CN106084158A - Solidification compound, cured film, organic EL display device, liquid crystal indicator, touch panel and touch panel display device - Google Patents

Abstract

Even if the present invention provides coating excellence to solidify at low temperatures and also can get the solidification compound of high hardness, the cured film solidification of above-mentioned solidification compound obtained and have the liquid crystal indicator of above-mentioned cured film, organic EL display, touch panel and touch panel display device.Above-mentioned solidification compound contains the alefinically unsaturated compounds as composition A, polymerization initiator as composition B, alkoxysilane compound containing trialkylsilyl group in molecular structure as composition C, organic solvent as components D and the inorganic particulate as composition E, composition A comprises 5 officials can above carbamate (methyl) acrylate, its content content 100 mass parts relative to composition A is 20～100 mass parts, above-mentioned 5 officials can carbamate (methyl) acrylate above to comprise weight average molecular weight be 10, carbamate (methyl) acrylate of more than 000 and molecular weight are 5, carbamate (methyl) acrylate of less than 000.

Description

Solidification compound, cured film, organic EL display, liquid crystal indicator, touch Panel and touch panel display device

Technical field

The present invention relates to solidification compound, cured film, organic EL display, liquid crystal indicator, touch panel and Touch panel display device.

Background technology

The flat faced displays such as liquid crystal indicator, organic EL (Electroluminescence) display device are extensively made With.Additionally, in recent years, along with smart mobile phone, tablet terminal universal, capacitive touch panel attracts attention.Direct capacitance The structure of the sensor base plate of amount formula touch panel is usually has transparency electrode (ITO (indium stannum oxidation on glass or thin film Thing, Indium Tin Oxide) and IZO (indium-zinc oxide, Indium Zinc Oxide) etc.) and metal electrode (silver, copper, Molybdenum, titanium, aluminum etc. and their duplexer and alloy etc.) wiring that is patterned, the cross part of this external wiring has Dielectric film, protection ITO and the protecting film of metal.

As the solidification compound used in such dielectric film or protecting film, such as, disclosed in patent documentation 1 A kind of hot curing resin composition, it is characterised in that its be unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides with containing epoxy radicals The copolymer of free-radical polymerised compound and monoene hydrocarbon system unsaturated compound be dissolved in organic solvent.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 6-157716 publication

Summary of the invention

Invent problem to be solved

Recently, in the manufacturing process of these display etc., from reduce to the damage of substrate, circuit etc., save energetic etc. Viewpoint is set out, and needs the low temperature of the heating-up temperature of various cured film in manufacturing process.

But, the solidification compound described in patent documentation 1 needs heating-up temperature to be more than 200 DEG C, if in low temperature (example Such as less than 180 DEG C and then less than 150 DEG C) under solidify, then can not get sufficient hardness.

Even if problem to be solved by this invention is to provide coating, excellent solidification at low temperatures also can get high hardness Solidification compound.

Additionally, another problem to be solved by this invention is to provide the solidification solidification of above-mentioned solidification compound obtained Film and there is the liquid crystal indicator of above-mentioned cured film, organic EL display, touch panel and touch panel display device.

For the method solving problem

The above-mentioned problem of the present invention is solved by the scheme described in following<1>,<8>or<11>～<14>.With work It is recorded in following together for<2>～<7>,<9>and<10>preferred embodiment.

<1>a kind of solidification compound, it is characterised in that it contains the alefinically unsaturated compounds as composition A, conduct The polymerization initiator of composition B, the alkoxysilane compound containing trialkylsilyl group in molecular structure as composition C, the organic solvent as components D and as composition E Inorganic particulate, composition A comprise 5 officials can above carbamate (methyl) acrylate, above-mentioned 5 officials can above amino first The content of acid esters (methyl) acrylate content 100 mass parts relative to composition A is 20～100 mass parts, and above-mentioned 5 officials can be with On carbamate (methyl) acrylate comprise carbamate (methyl) propylene that weight average molecular weight is more than 10,000 Acid esters and carbamate (methyl) acrylate that molecular weight is less than 5,000.

<2>according to the solidification compound described in<1>, wherein, composition B comprises oxime ester compound.

<3>according to solidification compound described in<1>or<2>, wherein, composition A comprises except above-mentioned 5 officials can above amino Alefinically unsaturated compounds beyond formic acid esters (methyl) acrylate.

<4>according to solidification compound described in<3>, wherein, can above carbamate (methyl) third except above-mentioned 5 officials Alefinically unsaturated compounds beyond olefin(e) acid ester is polyfunctional ethylenically unsaturated compound.

<5>according to the solidification compound according to any one of<1>～<4>, wherein, the content of composition A is relative to solidification Whole organic solid compositions of property compositions are more than 70 mass %.

<6>according to solidification compound according to any one of<1>～<5>, wherein, above-mentioned 5 officials can above amino first Acid esters (methyl) acrylate comprises the two or more carbamate that above-mentioned molecular weight is less than 5,000 (methyl) acrylic acid Ester.

<7>according to the solidification compound according to any one of<1>～<6>, wherein, contain choosing further and freely there is ring The compound of epoxide, there is the compound of oxetanyl, blocked isocyanate compounds and multifunctional sulfhydryl compound group At least one in the group become.

<8>a kind of cured film, it is to be solidified by the solidification compound according to any one of<1>～<7>.

<9>according to the cured film described in<8>, it is protecting film.

<10>according to the cured film described in<8>or<9>, it is according to the lead under load 750g of JIS K5600:1999 mensuration Hardness is more than 3H.

<11>a kind of organic EL display, it has the cured film according to any one of<8>～<10>.

<12>a kind of liquid crystal indicator, it has the cured film according to any one of<8>～<10>.

<13>a kind of touch panel, it has the cured film according to any one of<8>～<10>.

<14>a kind of touch panel display device, it has the cured film according to any one of<8>～<10>.

Invention effect

Even if in accordance with the invention it is possible to providing coating excellence to solidify the solidification that also can get high hardness at low temperatures Property compositions.

Additionally, in accordance with the invention it is possible to provide the cured film solidification of above-mentioned solidification compound obtained and have The liquid crystal indicator of above-mentioned cured film, organic EL display, touch panel and touch panel display device.

Accompanying drawing explanation

Fig. 1 represents the composition concept map of an example of organic EL display.Represent organic EL display dress of bottom emission type The schematic sectional view of the substrate in putting, has planarization film 4.

Fig. 2 represents the composition concept map of an example of liquid crystal indicator.Represent the active matrix base in liquid crystal indicator The schematic sectional view of plate, has the cured film 17 as interlayer dielectric.

Fig. 3 represents the composition concept map of an example of the liquid crystal indicator of the function with touch panel.

Fig. 4 represents the composition concept map of another example of the liquid crystal indicator of the function with touch panel.

Detailed description of the invention

Hereinafter, present disclosure is described in detail.The explanation of constitutive requirements set forth below is based on this sometimes The representative embodiments of invention and carry out, but the present invention is not limited to such embodiment.It addition, the application explanation In book "～" so that the meaning that the numerical value recorded before and after it comprises as lower limit and higher limit is used.Additionally, in the present invention Organic EL element refers to organic electroluminescent device.

In the statement of group (atomic group) in this manual, it is silent on replacement and unsubstituted being expressed in comprises not The group with substituent group is also comprised while there is the group of substituent group.Such as " alkyl " not only comprises and does not have substituent group Alkyl (unsubstituted alkyl), also comprises the alkyl (replacement alkyl) with substituent group.

It addition, in this specification, " (methyl) acrylate " represents acrylate and methacrylate, " (methyl) third Olefin(e) acid " represent acrylic acid and methacrylic acid, " (methyl) acryloyl group " represents acryloyl group and methylacryloyl.

In the present invention, " alefinically unsaturated compounds " etc. is also referred to as " composition A " etc..

Additionally, in the present invention, " quality % " is identical with " weight % " implication, " mass parts " is identical with " weight portion " implication.

Additionally, in the present invention, plural preferred mode be combined as preferred mode.

About the molecular weight of the compound in the present invention, for can determine the low molecular compound of molecular weight, it is to pass through ESI-MS (electrospray ionization mass spectrometry) measures the molecular weight obtained, and for having the compound of the distribution of molecular weight, is set to lead to Cross the Weight-average molecular of the polystyrene conversion measured using oxolane (THF) as the gel permeation chromatography (GPC) during solvent Amount.

(solidification compound)

The solidification compound (following, also referred to as " compositions ") of the present invention is characterised by, containing as composition A's Alefinically unsaturated compounds, as the polymerization initiator of composition B, as the alkoxysilane compound containing trialkylsilyl group in molecular structure of composition C, as components D Organic solvent and as the inorganic particulate of composition E, composition A comprise 5 officials can above carbamate (methyl) acrylate, Above-mentioned 5 officials can the content of above carbamate (methyl) acrylate content 100 mass parts relative to composition A be 20～ 100 mass parts, above-mentioned 5 officials can carbamate (methyl) acrylate above to comprise weight average molecular weight be 10, more than 000 Carbamate (methyl) acrylate and carbamate (methyl) acrylate that molecular weight is less than 5,000.

By comprising these compositions, it is possible to reach taking into account of pencil hardness and coating.Estimate as follows as mechanism.Pass through Use two kinds of carbamate (methyl) acrylate that molecular weight is different, with alkoxysilane compound containing trialkylsilyl group in molecular structure in film after coating The compatibility improve.Think by this coated film is solidified, thus in film, there is the soft chain from carbamate equably Section and from (methyl) acrylate or the hard segment of alkoxy silane, it is possible to reach scar when measuring pencil hardness and prevents The peeling only and brought by distractive load prevents.Additionally, when being applied to have on the concavo-convex substrates such as electrode in substrate, if using The compositions being only made up of the composition that molecular weight is high, uneven thickness or generation along concavo-convex generation coated film the most sometimes exists The extension of end solution of coating becomes the unfavorable condition such as uneven.On the other hand, only it is being made up of the composition that molecular weight is low In the case of, the extension of the solution of the end being sometimes coated with also can become excessive.Additionally, the hardness of film also occurs bad sometimes Change.The compositions of presumption the application of the invention, it is possible to solve above-mentioned problem.

The solidification compound of the present invention can also comprise further except 5 officials can above carbamate (methyl) propylene Other the one-tenth such as the alefinically unsaturated compounds beyond acid esters, multifunctional sulfhydryl compound and/or blocked isocyanate compounds Point.

Composition A: alefinically unsaturated compounds

The solidification compound of the present invention contains the alefinically unsaturated compounds as composition A.

Additionally, the solidification compound of the present invention contain 5 officials can above carbamate (methyl) acrylate conduct Alefinically unsaturated compounds.

As long as the alefinically unsaturated compounds in the present invention has ethylenic unsaturated bond, can be low molecularization Compound, it is also possible to be oligomer, it is also possible to be polymer.

Additionally, the content of alefinically unsaturated compounds is preferably 40 in whole organic solid compositions of solidification compound More than quality %, more than more preferably 50 mass %, more preferably more than 60 mass %, particularly preferably 70 mass % with On.The upper limit does not has special provision, but below preferably 100 mass %, below more preferably 99 mass %, and more preferably 98 Below quality %, below particularly preferably 95 mass %.

Additionally, in the case of the inorganic particulate stated after engagement, the content of alefinically unsaturated compounds combines in curable The all solids composition of thing is preferably below 80 mass %, below more preferably 75 mass %.As lower limit, preferably 20 More than quality %, more than more preferably 30 mass %, more preferably more than 40 mass %, particularly preferably 50 mass % with On.It addition, " solid constituent " in solidification compound represents the composition in addition to the volatile ingredients such as organic solvent, curable " organic solid composition " in compositions represents in addition to the volatile ingredients such as inorganic constituents and organic solvent such as inorganic particulate Composition.

