") and the compound (a2-1) that in the presence of the compound of above-mentioned formula (8) expression, to carry out free radical polymerization by at least a unsaturated compound that forms of selecting in compound (a1) and the group that is consisted of by compound (a2-2) and compound (a2-3) and to make react prepared reaction product polymer.Polymkeric substance [A2-2]: make the multipolymer (hereinafter referred to as " precursor polymer [A2-2] ") that in the presence of the compound of above-mentioned formula (8) expression, to carry out free radical polymerization by at least a unsaturated compound that forms of selecting in compound (a1), compound (a2-2) and the group that is consisted of by compound (a2-1) and compound (a2-3) and to make and unsaturated isocyanate compound react the reaction product polymer of gained.In addition, hereinafter, compound (a2-1), compound (a2-2) and compound (a2-3) also can be referred to as " compound (a2) ".
Object lesson as above-claimed cpd (a1), unsaturated carboxylic acid can be enumerated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl hexahydrophthalic acid, and the dicarboxylic acid such as maleic acid, fumaric acid; As unsaturated carboxylic acid anhydrides, can enumerate acid anhydrides such as above illustrative dicarboxylic acid etc.
In these compounds (a1), the overlay film that forms from copolyreaction, by the gained radiation sensitive linear resin composition to the good aspect of the dissolubility of alkaline developer and and the aspect that obtains easily consider preferred acrylic acid, methacrylic acid, maleic anhydride or 2-methacryloxyethyl hexahydrophthalic acid.
Object lesson as above-claimed cpd (a2-1), as the unsaturated compound with epoxy ethyl, can enumerate for example 4-methacryloxy methyl-2-cyclohexyl-1,3-dioxolanes acrylic acid glycidyl esters, acrylic acid 2-methyl glycidyl esters, acrylic acid 3,4-epoxy radicals butyl ester, acrylic acid 6,7-epoxy radicals heptyl ester, acrylic acid 3,4-epoxy radicals cyclohexyl ester, acrylic acid 3, the acrylic acid epoxy base Arrcostabs such as 4-epoxy radicals cyclohexyl methyl ester; Methyl propenoic acid glycidyl base ester, methacrylic acid 2-methyl glycidyl esters, methacrylic acid 3,4-epoxy radicals butyl ester, methacrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl ester, methacrylic acid 3, the methacrylic acid epoxy radicals Arrcostabs such as 4-epoxy radicals cyclohexyl methyl ester; α-ethylacrylate glycidyl esters, α-n-pro-pyl acrylic acid glycidyl esters, α-normal-butyl acrylic acid glycidyl esters, α-ethylacrylate 6, the alpha-alkyl acrylic acid epoxy base Arrcostabs such as 7-epoxy radicals heptyl ester; Adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to glycidyl ethers such as vinyl benzyl glycidyl ethers etc.
As the unsaturated compound with oxa-cyclobutyl, can enumerate for example 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-3-Ethyloxetane, 2-ethyl-3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-2-phenyl oxetanes etc. has the methacrylate of oxa-cyclobutyl;
3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-3-Ethyloxetane, 2-ethyl-3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-2-phenyl oxetanes, 2,2-, two fluoro-3-(acryloxy ethyl) oxetanes etc. has the acrylate of oxa-cyclobutyl etc.
Object lesson as above-claimed cpd (a2-2), can enumerate for example acrylic acid 2-hydroxy methacrylate, acrylic acid 3-hydroxy propyl ester, acrylic acid 4-hydroxyl butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, acrylic acid 2,3-dihydroxy propyl ester, methacrylic acid 2,3-dihydroxy propyl ester, acrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester etc.
As the object lesson of above-claimed cpd (a2-3), can enumerate alkyl acrylates such as methyl acrylate, isopropyl acrylate; The alkyl methacrylates such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate;
Acrylic acid cyclohexyl ester, acrylic acid 2-methylcyclohexyl ester, acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, acrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) the acrylate ring type esters such as ethyl ester, isobornyl acrylate;
Methacrylic acid cyclohexyl ester, methacrylic acid 2-methylcyclohexyl ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, methacrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) the methacrylic acid ester ring type esters such as ethyl ester, IBOMA;
Acrylic acid aryl ester and the acrylic acid aralkyl esters such as phenyl acrylate, acrylic acid benzyl ester;
Aryl methacrylate and the methacrylic acid aralkyl esters such as methacrylic acid phenylester, methacrylic acid benzyl ester;
The dicarboxylic acid dialkyl esters such as diethyl maleate, DEF, diethyl itaconate; Methacrylic acid tetrahydro furfuryl ester, methacrylic acid tetrahydrofuran base ester, methacrylic acid oxinane-2-methyl ester etc. have the saturated five-ring heterocycles that contains an oxygen atom or the methacrylate of hexa-member heterocycle;
4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-isobutyl-1,3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclohexyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-isobutyl-DOX etc. have the acrylate of the saturated five-ring heterocycles that contains two oxygen atoms;
4-acryloyl-oxy ylmethyl-2,2-dimethyl-1, the 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-1, the 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2,2-diethyl-1, the 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-isobutyl-1, the 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclopentyl-1, the 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclohexyl-1, the 3-dioxolanes, 4-acryloxy Ethyl-2-Methyl-2-ethyl-1, the 3-dioxolanes, 4-acryloxy propyl group-2-methyl-2-ethyl-1, the 3-dioxolanes, 4-methacryloxy butyl-2-methyl-2-ethyl-DOX etc. has the acrylate of the saturated five-ring heterocycles that contains two oxygen atoms;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrenes;
The maleimide of the N position-replacements such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-dimaleoyl imino benzoic ether, N-succinimido-4-dimaleoyl imino butyric ester, N-succinimido-6-dimaleoyl imino capronate, N-succinimido-3-dimaleoyl imino propionic ester, N-(9-acridinyl) maleimide;
In addition 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate diene can also enumerate vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide isopolarity unsaturated compound etc.
The compound (a2) that uses during as manufacturing polymkeric substance [A1] is considered from the development of raising copolymerization, overlay film and the compression performance aspect of gained separator, and preferred use is by styrene, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base (methacrylate three ring decyl ester), methyl propenoic acid glycidyl base ester, methacrylic acid 2-methyl glycidyl esters, methacrylic acid 3,4-epoxy radicals cyclohexyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl methyl ester, 3-methyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, the methacrylic acid tetrahydro furfuryl ester, 1, the 3-butadiene, acrylic acid 2-hydroxyethyl ester, that selects in the group that methacrylic acid 2-(6-hydroxyethyl hexylyloxy) ethyl ester and 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX consists of is at least a.
Derive from the content ratio of the repetitive of compound (a1) in the polymkeric substance [A1], based on the total amount of whole repetitives, be preferably 5～50 % by weight, more preferably 5～40 % by weight are particularly preferably 10～30 % by weight.If derive from content ratio less than 5 % by weight of the repetitive of compound (a1), then can occur for the imperfect tendency of the dissolubility of alkaline developer, on the other hand, if surpass 50 % by weight, then can occur for the excessive possibility of the dissolubility of alkaline developer.
Derive from the content ratio of the repetitive of compound (a1) in the precursor polymer [A2-1], based on the total amount of whole repetitives, be preferably 10～60 % by weight, more preferably 15～50 % by weight.
Derive from the content ratio of the repetitive of compound (a1) in the precursor polymer [A2-2], based on the total amount of whole repetitives, be preferably 5～50 % by weight, more preferably 10～40 % by weight.Derive from the content ratio of the repetitive of compound (a2-2) in the precursor polymer [A2-2], based on the total amount of whole repetitives, be preferably 5～60 % by weight, more preferably 10～50 % by weight.Derive from the content ratio of at least a repetitive of selecting in the group that is consisted of by compound (a2-1) and compound (a2-3) in the precursor polymer [A2-2], total amount based on whole repetitives, be preferably 20～80 % by weight, more preferably 25～70 % by weight.
Polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] can by respectively with aforesaid unsaturated compound in the presence of the compound (hereinafter referred to as " multi-thiol compound ") of above-mentioned formula (8) expression, preferably in suitable solvent, in the presence of polymerization initiator, carry out free radical polymerization and prepare.
