CN106084158B - Solidification compound, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device - Google Patents

Abstract

Cured film and liquid crystal display device, organic EL display device, touch panel and touch panel display device with above-mentioned cured film obtained from the present invention provides the solidification compound that coating is excellent, high hardness can be obtained solidifying at low temperature, solidifies above-mentioned solidification compound.Above-mentioned solidification compound contains the olefinic unsaturated compound as ingredient A, polymerization initiator as ingredient B, alkoxysilane compound containing trialkylsilyl group in molecular structure as ingredient C, organic solvent as ingredient D and the inorganic particulate as ingredient E, ingredient A includes carbamate (methyl) acrylate of 5 functions or more, its content is 20~100 mass parts relative to 100 mass parts of content of ingredient A, carbamate (methyl) acrylate more than above-mentioned 5 function includes that weight average molecular weight is 10, 000 or more carbamate (methyl) acrylate and molecular weight is 5, 000 carbamate (methyl) acrylate below.

Description

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

Technical field

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

Background technique

The flat-panel monitors such as liquid crystal display device, organic EL (Electroluminescence) display device are made extensively With.In addition, in recent years, with smart phone, tablet terminal it is universal, capacitive touch panel attracts attention.Direct capacitance The structure of the sensor base plate of amount formula touch panel is usually to have transparent electrode (ITO (indium tin oxidation on glass or film Object, Indium Tin Oxide) and IZO (indium-zinc oxide, Indium Zinc Oxide) etc.) and metal electrode (silver, copper, Molybdenum, titanium, aluminium etc. and their laminated body and alloy etc.) be patterned made of wiring, furthermore have in the cross part of wiring The protective film of insulating film, protection ITO and metal.

As the solidification compound used in such insulating film or protective film, for example, disclosing in patent document 1 A kind of hot curing resin composition, which is characterized in that its be unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides with containing epoxy group Free-radical polymerised compound and monoene hydrocarbon system unsaturated compound copolymer be dissolved into organic solvent made of.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 6-157716 bulletin

Summary of the invention

Problem to be solved by the invention

Recently, energetic etc. from the damage, province reduced to substrate, circuit etc. in the manufacturing process of these displays etc. Viewpoint is set out, and the low temperature of the heating temperature of the various cured films in manufacturing process is needed.

However, it is 200 DEG C or more that the solidification compound recorded in patent document 1, which needs heating temperature, if in low temperature (example As 180 DEG C or less, in turn 150 DEG C or less) under solidify, then cannot get sufficient hardness.

Project to be solved by this invention is to provide that coating is excellent, high hardness can be obtained solidifying at low temperature Solidification compound.

In addition, another project to be solved by this invention is to provide solidification obtained from the solidification of above-mentioned solidification compound Film and liquid crystal display device, organic EL display device, touch panel and touch panel display device with above-mentioned cured film.

The method for solving problem

The above subject of the invention is solved by the scheme recorded in<1>below,<8>or<11>~<14>.With work For preferred embodiment<2>~<7>,<9>and<10>be recorded in together it is following.

<1>a kind of solidification compound, which is characterized in that it contains the olefinic unsaturated compound as ingredient A, conduct The polymerization initiator of ingredient B, the alkoxysilane compound containing trialkylsilyl group in molecular structure as ingredient C, the organic solvent as ingredient D and as ingredient E Inorganic particulate, ingredient A includes carbamate (methyl) acrylate of 5 functions or more, amino first more than above-mentioned 5 function The content of acid esters (methyl) acrylate relative to ingredient A 100 mass parts of content be 20~100 mass parts, above-mentioned 5 function with On carbamate (methyl) acrylate include weight average molecular weight be 10,000 or more carbamate (methyl) propylene Acid esters and molecular weight are 5,000 carbamate (methyl) acrylate below.

<2>solidification compound according to<1>, wherein ingredient B includes oxime ester compound.

<3>solidification compound according to<1>or<2>, wherein ingredient A includes except amino more than above-mentioned 5 function Olefinic unsaturated compound other than formic acid esters (methyl) acrylate.

<4>solidification compound according to<3>, wherein except carbamate (methyl) third more than above-mentioned 5 function Olefinic unsaturated compound other than olefin(e) acid ester is polyfunctional ethylenically unsaturated compound.

<5>solidification compound according to any one of<1>~<4>, wherein the content of ingredient A is relative to solidification Property composition whole organic solid ingredients be 70 mass % or more.