It addition, in the present invention, as alefinically unsaturated compounds and the change that is equivalent to alkoxysilane compound containing trialkylsilyl group in molecular structure described later Compound, the compound i.e. with alkoxysilyl and olefinic unsaturated group are set to alkoxysilane compound containing trialkylsilyl group in molecular structure.

Additionally, in the present invention, carbamate (methyl) acrylate is to have the amino-formate bond and 1 of more than 1 The compound of individual above (methyl) acryloxy.

<5 officials can carbamate (methyl) acrylate>above

In the solidification compound of the present invention, 5 officials can the content of above carbamate (methyl) acrylate relative Content 100 mass parts in composition A is 20～100 mass parts, preferably 20～69 mass parts.If above-mentioned scope, the most permissible More effectively play the effect of the present invention.

5 officials the number of (methyl) acryloxy in carbamate (methyl) acrylate above can be preferably 6 Above, more preferably more than 10, particularly preferably more than 12.By being set to such composition, can more effectively play this Bright effect.

Additionally, the upper limit of the number of above-mentioned (methyl) acryloxy is not particularly limited, but preferably less than 500, In the case of not being macromolecular structure, more preferably less than 50, more preferably less than 30, particularly preferably less than 20.

The solidification compound of the present invention can only comprise a kind of 5 officials can above carbamate (methyl) acrylic acid Ester, it is also possible to comprise two or more.Comprise two or more in the case of, preferably total amount reaches above-mentioned scope.

As 5 officials that can use in the present invention can above carbamate (methyl) acrylate, profit can be exemplified The carbamate addition polymerization compound manufactured with isocyanates and the additive reaction of hydroxyl, can exemplify Japanese Unexamined Patent Publication As described in clear 51-37193 publication, Japanese Patent Publication 2-32293 publication, Japanese Patent Publication 2-16765 publication Urethane acrylate class, their record is included in present specification.

5 officials can (methyl) acryloxy in carbamate (methyl) acrylate above can be acryloyl-oxy Any one in base, methacryloxy, it is also possible to be both, but preferably acryloxy.

5 officials can carbamate (methyl) acrylate above be preferably 5 officials can above aliphatic carbamate (methyl) acrylate.

Additionally, 5 officials can preferably have isocyanuric acid class ring structure by carbamate (methyl) acrylate above.

Additionally, 5 officials can be preferably by the carbamic acid with more than 1 by carbamate (methyl) acrylate above The core part of ester bond and being bonded with core part and chemical combination that the end section of (methyl) acryloxy with more than 1 is constituted Thing, has more preferably been bonded the compound of the above-mentioned end part of more than 2 in above-mentioned core part.

5 officials can preferably at least have following formula Ae-1 or formula Ae-2 institute by carbamate (methyl) acrylate above The compound of the group shown, more preferably at least has the compound of the group shown in following formula Ae-1.Additionally, 5 officials can more than Carbamate (methyl) acrylate more preferably there are more than 2 choosing groups shown in free following formula Ae-1 and formula The compound of the group in the group of the group composition shown in Ae-2.

Additionally, 5 officials the above-mentioned end part in carbamate (methyl) acrylate above can be preferably following formula Group shown in Ae-1 or formula Ae-2.

[chemical formula 1]

In formula Ae-1 and formula Ae-2, R separately represents that acryloyl group or methylacryloyl, wave-like line part represent Bonding position with other structures.

The solidification compound of the present invention contains carbamate (methyl) propylene that weight average molecular weight is more than 10,000 Acid esters and carbamate (methyl) acrylate that molecular weight is less than 5,000 can above carbamate (first as 5 officials Base) acrylate.

In the solidification compound of the present invention, weight average molecular weight is carbamate (methyl) acrylic acid of 10, more than 000 The content of ester content 100 mass parts of above carbamate (methyl) acrylate can be preferably 1～90 weights relative to 5 officials Amount part, more preferably 5～70 weight portions, particularly preferably 10～60 weight portions.

In the solidification compound of the present invention, molecular weight is carbamate (methyl) acrylate of 5, less than 000 Content content 100 mass parts of above carbamate (methyl) acrylate can be preferably 10～99 weight relative to 5 officials Part, more preferably 15～95 weight portions, particularly preferably 20～90 weight portions.

<carbamate (methyl) acrylate of more than 10,000<weight average molecular weight be>>

The solidification compound of the present invention contains carbamate (methyl) propylene that weight average molecular weight is more than 10,000 Acid esters can above carbamate (methyl) acrylate as 5 officials.

That is, above-mentioned weight average molecular weight be carbamate (methyl) acrylate of 10, more than 000 be that weight average molecular weight is More than 10,000 and 5 officials can above carbamate (methyl) acrylate.

Above-mentioned weight average molecular weight is that the weight average molecular weight of carbamate (methyl) acrylate of more than 10,000 is preferred It is 10,000～100,000, more preferably 10,000～50,000.

Above-mentioned weight average molecular weight be more than 10,000 carbamate (methyl) acrylate preferably there is following formula The polymer constituting repetitive shown in Aa-1 or formula Aa-2.

[chemical formula 2]

In formula Aa-1 and formula Aa-2, L⁵～L⁸Separately representing the linking group of bivalence, A represents have (methyl) third The group of enoyl-, R^aRepresent hydrogen atom or the alkyl that carbon number is 1～5.

L⁵～L⁸Separately being preferably the alkylidene that carbon number is 2～20, more preferably carbon number is 2～10 Alkylidene, more preferably carbon number is the alkylidene of 4～8.Additionally, above-mentioned alkylidene can also have side chain or ring Structure, but preferably straight-chain alkyl-sub-.

A is preferably the group shown in above-mentioned formula Ae-1 or formula Ae-2.

R^aIt is preferably hydrogen atom or methyl.

<carbamate (methyl) acrylate of less than 5,000<molecular weight be>>

The solidification compound of the present invention contains carbamate (methyl) acrylate that molecular weight is less than 5,000 and makees It is that 5 officials can above carbamate (methyl) acrylate.

That is, above-mentioned molecular weight be carbamate (methyl) acrylate of 5, less than 000 be molecular weight be 5, less than 000 And be that 5 officials can above carbamate (methyl) acrylate.

It addition, the carbamate that above-mentioned molecular weight is 5, less than 000 (methyl) acrylate is that molecular weight has distribution Oligomer or during polymer, above-mentioned molecular weight can also be weight average molecular weight.

Above-mentioned molecular weight is the number of the amino-formate bond in carbamate (methyl) acrylate of less than 5,000 It is not particularly limited, but preferably 1～30, more preferably 1～20, more preferably 2～10, particularly preferably 2～5.

Above-mentioned molecular weight is that the molecular weight of carbamate (methyl) acrylate of less than 5,000 is from cured film hardness Viewpoint is set out, preferably 500～5, and 000, more preferably 800～5,000, particularly preferably 800～3,000.

Above-mentioned 5 officials can preferably comprise two or more above-mentioned molecular weight and be by carbamate (methyl) acrylate above Carbamate (methyl) acrylate of less than 5,000, more preferably comprises 2～ammonia that 4 kind of above-mentioned molecular weight is 5, less than 000 Carbamate (methyl) acrylate, particularly preferably comprises 2 or carbamate (first that 3 kind of above-mentioned molecular weight is 5, less than 000 Base) acrylate.If aforesaid way, then the hardness of obtained cured film is more excellent.

Additionally, (methyl) acryloyl in the carbamate that above-mentioned molecular weight is 5, less than 000 (methyl) acrylate The number of epoxide is preferably 5～30, more preferably 8～25, particularly preferably 10～20.If above-mentioned scope, then obtained by The hardness of cured film is more excellent.

And then, above-mentioned molecular weight be 5, less than 000 carbamate (methyl) acrylate preferably at least have under State the compound of the group shown in formula Ac-1 or formula Ac-2, more preferably at least there is the chemical combination of the group shown in following formula Ac-1 Thing.

Additionally, 5 officials the above-mentioned core part in carbamate (methyl) acrylate above can be preferably following formula Ac- 1 or formula Ac-2 shown in group.

[chemical formula 3]

In formula Ac-1 and formula Ac-2, L¹～L⁴Separately represent the alkyl of the bivalence that carbon number is 2～20, wavy Line part represents the bonding position with other structures.

L¹～L⁴Separately being preferably the alkylidene that carbon number is 2～20, more preferably carbon number is 2～10 Alkylidene, more preferably carbon number is the alkylidene of 4～8.Additionally, above-mentioned alkylidene can also have side chain or ring Structure, but preferably straight-chain alkyl-sub-.

Additionally, the carbamate that above-mentioned molecular weight is 5, less than 000 (methyl) acrylate is particularly preferably above-mentioned formula Group shown in Ac-1 or formula Ac-2 and the choosing freely group shown in above-mentioned formula Ae-1 and the group of the composition of the group shown in formula Ae-2 In the compound of group bonding of 2 or 3.

Hereinafter, the carbamate that above-mentioned molecular weight is 5, less than 000 (methyl) being preferably used in the present invention is exemplified Acrylate, but the present invention is not limited to these certainly.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

As 5 officials can the commercially available product of above carbamate (methyl) acrylate, can exemplify can be by Xin Zhong village Chemical industry Co., Ltd. obtain U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, UA-53H, UA-33H (being registered trade mark), the UA-306H that can be obtained by Kyoeisha Chemical Co., Ltd., UA-306T, UA-306I, UA-510H, the Laromer UA-9048 that can be obtained by BASF AG, UA-9050, PR9052, can be by DAICEL- EBECRYL220 that ALLNEX LTD. obtains, 5129,8301, KRM8200,8200AE, 8452 etc..

<other alefinically unsaturated compounds>

The solidification compound of the present invention can also comprise except 5 officials can above carbamate (methyl) acrylate with Outer alefinically unsaturated compounds (also referred to as " other alefinically unsaturated compounds ") is as composition A.

As except 5 officials can alefinically unsaturated compounds in addition to carbamate (methyl) acrylate above, permissible Macromolecule (such as, molecular weight is 2, more than 000), it is also possible to be monomer (such as, molecular weight less than 2,000, preferred molecular weight It is 100 less than 2,000), preferably monomer.

As except 5 officials can alefinically unsaturated compounds in addition to carbamate (methyl) acrylate above, preferably For polyfunctional ethylenically unsaturated compound, more preferably 3～6 officials can alefinically unsaturated compounds.

As except 5 officials can alefinically unsaturated compounds in addition to carbamate (methyl) acrylate above, preferably For (methyl) acrylate compounds.The number of (methyl) acryloxy of (methyl) acrylate compounds be preferably 2～ 15, more preferably 3～6.By being set to such composition, can more effectively play the effect of the present invention.

Specifically, can list tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two Tetramethylolmethane five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three ((methyl) acryloyl-oxyethyl) Isocyanuric acid ester, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylated epoxy ethane (EO) Modified body, dipentaerythritol six (methyl) acrylate EO modification body etc..

Additionally, as other alefinically unsaturated compounds, it is also possible to comprising 4 officials can following carbamate (methyl) Acrylate.

As 4 officials can following carbamate (methyl) acrylate, following compound can be exemplified.

[chemical formula 7]

[chemical formula 8]

The solidification compound of the present invention comprises except 5 officials can alkene in addition to carbamate (methyl) acrylate above During ethylenically unsaturated compounds, except 5 officials can alefinically unsaturated compounds in addition to carbamate (methyl) acrylate above Content be preferably the scope of 0.1～50 mass % relative to whole organic solid compositions of solidification compound, more preferably The scope of 0.5～40 mass %, the more preferably scope of 1～25 mass %.