Above-mentioned multi-thiol compound is the composition that plays the chain-transferring agent effect when polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] synthetic.
As above-mentioned multi-thiol compound, can use carboxylate such as mercaptan carboxylic acid and polyvalent alcohol etc.
As above-mentioned mercaptan carboxylic acid, can enumerate such as mercaptoacetic acid, 3-mercaptopropionic acid, 3-sulfydryl butyric acid, 3-mercaptopentanoic acid etc.; As polyvalent alcohol, can enumerate for example ethylene glycol, tetraethylene glycol, butylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,3,5-three (2-hydroxyethyl) cyanurate, D-sorbite etc.
Object lesson as the preferred multi-thiol compound that uses among the present invention, can enumerate for example trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), tetraethylene glycol two (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), pentaerythrite four (mercaptoacetate), 1,4-two (3-sulfydryl butyryl acyloxy) butane, pentaerythrite four (3-sulfydryl butyric ester), 1,3,5-three (3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone etc.
Above-mentioned multi-thiol compound can use in independent or two or more mixing.
The usage ratio of multi-thiol compound when polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] synthetic, with respect to 100 whole unsaturated compounds, be preferably 0.5～30 weight portion, more preferably 1～20 weight portion is particularly preferably 1.5～10 weight portions.When usage ratio less than 0.5 weight portion of multi-thiol compound, can occur to obtain the situation that the desired molecule amount distributes.On the other hand, when surpassing 30 weight portion, the situation of high polymerisation conversion then can appear being not easy to obtain.
Operable solvent during as polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] synthetic can be enumerated such as ethylene glycol alkyl ether acetic acid esters, diglycol, dipropylene glycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, ketone, ester class etc.
As diglycol, can enumerate such as diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether etc.;
As dipropylene glycol, can enumerate such as dipropylene glycol monomethyl ether, DPE, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, two sweet glycol ethyl-methyl ethers etc.;
As propylene-glycol monoalky lether, can enumerate such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate such as methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.;
As propylene glycol alkyl ether propionic ester, can enumerate such as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
As ketone, can enumerate such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone etc.;
As the ester class, can enumerate for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, ethoxy acetate, ethoxy ethyl acetate, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, acetic acid 3-methoxyl butyl ester, the 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-butoxy methyl propionate, the ester classes such as 3-butoxy ethyl propionate.
Wherein, preferred ethylene glycol alkyl ether acetic acid esters, diglycol, dipropylene glycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, wherein, particularly preferably diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, methyl proxitol, methyl proxitol acetate or acetic acid 3-methoxyl butyl ester.
Above-mentioned solvent can use in independent or two or more mixing.
As polymkeric substance [A1], operable radical polymerization initiator during the manufacturing of precursor polymer [A2-1] and precursor polymer [A2-2], it is had no particular limits, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl-2, the 4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo-compounds such as 2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile).These radical polymerization initiators can use in independent or two or more mixing.
By so carrying out polymerization, can control the molecular weight distribution of resulting polymers, simultaneously, can reduce unreacted unsaturated compound.The unsaturated compound that as a result, can make the free radical polymerization of supplying with polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] reaches more than 95 % by weight to the conversion ratio (hereinafter referred to as " conversion ratio ") of polymkeric substance.
Here, polymerisation conversion can (refer to that the total weight of the whole compositions beyond the solvent contained in the radiation sensitive linear resin composition accounts for the ratio (% by weight) of composition total weight by the solids content concn of polymer solution after the actual adding weight of each composition of supplying with free radical polymerization and the polymerization.Together lower) obtain by following formula.Solids content concn places aluminum dish by weighing resulting polymers solution, and 175 ℃ heating plate heating 1 hour, mensuration heated the weight of front and back and calculates (weight before the weight after the heating * 100/ heating).
The actual adding general assembly (TW) of the composition beyond the actual adding general assembly (TW)/solvent of the solids content concn (% by weight) of the polymer solution after polymerization adding rate (% by weight)=polymerization * whole compositions.
In the preparation of polymkeric substance [A2-1], front precursor copolymer [A2-1] can adopt known method to carry out with the reaction of compound (a2-1).
As compound used herein (a2-1), from the storage stability that improves the gained radiation sensitive linear resin composition and further the thermotolerance of the separator that makes thus of raising and the angle of chemical reagent resistance are considered, preferably use by methyl propenoic acid glycidyl base ester, methacrylic acid 2-methyl glycidyl esters and (methyl) acrylic acid 3, that selects in the group that 4-epoxy radicals cyclohexyl methyl ester consists of is at least a.
The usage ratio of compound (a2-1) during synthetic polymer [A2-1] is preferably set to the suitable level of alkali-soluble that the residual quantity that does not have at least a group of selecting in the contained group that is made of carboxyl and acid anhydride in the front precursor copolymer [A2-1] to be used for the group (unreacted group) of compound (a2-1) reaction is in make resulting polymers [A2-1].Specifically, preferably making the content ratio that has the repetitive of above-mentioned unreacted group in the reacted polymkeric substance (polymkeric substance [A2-1]), based on the total amount of whole repetitives, is 5～30 % by weight, more preferably is 10～20 % by weight.
In polymkeric substance [A2-2] synthetic, front precursor copolymer [A2-2] and the reaction of unsaturated isocyanate compound can adopt known method to carry out.
As the unsaturated isocyanate compound, so long as have the unsaturated compound of isocyanate group, then it is had no particular limits, can enumerate 2-acryloxy ethyl isocyanate, 3-acryloxy propyl group isocyanates, 4-acryloxy butyl isocyanate, 6-acryloxy hexyl isocyanates, 8-acryloxy octyl group isocyanates, 10-acryloxy decyl isocyanates, 1, the acrylic acid derivatives such as 1-(two propylene acyloxy methyl) ethyl isocyanate, acrylic acid 2-(2-isocyanates base oxethyl) ethyl ester;
2-methacryloxyethyl isocyanates, 3-methacryloxypropyl isocyanates, 4-methacryloxy butyl isocyanate, 6-methacryloxy hexyl isocyanates, 8-methacryloxy octyl group isocyanates, 10-methacryloxy decyl isocyanates, 1, the methacrylic acid derivatives such as 1-(dimethyl allene acyloxy methyl) ethyl isocyanate, methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester;
In these unsaturated isocyanate compounds, from consider preferred 2-acryloxy ethyl isocyanate, 2-methacryloxyethyl isocyanates, methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester etc. with the reactive aspect of front precursor copolymer [A2-2].In polymkeric substance [A2-2] synthetic, the unsaturated isocyanate compound can use in independent or two or more mixing.
The usage ratio of unsaturated isocyanate compound with respect to the hydroxyl that front precursor copolymer [A2-2] has, is preferably 0.1～90 % by mole during preparation polymkeric substance [A2-2], more preferably 10～80 % by mole, is particularly preferably 25～75 % by mole.When 0.1 % by mole of the usefulness quantity not sufficient of unsaturated isocyanate compound, then to the susceptibility of gained radiation sensitive linear resin composition and less by the effect of the raising of the elastic performance of its display element separator that makes, on the other hand, if above 90 % by mole, then understand the unsaturated isocyanate compound of remained unreacted in the reactant liquor, thereby have the imperfect tendency of storage stability of resulting polymers solution and radiation sensitive linear resin composition.
[polymerizable compound [B]]
Polymerizable compound in the radiation sensitive linear resin composition of the present invention [B] is the compound with polymerism unsaturated link.
As polymerizable compound [B], it is had no particular limits, and the angle of the raising of, gained separator intensity good from polymerism is considered, preferably uses above (methyl) acrylate of simple function, difunctionality or trifunctional.
As (methyl) acrylate of above-mentioned simple function, can enumerate such as acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, IBOMA, acrylic acid 3-methoxyl butyl ester, methacrylic acid 3-methoxyl butyl ester, 2-acryloxy ethyl-2-hydroxypropyl phthalic ester, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester, ω-carboxyl polycaprolactone single-acrylate etc.As its commercially available product, can enumerate for example ァ ロ ニ ッ Network ス M-101, ァ ロ ニ ッ Network ス M-111, ァ ロ ニ ッ Network ス M-114, ァ ロ ニ ッ Network ス M-5300 (being produced by East Asia synthetic (strain)); KAYARAD TC-110S, KAYARAD TC-120S (being produced by Japanese chemical drug (strain)); PVC ス コ one ト 158, PVC ス コ one ト 2311 (being produced by Osaka organic chemistry industry (strain)) etc.