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

<7>solidification compound according to any one of<1>~<6>, wherein further containing selected from by with ring The compound of oxygroup, the compound with oxetanyl, blocked isocyanate compounds and multifunctional sulfhydryl compound group At group in it is at least one kind of.

<8>a kind of cured film, being will be made of the solidification of solidification compound described in any one of<1>~<7>.

<9>cured film according to<8>, is protective film.

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

<11>a kind of organic EL display device, with cured film described in any one of<8>~<10>.

<12>a kind of liquid crystal display device, with cured film described in any one of<8>~<10>.

<13>a kind of touch panel, with cured film described in any one of<8>~<10>.

<14>a kind of touch panel display device, with cured film described in any one of<8>~<10>.

Invention effect

In accordance with the invention it is possible to provide the solidification that coating is excellent, high hardness can be obtained solidifying at low temperature Property composition.

In addition, in accordance with the invention it is possible to providing cured film obtained from the solidification of above-mentioned solidification compound and having Liquid crystal display device, organic EL display device, touch panel and the touch panel display device of above-mentioned cured film.

Detailed description of the invention

Fig. 1 shows the composition concept maps of an example of organic EL display device.Indicate that organic EL of bottom emission type shows dress The schematic sectional view of substrate in setting has planarization film 4.

Fig. 2 indicates the composition concept map of an example of liquid crystal display device.Indicate the active matrix base in liquid crystal display device The schematic sectional view of plate has the cured film 17 as interlayer dielectric.

Fig. 3 indicates the composition concept map with an example of the liquid crystal display device of touch panel.

Fig. 4 indicates another composition concept map with the liquid crystal display device of touch panel.

Specific embodiment

Hereinafter, the contents of the present invention are described in detail.The explanation for the constitutive requirements recorded below is sometimes based on this The representative embodiments of invention and carry out, but the present invention is not limited to such embodiments.In addition, the application explanation "~" is used using the numerical value recorded before and after by it as the meaning that lower limit value and upper limit value include in book.In addition, in the present invention Organic EL element refers to organic electroluminescent device.

In the statement of group (atomic group) in the present specification, not recording substitution and unsubstituted be expressed in includes not It also include the group with substituent group while group with substituent group.Such as " alkyl " not only includes without substituent group Alkyl (unsubstituted alkyl), also comprising the alkyl (replacing alkyl) with substituent group.

In addition, " (methyl) acrylate " indicates acrylate and methacrylate, " (methyl) third in this specification Olefin(e) acid " indicates that acrylic acid and methacrylic acid, " (methyl) acryloyl group " indicate acryloyl group and methylacryloyl.

In the present invention, " olefinic unsaturated compound " etc. is also referred to as " ingredient A " etc..

In addition, " quality % " is identical as " weight % " meaning, and " mass parts " are identical as " parts by weight " meaning in the present invention.

In addition, the group of more than two preferred modes is combined into preferred mode in the present invention.

It is to pass through for can determine the low molecular compound of molecular weight about the molecular weight of the compound in the present invention The molecular weight that ESI-MS (electrospray ionization mass spectrometry) measurement obtains is set as logical for the compound of the distribution with molecular weight The Weight-average molecular of the polystyrene conversion of gel permeation chromatography (GPC) measurement when crossing using tetrahydrofuran (THF) as solvent Amount.

(solidification compound)

Solidification compound (hereinafter, also referred to as " composition ") of the invention is characterized in that, containing as ingredient A's Olefinic unsaturated compound, the polymerization initiator as ingredient B, the alkoxysilane compound containing trialkylsilyl group in molecular structure as ingredient C, as ingredient D Organic solvent and inorganic particulate as ingredient E, ingredient A include carbamate (methyl) acrylate of 5 functions or more, The content of carbamate (methyl) acrylate more than above-mentioned 5 function relative to ingredient A 100 mass parts of content be 20~ 100 mass parts, carbamate (methyl) acrylate more than above-mentioned 5 function include that weight average molecular weight is 10,000 or more Carbamate (methyl) acrylate and molecular weight are 5,000 carbamate (methyl) acrylate below.