The solidification compound of the present invention can only comprise a kind can above carbamate (methyl) acrylic acid except 5 officials Alefinically unsaturated compounds beyond ester, it is also possible to comprise two or more.Comprise two or more in the case of, preferably total amount Reach above-mentioned scope.

Composition B: polymerization initiator

The solidification compound of the present invention contains the polymerization initiator as composition B.

As polymerization initiator, preferably comprise radical polymerization initiator.

The radical polymerization initiator that can use in the present invention is can be caused by light and/or heat, promote that olefinic is not The compound of the polymerization of saturated compounds.Wherein, preferably Photoepolymerizationinitiater initiater, more preferably optical free radical polymerization initiator.

So-called " light ", as long as irradiate the activity energy that can give the energy that can be produced initiation kind by composition B by it Amount line, then be not particularly limited, extensively comprise alpha ray, gamma-rays, X-ray, ultraviolet (UV), luminous ray, electron ray Deng.In them, preferably at least bag light with violet rays.

As Photoepolymerizationinitiater initiater, include, for example out oxime ester compound, halogenated organic compound, diazole compounds, Carbonyl compound, ketal compound, benzoin compound, acridine compounds, organic peroxy compound, azo-compound, perfume (or spice) Legumin compound, azido compound, Metallocenic compound, six aryl united imidazoles, organic boric acid compounds, disulfonated Compound, salt compound, acylphosphanes (oxide) compound.In them, from the aspect of sensitivity, preferably oxime ester compound And/or six aryl united imidazole, more preferably oxime ester compound.

As oxime ester compound, it is possible to use Japanese Unexamined Patent Publication 2000-80068 publication, Japanese Unexamined Patent Publication No. 2001-233842 number Publication, Japanese Unexamined Patent Application Publication 2004-534797 publication, Japanese Unexamined Patent Publication 2007-231000 publication, Japanese Unexamined Patent Publication 2009-134289 Number publication and the compound described in paragraph 0046～0059 of No. 2012/057165 publication of International Publication.

As the example of halogenated organic compound, specifically, if can list " Bull Chem.Soc.Japan " such as woodss 42,2924 (1969), No. 3,905,815 description of U.S. Patent No., Japanese Patent Publication 46-4605 publication, Japanese Laid-Open Patent Publication 48-36281 publication, Japanese Laid-Open Patent Publication 55-32070 publication, Japanese Laid-Open Patent Publication 60-239736 publication, Japanese Laid-Open Patent Publication 61-169835 publication, Japanese Laid-Open Patent Publication 61-169837 publication, Japanese Laid-Open Patent Publication 62-58241 publication, Japanese Laid-Open Patent Publication 62-212401 publication, Japanese Laid-Open Patent Publication 63-70243 publication, Japanese Laid-Open Patent Publication 63-298339 publication, M.P.Hutt, Compound described in et al., " Journal of Heterocyclic Chemistry " 7,511 (1970) etc., particularly The substituted azole compounds of trihalomethyl group, s-triaizine compounds can be listed.

As the example of six aryl united imidazoles, include, for example out Japanese Patent Publication 6-29285 publication, the U.S. Described in each description such as patent the 3,479,185th, U.S. Patent No. 4,311,783, U.S. Patent No. 4,622,286 Various compounds.

As acylphosphanes (oxide) compound, monoacylphosphine oxides compound and bisacylphosphine oxides can be exemplified Compound, specifically, include, for example out the IRGACURE 819 of BASF AG, DAROCUR 4265, DAROCUR TPO Deng.

Polymerization initiator can use a kind or be used in combination of two or more.

Whole relative in solidification compound of the total amount of the Photoepolymerizationinitiater initiater in the solidification compound of the present invention Solid constituent is preferably 0.5～30 mass %, more preferably 1～20 mass %, more preferably 1～10 mass %, especially It is preferably 2～5 mass %.

<sensitizer>

In the solidification compound of the present invention, in addition to polymerization initiator, it is also possible to add sensitizer.

As the typical sensitizer that can use in the present invention, can list Crivello (J.V.Crivello, Adv.in Polymer Sci., 62,1 (1984)) material disclosed in, specifically, can list pyrene, acridine orange, thiophene Ton ketone, CTX, benzoflavine (benzoflavin), N-VCz, 9,10-dibutoxy anthracene, anthraquinone, tonkabean Element, ketone coumarin, phenanthrene, camphorquinone, phenothiazine derivative etc..Sensitizer is excellent relative to content 100 mass parts of polymerization initiator The ratio with 50～200 mass parts is selected to add.

Composition C: alkoxysilane compound containing trialkylsilyl group in molecular structure

The solidification compound of the present invention contains the alkoxysilane compound containing trialkylsilyl group in molecular structure as composition C.If use alkoxy silane Compound, then the hardness of coating and obtained cured film is excellent, it is possible to increase by the solidification compound shape of the present invention The film become and the adaptation of substrate.

As alkoxysilane compound containing trialkylsilyl group in molecular structure, as long as at least have the alkoxyl group with silicon atom Direct Bonding Compound, then be not particularly limited, but preferably has the chemical combination of dialkoxy silicyl and/or trialkoxysilyl Thing, more preferably has the compound of trialkoxysilyl.

Additionally, as alkoxysilane compound containing trialkylsilyl group in molecular structure, there is olefinic unsaturated as silane coupler the most described later Base and/or the alkoxysilane compound containing trialkylsilyl group in molecular structure of epoxy radicals.

The alkoxysilane compound containing trialkylsilyl group in molecular structure that can use in the solidification compound of the present invention preferably make base material, such as silicon, The compound that the adaptation of the metals such as the silicon compound such as silicon oxide, silicon nitride, gold, copper, molybdenum, titanium, aluminum and dielectric film improves.Specifically For, known silane coupler etc. is also effective.If using the silane coupler with olefinic unsaturated group, the most particularly With the excellent adhesion of ITO, it is advantageous to.If it is additionally, use the silane coupler with epoxy radicals, the most of excellent in reliability.

As silane coupler, include, for example out gamma-amino propyl trimethoxy silicane, gamma-amino propyl group three ethoxy Base silane, γ-glycidoxypropyl group trialkoxy silane, γ-glycidoxypropyl group dialkoxy silicane, γ-methyl-prop Alkene propyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl tri-alkoxy Silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes and vinyl three alcoxyl Base silane.In them, more preferably γ-methacryloxypropyl trialkoxy silane, γ-acryloxypropyl three alcoxyl Base silane, vinyl trialkyl oxysilane and/or γ-glycidoxypropyl group trialkoxy silane.They can be used alone 1 Plant or be used in combination of two or more.

As commercially available product, can exemplify the KBM-403 of Shin-Etsu Chemial Co., Ltd, KBM-5103, KBM-303, KBM-503, KBE-503, KBM-3103 and KBE-403 etc..

Complete relative to solidification compound of the content of the alkoxysilane compound containing trialkylsilyl group in molecular structure in the solidification compound of the present invention Portion's solid constituent is preferably 0.1～30 mass %, more preferably 0.5～15 mass %, more preferably 2～10 mass %. Alkoxysilane compound containing trialkylsilyl group in molecular structure can be only a kind, it is also possible to comprises two or more.When comprising two or more, preferably total amount reaches To above-mentioned scope.

Components D: organic solvent

The solidification compound of the present invention contains the organic solvent as components D.The solidification compound of the present invention is preferred Dissolve as using composition A, composition B, composition C and composition E and any composition described later as essential component or be distributed to organic The solution obtained in solvent is modulated.

As the organic solvent used in the solidification compound of the present invention, it is possible to use known solvent, can illustrate Go out ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, Propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalky lether second Esters of gallic acid, dipropylene glycol monoalkylether class, butanediol oxalic acid esters, dipropylene glycol dialkyl ether, dipropylene glycol monoalkyl Ether acetic acid esters, alcohols, esters, ketone, amide-type and lactone etc..As the object lesson of these organic solvents, Ke Yican Paragraph 0062 according to Japanese Unexamined Patent Publication 2009-098616 publication.

Specifically, preferably propylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl Ether, propylene glycol monomethyl ether, 1,3 butylene glycol diacetate esters, adnoral acetate, propylene-glycol diacetate and/or tetrahydrofurfuryl Alcohol.

From the viewpoint of coating, the boiling point of organic solvent is preferably 100 DEG C～300 DEG C, more preferably 120 DEG C～ 250℃。

The organic solvent that can use in the present invention can be used alone a kind or by two or more and use.Further preferably will boiling The different solvent of point is also used.

From the viewpoint of being adjusted to the viscosity being suitable for coating, the organic solvent in the solidification compound of the present invention Content is preferably 100～3 relative to all solids composition 100 mass parts of solidification compound, 000 mass parts, more preferably 200～2,000 mass parts, more preferably 250～1,000 mass parts.

As the solid constituent amount of the solidification compound of the present invention, preferably 3～50 mass %, more preferably 20～40 Quality %.

The viscosity of the solidification compound of the present invention is preferably 1～200mPa s, and more preferably 2～100mPa s, It is preferably 3～80mPa s.Viscosity the most such as uses the RE-80L type rotating cylinder viscometer of Toki Sangyo Co., Ltd. 25 It is measured at ± 0.2 DEG C.About rotary speed when measuring, preferably carry out with 100rpm when viscosity is less than 5mPa s, viscosity Preferably carrying out with 50rpm during for 5mPa s less than 10mPa s, concentration is that 10mPa s is less than 30mPa s Shi Youxuan is carried out with 20rpm, and viscosity is that more than 30mPa s is preferably carried out with 10rpm.

Composition E: inorganic particulate

The solidification compound of the present invention contains the inorganic particulate as composition E.By containing inorganic particulate, cured film Hardness becomes excellent.Furthermore it is possible to improve the adaptation with substrate.

The mean diameter of inorganic particulate used in the present invention is preferably 1～200nm, more preferably 5～100nm, especially It is preferably 5～50nm.Mean diameter refer to the particle diameter by arbitrary 200 particles of determination of electron microscopy and obtain its calculate Art is average.Additionally, the shape of particle be not spherical in the case of, using the longest limit as diameter.

Additionally, from the viewpoint of the hardness of cured film, the voidage of inorganic particulate is preferably shorter than 10%, more preferably less than 3%, most preferably there is no space.The voidage of particle is gap and the particle of the cross-sectional image utilizing ultramicroscope to obtain The arithmetic average of 200 of overall area ratio.

As inorganic particulate, preferably metal oxide particle.

It addition, in the metal of metal-oxide in the present invention, also comprise the semimetals such as B, Si, Ge, As, Sb, Te.

As metal oxide particle, preferably comprise Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, The equiatomic metal oxide particle of Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, more preferably selects Free oxidation silicon, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin-oxide and the group of antimony/tin-oxide composition In the particle of metal-oxide, further preferably select free silicon oxide, titanium oxide, titanium composite oxide and zirconium oxide to form The particle of the metal-oxide in group, silicon oxide particle or Titanium particles are from the stability of particle, accessibility, cured film It is particularly preferred that the viewpoints such as hardness, the transparency and refractive index adjustment are set out.

As silicon oxide particle, preferably list silicon dioxide (Silicon stone) particle.