As above-mentioned dual functional (methyl) acrylate, can enumerate for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate, two (phenoxetol) fluorenes diacrylate, two (phenoxetol) fluorenes dimethylacrylate etc.As its commercially available product, can enumerate for example ァ ロ ニ ッ Network ス M-210, ァ ロ ニ ッ Network ス M-240, ァ ロ ニ ッ Network ス M-6200 (being produced by East Asia synthetic (strain)); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (being produced by Japanese chemical drug (strain)); PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (being produced by Osaka organic chemistry industry (strain)) etc.
As (methyl) acrylate more than the above-mentioned trifunctional, can enumerate for example trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, three (2-acryloxy ethyl) phosphonate ester, three (2-methacryloxyethyl) phosphonate ester, the dipentaerythritol acrylate of oxirane modification etc., in addition, can also enumerate and make three that have an above hydroxyl in the compound that has straight-chain alkyl-sub-and ester ring type structure in the molecule and have two above isocyanate group and the molecule, urethane (methyl) acrylate compounds of (methyl) acrylate compounds reaction gained of four or five functional groups etc.This urethane (methyl) acrylate compounds is preferably the above compound of nine senses.
As the commercially available product of (methyl) acrylate more than the above-mentioned trifunctional, can enumerate for example ァ ロ ニ ッ Network ス M-309, ァ ロ ニ ッ Network ス M-400, ァ ロ ニ ッ Network ス M-405, ァ ロ ニ ッ Network ス M-450, ァ ロ ニ ッ Network ス M-7100, ァ ロ ニ ッ Network ス M-8030, ァ ロ ニ ッ Network ス M-8060, ァ ロ ニ ッ Network ス TO-1450 (being produced by East Asia synthetic (strain)); KAYARAD TMPTA, KAYARADDPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARADDPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 (being produced by Japanese chemical drug (strain)); PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (being produced by Osaka organic chemistry industry (strain)) etc., particularly as the above urethane of nine senses (methyl) acrylate compounds, can enumerate ニ ュ one Off ロ Application テ ィ ァ R-1150 (above by the first industrial pharmacy (strain) production), KAYARAD DPHA-40H (above by Japanese chemical drug (strain) production) etc.
As the polymerizable compound among the present invention [B], in the middle of above-mentioned, preferred above (methyl) acrylate of trifunctional that uses, as particularly preferred, can enumerate the dipentaerythritol acrylate of trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate and oxirane modification.
Above (methyl) acrylate of above-mentioned simple function, difunctionality or trifunctional can be used alone or in combination of two or more.
In the radiation sensitive linear resin composition of the present invention, the usage ratio of polymerizable compound [B] with respect to 100 parts by weight polymer [A], is preferably 50～200 weight portions, more preferably 60～150 weight portions.When usefulness quantity not sufficient 50 weight portion of polymerizable compound [B], then when developing, exist to produce the residual possibility of developing, on the other hand, if surpass 200 weight portions, the gained separator then appears to the imperfect tendency of the adhesiveness of substrate.
[[C] radiation sensitive linear polymerization initiator]
[C] radiation sensitive linear polymerization initiator in the radiation sensitive linear resin composition of the present invention is by rays such as irradiation visible light, ultraviolet ray, far ultraviolet, charged particle beam, X ray, the composition of the active seed that generation can initiated polymerization compound [B] polymerization.As this [C] radiation sensitive linear polymerization initiator, can enumerate such as radiation sensitive linear radical polymerization initiator, radiation sensitive linear cationic polymerization initiators etc.As above-mentioned radiation sensitive linear radical polymerization initiator, can enumerate such as O-acyl group oxime compound, acetophenone compound, diimidazole compound, benzoin compound, benzophenone compound, α-dione compounds, multinuclear naphtoquinone compounds, xanthone compound, phosphine compound, triaizine compounds etc.As the radiation sensitive linear cationic polymerization initiators, can enumerate such as salt, metallocene compound etc.
As above-mentioned O-acyl group oxime compound; can enumerate for example ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime); 1-[9-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; ethyl ketone; 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime); 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes); 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes); 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl group oxime); 1; 2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oximes); 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-methyl benzoyl oxime) etc.
In these O-acyl group oxime compounds; ethyl ketone particularly preferably; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime), ethyl ketone; 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-DOX base) methoxybenzoyl base]-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime), 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes).
Above-mentioned O-acyl group oxime compound can use in independent or two or more mixing.
As above-mentioned acetophenone compound, can enumerate such as alpha-hydroxyacetone compounds, alpha-amido ketonic compound and the compound beyond them etc.
As above-mentioned alpha-hydroxyacetone compounds, can enumerate such as 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc.;
As above-mentioned alpha-amido ketonic compound, can enumerate such as 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl)-butane-1-ketone etc.;
As the compound beyond them, for example can enumerate 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.
In these acetophenone compounds, particularly preferably 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone or 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl)-butane-1-ketone.
These acetophenone compounds can use in independent or two or more mixing.
As above-mentioned diimidazole compound, can enumerate for example 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc.
In these diimidazole compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc., particularly preferably 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Above-mentioned diimidazole compound can use in independent or two or more mixing.
By using these diimidazole compounds, can further improve the separator of radiation-sensitive degree, resolution and manufacturing to the adhesiveness of substrate.
In radiation sensitive linear resin composition of the present invention, when using the diimidazole compound as [C] radiation sensitive linear polymerization initiator, can add select in the group that is consisted of by the aliphatics with dialkyl amido or aromatics (below, be called " amino sensitizer ") and mercaptan compound at least a.
Above-mentioned amino sensitizer is to have the radiation-sensitive degree that increases the diimidazole compound, a compound that improves imidazole radical generation efficiency function, can and further improve formed separator or diaphragm adds the adhering purpose of substrate for the susceptibility and the resolution that improve radiation sensitive linear resin composition.As this amino sensitizer, can enumerate for example N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, (dimethylamino)-ethyl benzoate, IADB etc.In these amino sensitizers, 4,4 '-two (diethylamino) benzophenone particularly preferably.These amino sensitizers can use in independent or two or more mixing.
The addition of amino sensitizer with respect to 100 weight portion diimidazole compounds, is preferably 0.1～50 weight portion, more preferably 1～20 weight portion.When addition less than 0.1 weight portion of amino sensitizer, susceptibility, resolution and the imperfect situation of adhering improvement effect then can appear, and on the other hand, if surpass 50 weight portions, the situation of the shape of formed separator can appear then damaging.
Above-mentioned mercaptan compound is to have to imidazole radical to provide hydroperoxyl radical, result to produce the compound of the function of the composition with Thiyl Radical.The diimidazole compound is accepted fracture behind the radiation exposure and the polymerization that produces imidazole radical causes and can be medium level, be not very high, therefore, if it is directly used in the separator that forms liquid crystal display cells, the section configuration that separator then can occur is the situation of the undesirable shape of back taper.But, by to wherein adding mercaptan compound, provide hydroperoxyl radical by mercaptan compound to imidazole radical, the result, imidazole radical is converted into neutral imidazoles, simultaneously, generation has the composition that polymerization causes Thiyl Radical that can be higher, can guarantee that like this shape of separator becomes preferred positive taper.As this mercaptan compound, can enumerate such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxybenzothiazole, the 2-sulfydryl-aromatic mercaptans compounds such as 5-methoxyl benzo imidazoles; The single mercaptan compound of the aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester; 3,6-dioxa-1, the analiphatic sulphur alcoholic compound that 2 officials such as hot two mercaptan of 8-, pentaerythrite four (mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester) can be above etc.In these mercaptan compounds, 2-mercaptobenzothiazole particularly preferably.