By the inclusion of these ingredients, taking into account for pencil hardness and coating can be reached.It is estimated as follows as mechanism.Pass through Using two kinds of different carbamate (methyl) acrylate of molecular weight, in film after coating with alkoxysilane compound containing trialkylsilyl group in molecular structure Compatibility improve.Think by solidifying the coated film, to equably there is the soft chain from carbamate in film Section and the hard segment for coming from (methyl) acrylate or alkoxy silane, thus, it is possible to scar when reaching measurement pencil hardness is anti- Only and by the peeling of distractive load bring prevent.In addition, when on the substrate for having the bumps such as electrode on being applied to substrate, if using The composition being only made of the high ingredient of molecular weight then exists along the concave-convex uneven thickness for generating coated film or generation sometimes The extension of the end solution of coating becomes a problem that uneven.On the other hand, it is only being made of the low ingredient of molecular weight In the case where, the extension of the solution for the end being coated with sometimes can also become excessive.In addition, sometimes the hardness of film also occur it is bad Change.Presumption is able to solve the above subject by using composition of the invention.

Solidification compound of the invention can also be further included except carbamate (methyl) propylene more than 5 functions Olefinic unsaturated compound, multifunctional sulfhydryl compound and/or blocked isocyanate compounds other than acid esters etc. it is other at Point.

Ingredient A: olefinic unsaturated compound

Solidification compound of the invention contains the olefinic unsaturated compound as ingredient A.

In addition, solidification compound of the invention contains carbamate (methyl) acrylate conduct of 5 functions or more Olefinic unsaturated compound.

As long as the olefinic unsaturated compound in the present invention has ethylenic unsaturated bond, low molecularization can be Object is closed, is also possible to oligomer, can also be polymer.

In addition, the content of olefinic unsaturated compound is preferably 40 in whole organic solid ingredients of solidification compound Quality % or more, more preferably 50 mass % or more, further preferably 60 mass % or more, particularly preferably 70 mass % with On.The upper limit does not have special provision, but preferably 100 mass % are hereinafter, more preferably 99 mass % are hereinafter, further preferably 98 Quality % is hereinafter, particularly preferably 95 mass % or less.

In addition, the content of olefinic unsaturated compound is combined in curability in the case where the inorganic particulate stated after engagement It is preferably 80 mass % in all solids ingredient of object hereinafter, more preferably 75 mass % or less.As lower limit value, preferably 20 Quality % or more, more preferably 30 mass % or more, further preferably 40 mass % or more, particularly preferably 50 mass % with On.In addition, " solid component " in solidification compound indicates the ingredient in addition to the volatile components such as organic solvent, curability " organic solid ingredient " in composition indicates in addition to the volatile components such as the inorganic constituents such as inorganic particulate and organic solvent Ingredient.

In addition, in the present invention, as olefinic unsaturated compound and it is equivalent to the change of aftermentioned alkoxysilane compound containing trialkylsilyl group in molecular structure Close object, the compound i.e. with alkoxysilyl and olefinic unsaturated group is set as alkoxysilane compound containing trialkylsilyl group in molecular structure.

In addition, carbamate (methyl) acrylate is the urethane bond and 1 with 1 or more in the present invention The compound of a above (methyl) acryloxy.

<carbamate (methyl) acrylate more than 5 functions>

In solidification compound of the invention, the content of carbamate (methyl) acrylate more than 5 functions is opposite In ingredient A 100 mass parts of content be 20~100 mass parts, preferably 20~69 mass parts.It, then can be with if above range More effectively play effect of the invention.

The number of (methyl) acryloxies in carbamate (methyl) acrylate more than 5 functions is preferably 6 More than, more preferably 10 or more, particularly preferably 12 or more.By being set as such composition, this hair can be more effectively played Bright effect.

In addition, the upper limit of the number of above-mentioned (methyl) acryloxy is not particularly limited, but preferably 500 hereinafter, Not in the case where macromolecular structure, more preferably 50 hereinafter, further preferably 30 hereinafter, particularly preferably 20 or less.

Solidification compound of the invention can be only comprising carbamate (methyl) acrylic acid more than a kind of 5 functions Ester also may include two or more.Comprising two or more, preferably total amount reaches above range.

As carbamate (methyl) acrylate more than 5 functions that can be used in the present invention, benefit can be exemplified The carbamate addition polymerization compound manufactured with the addition reaction of isocyanates and hydroxyl, can exemplify Japanese Unexamined Patent Publication Clear 51-37193 bulletin, Japanese Patent Publication 2-32293 bulletin, as recording in Japanese Patent Publication 2-16765 bulletin Urethane acrylate class, their record is included into present specification.