As silicon dioxide granule, as long as the particle wrapping silica containing inorganic oxide does not then have special problem, Preferably comprise silicon dioxide or its hydrate particle as main component (more than preferably 80 mass %).Above-mentioned particle is also Aluminate can be comprised as a small amount of composition (such as less than 5 mass %).As the aluminic acid sometimes comprised as a small amount of composition Salt, can list sodium aluminate, potassium aluminate etc..Additionally, silicon dioxide granule can also comprise sodium hydroxide, potassium hydroxide, hydrogen-oxygen Change the organic salt such as the inorganic salts such as lithium, ammonium hydroxide or Tetramethylammonium hydroxide.As the example of such compound, can example Colloidal silica is shown.

As the disperse medium of colloidal silica, it is not particularly limited, can be water, organic solvent and their mixing Any one in thing.They can be used alone a kind, it is also possible to by two or more and use.

In the present invention, particle can also be as by using ball mill, rod mill etc. in suitable dispersant and solvent Mixing arrangement carry out the dispersion liquid that mixes and/or disperse and modulate and for using.It addition, the solidification compound of the present invention In, colloidal silica not necessarily exists with colloidal state.

From the viewpoint of hardness, the content of the inorganic particulate in the solidification compound of the present invention is relative to curable group All solids composition 100 mass parts of compound is preferably more than 1 mass parts, more than more preferably 5 mass parts, more preferably More than 10 mass parts.Furthermore it is preferred that be below 80 mass parts, below more preferably 50 mass parts, more preferably 40 mass Below Fen, below particularly preferably 30 mass parts.

Inorganic particulate can only comprise a kind, it is also possible to comprises two or more.Comprise two or more in the case of, preferably Its total amount reaches above-mentioned scope.

< compound with epoxy radicals, the compound with oxetanyl, blocked isocyanate compounds, many officials The curable compound in addition to composition A～composition C of energy sulfhydryl compound etc. >

The solidification compound of the present invention preferably comprises and carries out solidifying by heat or light in addition to composition A～composition C Composition i.e. curable compound, more preferably comprises choosing and freely has the compound of epoxy radicals, has the chemical combination of oxetanyl At least one in the group of thing, blocked isocyanate compounds and multifunctional sulfhydryl compound composition.If aforesaid way, then institute The hardness of the solidfied material obtained is more excellent.

<<there is the compound of epoxy radicals>>

The solidification compound of the present invention can also comprise the compound with epoxy radicals.There is the compound of epoxy radicals also Can have 1 epoxy radicals in the molecule, but preferably more than 2.

As the object lesson of the compound of the epoxy radicals in intramolecular with more than 2, bisphenol type epoxy can be listed Resin, bisphenol f type epoxy resin, novolac type epoxy resins, cresol novolac type epoxy resin, aliphatic epoxy Resin etc..

They can obtain as commercially available product.Such as, as bisphenol A type epoxy resin, for JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (more than, Japan Epoxy Resin Co., Ltd. system), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (more than, Dainippon Ink Chemicals's system) etc., as bisphenol f type epoxy resin, for JER806, JER807, JER4004, JER4005, JER4007, JER4010 (more than, Japan Epoxy Resin Co., Ltd. system), EPICLON830, EPICLON835 (are DIC strain formula above Commercial firm's system), LCE-21, RE-602S (is Nippon Kayaku K. K system above) etc., as novolac type epoxy tree Fat, for JER152, JER154, JER157S70, JER157S65 (be above Japan Epoxy Resin Co., Ltd. system), EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775 (being Dainippon Ink Chemicals's system above) etc., make For cresol novolac type epoxy resin, for EPICLONN-660, EPICLONN-665, EPICLONN-670, EPICLONN- 673, EPICLONN-680, EPICLONN-690, EPICLONN-695 (is Dainippon Ink Chemicals system above), EOCN-1020 (with Upper for Nippon Kayaku K. K's system) etc., as aliphatic epoxy resin, for ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (is Asahi Denka Co., Ltd. system above), CELLOXIDE 2021P, CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、EHPE3150、EPOLEAD PB 3600、EPOLEAD PB 4700 (being Daicel Chemical Industries. above, Ltd. system) etc..Additionally, ADEKA RESIN can be listed EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (more than For Asahi Denka Co., Ltd.'s system), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 be (above for strain Formula commercial firm ADEKA system) etc..

In addition it is also possible to suitably use Japanese Patent Publication 58-49860 publication, Japanese Patent Publication 56-17654 publication, There is skeletal oxirane described in Japanese Patent Publication 62-39417 publication or Japanese Patent Publication 62-39418 publication Carbamate compounds class, their content is included in present specification.

When the solidification compound of the present invention comprises the compound with epoxy radicals, there is the content of the compound of epoxy radicals The scope of 0.1～20 mass %, more preferably 0.5～10 matter it are preferably relative to all solids composition of solidification compound The scope of amount %, the more preferably scope of 1～5 mass %.

The solidification compound of the present invention can only comprise a kind of compound with epoxy radicals, it is also possible to comprise two kinds with On.Comprise two or more in the case of, preferably total amount reaches above-mentioned scope.

<<there is the compound of oxetanyl>>

The solidification compound of the present invention can also comprise the compound with oxetanyl.There is oxetanes The compound of base can also have 1 oxetanyl in the molecule, but preferably more than 2.

Object lesson as the compound with oxetanyl, it is possible to use ARON OXETANE OXT-121, OXT-221, OX-SQ, PNOX (being Toagosei Co., Ltd's system above).

Additionally, the compound comprising oxetanyl preferably individually or is used in mixed way with the compound comprising epoxy radicals.

When the solidification compound of the present invention comprises the compound with oxetanyl, there is oxetanyl The content of compound is preferably the scope of 0.1～20 mass % relative to all solids composition of solidification compound, more preferably It is the scope of 0.5～10 mass %, the more preferably scope of 1～5 mass %.

The solidification compound of the present invention can only comprise a kind of compound with oxetanyl, it is also possible to comprises Two or more.Comprise two or more in the case of, preferably total amount reaches above-mentioned scope.

<<blocked isocyanate compounds>>

The solidification compound of the present invention can also comprise blocked isocyanate compounds.

As blocked isocyanate compounds, as long as the compound with blocked isocyanate base limits the most especially System, from the viewpoint of curable, preferably 1 intramolecular has the compound of the blocked isocyanate base of more than 2.Block different The upper limit of the number of cyanic acid ester group does not has a special provision, but preferably less than 6.

Additionally, as blocked isocyanate compounds, its skeleton is not particularly limited, as long as 1 molecule has 2 different The compound of cyanic acid ester group can be then any compound, can be aliphatic, alicyclic or aromatic polyisocyanate.Example As can suitably use 2,4-first phenylene diisocyanate, 2,6-first phenylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-front three Base hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1, 10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, diphenylmethyl Alkane-4,4 '-diisocyanate, o-Dimethylbenzene diisocyanate, m xylene diisocyanate, xylol diisocyanate, Di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexamethylene-1,3-dimethylene diisocyanate, hexamethylene-1,4-dimethylene two Isocyanates, 1,5-naphthalene diisocyanate, to phenylene diisocyanate, 3,3 '-xylene support-4,4 '-two Carbimide .s Ester, 4,4 '-diphenyl ether diisocyanate, tetrachloro phenylene diisocyanate, norbornene alkyl diisocyanate, hydrogenation 1,3-benzene two Methyl diisocyanate, the hydrogenation isocyanate compound such as 1,4-xylylene diisocyanate and derived from by these compounds The compound of the skeleton of prepolymer type.In them, particularly preferred first phenylene diisocyanate (TDI), diphenyl methane two isocyanide Acid esters (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).

As the precursor structure of the blocked isocyanate compounds in the solidification compound of the present invention, contracting two can be listed Urea type, isocyanurate type, adduct type, 2 functional prepolymer types etc..

As forming the end-capping reagent of closed-end structure of above-mentioned blocked isocyanate compounds, oxime compound, interior can be listed Amide compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, Imidazole compound, imide series compound etc..In them, particularly preferably close selected from oxime compound, lactam compound, phenolate End-capping reagent in thing, alcoholic compound, amines, activity methene compound, pyrazole compound.

The blocked isocyanate compounds that can use in the solidification compound of the present invention can obtain as commercially available product , such as can be preferably used CORONATE AP-STABLE M, CORONATE 2503,2515,2507,2513,2555, MILLIONATE MS-50 (being Nippon Polyurethane Industry Co. above, Ltd. system), TAKENATE B- 830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (are Mitsui Chemicals, Inc above System), DURANATE 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF- K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (are Asahi Kasei Chemicals above Corporation system), Desmodur BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur BL3175 (is above Sumika Bayer Urethane Co., Ltd. system) etc..

When the solidification compound of the present invention comprises blocked isocyanate compounds, the content of blocked isocyanate compounds The scope of 0.1～20 mass %, more preferably 0.5～10 matter it are preferably relative to all solids composition of solidification compound The scope of amount %, the more preferably scope of 1～5 mass %.

The solidification compound of the present invention can only comprise a kind of blocked isocyanate compounds, it is also possible to comprise two kinds with On.Comprise two or more in the case of, preferably total amount reaches above-mentioned scope.

<<multifunctional sulfhydryl compound>>

The solidification compound of the present invention can also comprise multifunctional sulfhydryl compound.

As multifunctional sulfhydryl compound, as long as the compound with more than 2 sulfydryls is then not particularly limited, preferably There is the compound of 2～6 sulfydryls, more preferably there is the compound of 2～4 sulfydryls.As multifunctional sulfhydryl compound, preferably The multifunctional sulfhydryl compound of aliphatic.As the preferred example of the multifunctional sulfhydryl compound of aliphatic, can exemplify by fat Race's alkyl and-O-,-C (=O)-the compound that constitutes of combination and at least 2 of hydrogen atom of aliphatic alkyl taken by sulfydryl The compound in generation.

As the multifunctional sulfhydryl compound of aliphatic, tetramethylolmethane four (3-mercaptobutylate), Isosorbide-5-Nitrae-bis-(3-can be listed Sulfydryl butyryl acyloxy) butane etc..As commercially available product, can list such as Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1 (Showa Denko K. K's system) etc..

When the solidification compound of the present invention comprises multifunctional sulfhydryl compound, the content of multifunctional sulfhydryl compound is excellent The scope of 0.1～20 mass % being selected in all solids composition of solidification compound comprises, more preferably in 0.5～10 mass % Scope comprise, the further preferably scope in 1～5 mass % comprises.

The solidification compound of the present invention can only comprise a kind of multifunctional sulfhydryl compound, it is also possible to comprises two or more. Comprise two or more in the case of, preferably total amount reaches above-mentioned scope.

<<polythiaether compound>>

Additionally, the solidification compound of the present invention can also comprise polythiaether compound.By containing polythiaether compound, Available base material adaptation and the cured film of excellent moisture resistance.

It is not particularly limited as long as polythiaether compound has polythiaether key, it is however preferred to have disulfide key, trithioether Key, four thioether bonds, five thioether bonds, the compound of six thioether bonds, more preferably have disulfide key, trithio ehter bond, four thioether bonds Compound, more preferably there is disulfide key or the compound of four thioether bonds.If using and there are disulfide key or four thioether bonds Compound, then moisture-proof is more excellent.

It addition, polythiaether key can be straight-chain, branched or ring-type in any one, but many sulfur of preferably straight-chain Ehter bond.

Additionally, as polythiaether compound, be preferably bonded with aliphatic alkyl, aromatic series respectively in the both sides of polythiaether key Alkyl, heterocyclic radical or the compound of the group of 1 valency they 2 combination of the above obtained, more preferably at the two of polythiaether key Side is bonded with aliphatic alkyl, aromatic hydrocarbyl or the chemical combination of the group of 1 valency they 2 combination of the above obtained respectively Thing.Above-mentioned aliphatic alkyl, aromatic hydrocarbyl or heterocyclic radical can also have substituent group.Alternatively base, is not particularly limited, Can list aliphatic alkyl, aromatic hydrocarbyl, heterocyclic radical, halogen atom, carboxyl, amide groups, alkoxyl, alkoxy carbonyl, Silicyl etc..Wherein, particularly preferably there is trialkoxysilyl alternatively base.That is, as polythiaether compound, special The compound of the aliphatic alkyl with trialkoxysilyl the most preferably it is bonded with respectively in the both sides of polythiaether key.