As the addition of mercaptan compound, with respect to 100 weight portion diimidazole compounds, be preferably 0.1～50 weight portion, more preferably 1～20 weight portion.When addition less than 0.1 weight portion of mercaptan compound, the imperfect situation of effect of improving of separator shape can appear, and on the other hand, if surpass 50 weight portions, the situation of the shape of formed separator can appear then damaging on the contrary.
In radiation sensitive linear resin composition of the present invention, when using the diimidazole compound as [C] radiation sensitive linear polymerization initiator, preferred above-mentioned amino sensitizer and mercaptan compound both add.
As the salt in the above-mentioned radiation sensitive linear cationic polymerization initiators, can enumerate diazo salts such as phenyl diazonium tetrafluoroborate, phenyl diazonium hexafluoro phosphonate, phenyl diazonium hexafluoro arsenate.
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoro phosphonate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium fluoroform sulphonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium tosilate etc.
As metallocene compound, can enumerate (1-6-η-cumene) (η-cyclopentadienyl group) iron (1 +) phosphorus hexafluoride acid (1 -) etc.
Above-mentioned radiation sensitive linear cationic polymerization initiators can use in independent or two or more mixing.
The usage ratio of [C] radiation sensitive linear polymerization initiator with respect to 100 parts by weight polymer [A], is preferably 0.01～120 weight portion, more preferably 1～100 weight portion in the radiation sensitive linear resin composition of the present invention.When usage ratio less than 0.01 weight portion of [C] radiation sensitive linear polymerization initiator, the inadequate tendency of residual film ratio in the time of can occurring developing, on the other hand, if surpass 120 weight portions, unexposed part is in the imperfect situation of the dissolubility of alkaline developer in the time of then can occurring developing.
In the radiation sensitive linear resin composition of the present invention, as [C] radiation sensitive linear polymerization initiator, preferably contain O-acyl group oxime compound.In radiation sensitive linear resin composition of the present invention, by using O-acyl group oxime compound, can obtain high sensitive radiation sensitive linear resin composition, and can make and have good adhering separator.In radiation sensitive linear resin composition of the present invention; when using O-acyl group oxime compound as [C] radiation sensitive linear polymerization initiator, the usage ratio of O-acyl group oxime compound is with respect to 100 parts by weight polymer [A]; be preferably 0.01～30 % by weight, more preferably 0.05～20 % by weight.When usefulness quantity not sufficient 0.01 weight portion of O-acyl group oxime type polymerization initiator; the inadequate situation of residual film ratio in the time of then can occurring developing; on the other hand, if surpass 30 weight portions, unexposed part is for the imperfect situation of the dissolubility of alkaline developer when then occurring developing.
In radiation sensitive linear resin composition of the present invention, as [C] radiation sensitive linear polymerization initiator, can be with O-acyl group oxime polymerization initiator with more than one other radiation sensitive linear polymerization initiator couplings.As other radiation sensitive linear polymerization initiators, that selects in the group that preferably is made of acetophenone compound, diimidazole compound and radiation sensitive linear cationic polymerization initiators is at least a.In radiation sensitive linear resin composition of the present invention; when with O-acyl group oxime polymerization initiator and other radiation sensitive linear polymerization initiator couplings; the usage ratio of other radiation sensitive linear polymerization initiators; in whole radiation sensitive linear polymerization initiators; be preferably below 80 % by weight, more preferably 70 % by weight.In the present invention, by using select in the group that is consisted of by acetophenone compound and diimidazole compound at least a as other polymerization initiators, can further improve the shape of gained separator and compression strenght etc.
＜other adjuvants 〉
Radiation sensitive linear resin composition of the present invention contains aforesaid polymkeric substance [A], polymerizable compound [B] and [C] radiation sensitive linear polymerization initiator as essential composition, and in the scope of not damaging Expected Results of the present invention, as required, can also contain above-mentioned other adjuvants in addition.
As this other adjuvants, can enumerate such as [D] surfactant, [E] bonding agent, [F] preserving stabilizer, [G] heat resistance improver etc.
[[D] surfactant]
Above-mentioned [D] surfactant can be to be contained in the radiation sensitive linear resin composition of the present invention in order to improve screening characteristics.As this [D] surfactant, can enumerate fluorine class surfactant, siloxane type surfactants or other surfactants.As above-mentioned fluorine class surfactant, preferred use endways, arbitrary at least position of main chain and side chain has the compound of fluoro-alkyl or fluoro alkylidene.As its object lesson, can enumerate 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro butyl) ether, six ethylene glycol bisthioglycolates (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, the fluoro-alkyl polyoxyethylene ether, diglycerol four (fluoro-alkyl polyoxyethylene ether), the perfluoroalkyl poly(ethylene oxide)polymers, the perfluoroalkyl alkoxide, fluoroalkyl etc.
As its commercially available product, for example can enumerate メ ガ Off ァ ッ Network F142D, メ ガ Off ァ ッ Network F172, メ ガ Off ァ ッ Network F173, メ ガ Off ァ ッ Network F183, メ ガ Off ァ ッ Network F178, メ ガ Off ァ ッ Network F191, メ ガ Off ァ ッ Network F471, メ ガ Off ァ ッ Network F476 (more than, produced by DIC (strain)), Off タ one ジ ェApplication ト FT-100, Off タ one ジ ェApplication ト FT-110, Off タ one ジ ェApplication ト FT-140A, Off タ one ジ ェApplication ト FT-150, Off タ one ジ ェApplication ト FT-250, Off タ one ジ ェApplication ト FT-251, Off タ one ジ ェApplication ト FTX-251, Off タ one ジ ェApplication ト FTX-218, Off タ one ジ ェApplication ト FT-300, Off タ one ジ ェApplication ト FT-310, Off タ one ジ ェApplication ト FT-400S (more than, produced by (strain) ネ ォ ス) etc.
As above-mentioned polysiloxane-based surfactant, the commercially available product trade name can be enumerated for example ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (more than, produced by eastern レ ダ ゥ コ one ニ Application グ シ リ コ one Application (strain)) etc.
As above-mentioned other surfactants, can enumerate non-ionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether, as commercially available product, can enumerate KP 341 (SHIN-ETSU HANTOTAI's chemical industry (strain) production), Port リ Off ロ-No.57,95 (common prosperity society chemistry (strain) is produced) etc.
These surfactants can use in independent or two or more mixing.
The combined amount of [D] surfactant with respect to 100 parts by weight polymer [A], is preferably below 5 weight portions, more preferably below 2 weight portions.If the combined amount of [D] surfactant surpasses 5 weight portions, produce easily the tendency of film be full of cracks in the time of then can occurring applying.
[[E] bonding agent]
Radiation sensitive linear resin composition of the present invention in order to improve the adhesiveness by separator and the substrate of its manufacturing, can contain [E] bonding agent.
As this [E] bonding agent, can preferably use the functional silanes couplant, as its example, can enumerate for example have carboxyl, the silane coupling agent of methacryl, isocyanate group, epoxy radicals isoreactivity functional group.More particularly, can enumerate for example trimethoxy silane base benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.These bonding agents can use in independent or two or more mixing.
The blending ratio of [E] bonding agent in the radiation sensitive linear resin composition of the present invention with respect to 100 parts by weight polymer [A], is preferably below 20 weight portions, more preferably below 10 weight portions.If the combined amount of [E] bonding agent surpasses 20 weight portions, the residual situation of developing then can appear occuring easily.
[[F] preserving stabilizer]
Radiation sensitive linear resin composition of the present invention in order to improve the purposes such as its storage stability, can contain [F] preserving stabilizer.As [F] preserving stabilizer, can enumerate such as sulphur, naphtoquinone compounds, hydroquinone compound, polyoxy compounds, amines, nitro nitroso compound etc.
In the radiation sensitive linear resin composition of the present invention, with respect to 100 parts by weight polymer [A], [F] preserving stabilizer is preferably with below 3.0 weight portions, more preferably the usage ratio of 0.001～0.5 weight portion is used.When this value surpasses 3.0 weight portion, then can not obtain sufficiently high radiation-sensitive degree, the situation of pattern form variation can appear.
[[G] heat resistance improver]
In order further to improve the thermotolerance of the separator of manufacturing, can add the compound that has the above epoxy radicals of two senses in N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound or a part in the radiation sensitive linear resin composition of the present invention.