(methyl) acryloxies in carbamate (methyl) acrylate more than 5 functions can be acryloyl-oxy Both any one of base, methacryloxy, be also possible to, but preferably acryloxy.

Carbamate (methyl) acrylate more than 5 functions is preferably the aliphatic carbamate of 5 functions or more (methyl) acrylate.

In addition, carbamate (methyl) acrylate more than 5 functions preferably has isocyanuric acid class ring structure.

In addition, carbamate (methyl) acrylate more than 5 functions is preferably by the carbamic acid with 1 or more The core part of ester bond and the chemical combination for being bonded with core part and being constituted with the end section of 1 or more (methyl) acryloxy Object has more preferably been bonded the compound of 2 or more above-mentioned end parts on above-mentioned core part.

Carbamate (methyl) acrylate more than 5 functions, which is preferably at least, has following formula Ae-1 or formula Ae-2 institute The compound of the group shown, the more preferably at least compound with group shown in following formula Ae-1.In addition, more than 5 functions Carbamate (methyl) acrylate more preferably have 2 or more be selected from the group as shown in following formula Ae-1 and formula The compound of group in the group of the composition of group shown in Ae-2.

In addition, the above-mentioned end part in more than 5 functions carbamate (methyl) acrylate is 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 indicates acryloyl group or methylacryloyl, and wave-like line part indicates With the bonding position of other structures.

Solidification compound of the invention contains carbamate (methyl) propylene that weight average molecular weight is 10,000 or more Acid esters and molecular weight are 5,000 carbamate (methyl) acrylate below as carbamate (first more than 5 functions Base) acrylate.

In solidification compound of the invention, carbamate (methyl) acrylic acid of weight average molecular weight 10,000 or more The content of ester is preferably 1~90 weight relative to 100 mass parts of content of carbamate (methyl) acrylate more than 5 functions Measure part, more preferably 5~70 parts by weight, particularly preferably 10~60 parts by weight.

In solidification compound of the invention, molecular weight 5,000 carbamate (methyl) acrylate below Content is preferably 10~99 weight relative to 100 mass parts of content of carbamate (methyl) acrylate more than 5 functions Part, more preferably 15~95 parts by weight, particularly preferably 20~90 parts by weight.

<<carbamate (methyl) acrylate that weight average molecular weight is 10,000 or more>>

Solidification compound of the invention contains carbamate (methyl) propylene that weight average molecular weight is 10,000 or more Acid esters is as carbamate (methyl) acrylate more than 5 functions.

That is, carbamate (methyl) acrylate that above-mentioned weight average molecular weight is 10,000 or more is that weight average molecular weight is Carbamate (methyl) acrylate more than 10,000 or more and 5 functions.

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

Carbamate (methyl) acrylate that above-mentioned weight average molecular weight is 10,000 or more preferably has following formula The polymer of repetitive unit is constituted shown in Aa-1 or formula Aa-2.

[chemical formula 2]

In formula Aa-1 and formula Aa-2, L⁵~L⁸Separately indicate that the linking group of divalent, A indicate there is (methyl) third The group of enoyl-, R^aThe alkyl that expression hydrogen atom or carbon atom number are 1~5.

L⁵~L⁸It is separately preferably the alkylidene that carbon atom number is 2~20, more preferably carbon atom number is 2~10 Alkylidene, further preferably carbon atom number be 4~8 alkylidene.In addition, above-mentioned alkylidene also can have branch or ring Structure, but preferably straight-chain alkyl-sub.

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

R^aPreferably hydrogen atom or methyl.

<<molecular weight is 5,000 carbamate (methyl) acrylate below>>

It is that 5,000 carbamate (methyl) acrylate below are made that solidification compound of the invention, which contains molecular weight, For carbamate (methyl) acrylate more than 5 functions.

That is, it is 5,000 or less that above-mentioned molecular weight, which is molecular weight for 5,000 carbamate (methyl) acrylate below, It and is carbamate (methyl) acrylate more than 5 functions.

In addition, it is that molecular weight has distribution that above-mentioned molecular weight, which is 5,000 carbamate (methyl) acrylate below, Oligomer or polymer when, above-mentioned molecular weight may be weight average molecular weight.