The object lesson of polythiaether compound described below, but the present invention is not limited to following object lesson.It addition, In following formula, Ph represents that phenyl, Me represent that methyl, Et represent ethyl.

[chemical formula 9]

In the present invention, polythiaether compound can be used alone a kind, it is also possible to by two or more and use.

In the present invention, the content of polythiaether compound, relative to all solids composition of solidification compound, is preferably 0.01～20 mass %, more preferably 0.1～10 mass %, more preferably 0.5～5 mass %.If above-mentioned scope, can Obtain the cured film of base material adaptation and excellent moisture resistance.

In the solidification compound of the present invention, it is also possible to comprise without departing from the spirit and scope of the invention except above-mentioned with Outer other compounds (such as, containing alkoxy methyl compound etc.).

As containing alkoxy methyl compound, can list Japanese Unexamined Patent Publication 2011-221494 publication paragraph 0192～ Compound described in 0194.

In the present invention, alefinically unsaturated compounds, there is the compound of epoxy radicals, there is the chemical combination of oxetanyl The total content of thing, blocked isocyanate compounds and multifunctional sulfhydryl compound preferably comprises leading to included in solidification compound Overheated or light carries out more than 90 mass % of the total amount of composition that solidify (more than more preferably 95 mass %), olefinic unsaturation The total content of compound and blocked isocyanate compounds more preferably accounts for being carried out by heat or light included in solidification compound More than 90 mass % of the total amount of the composition of solidification (more than further preferred 95 mass %).

Additionally, when the compound comprising the compound with epoxy radicals, there is oxetanyl, blocked isocyanate During at least one of compound and multifunctional sulfhydryl compound, in terms of their total, preferably comprise included in solidification compound Carried out 0.1～20 mass % of the total amount of the composition solidified by heat or light, further preferably account for 1～10 mass %.Pass through It is set to such composition, can more effectively play the effect of the present invention.

<surfactant>

The solidification compound of the present invention can also contain surfactant.

As surfactant, it is possible to use any one in anion system, cation system, nonionic system or both sexes, excellent The surfactant of choosing is nonionic system surfactant.Surfactant preferred nonionic system surfactant, more preferably fluorine It it is surfactant.

As the surfactant that can use in the present invention, include, for example out the Megafac as commercially available product F142D、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F183、 Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781、Megafac F781-F、Megafac R30、Megafac R08、Megafac F-472SF、Megafac BL20、Megafac R-61、 Megafac R-90 (Dainippon Ink Chemicals's system), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, NovecFC-4430 (Sumitomo 3M Limited system), AsahiGuard AG7105, AsahiGuard AG7000、AsahiGuard AG950、AsahiGuard AG7600、Surflon S-112、Surflon S- 113、Surflon S-131、Surflon S-141、Surflon S-145、Surflon S-382、Surflon SC-101、 Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, the Surflon SC-106 (rising sun Xiao Zi Co., Ltd. system), EFTOP EF351, EFTOP EF352, EFTOP EF801, EFTOP EF802 (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Ftergent 250 (Neos Corporation system). Additionally, in addition to the foregoing, KP (Shin-Etsu Chemial Co., Ltd's system), POLYFLOW (common prosperity society chemistry strain formula can be listed Commercial firm's system), EFTOP (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Megafac (Dainippon Ink Chemicals's system), Fluorad (Sumitomo 3M Limited system), AsahiGuard, Surflon (Asahi Glass strain formula Commercial firm's system), each series of PolyFox (OMNOVA society system) etc..

Additionally, as surfactant, also can list Japanese Unexamined Patent Publication 2014-238438 publication paragraph 0119～ Compound described in 0123 is as preferred example.

The content of the surfactant in the solidification compound of the present invention is when coordinating, relative to solidification compound All solids composition, preferably 0.001～5.0 mass %, more preferably 0.01～2.0 mass %.

Surfactant can only comprise a kind, it is also possible to comprises two or more.Comprise two or more in the case of, its Preferably total amount reaches above-mentioned scope.

<antioxidant>

The solidification compound of the present invention can also contain antioxidant.As antioxidant, can be containing known anti- Oxidant.By adding antioxidant, have the advantage that the coloring preventing cured film, maybe can reduce because of decomposition The thickness caused reduces, additionally, heat resistant transparent is excellent.

As such antioxidant, include, for example out phosphorous antioxidant, amide-type, hydrazides class, hindered amine system resist Oxidant, sulfur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, saccharide, nitrite, sulphite, sulfur Thiosulfate, hydroxy amine derivatives etc..In them, from the viewpoint of the coloring of cured film, thickness reduce, particularly preferred phenol system Antioxidant, hindered amine system antioxidant, phosphorous antioxidant and/or sulfur system antioxidant, most preferably phenol system antioxidant.It Can be used alone a kind, it is also possible to by two or more mixing.

As object lesson, can list described in the paragraph 0026～0031 of Japanese Unexamined Patent Publication 2005-29515 publication Compound, the compound described in paragraph 0106～0116 of Japanese Unexamined Patent Publication 2011-227106 publication, their content is received Enter in present specification.

As preferred commercially available product, ADEKA STAB AO-60, ADEKA STAB AO-80, ADEKA STAB can be listed AO-412S (being Asahi Denka Co., Ltd.'s system above), IRGANOX 1035, IRGANOX 1098 (above for BASF AG's system).

The content of antioxidant is not particularly limited, but relative to all solids composition of solidification compound, is preferably 0.1～10 mass %, more preferably 0.2～5 mass %, more preferably 0.5～4 mass %.

<polymerization inhibitor>

The solidification compound of the present invention can also contain polymerization inhibitor.So-called polymerization inhibitor is for passing through exposure or heat by gathering Close the polymerization initiation radical composition that initiator produces implement hydrogen for (or hydrogen authorize), energy for (or energy authorize), electricity Son for (or electronics authorize) etc., play the material making polymerization initiation radical inactivate and forbidding being polymerized the effect of initiation.Such as, The compound etc. described in paragraph 0154～0173 of Japanese Unexamined Patent Publication 2007-334322 publication can be used.

As preferred compound, can list phenothiazine, azophenlyene, hydroquinone, 3,5-dibutyl-4-hydroxy-methylbenzene.

The content of polymerization inhibitor is not particularly limited, but relative to all solids composition of solidification compound, is preferably 0.0001～5 mass %.

<binder polymer>

From viewpoints such as resolution and epithelium characteristic raisings, the solidification compound of the present invention can also contain binding agent Polymer.

As binder polymer, it is not particularly limited, it is possible to use known polymer, but it is organic that wire is preferably used Polymer.As such threadlike organic polymers, can arbitrarily use known polymer.Show preferred to water can be carried out Shadow or week-base water development, selection is the threadlike organic polymers of solubility or swellability in water or week-base water.Wire is organic poly- Compound serves not only as peel-forming agent, also can be according to the development as the developer solution relative to water, week-base water or organic solvent system The purposes of agent and select to use.Such as, if using water dissolvable organic polymer, water development can be carried out.As such line Shape organic polymer, can list and have the free radical polyalcohol of carboxylic acid group, such as Japanese Laid-Open Patent Publication No. 59-44615 number at side chain Publication, Japanese Patent Publication 54-34327 publication, Japanese Patent Publication 58-12577 publication, Japanese Patent Publication 54-25957 public affairs Report, Japanese Laid-Open Patent Publication 54-92723 publication, Japanese Laid-Open Patent Publication 59-53836 publication, Japanese Laid-Open Patent Publication 59-71048 publication Described in polymer, i.e., by the resin that there is the monomer homopolymerization of carboxyl or copolymerization and obtain, will have the monomer homopolymerization of anhydride Copolymerization and make anhydride unit hydrolysis or half-esterification or semi-amidation and obtain resin, by epoxy resin with unsaturated monocarboxylic And anhydride modified and that obtain epoxy acrylate etc..As having the monomer of carboxyl, acrylic acid, metering system can be listed Acid, itaconic acid .beta.-methylacrylic acid, maleic acid, fumaric acid, 4-carboxyl styrene etc., as having the monomer of anhydride, can list Malaysia Anhydride etc..

Additionally, also have the same acid cellulose derivant at side chain with carboxylic acid group.This external polymerization with hydroxyl Addition cyclic acid anhydride on thing and the material etc. that obtains is useful.

As binder polymer, it is preferably and (methyl) acrylic acid and other (methyl) acrylic ester copolymer are obtained Acrylic resin.

The content of the binder polymer in the solidification compound of the present invention is not particularly limited, but relative to curable The all solids composition of compositions, preferably 1～40 mass %, more preferably 3～30 mass %, more preferably 4～20 Quality %.

<other composition>

In the solidification compound of the present invention, as required, in addition to the foregoing, can add plasticizer, hot acid produces Other the composition such as agent, acid proliferation generator.About these compositions, such as, can use Japanese Unexamined Patent Publication 2009-98616 publication or day Material described in this JP 2009-244801 publication and material known to other.In addition it is also possible to will " macromolecule interpolation The new of agent launches (Nikkan Kogyo Shimbun of Co., Ltd.) " described in various UV absorbent, metal inactivator etc. adds In the solidification compound of the present invention.

(solidfied material, cured film and their manufacture method)

The solidfied material of the present invention is the solidfied material solidified by the solidification compound of the present invention, is preferably the present invention Solidification compound in organic solvent at least some of remove and solidify and the solidfied material that obtains.As above-mentioned solidification Thing, preferably cured film.Additionally, the solidfied material of the present invention obtains preferably by the manufacture method of the solidfied material of the present invention Solidfied material.

As long as the solidification compound solidification that the manufacture method of the solidfied material of the present invention makes the present invention manufactures solidfied material Method, then be not particularly limited, preferably comprise following (1)～the operation of (3).

(1) operation that the solidification compound of the present invention is applied on substrate

(2) from the solidification compound being coated with, remove the operation of solvent

(3) operation of heat cure is carried out

Additionally, the manufacture method of the solidfied material of the present invention more preferably comprises following (1), (2), (2 ') and the operation of (3).

(1) operation that the solidification compound of the present invention is applied on substrate

(2) from the solidification compound being coated with, remove the operation of organic solvent

The solidification compound eliminating organic solvent is carried out the operation solidified by (2 ') by light

(3) solidfied material solidified by light is carried out further by heat the operation solidified

Additionally, the manufacture method of the solidfied material of the invention described above is preferably the manufacture method of cured film.

In the operation being coated of (1), preferably it is applied on substrate make by the solidification compound of the present invention Wrap solvent-laden moistening film.Before solidification compound is applied on substrate, neutralizing treatment can be carried out or plasma is washed The washing of the substrate washed etc.And then with hexamethyldisiloxane etc., substrate surface can be processed after substrate washs. By carrying out this process, there is the tendency that the adaptation with substrate of solidification compound improves.

As above-mentioned substrate, inorganic substrate, resin, resin composite materials etc. can be listed.

As inorganic substrate, include, for example out glass, quartz, silicon, silicon nitride and on such substrate evaporation have molybdenum, The composite base plate of titanium, aluminum, copper etc..