As the object lesson of above-mentioned N-(alkoxy methyl) glycoluril compounds, can enumerate N, N, N ', N '-four (methoxy) glycoluril, N, N, N ', N '-four (ethoxyl methyl) glycoluril etc.N particularly preferably wherein, N, N ', N '-four (methoxy) glycoluril.
In above-mentioned N-(alkoxy methyl) melamine compound, N particularly preferably, N, N ', N ', N ", N " and-six (methoxy) melamine.As its commercially available product, can enumerate ニ カ ラ ッ Network N-2702, MW-30M (above by three and ケ ミ カ Le (strain) produce) etc.
As the compound that has the above epoxy radicals of two senses in above-mentioned a part, can enumerate trimethylolpropane tris glycidyl ether, hydrogenation bisphenol-A diglycidyl ether, bisphenol-A diglycidyl ether etc.As the object lesson of its commercially available product, can enumerate ェ Port ラ ィ ト 40E, ェ Port ラ ィ ト 100E, ェ Port ラ ィ ト 200E, ェ Port ラ ィ ト 70P, ェ Port ラ ィ ト 200P, ェ Port ラ ィ ト 400P, ェ Port ラ ィ ト 1500NP, ェ Port ラ ィ ト 1600, ェ Port ラ ィ ト 80MF, ェ Port ラ ィ ト 100MF, ェ Port ラ ィ ト 4000, ェ Port ラ ィ ト 3002 (above by common prosperity society chemistry (strain) production) etc.They can be used alone or in combination of two or more.
[radiation sensitive linear resin composition]
Radiation sensitive linear resin composition of the present invention preferably is dissolved in polymkeric substance [A], polymerizable compound [B] and [C] radiation sensitive linear polymerization initiator and optional other composition that uses in the suitable solvent, is mixed with solution shape composition.
The solvent that uses in the preparation as above-mentioned composition solution, use can dissolve each composition that consists of radiation sensitive linear resin composition equably, and not with the solvent of each composition reaction.
As such solvent, can enumerate with as can be for the manufacture of the solvent of above-mentioned polymkeric substance [A1], precursor polymer [A2-1] and precursor polymer [A2-2] illustrative same solvent.
In this solvent, from the dissolubility of each composition, with the reactivity of each composition, form the aspects such as easiness of filming and consider preferred for example alcohol, sweet glycol ethers, ethylene glycol alkyl ether acetic acid esters, ester class and the diglycol of using.Wherein can particularly preferably use for example benzylalcohol, 2 phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, diethyl carbitol, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, methoxy methyl propionate, ethoxyl ethyl propionate, acetic acid 3-methoxyl butyl ester.
In addition, be the inner evenness of the thickness that improves formed overlay film, can also be with above-mentioned solvent coupling high boiling solvent.As high boiling solvent that can coupling, can enumerate for example N-METHYLFORMAMIDE, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters etc.Wherein, preferred 1-METHYLPYRROLIDONE, gamma-butyrolacton, DMA.
It is such as resupplying use after the filtrations such as millipore filter about 0.2～0.5 μ m that the composition solution of so preparing can also adopt the aperture as required.
Radiation sensitive linear resin composition of the present invention is especially suitable for use as the material of using separator into forming the display elements such as liquid crystal panel and touch pad.
＜display element the manufacture method of separator 〉
Next, the method for making separator of the present invention with radiation sensitive linear resin composition of the present invention is described.
The manufacturing of separator of the present invention comprises following operation at least in the following order.
(1) operation of the overlay film of formation radiation sensitive linear resin composition of the present invention,
The operation of (2) at least a portion of this overlay film being exposed,
(3) operation of developing of the overlay film after will exposing, and
(4) operation that heats of the overlay film after will developing.
Below, these each operations are described successively.
[(1) operation]
One side at transparency carrier forms nesa coating, at this nesa coating coating radiation sensitive linear resin composition of the present invention, forms overlay film.
As transparency carrier used herein, can enumerate such as glass substrate, resin substrate etc., more particularly, can enumerate the glass substrates such as soda-lime glass, alkali-free glass; The plastics resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide.
Nesa coating as transparency carrier simultaneously upward arranges can use tin oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film etc. of system.
As the formation method of overlay film, can adopt coating process or dry film method.
When adopting coating process to form overlay film, can be by behind above-mentioned nesa coating coating radiation sensitive linear resin composition of the present invention, heating applicator surface (prebake) desolventizing and form overlay film.(the total weight of the whole compositions beyond referring to desolventize in the radiation sensitive linear resin composition accounts for the ratio (% by weight) of radiation sensitive linear resin composition general assembly (TW) to the solids content concn of the radiation sensitive linear resin composition that uses in the coating process.Be preferably 5～50 % by weight, more preferably 10～40 % by weight, more preferably 15～35 % by weight down together).As coating method, it is had no particular limits, can adopt such as spraying process, rolling method, method of spin coating (spin-coating method), slit die coating process, rod and be coated with the suitable methods such as method, ink-jet coating method, particularly preferably spin-coating method or slit die coating process.
Radiation sensitive linear resin composition of the present invention is specially adapted to the slit die coating process, even be 150mm/ during second in the translational speed of slit die, it is irregular also can not produce coating.
In addition, when adopting the dry film method to form overlay film, employed dry film, form at the radiation sensitive linear layer that lamination on basement membrane, the preferred plasticity basement membrane is made of radiation sensitive linear resin composition of the present invention (below, be called " radiation sensitive linear dry film ").
Above-mentioned radiation sensitive linear dry film can be by desolventizing after preferably applying radiation sensitive linear resin composition of the present invention with the form of solution shape composition on the basement membrane, thus lamination radiation sensitive linear layer and forming.Be used for the solids content concn of composition solution of the radiation sensitive linear layer of lamination radiation sensitive linear dry film, be preferably 5～50 % by weight, 10～50 % by weight more preferably, more preferably 20～50 % by weight are particularly preferably 30～50 % by weight.As the basement membrane of radiation sensitive linear dry film, can use synthetic resin films such as polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate, Polyvinylchloride.The thickness of basement membrane is that the scope of 15～125 μ m is more suitable.The thickness of radiation sensitive linear layer is preferably 1～30 μ m.
The radiation sensitive linear dry film also can the lamination overlay film on its radiation sensitive linear layer and preserve when not using.This overlay film preferably has the release property of appropriateness, its when not using (in preservation process) can not come off, and can easily be stripped from use.As the overlay film that satisfies this condition, can use such as the film at the coating of the surface of the synthetic resin films such as PET film, polypropylene screen, polyethylene film, polychloroethylene film, polyurethane film or the polysiloxane-based release agent of sintering.The thickness of overlay film is preferably 5～30 μ m.Can also to be lamination two-layer or three layers lamination-type overlay film for these overlay films.
This dry film can adopt the suitable method of the legal grade of hot pressing, and the nesa coating at transparency carrier forms overlay film by lamination.
Then the overlay film that so forms preferably carries out prebake.The prebake condition is preferably being carried out about 1～15 minute under 70～120 ℃ according to the kind of each composition, mixing ratio etc. and different.
Thickness after the overlay film prebake is preferably 0.5～10 μ m, more preferably 1.0～7.0 μ m.
[(2) operation]
Then, at least a portion of formed overlay film is exposed.At this moment, when the part of overlay film is exposed, usually expose by the photomask with predetermined pattern.
The ray that uses during as exposure can use such as visible light, ultraviolet ray, far ultraviolet, electron beam, X ray etc., and optimal wavelength is the ray of 190～450nm scope, particularly preferably contains the ultraviolet ray of 365nm.
Exposure is the value that the intensity of beam wavelength when being 365nm of exposure adopts illuminometer (OAImodel 356 types, OAI Optical Associates Inc. makes) to measure, and it is preferably 100～10000J/m 2, 500～3000J/m more preferably 2
[(3) operation]
Then, by the overlay film after the exposure is developed, remove useless part, form predetermined pattern.
The developer solution that uses during as development, the preferred bases developer solution as its example, can be enumerated the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; The aqueous solution of the alkali compounds such as the quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.