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

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

Carbamate (methyl) acrylate more than above-mentioned 5 function preferably comprises two or more above-mentioned molecular weight and is 5,000 carbamate (methyl) acrylate below are more preferably 5,000 ammonia below comprising 2~4 kinds of above-mentioned molecular weight Carbamate (methyl) acrylate is particularly preferably 5,000 carbamate (first below comprising 2 or 3 kind of above-mentioned molecular weight Base) acrylate.If aforesaid way, then the hardness of obtained cured film is more excellent.

In addition, above-mentioned molecular weight is (methyl) acryloyl in 5,000 carbamate (methyl) acrylate below The number of oxygroup is preferably 5~30, and more preferably 8~25, particularly preferably 10~20.It is if above range, then obtained The hardness of cured film is more excellent.

In turn, above-mentioned molecular weight is under 5,000 carbamate (methyl) acrylate below preferably at least has State the compound of group shown in formula Ac-1 or formula Ac-2, the more preferably at least chemical combination with group shown in following formula Ac-1 Object.

In addition, the above-mentioned core part in more than 5 functions carbamate (methyl) acrylate is preferably following formula Ac- Group shown in 1 or formula Ac-2.

[chemical formula 3]

In formula Ac-1 and formula Ac-2, L¹~L⁴Separately indicate that carbon atom number is the alkyl of 2~20 divalent, it is wavy Line part indicates the bonding position with other structures.

L¹~L⁴It is separately preferably the alkylidene that carbon atom number is 2~20, more preferably carbon atom number is 2~10 Alkylidene, further preferably carbon atom number be 4~8 alkylidene.In addition, above-mentioned alkylidene also can have branch or ring Structure, but preferably straight-chain alkyl-sub.

In addition, above-mentioned molecular weight is that 5,000 carbamate (methyl) acrylate below is particularly preferably above-mentioned formula The group that group shown in Ac-1 or formula Ac-2 is formed with the group shown in the group shown in above-mentioned formula Ae-1 and the formula Ae-2 In 2 or 3 group bondings made of compound.

Hereinafter, exemplify in the present invention it is preferable to use above-mentioned molecular weight be 5,000 carbamate (methyl) below Acrylate, but the present invention is not limited to these certainly.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

As the commercially available product of carbamate (methyl) acrylate more than 5 functions, can exemplify can be by the village Xin Zhong 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 trademark), can by Kyoeisha Chemical Co., Ltd. obtain UA-306H, UA-306T, UA-306I, UA-510H, can by BASF AG obtain Laromer UA-9048, UA-9050, PR9052, can be by DAICEL- The EBECRYL220 of ALLNEX LTD. acquisition, 5129,8301, KRM8200,8200AE, 8452 etc..

<other olefinic unsaturated compounds>

Solidification compound of the invention also may include except carbamate (methyl) acrylate more than 5 functions with Outer olefinic unsaturated compound (also referred to as " other olefinic unsaturated compounds ") is used as ingredient A.

It, can be with as the olefinic unsaturated compound in addition to carbamate (methyl) acrylate more than 5 functions It is macromolecule (for example, molecular weight is 2,000 or more), is also possible to monomer (for example, molecular weight is lower than 2,000, preferred molecular weight For 100 more than or lower than 2,000), preferably monomer.

As the olefinic unsaturated compound in addition to carbamate (methyl) acrylate more than 5 functions, preferably For polyfunctional ethylenically unsaturated compound, more preferably 3~6 function olefinic unsaturated compounds.

As the olefinic unsaturated compound in addition to carbamate (methyl) acrylate more than 5 functions, preferably For (methyl) acrylate compounds.The number of (methyl) acryloxy of (methyl) acrylate compounds is preferably 2~ 15, more preferably 3~6.By being set as such composition, effect of the invention can be more effectively played.

Specifically, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two can be enumerated Pentaerythrite five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three ((methyl) acryloyl-oxyethyls) Isocyanuric acid ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate ethylene oxide (EO) Modified body, dipentaerythritol six (methyl) acrylate EO modified body etc..

In addition, also may include 4 functions carbamate below (methyl) as other olefinic unsaturated compounds Acrylate.

As 4 functions carbamate below (methyl) acrylate, following compounds can be exemplified.