As resin, can list by polybutylene terephthalate (PBT), polyethylene terephthalate, poly-naphthalene diformazan Acid glycol ester, PBN, polystyrene, Merlon, polysulfones, polyether sulfone, polyarylate, pi-allyl two are sweet Alcohol carbonic ester, polyamide, polyimides, polyamidoimide, Polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene Fluororesin, liquid crystal polymer, acrylic resin, epoxy resin, the organosilicon trees such as hydrocarbon, norbornene resin, polychlorotrifluoroethylene Fat, ionomer resin, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide-alkene are common The substrate that the synthetic resin such as polymers, cellulose, episulfide resin are constituted.The feelings that these substrates directly use with above-mentioned form Condition is less, generally, according to the form of end article, such as, forms TFT (Thin-Film Transistor, thin film transistor (TFT)) unit Multilayer laminate constructions as part.

The solidification compound of the present invention is due to the metal film of masking or metal-oxide close with respect to sputtering Close good, so preferably comprising the metal film of masking by sputtering as substrate.As metal, preferably titanium, copper, aluminum, indium, Stannum, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and their oxide or alloy, more preferably molybdenum, titanium, aluminum, copper and they Alloy.It addition, metal or metal-oxide can be used alone a kind, it is also possible to by multiple and use.

Coating process on substrate is not particularly limited, such as can use ink-jet method, slot coated method, nebulization, The methods such as rolling method, method of spin coating, cast coating method, slit circumgyration, print process.

(2) remove solvent operation in, preferably from the above-mentioned film being coated with, by decompression (vacuum) and/or Heating etc. remove solvent and form dry coating on substrate.The heating condition of solvent removal step be preferably 70～130 DEG C and About 30～300 seconds.Additionally, in above-mentioned solvent removal step, it is not necessary that by the organic solvent in solidification compound Completely remove, as long as being removed at least partially.

And then in the present invention, after (2) remove the operation of solvent and before (3) carry out the operation of heat cure, carry from film hardness From the viewpoint of height, it is also possible to comprise the operation carrying out whole exposure.

Additionally, after (2) remove the operation of solvent and before (3) carry out the operation of heat cure, the viewpoint improved from film hardness Set out, preferably comprise the operation that the solidification compound eliminating organic solvent is carried out by light solidifying by (2 '), more preferably wrap Contain the operation being carried out the solidification compound eliminating organic solvent by whole exposure solidifying.Additionally, in the manner described above that When sample is solidified by light, the solidification compound of the present invention preferably comprises Photoepolymerizationinitiater initiater.

In this case, preferably 50～3,000mJ/cm are carried out with mercury lamp or LED (light emitting diode) lamp etc.²The energy of left and right Amount exposure.

Additionally, in order to form pattern, it is also possible to after the solvent removal step of (2), carry out the operation of pattern exposure, development. The method of pattern exposure is preferably used the methods such as the method for mask or the direct description utilizing laser etc..In the state that oxygen blocks Under carry out these whole exposure or pattern exposure from solidification promote from the viewpoint of be preferred.As the means that oxygen is blocked, Can exemplify and be exposed or arrange oxygen barrier film under nitrogen atmosphere.

About pattern exposure and development, it is possible to use known method, known developer solution.Such as can suitably use day Pattern exposure method described in this JP 2011-186398 publication, Japanese Unexamined Patent Publication 2013-83937 publication and development side Method.

In (3) carry out the operation of heat cure, and the polymerizations such as alefinically unsaturated compounds can be formed solid by heating Change film, it is also possible to solidified further by the solidfied material after solidification.When being polymerized by heating, the curable combination of the present invention Thing preferably comprises thermal polymerization.

As heating-up temperature, preferably less than 180 DEG C, more preferably less than 150 DEG C, more preferably less than 130 DEG C. Lower limit is preferably more than 80 DEG C, more preferably more than 90 DEG C.The method of heating is not particularly limited, it is possible to use known side Method.Include, for example out hot plate, baking oven, infrared heater etc..

Additionally, as heat time heating time, in the case of hot plate preferably 1 minute～about 30 minutes, in addition in the case of Preferably 20 minutes～about 120 minutes.Can solidify in the case of substrate, device are not damaged within the range. From the viewpoint of Adjusting Shape after heating, it is also possible to first carry out heating, carrying out the most at higher temperatures under relatively low temperature Heating (adding of middle roasting procedure.First carry out 90 DEG C, heating in 30 minutes, carry out 120 DEG C, 30 minutes afterwards and add Heat).

The cured film of the present invention is to carry out solidifying the solidification obtained by the film formed by the solidification compound of the present invention Film, is preferably the film solidification formed removing at least some of of organic solvent from the solidification compound of the present invention and obtains The cured film arrived.

The cured film of the present invention suitably can use as protecting film or interlayer dielectric.Additionally, the cured film of the present invention The cured film obtained preferably by the manufacture method of cured film of the present invention.

By the solidification compound of the present invention, also can obtain that there is sufficient hardness even if carrying out at low temperatures solidifying Cured film.Such as, available according to the solidification that pencil hardness is more than 3H under load 750g of JIS K5600:1999 mensuration Film.The protecting film being solidified to form by the solidification compound of the present invention is due to cured film physical properties excellent, so for organic EL Display device or liquid crystal indicator, touch panel, the purposes of touch panel display device are useful.

The solidification compound of the present invention is due to curable and cured film excellent, so as MEMS (Micro Electro Mechanical Systems, MEMS) structure member of equipment, can combine the curable of the present invention Solidfied material or a corrosion-resisting pattern part as partition walls or as mechanical driving member that thing solidifies and obtains assemble and make With.As such MEMS equipment, such as SAW (Surface Acoustic Wave, surface acoustic wave) filtering can be listed Device, BAW (Bulk Acoustic Wave, acoustic bulk wave) wave filter, gyro sensor, display micro-shutter, image sensing The parts such as device, Electronic Paper, ink gun, biochip, sealant.More specifically example is illustrated in Japanese Unexamined Patent Application Publication 2007-522531 In number publication, Japanese Unexamined Patent Publication 2008-250200 publication and Japanese Unexamined Patent Publication 2009-263544 publication etc..

The solidification compound of the present invention is excellent, so can be used for such as Japanese Unexamined Patent Publication due to flatness, the transparency Bank layer (16) described in Fig. 2 of 2011-107476 publication and planarization film (57), Japanese Unexamined Patent Publication 2010-9793 public affairs Report the partition walls (12) described in Fig. 4 (a) and planarization film (102), Japanese Unexamined Patent Publication 2010-27591 publication Figure 10 in The middle note of Fig. 4 (a) of the bank layer (221) recorded and the 3rd interlayer dielectric (216b), Japanese Unexamined Patent Publication 2009-128577 publication Carry the 2nd interlayer dielectric (125) and the 3rd interlayer dielectric (126), Japanese Unexamined Patent Publication 2010-182638 publication Fig. 3 in remember In the formation of the planarization film (12) carried and pixel separation dielectric film (14) etc..In addition it is also possible to be suitable for liquid crystal display dress In putting for the thickness of liquid crystal layer is kept fixing sept, the color filter of liquid crystal indicator or color filter protecting layer, The imaging optical system of the sheet providing color filters of fax, electronic copier, solid-state imager etc. or the lenticule of the joints of optical fibre.

(organic EL display)

The organic EL display of the present invention is characterised by, has the cured film of the present invention.

As the organic EL display of the present invention, formed except having the solidification compound using the invention described above Planarization film or interlayer dielectric beyond be not particularly limited, the known various organic EL taking various structure can be listed Display device or liquid crystal indicator.

Such as, as the object lesson of the TFT that the organic EL display of the present invention is had, can list non-crystalline silicon- TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention is excellent due to electrical characteristics, it is possible to group Close and be preferably used in these TFT.

Fig. 1 is the composition concept map of an example of organic EL display.Represent the organic EL display of bottom emission type In the schematic sectional view of substrate, there is planarization film 4.

Glass substrate 6 forms the TFT1 of bottom gate type, to cover the state formation of this TFT1 by Si₃N₄The insulation constituted Film 3.After formation is omitted here the contact hole of diagram on the insulating film 3, formed on the insulating film 3 via this contact hole and TFT1 The wiring 2 (height is 1.0 μm) connected.Wiring 2 is the organic EL element formed between by TFT1 or by operation below The wiring being connected with TFT1.

And then, in order to will the concavo-convex planarization that produce because the formation of wiring 2, concavo-convex to fill out produce because of wiring 2 The state buried forms planarization film 4 on the insulating film 3.

Planarization film 4 is formed the organic EL element of bottom emission type.That is, on planarization film 4, it is made up of ITO The first electrode 5 be connected via contact hole 7 with wiring 2 and formed.Additionally, the first electrode 5 is equivalent to the anode of organic EL element.

Form the dielectric film 8 of the shape of the periphery covering the first electrode 5, by arranging this dielectric film 8, it is possible to prevent first Electrode 5 and the short circuit passed through between the second electrode that operation thereafter is formed.

And then, although the most do not illustrate, but via desired pattern mask, be deposited with successively and to arrange hole defeated Send layer, organic luminous layer, electron supplying layer, then, whole of surface is formed the second electrode being made up of Al, passes through Use glass for sealing plate and ultraviolet hardening epoxy resin to fit and seal, can get and connect in each organic EL element It is connected to the organic EL display of the active array type of TFT1 for driving it.

(liquid crystal indicator)

The liquid crystal indicator of the present invention is characterised by, has the cured film of the present invention.

As the liquid crystal indicator of the present invention, formed except having the solidification compound using the invention described above It is not particularly limited beyond protecting film, planarization film or interlayer dielectric, the known liquid crystal taking various structure can be listed Display device.

Additionally, the liquid crystal indicator as the present invention can list TN in the liquid crystal drive mode taked (Twisted Nematic, twisted-nematic) mode, VA (Vertical Alignment, vertical orientated) mode, IPS (In- Plane-Switching, in-plane switching) mode, FFS (Fringe Field Switching, fringing field switches) mode, OCB (Optically Compensated Bend, optical compensation curved) mode etc..

In panel is constituted, even the liquid crystal of COA (Color Filter on Array, colour filter array) mode Display device can also use the cured film of the present invention, such as can organic as Japanese Unexamined Patent Publication 2005-284291 publication Dielectric film (115), the organic insulating film (212) of Japanese Unexamined Patent Publication 2005-346054 publication use.Additionally, as the present invention's The liquid crystal orientation film that liquid crystal indicator can be taked concrete aligned, can list friction orientation method, optical alignment method Deng.In addition it is also possible to by described in Japanese Unexamined Patent Publication 2003-149647 publication, Japanese Unexamined Patent Publication 2011-257734 publication PSA (Polymer Sustained Alignment, polymer stabilizing is orientated) technology carries out polymer orientation support.

Additionally, the cured film of the solidification compound of the present invention and the present invention is not limited to such use, can be respectively Plant in purposes and use.Such as, in addition to planarization film, interlayer dielectric, it is also possible to be suitable for protecting film, for liquid crystal In showing device the thickness of liquid crystal layer is kept fixing sept, be arranged in solid-state imager on color filter micro- Mirror etc..

Fig. 2 is the conceptual sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This color liquid crystal Display device 10 is to have the liquid crystal panel of backlight unit 12 overleaf, and liquid crystal panel is configured with and is being pasted with polarizing film Two pieces of glass substrates 14,15 between the element of TFT 16 corresponding to the whole pixel of configuration.It is being formed on glass substrate Each element on, by cured film 17 formed contact hole 18, connect up the ito transparent electrode 19 of tangible pixel electrode.? On ito transparent electrode 19, the layer being provided with liquid crystal 20 and the RGB color filter 22 being configured with black matrix".