In addition, can also add the water-miscible organic solvents such as an amount of methyl alcohol, ethanol and surfactant in the aqueous solution of above-mentioned alkali compounds and use.
As developing method, contain liquid method, infusion process, douche etc. arbitrarily one all can, development time was preferably about 10～180 seconds.
After the development, after for example carrying out 30～90 seconds flowing water washing, for example advertise pressurized air or compressed nitrogen and carry out air-dryly, form required pattern.
[(4) operation]
Then, by adopting heating arrangements such as heating plate, baking oven, the temperature of regulation such as 100～230 ℃ under, the gained pattern is heated (curing afterwards), can make required separator.Heat time heating time, when heating when heating plate carries out preferred 5～30 minutes, when in baking oven, carrying out, be preferably 30～180 minutes.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention has the separator of being made by aforesaid radiation sensitive linear resin composition of the present invention.
Liquid crystal display cells of the present invention can be by for example following method (a) or (b) manufacturing.
(a) at first, prepare to have on a pair of (two) single face the transparency carrier of nesa coating (electrode), on the nesa coating of a substrate, adopt radiation sensitive linear resin composition of the present invention to form according to the method described above separator therein.Then nesa coating and the separator at these substrates forms the alignment films with liquid crystal aligning energy.With its one side that forms alignment films as the inboard, with these substrates with certain gap (box gap) relatively to the ground setting, make the mutual vertical or antiparallel of liquid crystal aligning direction of each alignment films, filling liquid crystal in the box gap that is surrounded by substrate surface (alignment films) and separator, the sealing filler opening consists of liquid crystal cell.Then, at two outside surfaces of the liquid crystal cell polaroid of fitting, simultaneously the liquid crystal aligning direction of the upper alignment films that forms is consistent or vertical to make its polarization direction and this substrate, can make liquid crystal display cells of the present invention.
(b) at first, prepare the transparency carrier that a pair of and said method (a) have similarly formed nesa coating, separator and alignment films.Then along the end of a substrate, with divider coating ultraviolet hardening sealant, then with the drip liquid crystal of fine droplet shape of liquid crystal dispensing apparatus, under vacuum, carry out the applying of two substrates.Then adopt high-pressure sodium lamp to above-mentioned sealant position irradiation ultraviolet radiation, with two substrate sealings.At last at two outside surfaces of the liquid crystal cell polaroid of fitting, can make liquid crystal display cells of the present invention.
As the liquid crystal that uses in above-mentioned each method, can enumerate for example nematic crystal, dish shape type liquid crystal.Wherein preferred nematic crystal can use such as schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal etc.In addition, can also add in these liquid crystal cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate and the chirality agent of selling with trade name " C-15 ", " CB-15 " (above produced by メ Le Network society), to the oxygen base benzylidene-ferroelectric liquid crystal such as amino-2-methyl butyl cinnamate is used in the last of the ten Heavenly stems.
As the polaroid that use in the liquid crystal cell outside, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as " H film " that orientation absorbs iodine simultaneously is clipped in the acetate fiber diaphragm and the polaroid that the polaroid of making or H film self are made etc.
Embodiment
Below, illustrative embodiments and comparative example carry out more specific description to the present invention, but the present invention is not limited to these embodiment.
In following synthesis example, the Mw of multipolymer and the mensuration of Mn are to adopt following apparatus and condition, are undertaken by gel permeation chromatography (GPC).
Device: GPC-101 (clear and electrician's (strain) makes)
The associating of post: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804.
Mobile phase: the tetrahydrofuran that contains 0.5 % by weight phosphoric acid.
Synthesis example 1
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 16 weight portion methacrylic acids, 34 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates), 40 weight portion methyl propenoic acid glycidyl base esters and 2 weight portion pentaerythrites four (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-1].Conversion ratio in this synthesis example is 98%, and the solids content concn of resulting polymers solution is 30.0 % by weight, and the Mw of polymkeric substance [A-1] is that 15000, Mw/Mn is 2.1.
Synthesis example 2
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 16 weight portion methacrylic acids, 34 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates), 40 weight portion methyl propenoic acid glycidyl base esters and 4 weight portion pentaerythrites four (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-2].Conversion ratio in this synthesis example is 99%, and the solids content concn of resulting polymers solution is 30.5 % by weight, and the Mw of polymkeric substance [A-2] is that 12000, Mw/Mn is 1.9.
Synthesis example 3
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (isobutyronotrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 10 weight portion methacrylic acids, 4 parts by weight of acrylic acid, 31 weight portion methacrylic acid benzyl esters, 45 weight portion methacrylic acid n-butyl and 4 weight portion dipentaerythritols six (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 80 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-3].Conversion ratio in this synthesis example is 96%, and the solids content concn of resulting polymers solution is 28.7 % by weight, and the Mw of polymkeric substance is that 12000, Mw/Mn is 1.7.
Synthesis example 4
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 12 weight portion methacrylic acids, 23 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates), 30 weight portion methyl propenoic acid glycidyl base esters, 25 weight portion 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyls-1,3-dioxolanes and 4 weight portion pentaerythrites four (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-4].Conversion ratio in this synthesis example is 96%, and the solids content concn of resulting polymers solution is 29.8 % by weight, and the Mw of polymkeric substance is that 12000, Mw/Mn is 1.7.
Synthesis example 5
In the flask that cooling tube and stirrer are housed, add 5 weight portions 2,2 '-azo two (isobutyronotrile), 250 weight portion acetic acid 3-methoxyl butyl esters continue to add 18 weight portion methacrylic acids, 30 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester, 5 parts by weight of styrene, 5 weight parts of butadiene, 25 weight portion methacrylic acid 2-hydroxyethyl esters, 17 weight portion methacrylic acid tetrahydrofurans-2-base ester and 2 weight portion trimethylolpropane tris (3-mercaptopropionic acid ester), behind nitrogen replacement, slowly stir on one side, make the temperature of solution rise to 80 ℃ on one side, kept this temperature 4 hours, then be warming up to 100 ℃, keep this temperature to carry out polymerization in 1 hour, obtain containing the polymer solution of front precursor copolymer [a-5].Conversion ratio in front precursor copolymer [a-5] synthetic is 98%, and the solids content concn of resulting polymers solution is 29.5 % by weight.
Then, forward in precursor copolymer [a-5] solution, add 14 weight portion 2-methacryloxyethyl isocyanates (trade name カ レ Application ズ MOI, clear and electrician's (strain) produces) and 0.08 weight portion 4-metoxyphenol after, reacted in 2 hours 60 ℃ of lower stirrings, obtain containing the polymer solution of polymkeric substance [A-5].
Here, derive from the isocyanate group of 2-methacryloxyethyl isocyanates and the carrying out of the reaction of the hydroxyl that derives from front precursor copolymer [a-5], adopt IR (infrared ray absorbing) spectrum to confirm.When reacting, derive from the 2270cm of the isocyanate group of 2-methacryloxyethyl isocyanates -1The state of minimizing is confirmed as near peak.The Mw of resulting polymers [A-5] is that 12000, Mw/Mn is 1.9.
Synthesis example 6
In synthesis example 5, forward in precursor copolymer [a-5] solution, add 15 weight portion methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester (trade name カ レ Application ズ MOI-EG, clear and electrician's (strain) produces) replacement 2-methacryloxyethyl isocyanates, and after adding 0.1 weight portion 4-metoxyphenol, 40 ℃ of lower stirrings 1 hour, reacted in 2 hours 60 ℃ of lower stirrings again, obtain containing the polymer solution of polymkeric substance [A-6].
Here, derive from the isocyanate group of methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester and the carrying out of the reaction of the hydroxyl that derives from front precursor copolymer [a-5], similarly adopt IR (infrared ray absorbing) spectrum to confirm with synthesis example 5.The Mw of resulting polymers [A-6] is that 12500, Mw/Mn is 1.9.
Synthesis example 7
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 20 weight portion methacrylic acids, 38 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates), 10 weight portion 3-(methacryloxy methyl)-3-Ethyloxetane, 30 weight portion 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyls-1,3-dioxolanes and 4 weight portion pentaerythrites four (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of front precursor copolymer (a-7).Conversion ratio in this synthesis example is 96%, and the solids content concn of resulting polymers solution is 29.8 % by weight, and the Mw of polymkeric substance is that 12000, Mw/Mn is 1.7.