[chemical formula 7]

[chemical formula 8]

Solidification compound of the invention includes the alkene in addition to carbamate (methyl) acrylate more than 5 functions Olefinic unsaturated compound when ethylenically unsaturated compounds, in addition to carbamate (methyl) acrylate more than 5 functions Content relative to whole organic solid ingredients of solidification compound be preferably 0.1~50 mass % range, more preferably The range of 0.5~40 mass %, the further preferably range of 1~25 mass %.

Solidification compound of the invention can be only comprising a kind except carbamate (methyl) acrylic acid more than 5 functions Olefinic unsaturated compound other than ester also may include two or more.Comprising two or more, preferred total amount Reach above range.

Ingredient B: polymerization initiator

Solidification compound of the invention contains the polymerization initiator as ingredient B.

As polymerization initiator, radical polymerization initiator is preferably comprised.

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

So-called " light ", as long as can be assigned by its irradiation can be generated the active energy for causing the energy of kind by ingredient B Line is measured, then is not particularly limited, extensively includes alpha ray, gamma-rays, X-ray, ultraviolet light (UV), luminous ray, electron ray Deng.In them, preferably at least packet light with violet rays.

As Photoepolymerizationinitiater initiater, for example, can enumerate oxime ester compound, halogenated organic compound, oxadiazole compound, Carbonyls, ketal compound, benzoin compound, acridine compounds, organic peroxy compound, azo-compound, perfume (or spice) It is legumin compound, azido compound, Metallocenic compound, six aryl united imidazoles, organic boric acid compounds, disulfonated Close object, salt compound, acylphosphanes (oxide) compound.In them, from sensitivity aspect, preferably oxime ester compound And/or six aryl united imidazoles, more preferable oxime ester compound.

As oxime ester compound, Japanese Unexamined Patent Publication 2000-80068 bulletin, Japanese Unexamined Patent Publication No. 2001-233842 number can be used Bulletin, Japanese Unexamined Patent Application Publication 2004-534797 bulletin, Japanese Unexamined Patent Publication 2007-231000 bulletin, Japanese Unexamined Patent Publication 2009-134289 The compound recorded in the paragraph 0046~0059 of number No. 2012/057165 bulletin of bulletin and International Publication No..

As the example of halogenated organic compound, if specifically, woods etc. " Bull Chem.Soc.Japan " can be enumerated 42,2924 (1969), No. 3,905,815 specifications of U.S. Patent No., Japanese Patent Publication 46-4605 bulletin, Japanese Unexamined Patent Application 48-36281 bulletin, Japanese Unexamined Patent Application 55-32070 bulletin, Japanese Unexamined Patent Application 60-239736 bulletin, Japanese Unexamined Patent Application 61-169835 bulletin, Japanese Unexamined Patent Application 61-169837 bulletin, Japanese Unexamined Patent Application 62-58241 bulletin, Japanese Unexamined Patent Application 62-212401 bulletin, Japanese Unexamined Patent Application 63-70243 bulletin, Japanese Unexamined Patent Application 63-298339 bulletin, M.P.Hutt, The compound recorded in et al., " Journal of Heterocyclic Chemistry " 7,511 (1970) etc., especially Oxazoline compound, the s- triaizine compounds of trihalomethyl group substitution can be enumerated.

As the example of six aryl united imidazoles, such as Japanese Patent Publication 6-29285 bulletin, the U.S. can be enumerated It is recorded in each specifications 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, can for example enumerate the IRGACURE 819 of BASF AG, DAROCUR 4265, DAROCUR TPO Deng.

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

The total amount of Photoepolymerizationinitiater initiater in solidification compound of the invention is relative to the whole in solidification compound Solid component is preferably 0.5~30 mass %, more preferably 1~20 mass %, further preferably 1~10 mass %, especially Preferably 2~5 mass %.

<sensitizer>

In solidification compound of the invention, other than polymerization initiator, sensitizer can also be added.

As the typical sensitizer that can be used in the present invention, can enumerate Crivello (J.V.Crivello, Adv.in Polymer Sci., 62,1 (1984)) disclosed in substance, specifically, can enumerate pyrene, acridine orange, thiophene Ton ketone, 2-chlorothioxanthone, benzoflavine (benzoflavin), N- vinyl carbazole, 9,10- dibutoxy anthracene, anthraquinone, tonka-bean Element, ketone cumarin, phenanthrene, camphorquinone, phenothiazine derivative etc..Sensitizer is excellent relative to 100 mass parts of content of polymerization initiator Choosing is added with the ratio of 50~200 mass parts.