As the light source of backlight, it is not particularly limited, it is possible to use known light source.Such as, white can be listed LED, blueness, multi-colored led, fluorescent lamp (cold-cathode tube), organic EL etc. such as red or green.

Additionally, liquid crystal indicator can make the liquid crystal indicator of 3D (stereopsis) type or touch panel type Liquid crystal indicator.And then flexible type can also be made, can be as described in Japanese Unexamined Patent Publication 2011-145686 publication Interlayer dielectric (520) described in 2 interlayer dielectrics (48), Japanese Unexamined Patent Publication 2009-258758 publication uses.

(touch panel and touch panel display device)

The touch panel of the present invention is the touch panel of the cured film with the present invention.

The touch panel display device of the present invention is the touch panel display device of the cured film with the present invention, is preferably There is the touch panel display device of the touch panel of the present invention.

As the touch panel of the present invention, can be to be resistive film mode, capacitance-type, ultrasound wave mode, electromagnetism sense Answer the known modes such as mode.Wherein, preferred capacitance-type.

As touch panel type, so-called embedded (in-cell) type (such as, Japanese Unexamined Patent Application Publication 2012-517051 can be listed The touch panel described in Fig. 5, Fig. 6, Fig. 7 and Fig. 8 of number publication), so-called outer (on-cell) type (such as, Japanese Unexamined Patent Publication Touch panel described in Figure 19 of 2013-168125 publication, Fig. 1, Fig. 5 of Japanese Unexamined Patent Publication 2012-89102 publication remember Carry touch panel), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (such as, Japanese Unexamined Patent Publication Touch panel described in Fig. 2 of 2013-54727 publication and Fig. 2 of Japanese Unexamined Patent Publication 2015-15042 publication, Fig. 3, figure Touch panel described in 4 and Fig. 5), other composition is (such as, described in Fig. 6 of Japanese Unexamined Patent Publication 2013-164871 publication Touch panel) various plug-in (out-cell) type (so-called GG, G1 G2, GFF, GF2, GF1, G1F etc.).

Additionally, Fig. 3 represents the composition concept map of an example of the liquid crystal indicator of the function with touch panel.

Such as, the protecting film between the cured film of the present invention suitably each layer be applicable to Fig. 3, it is suitable for additionally, the most suitable The interlayer dielectric separated between by the detecting electrode of touch panel.It addition, as the detecting electrode of touch panel, be preferably Transparency electrode (ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) etc.) and metal electrode (silver, copper, molybdenum, Titanium, aluminum etc. and their duplexer and alloy etc.) or their duplexer.

In Fig. 3,110 represent pixel substrate, and 140 represent liquid crystal layer, and 120 represent counter substrate, and 130 represent sensor portion. Pixel substrate 110 have successively from the downside of Fig. 3 polaroid 111, transparency carrier 112, common electrode 113, insulating barrier 114, Pixel electrode 115, alignment films 116.Counter substrate 120 has alignment films 121, color filter 122, thoroughly from the downside of Fig. 3 successively Bright substrate 123.Sensor portion 130 is respectively provided with phase-contrast film 124, adhesive linkage 126, polaroid 127.Additionally, in Fig. 3,125 For sensor detecting electrode.The cured film of the present invention can (also referred to as interlayer be exhausted at the insulating barrier (114) of pixel substrate part Velum), various protecting film (not shown), the various protecting film (not shown) of pixel substrate part, counter substrate part various Protecting film (not shown), Sensor section various protecting film (not shown) etc. in use.

In adhesive linkage 126, polaroid 127, it is possible to use known adhesive linkage compositions.

As polaroid, the object lesson of adhesive linkage, the embodiment of Japanese Unexamined Patent Publication 2014-152319 publication can be listed 1, the polaroid of band adhesive linkage described in embodiment 7, embodiment 13, the embodiment of Japanese Unexamined Patent Publication 2014-191005 publication 1, embodiment 3 and the polaroid of band adhesive linkage described in embodiment 6, the embodiment of Japanese Unexamined Patent Publication 2013-100386 publication 1, embodiment 3, embodiment 6, embodiment 11 and the polaroid of the band adhesive linkage described in embodiment 14 and Japanese Unexamined Patent Publication 2013- The embodiment 1 of No. 163783 publications, embodiment 2, embodiment 3 and the adhesive linkage described in embodiment 4.

In adhesive linkage, in order to prevent electrostatic, preferably comprise antistatic additive.

As antistatic additive, it is possible to use known antistatic additive.Such as can use metallic, metal-oxide, Electric conductive polymer and quaternary ammonium salt, lithium salts isoiony compound.

As the object lesson of antistatic additive, can list Japanese Unexamined Patent Publication 2014-191005 publication paragraph 0107～ Antistatic additive described in 0115, the antistatic described in paragraph 0046～0054 of Japanese Unexamined Patent Publication 2013-100386 publication The antistatic additive described in paragraph 0027～0047 of agent and Japanese Unexamined Patent Application Publication 2014-515046 publication.

And then, even the liquid crystal indicator of static drive mode, it also is able to show design by the applicable present invention High pattern.As an example, as the polymer network type liquid crystal as described in Japanese Unexamined Patent Publication 2001-125086 publication Dielectric film can be suitable for the present invention.

Additionally, Fig. 4 is the composition concept map of another example of the liquid crystal indicator of the function with touch panel.

Comprise possess thin film transistor (TFT) (TFT) 440 the bottom display panel 200 being equivalent to thin film transistor display panel and Bottom display panel 200 opposed and on the face opposed with bottom display panel 200, possess multiple color filter 330 be equivalent to color filter The top display panel 300 of display panel and the liquid crystal layer 400 being formed between bottom display panel 200 and top display panel 300. Liquid crystal layer 400 comprises liquid crystal molecule (not shown).

The thin film transistor (TFT) that bottom display panel 200 comprises the 1st insulated substrate 210, is configured on the 1st insulated substrate 210 (TFT), it is formed at the dielectric film 280 of the upper surface of thin film transistor (TFT) (TFT) and is configured at the pixel electricity on dielectric film 280 Pole 290.Thin film transistor (TFT) (TFT) can comprise gate electrode 220, cover the gate insulation film 240 of gate electrode 220, semiconductor layer 250, ohmic contact layer 260,262, source electrode 270 and drain electrode 272.

The mode exposed according to the drain electrode 272 of thin film transistor (TFT) (TFT) on dielectric film 280 forms contact hole 282.

Top display panel 300 comprises in the one side being configured at the 2nd insulated substrate 310 and with the light-blocking member of rectangular arrangement 320, it is configured at the color filter 330 on the 2nd insulated substrate 310 and is configured at the alignment films on light-blocking member 320 and color filter 330 350 and be configured in alignment films 350 and accordingly liquid crystal layer 400 applied voltage with the pixel electrode 290 of bottom display panel 200 Common electrode 370.

In the liquid crystal indicator shown in Fig. 4, the another side of the 2nd insulated substrate 310 is configured with sensing electrode 410, dielectric film 420, drive electrode 430 and protecting film 280.Like this, in the manufacture of the liquid crystal indicator shown in Fig. 4, When forming top display panel 300, the sensing electrode 410 of the element as touch screen, dielectric film 420 can be formed together And drive electrode 430 etc..The cured film particularly solidified by the solidification compound of the present invention and obtain can be suitable for absolutely In velum 420.

On protecting film 280, it is also possible to the band adhesive linkage that illustrates with above-mentioned adhesive linkage 126 and polaroid 127 of fitting inclined Shake sheet or adhesive linkage.

Embodiment

It is exemplified below out embodiment the present invention is more specifically illustrated.Material shown in below example, make Consumption, ratio, process content, process step etc., without departing from the purport of the present invention, can suitably change.Therefore, originally The scope of invention is not limited to object lesson shown below.It addition, unless otherwise specified, " part ", " % " are quality Benchmark.

The synthesis of-1<synthesis example 1:(a-1)>

By hexamethylene diisocyanate trimer (Asahi Kasei Corporation's system, TPA-100) 50.4 parts at toluene solvant Middle mixing, adds U-CAT SA 102 (diazabicylo endecatylene (DBU)-caprylate, San-as curing catalysts Apro Ltd. system) 0.15 part, carry out heating in 1 hour at 60 DEG C under nitrogen atmosphere.Dropping mixing is by dipentaerythritol five wherein Acrylate (using after Aldrich society goods are carried out column purification) 157.4 parts is dissolved into the solution obtained in toluene solvant, Carry out heating in 5 hours under nitrogen atmosphere at 60 DEG C.

After letting cool, reactant mixture silica gel column chromatography is purified, point takes and obtain (a-1)-1.Obtained by (a-1) weight average molecular weight measured by gel permeation chromatography (GPC) of-1 is 15,300.

The synthesis of-2<synthesis example 2:(a-1)>

[chemical formula 10]

By methacrylic acid 2-isocyanato ethyl (116.4 parts) and propylene glycol monomethyl ether (PGMEA, 135.8 parts) mixed solution be heated to 70 DEG C under nitrogen flowing.Being stirred on this mixed solution limit, limit dripped free radical with 2 hours Polymerization initiator V-65 (trade name, 2,2 '-azo double (2,4-methyl pentane nitrile), Wako Pure Chemical Industries, Ltd.'s system, 4 parts) And the mixed solution of PGMEA (135.8 parts).After completion of dropwise addition, at 70 DEG C, carry out reaction in 4 hours.

Acrylic acid 2-hydroxy methacrylate (Tokyo HuaCheng Industry Co., Ltd's system) 87.1 parts is added in obtained polymer, Add p methoxy phenol (Wako Pure Chemical Industries, Ltd.'s system) 0.3 part, U-CAT SA 102 (San-Apro Ltd. system) 0.2 part, at 60 DEG C, carry out heating in 6 hours and obtain (a-1)-2.

Obtained by the weight average molecular weight measured by gel permeation chromatography (GPC) of (a-1)-2 be 30,000.

The synthesis of '-3<synthesis example 3:(a-1)>

[chemical formula 11]

In synthesis example 2, the addition of polymerization initiator V-65 is changed to 8 parts, the addition of PGMEA is all set to 232.7 parts, in addition, operate in the same manner as synthesis example 2, obtain polymer (a-1) '-3.

Obtained by the weight average molecular weight measured by gel permeation chromatography (GPC) of (a-1) '-3 be 8,000.

The synthesis of-1<synthesis example 4:(a-2)>

[chemical formula 12]

By hexamethylene diisocyanate trimer (Asahi Kasei Corporation's system, TPA-100) 50.4 parts and two seasons penta 4 Alcohol five acrylate (uses after Aldrich society goods carry out column purification.) 157.4 parts mix in toluene solvant, add and make For the U-CAT SA 102 (San-Apro Ltd. system) 0.2 part of curing catalysts, carry out 6 hours adding at 60 DEG C under nitrogen atmosphere Heat.

After letting cool, reactant mixture silica gel column chromatography is purified, point takes and obtain (a-2)-1.

The synthesis of-2<synthesis example 5:(a-2)>

[chemical formula 13]

Except the hexamethylene diisocyanate trimer in synthesis example 4 being changed to hexamethylene diisocyanate (east Capital chemical conversion Industrial Co., Ltd system) beyond, carry out synthesizing in the same manner as synthesis example 4, purification and obtain (a-2)-2.

The synthesis of-3<synthesis example 6:(a-2)>

[chemical formula 14]

(will except the Dipentaerythritol Pentaacrylate in synthesis example 5 being changed to pentaerythritol triacrylate Aldrich society goods carry out using after column purification) beyond, carry out synthesizing in the same manner as synthesis example 5, purification and obtain (a-2)-3.