Then, in precursor copolymer (a-7) solution, add 0.16 weight portion triphenylphosphine and 0.08 weight portion 4-metoxyphenol forward, be warming up to 90 ℃.Then, add 7 weight portion methyl propenoic acid glycidyl base esters after, 90 ℃ of lower stirrings 8 hours, obtain containing the polymer solution of polymkeric substance [A-7].
Here, derive from the glycidyl of methyl propenoic acid glycidyl base ester and the carrying out of the reaction of the carboxyl that derives from front precursor copolymer (a-7), adopt IR (infrared ray absorbing) spectrum to confirm.When reacting, affirmation derives from the 800cm of the glycidyl of methyl propenoic acid glycidyl base ester -1Near peak is reducing.
The Mw of resulting polymers [A-7] is that 13000, Mw/Mn is 2.0.
Compare synthesis example 1
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 16 weight portion methacrylic acids, 34 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates) and 40 weight portion methyl propenoic acid glycidyl base esters, behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-7].Conversion ratio in this synthesis example is 94%, and the solids content concn of resulting polymers solution is 28.8 % by weight, and the Mw of polymkeric substance [A-7] is that 15000, Mw/Mn is 3.1.
Compare synthesis example 2
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (isobutyronotrile) and 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 10 weight portion methacrylic acids, 4 parts by weight of acrylic acid, 31 weight portion methacrylic acid benzyl esters, 45 weight portion methacrylic acid n-butyl and 4 weight portion α-methylstyrenedimers, behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 80 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-8].Conversion ratio in this synthesis example is 92%, and the solids content concn of resulting polymers solution is 27.5 % by weight, and the Mw of [A-8] of polymkeric substance is that 12000, Mw/Mn is 2.8.
Compare synthesis example 3
In the flask that cooling tube and stirrer are housed, add 5 weight portions 2,2 '-azo two (isobutyronotrile) and 250 weight portion acetic acid 3-methoxyl butyl esters continue to add 18 weight portion methacrylic acids, 30 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester, 5 parts by weight of styrene, 5 weight parts of butadiene, 25 weight portion methacrylic acid 2-hydroxyethyl esters and 17 weight portion methacrylic acid tetrahydrofurans-2-base ester, behind nitrogen replacement, slowly stir on one side, make the temperature of solution rise to 80 ℃ on one side, kept this temperature 4 hours, then be warming up to 100 ℃, keep this temperature to carry out polymerization in 1 hour, obtain containing the polymer solution of front precursor copolymer [a-9].Conversion ratio in front precursor copolymer [a-9] synthetic is 94%, and the solids content concn of resulting polymers solution is 29.0 % by weight.
Adopt GPC (gel permeation chromatography) HLC-8020 (trade name, East ソ one (strain) makes) that precursor copolymer before the gained [a-9] is measured Mw, Mw is 14000, Mw/Mn=2.5.
Then, forward in precursor copolymer [a-9] solution, add 14 weight portion 2-methacryloxyethyl isocyanates (trade name カ レ Application ズ MOI, clear and electrician's (strain) produces) and 0.08 weight portion 4-metoxyphenol after, reacted in 2 hours 60 ℃ of lower stirrings, obtain containing the polymer solution of polymkeric substance [A-9].
Here, similarly adopt IR (infrared ray absorbing) spectrum to confirm to derive from the isocyanate group of 2-methacryloxyethyl isocyanates and the carrying out of the reaction of the hydroxyl that derives from front precursor copolymer [a-9] with synthesis example 5.The Mw of resulting polymers [A-9] is that 14000, Mw/Mn is 2.5.
Compare synthesis example 4
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 250 weight portion acetic acid 3-methoxyl butyl esters.Continue to add 5 parts by weight of styrene, 16 weight portion methacrylic acids, 34 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base (three ring decyl methacrylates), 40 weight portion methyl propenoic acid glycidyl base esters and 0.5 weight portion pentaerythrite four (3-mercaptopropionic acid ester), behind nitrogen replacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of polymkeric substance [A-10].Conversion ratio in this synthesis example is 98%, and the solids content concn of resulting polymers solution is 28.8 % by weight, and the Mw of polymkeric substance [A-10] is that 16000, Mw/Mn is 2.9.
Embodiment 1
The preparation of＜radiation sensitive linear resin composition 〉
The polymer solution that contains polymkeric substance [A-1] that makes in will the synthesis example 1 as polymkeric substance [A] is equivalent to the amount of 100 weight portions to be scaled polymkeric substance [A]; with as KAYARAD DPHA (Japanese chemical drug (strain) production) 100 weight portions of polymerizable compound [B] and as the ethyl ketone of [C] radiation sensitive linear polymerization initiator; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime) (the ィ Le ガ キ that チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces ュァ OX02) 5 weight portions and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinyl-4-base-phenyl)-butane-1-ketone (ィ Le ガ キ that チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces ュァ 379) 10 weight portions are dissolved in the propylene glycol methyl ether acetate, and making its solids content concn is 21 % by weight, is that the millipore filter of 0.2 μ m filters with the aperture then, makes radiation sensitive linear resin composition (S-1).
Adopt following evaluation of this radiation sensitive linear resin composition (S-1).Evaluation result is listed in table 2.
The evaluation of＜radiation sensitive linear resin composition 〉
(1) evaluation of susceptibility
After adopting spin coater to be coated on radiation sensitive linear resin composition (S-1) on the alkali-free glass substrate, prebake is 3 minutes on 90 ℃ heating plate, and forming film thickness is filming of 3.0 μ m.
Then, by have diameter be the circular pattern of 15 μ m as the photomask of peristome, adopting the intensity at 365nm place is 250W/m 2Ultraviolet ray, with the time shutter as variable, gained filmed exposes.Then, the potassium hydroxide aqueous solution that adopts 0.05 % by weight with pure water washing 1 minute, cured 20 minutes after again in 230 ℃ baking oven after 25 ℃ of lower 60 seconds of developing, and formed separator.At this moment, the residual film ratio after curing later on (film thickness after the film thickness after curing afterwards * 100/ exposure) is that minimum exposure amount more than 90% is as susceptibility.
(2) evaluation of the amount of volatile ingredient
After adopting spin coater to be coated on radiation sensitive linear resin composition (S-1) on the silicon chip, prebake is 3 minutes on 90 ℃ heating plate, and forming film thickness is filming of 3.0 μ m.
With after forming this substrate of filming and being cut into billet shape test film, by headspace gas chromatography/quality analysis (headspace sampler: the JHS-100A that Japanese analytical industry (strain) is made, gas chromatography/quality analysis apparatus: JEOL JMS-AX505W type mass-synchrometer) analyze.The purging condition is 100 ℃/10min, obtains the peak area of volatile ingredient.Standard substance employing octane (proportion of octane: 0.701, the injection rate IR of octane: 0.02 μ l), as benchmark, obtained the amount of the whole volatile ingredients that are scaled octane with its peak area by following formula.
The amount of volatile ingredient (μ g)=(peak area of the peak area ÷ octane of volatile ingredient) * 0.02 * 0.701.
(3) the screening characteristics evaluation of employing slit die coating process
Adopt the slit die coating process that radiation sensitive linear resin composition (S-1) is coated on the chromium film forming glass of 550 * 650mm.The slit die rate travel is 150mm/ second, be decompressed to 0.5Torr desolventizing, drying after, prebake 3 minutes forms and films in 100 ℃ cleaning oven, again with 2000J/m 2Exposure expose, the formation thickness is the film of 3 μ m above the chromium film forming glass.
This face is shone with sodium vapor lamp, and the coating face is identified in range estimation.When evaluation have striped irregular (before the slit die line direction or with its direction of intersecting on one or more straight line that can observe irregular) time, be evaluated as screening characteristics " * " (bad), when confirming to have a little when a bit, be evaluated as " △ " (bad a little), when not identifying, be evaluated as " zero " (well).