Ingredient C: alkoxysilane compound containing trialkylsilyl group in molecular structure

Solidification compound of the invention contains the alkoxysilane compound containing trialkylsilyl group in molecular structure as ingredient C.If using alkoxy silane Compound, then the hardness of coating and obtained cured film is excellent, can be improved solidification compound shape through the invention At film and substrate adaptation.

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

In addition, preferably aftermentioned silane coupling agent is such to have olefinic unsaturated as alkoxysilane compound containing trialkylsilyl group in molecular structure The alkoxysilane compound containing trialkylsilyl group in molecular structure of base and/or epoxy group.

The alkoxysilane compound containing trialkylsilyl group in molecular structure being able to use in solidification compound of the invention preferably make substrate, such as silicon, The compound that the adaptation of the metals such as the silicon compounds such as silica, silicon nitride, gold, copper, molybdenum, titanium, aluminium and insulating film improves.Specifically For, well known silane coupling agent etc. is also effective.If being especially using the silane coupling agent with olefinic unsaturated group With the excellent adhesion of ITO, it is advantageous to.In addition, if using the silane coupling agent with epoxy group, it is excellent in reliability.

As silane coupling agent, such as gamma-amino propyl trimethoxy silicane, three ethoxy of gamma-amino propyl can be enumerated 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 three alcoxyl of vinyl Base silane.In them, more preferable γ-methacryloxypropyl trialkoxy silane, three alcoxyl of γ-acryloxypropyl Base silane, vinyl trialkyl oxysilane and/or γ-glycidoxypropyl group trialkoxy silane.They can be used alone 1 Kind is used in combination of two or more.

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

The content of alkoxysilane compound containing trialkylsilyl group in molecular structure in solidification compound of the invention is relative to the complete of solidification compound Portion's solid component is preferably 0.1~30 mass %, more preferably 0.5~15 mass %, further preferably 2~10 mass %. Alkoxysilane compound containing trialkylsilyl group in molecular structure can be only a kind, also may include two or more.When comprising two or more, preferably total amount reaches To above range.

Ingredient D: organic solvent

Solidification compound of the invention contains the organic solvent as ingredient D.Solidification compound of the invention is preferred It dissolves or is distributed to organic as by ingredient A, ingredient B, ingredient C and the ingredient E and aftermentioned any ingredient that are used as essential component Solution obtained from solvent is modulated.

As the organic solvent used in solidification compound of the invention, well known solvent can be used, can illustrate 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, amides and lactone etc..As the specific example of these organic solvents, Ke Yican According to the paragraph 0062 of Japanese Unexamined Patent Publication 2009-098616 bulletin.

Specifically, it is preferable that 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 be used in the present invention can be used alone or be used in combination two or more.It further preferably will boiling The different solvent of point is used in combination.

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

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

The viscosity of solidification compound of the invention is preferably 1~200mPas, more preferably 2~100mPas, most Preferably 3~80mPas.Viscosity is preferably for example using the RE-80L type rotational viscometer of Toki Sangyo Co., Ltd. 25 It is measured at ± 0.2 DEG C.Rotation speed when about measurement, viscosity are preferably carried out when being lower than 5mPas with 100rpm, viscosity It is preferably carried out when for 5mPas more than or lower than 10mPas with 50rpm, concentration is 10mPas more than or lower than 30mPas Shi Youxuan is carried out with 20rpm, and viscosity is that 30mPas or more is preferably carried out with 10rpm.

Ingredient E: inorganic particulate

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

The average grain diameter of inorganic particulate used in the present invention is preferably 1~200nm, more preferably 5~100nm, especially Preferably 5~50nm.Average grain diameter refers to that it is calculated as obtained from the partial size of arbitrary 200 particles of determination of electron microscopy Art is average.In addition, in the case that the shape of particle is not spherical shape, using longest side as diameter.

In addition, the voidage of inorganic particulate is preferably shorter than 10%, more preferably less than from the viewpoint of the hardness of cured film 3%, most preferably without gap.The voidage of particle is gap section and the particle of the cross-sectional image obtained using electron microscope 200 arithmetic averages of whole area ratio.

As inorganic particulate, preferably metal oxide particle.

In addition, in the metal of the metal oxide in the present invention, also comprising 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 antimony/tin-oxide composition group In metal oxide particle, further preferably selected from being made of silica, titanium oxide, titanium composite oxide and zirconium oxide The particle of 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, which are set out,.