The synthesis of '-4<synthesis example 7:(a-2)>

[chemical formula 15]

Except the Dipentaerythritol Pentaacrylate in synthesis example 4 is changed to acrylic acid 2-hydroxy methacrylate, (Tokyo is melted into Industrial Co., Ltd's system) beyond, carry out synthesizing in the same manner as synthesis example 4, purification and obtain (a-2) '-4.

<carbamate (methyl) acrylate>

(a-1)-1: the urethane acrylate of making, Mw:15,300, functional group number in synthesis example 1: many, tool There is the composition repetitive shown in above-mentioned formula Aa-1.

(a-1)-2: the urethane acrylate of making, Mw:30,000, functional group number in synthesis example 2: many, tool There is the composition repetitive shown in above-mentioned formula Aa-2.

(a-1) '-3: the urethane acrylate of making, Mw:8,000, functional group number in synthesis example 3: many, tool There is the composition repetitive shown in above-mentioned formula Aa-2.

(a-2)-1: the urethane acrylate of making, molecular weight in synthesis example 4: 2,078, functional group number: 15

(a-2)-2: the urethane acrylate of making, molecular weight in synthesis example 5: 1,218, functional group number: 10

(a-2)-3: the urethane acrylate of making, molecular weight in synthesis example 6: 764, functional group number: 6

(a-2) '-4: the urethane acrylate of making, molecular weight in synthesis example 7: 853, functional group number: 3

<alefinically unsaturated compounds in addition to carbamate (methyl) acrylate>

A-1: dipentaerythritol acrylate

A-2: Dipentaerythritol Pentaacrylate

A-3: tetramethylol methane tetraacrylate

It addition, A-1～A-3 uses after the material of Aldrich all carries out column purification.

<composition B: radical polymerization initiator>

B-1: following compound 1, oxime ester compound

[chemical formula 16]

B-2:IRGACURE OXE01 (BASF AG's system), oxime ester compound, following structure

B-3:IRGACURE OXE02 (BASF AG's system), oxime ester compound, following structure

B-4:IRGACURE 907 (BASF AG's system), amino alkylphenone compound, 2-methyl-4 '-(methyl thio)- 2-morpholino propiophenone

[chemical formula 17]

<composition C: alkoxysilane compound containing trialkylsilyl group in molecular structure>

C-1:KBM-403 (3-glycidoxypropyltrime,hoxysilane, Shin-Etsu Chemial Co., Ltd's system)

C-2:KBM-5103 (3-acryloxypropyl trimethoxy silane, Shin-Etsu Chemial Co., Ltd's system)

C-3:KBM-503 (3-methacryloxypropyl trimethoxy silane, Shin-Etsu Chemial Co., Ltd's system)

C-4:KBM-303 (2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, Shin-Etsu Chemial Co., Ltd System)

C-5:KBM-3103 (decyl trimethoxy silane, Shin-Etsu Chemial Co., Ltd's system)

<components D: organic solvent>

D-1: propylene glycol monomethyl ether (Daicel Corporation system)

D-2: Methylethyl diethylene glycol (emulsifying agent Co., Ltd. of Japan system)

D-3:1,3-butanediol diacetate esters

D-4: tetrahydrofurfuryl alcohol

<composition E: inorganic particulate>

(Nissan Chemical Ind Ltd's system, silicon dioxide granule, mean diameter are 10～15nm, consolidate E-1:PMA-ST Body constituent concentration is 30%)

E-2:MIBK-ST-L (Nissan Chemical Ind Ltd's system, silicon dioxide granule, mean diameter be 40～50nm, Solid component concentration is 30%)

E-3:Nanouse OZ-S30K-AC (Zirconia particles, Nissan Chemical Ind Ltd's system, solid component concentration It is 30%)

<multifunctional sulfhydryl compound>

S-1:Karenz MT-PE-1 (tetramethylolmethane four (3-mercaptobutylate), Showa Denko K. K's system), sense Group several 4

S-2:Karenz MT-BD-1 (1,4-double (3-sulfydryl butyryl acyloxy) butane, Showa Denko K. K's system), official Can group several 2

<blocked isocyanate compounds>

(the oxime end-blocking body of isophorone diisocyanate, solid component concentration are 60%, three to S-3:TAKENATE B870N Well KCC system)

(precursor structure has biuret structure, and the envelope that closed-end structure is oxime ester structure to S-4:DURANATE 17B-60P Isocyanate terminated compound, solid component concentration are 60%, Asahi Kasei Chemicals Corporation system)

<epoxide>

S-5:JER157S65 (Mitsubishi Chemical Holdings Corporation system)

<surfactant>

W-1:Megafac F554 (Dainippon Ink Chemicals's system), fluorine system surfactant

W-2:FTX-218 (Neos Corporation system), fluorine system surfactant

<sensitizer>

I-1:DBA (the dibutoxy anthracene of following structure, Kawasaki Kasei Chemicals Ltd.'s system)

[chemical formula 18]

(in formula, Bu represents butyl.)

<antioxidant>

J-1:ADEKA STAB AO-60 (hindered phenol system antioxidant, Asahi Denka Co., Ltd.'s system)

<polymerization inhibitor>

K-1:4-methoxyphenol

(embodiment 1～26 and comparative example 1～6)

<modulation of solidification compound>

As described in table 1 below～table 4, each components matching, stirring are made organic solvent solution and/or Dispersion liquid, filters with the politef filter that aperture is 0.3 μm, obtains the solidification compound of the present invention.Under about State the unit of each composition of table 1～table 4, except the ratio of the composition A in whole organic solid compositions and composition A are relative to entirely Beyond the ratio of portion's solid constituent, for mass parts.Additionally, except blocked isocyanate compounds, inorganic particulate and organic solvent In addition, the mass parts of solid constituent conversion is represented.About blocked isocyanate compounds and inorganic particulate, represent that above-mentioned solid becomes Divide the mass parts of the solution of concentration.It addition, in table "-" represent and do not contain the compound met.

<evaluation of pencil hardness>

It is spun to be deposited with on the glass substrate of titanium by each solidification compound of above-mentioned modulation, carries out 90 DEG C, 120 seconds Prebake conditions, obtains the coated film that thickness is 3.0 μm.Then pass through high voltage mercury lamp and carry out 500mJ/cm²The illumination of (conversion of i ray) Penetrate, and then carry out 120 DEG C, baking in 60 minutes with baking oven, thus make cured film.

Relative to obtained cured film, carry out pencil by the method (load is 750g) according to JIS K5600:1999 Hardness test, carrys out evaluated for film intensity according to following benchmark.A, B and C are usage range.

More than A:6H

B:5H

C:3H or 4H

Below D:2H or film peel off

<evaluation of coating (the moistening autgmentability on the glass substrate of band ITO)>

Each solidification compound is sputtered in the half of 550mm × 650mm ITO (thickness is 0.2 μm) and a semi-nudity Expose and reach the mode of 1.0 μm according to thickness on the glass substrate of glass and carry out slot coated, observe the end of solution.ITO and Two ends of glass are the most consistent more good, if a material side occurs moistening to extend compared with another, then for poor.Described below Metewand.A is usage range.

The difference of the extension of the end of A: solution is less than 300 μm

The difference of the extension of the end of B: solution is more than 300 μm

Table 1

Table 2

Table 3

Table 4

As shown by above-mentioned table 1～table 4, even if the solidification compound of the present invention solidifies at low temperatures, also have There is high hardness, additionally, coating is excellent.

(embodiment 27)

<making of display device>

In the display device shown in Fig. 4, it is respectively used to the solidification compound obtained in each embodiment 1～26 touch The formation of detecting electrode protecting film (dielectric film, 420), makes display device respectively.Specifically, protecting film (420) is to pass through The solidification compound obtained in each embodiment of ink-jet application, is carried out 90 DEG C, the prebake conditions of 120 seconds, is carried out by high voltage mercury lamp 500mJ/cm²The light of (conversion of i ray) irradiates, and then is formed so that baking oven carries out 120 DEG C, 60 minutes toasting.Display device Other part according in Japanese Unexamined Patent Publication 2013-168125 publication as Figure 19 record manufacture method and make.Made Make display device in any one display performance, touch detection performance the most excellent.

The explanation of symbol

1:TFT (thin film transistor (TFT)), 2: wiring, 3: dielectric film, 4: planarization film, 5: the first electrodes, 6: glass substrate, 7: Contact hole, 8: dielectric film, 10: liquid crystal indicator, 12: backlight unit, 14,15: glass substrate, 16:TFT, 17: solidification Film, 18: contact hole, 19:ITO transparency electrode, 20: liquid crystal, 22: color filter, 110: pixel substrate, 111: polaroid, 112: thoroughly Bright substrate, 113: common electrode, 114: insulating barrier, 115: pixel electrode, 116: alignment films, 120: counter substrate, 121: orientation Film, 122: color filter, 123: transparency carrier, 124: phase-contrast film, 126: adhesive linkage, 127: polaroid, 130: sensor portion, 140: liquid crystal layer, 200: bottom display panel, 210: the 1 insulated substrates, 220: gate electrode, 240: gate insulation film, 250: quasiconductor Layer, 260,262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: dielectric film, 282: contact hole, 290: image electricity Pole, 300: top display panel, 310: the 2 insulated substrates, 320: light-blocking member, 330: color filter, 350: alignment films, 370: common Electrode, 400: liquid crystal layer, 410: sensing electrode, 420: dielectric film, 430: drive electrode, 440:TFT.

Claims (14)

1. a solidification compound, it is characterised in that contain:

As composition A alefinically unsaturated compounds,

As composition B polymerization initiator,

As composition C alkoxysilane compound containing trialkylsilyl group in molecular structure,

As components D organic solvent and

As the inorganic particulate of composition E,

Composition A comprise 5 officials can above carbamate (methyl) acrylate,

Described 5 officials can the content of above carbamate (methyl) acrylate content 100 mass parts relative to composition A be 20～100 mass parts,

Described 5 officials can comprise the amino first that weight average molecular weight is more than 10,000 by carbamate (methyl) acrylate above Acid esters (methyl) acrylate and carbamate (methyl) acrylate that molecular weight is less than 5,000.

Solidification compound the most according to claim 1, wherein, composition B comprises oxime ester compound.

Solidification compound the most according to claim 1 and 2, wherein, composition A comprises except described 5 officials can above amino Alefinically unsaturated compounds beyond formic acid esters (methyl) acrylate.

Solidification compound the most according to claim 3, wherein, except described 5 officials can above carbamate (methyl) Alefinically unsaturated compounds beyond acrylate is polyfunctional ethylenically unsaturated compound.

Solidification compound the most according to claim 1 and 2, wherein, the content of composition A is relative to solidification compound All organic solid composition is more than 70 mass %.

Solidification compound the most according to claim 1 and 2, wherein, described 5 officials can above carbamate (methyl) Acrylate comprises the two or more carbamate that described molecular weight is less than 5,000 (methyl) acrylate.

Solidification compound the most according to claim 1 and 2, wherein, contains choosing further and freely has the change of epoxy radicals Compound, have the compound of oxetanyl, blocked isocyanate compounds and multifunctional sulfhydryl compound composition group in At least one.

8. a cured film, it is the cured film solidified by the solidification compound described in claim 1 or 2.

Cured film the most according to claim 8, it is protecting film.

Cured film the most according to claim 8, it is hard according to the pencil under load 750g of JIS K5600:1999 mensuration Degree is more than 3H.

11. 1 kinds of organic EL displays, it has the cured film described in claim 8.

12. a liquid crystal indicator, it has the cured film described in claim 8.

13. 1 kinds of touch panels, it has the cured film described in claim 8.

14. 1 kinds of touch panel display devices, it has the cured film described in claim 8.