Embodiment 2～13 and 15 and comparative example 1～4
In embodiment 1, each contained composition uses respectively the kind and consumption listed in the table 1 in radiation sensitive linear resin composition, prepares similarly to Example 1 each composition solution and estimates.Polymkeric substance [A] all uses with the polymer solution form, and the consumption in the table 1 (weight portion) is the value that is converted into the weight of contained polymkeric substance in the used polymer solution.In addition, the addition of [B] polymerizable compound and [C] radiation sensitive linear polymerization initiator is respectively the amount with respect to 100 parts by weight polymer [A].
In addition, when [C] radiation sensitive linear polymerization initiator during with amino sensitizer and mercaptan compound coupling, they are listed in [C] radiation sensitive linear polymerization initiator one hurdle in the table 1 in the lump.Evaluation result is listed in table 2.
Embodiment 14 and comparative example 5
The preparation of＜radiation sensitive linear resin composition 〉
As polymkeric substance [A], [B] polymerizable compound and [C] radiation sensitive linear polymerization initiator, use respectively kind listed in the table 1 and consumption, and be dissolved in the propylene glycol methyl ether acetate, making solids content concn is 40 % by weight, in addition, prepare similarly to Example 1 respectively radiation sensitive linear resin composition (S-14) and (s-5).
The evaluation of＜radiation sensitive linear resin composition 〉
Adopt respectively the radiation sensitive linear resin composition (S-14) of above preparation and (s-5), following manufacturing dry film is estimated its transfer printing to glass substrate.Evaluation result is listed in table 2.
(4) dry film is to the evaluation of the transfer printing of glass substrate
[manufacturing of dry film]
Adopt applicator that above-mentioned radiation sensitive linear resin composition is coated on the polyethylene terephthalate that thickness is 38 μ m (PET) film, gained is filmed in 100 ℃ of lower heating desolventizings in 5 minutes, produce at PET and have the radiation sensitive linear dry film that thickness is the radiation sensitive linear layer of 4 μ m.
[to the transfer printing evaluation of glass substrate]
Then, the surface of glass substrate is docked with radiation sensitive linear transfer printing layer surface, it is overlapped with above-mentioned radiation sensitive linear transfer printing dry film, by pressure sintering the radiation sensitive linear dry film is transferred to glass substrate.At this moment, when dry film can be transferred on the glass substrate equably, transfer printing was evaluated as " zero " (well), had on the residual or glass substrate of part dry film the dry film driving fit bad etc. on the basement membrane, dry film can not be transferred to the situation on the glass substrate equably, is evaluated as " * " (bad).
In the table 1, the abbreviation of each composition represents following compound.
B-1: dipentaerythritol acrylate (trade name " KAYARAD DPHA ", Japanese chemical drug (strain) is produced).
B-2: the polymerizable unsaturated compound (trade name " KAYARAD DPHA-40H ", Japanese chemical drug (strain) is produced) that contains the multifunctional urethane acrylate compounds.
B-3: tetramethylol methane tetraacrylate (trade name " ァ ロ ニ ッ Network ス M-450 ", East Asia synthetic (strain) produces).
B-4: ω-carboxyl polycaprolactone single-acrylate (trade name " ァ ロ ニ ッ Network ス M-5300 ", East Asia synthetic (strain) produces).
B-5:1,9-nonanediol diacrylate (trade name " ラ ィ ト ァ Network リ レ one ト 1,9-NDA ", common prosperity society (strain) produces).
C-1: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime) (trade name " ィ Le ガ キ ュァ OX02 ", チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces).
C-2: ethyl ketone; 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-DOX base) methoxybenzoyl base]-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime) (trade name " N-1919 ", (strain) ADEKA produces).
C-3:2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinyl-4-base-phenyl)-butane-1-ketone (trade name " ィ Le ガ キ ュァ 379 ", チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces).
C-4:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
C-5:4,4 '-two (diethylamino) benzophenone.
The C-6:2-mercaptobenzothiazoler.
C-7:2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone (trade name " ィ Le ガ キ ュァ 369 ", チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces).
C-8:2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone (trade name " ィ Le ガ キ ュァ 907 ", チ バ ス ペ シ ャ Le テ ィ one ケ ミ カ Le ズ society produces).
D-1: phenol novolac epoxy resins (trade name " ェ ピ コ one ト 152 ", ジ ャ パ Application ェ Port キ シ レ ジ Application (strain) is produced).
In the table 1, this composition is not added in "-" symbolic representation.
In the table 2, this evaluation is not carried out in "-" symbolic representation.
Figure G2009101270647D00451
Table 2
The composition kind Susceptibility (J/cm 2) The evaluation of the amount of volatile ingredient (μ g) The screening characteristics evaluation of slit die coating process Transfer printing
Embodiment 1 (S-1) 1200 1.42 ○ -
Embodiment 2 (S-2) 1000 1.45 ○ -
Embodiment 3 (S-3) 1000 1.42 ○ -
Embodiment 4 (S-4) 1000 1.44 ○ -
Embodiment 5 (S-5) 1000 1.46 ○ -
Embodiment 6 (S-6) 1200 1.54 ○ -
Embodiment 7 (S-7) 1000 1.55 ○ -
Embodiment 8 (S-8) 1000 1.51 ○ -
Embodiment 9 (S-9) 1000 1.12 ○ -
Embodiment 10 (S-10) 1000 1.12 ○ -
Embodiment 11 (S-11) 1000 2.01 ○ -
Embodiment 12 (S-12) 800 2.05 ○ -
Embodiment 13 (S-13) 800 2.05 ○ -
Embodiment 14 (S-14) - - - ○
Embodiment 15 (S-15) 1000 1.44 ○ -
Comparative example 1 (s-1) 1800 6.01 × -
Comparative example 2 (s-2) 2000 5.15 × -
Comparative example 3 (s-3) 800 7.21 △ -
Comparative example 4 (s-4) 1700 3.07 △ -
Comparative example 5 (s-5) - - - ○

Claims (7)

1. radiation sensitive linear resin composition is characterized in that comprising:
[A] has the n valency group of at least a group selected in the group that is made of carboxyl and acid anhydride and following formula (1) expression, and the ratio (Mw/Mn) of the weight-average molecular weight (Mw) of the polystyrene conversion that is recorded by gel permeation chromatography and the number-average molecular weight (Mn) of polystyrene conversion is 1.0～2.8 polymkeric substance;
[B] polymerizable unsaturated compound; And
[C] radiation sensitive linear polymerization initiator,
Figure FSB00000834552300011
In the formula (1), R IFor methylene or carbon number are 2～10 alkylidene or alkyl methylene, Y be singly-bound ,-CO-,-O-CO-* or-NHCO-*, wherein, with connecting key and the R of " * " IConnect, n is 2～10 integer and X for optional carbon number with one or more ehter bonds is 2～70 n valency alkyl, perhaps n be 3 and X be 3 valency groups of following formula (2) expression, "+" is expressed as connecting key,
Figure FSB00000834552300012
In the formula (2), R IIBe that methylene or carbon number are 2～6 alkylidene independently of one another, " * " is expressed as connecting key separately.
2. radiation sensitive linear resin composition claimed in claim 1, wherein above-mentioned [A] polymkeric substance is that at least (a1) contained the polymkeric substance that at least a unsaturated compound selected in the group that is made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides makes through the free radical polymerization operation in the presence of the compound of following formula (8) expression
In the formula (8), X, Y, R IWith n separately with above-mentioned formula (1) in X, Y, R IIdentical with the definition of n.
3. claim 1 or 2 described radiation sensitive linear resin compositions, wherein the Y in the above-mentioned formula (1) is-O-CO-*, wherein, with connecting key and the R of " * " IConnect.
4. claim 1 or 2 described radiation sensitive linear resin compositions, the separator of using for the manufacture of display element.
5. display element is characterized in that comprising at least in the following order following operation with the manufacture method of separator,
(1) operation of the overlay film of formation radiation sensitive linear resin composition claimed in claim 4,
The operation of (2) at least a portion of this overlay film being exposed,
(3) operation of developing of the overlay film after will exposing, and
(4) operation that heats of the overlay film after will developing.
6. a display element separator is characterized in that by radiation sensitive linear resin composition manufacturing claimed in claim 4.
7. a liquid crystal display cells is characterized in that having display element separator claimed in claim 6.
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