As silicon oxide particle, silica (silica) particle is preferably enumerated.

As silicon dioxide granule, as long as wrap the particle of silica containing inorganic oxide then without special problem, It preferably include the particle of silica or its hydrate as main component (preferably 80 mass % or more).Above-mentioned particle Aluminate be may include as a small amount of ingredient (such as less than 5 mass %).As sometimes as a small amount of ingredient and comprising aluminic acid Salt can enumerate sodium aluminate, potassium aluminate etc..In addition, silicon dioxide granule also may include sodium hydroxide, potassium hydroxide, hydrogen-oxygen Change the organic salts such as inorganic salts or tetramethylammonium hydroxide such as lithium, ammonium hydroxide.It, can example as the example of such compound Colloidal silicon dioxide is shown.

It as the decentralized medium of colloidal silicon dioxide, is not particularly limited, can be water, organic solvent and their mixing Any one of object.They can be used alone, and can also be used in combination two or more.

In the present invention, particle be can also be used as by using ball mill, rod mill etc. in dispersing agent appropriate and solvent Mixing arrangement mixed and/or dispersed and the dispersion liquid modulated and for using.In addition, solidification compound of the invention In, colloidal silicon dioxide not necessarily exists with colloidal state.

From the viewpoint of hardness, the content of the inorganic particulate in solidification compound of the invention is relative to curability group 100 mass parts of all solids ingredient for closing object are preferably 1 mass parts or more, more than more preferably 5 mass parts, further preferably It is more than 10 mass parts.Furthermore it is preferred that below the mass for 80, more preferably 50 below the mass, further preferably 40 mass Part hereinafter, particularly preferably 30 below the mass.

Inorganic particulate can only include a kind, also may include two or more.Comprising two or more, preferably Its total amount reaches above range.

< the compound with epoxy group, the compound with oxetanyl, blocked isocyanate compounds, more officials The curability compound in addition to ingredient A~ingredient C of energy sulfhydryl compound etc. >

Solidification compound of the invention preferably comprises cured by heat or light progress in addition to ingredient A~ingredient C Ingredient, that is, curability compound includes more preferably the compound being selected from by with epoxy group, with the chemical combination of oxetanyl It is at least one kind of in the group of object, blocked isocyanate compounds and multifunctional sulfhydryl compound composition.If aforesaid way, then institute The hardness of obtained solidfied material is more excellent.

<<compound with epoxy group>>

Solidification compound of the invention also may include the compound with epoxy group.Compound with epoxy group Can have 1 epoxy group, but preferably 2 or more in the molecule.

The specific example of compound as the epoxy group in the molecule with 2 or more, can enumerate bisphenol type epoxy Resin, bisphenol f type epoxy resin, novolac type epoxy resins, cresol novolac type epoxy resin, aliphatic epoxy Resin etc..

They can be used as commercially available product acquisition.For example, as bisphenol A type epoxy resin, be 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, be JER806, JER807, JER4004, JER4005, JER4007, JER4010 (more than, Japan Epoxy Resin Co. Ltd. system), (the above are DIC plants of formulas by EPICLON830, EPICLON835 Commercial firm's system), LCE-21, RE-602S (the above are Nippon Kayaku K. K's systems) etc., as novolac type epoxy tree Rouge, be JER152, JER154, JER157S70, JER157S65 (the above are Japan Epoxy Resin Co. Ltd. systems), EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775 (the above are Dainippon Ink Chemicals's systems) etc. make It is EPICLONN-660, EPICLONN-665, EPICLONN-670, EPICLONN- for cresol novolac type epoxy resin 673, EPICLONN-680, EPICLONN-690, EPICLONN-695 (the above are Dainippon Ink Chemicals's systems), EOCN-1020 (with Upper is Nippon Kayaku K. K's system) etc., it is ADEKA RESIN EP-4080S, ADEKA as aliphatic epoxy resin RESIN EP-4085S, ADEKA RESIN EP-4088S (the above are Asahi Denka Co., Ltd.'s systems), CELLOXIDE 2021P, CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、EHPE3150、EPOLEAD PB 3600、EPOLEAD PB 4700 (the above are Daicel Chemical Industries., Ltd. systems) etc..In addition, ADEKA RESIN can be enumerated EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (more than For Asahi Denka Co., Ltd.'s system), (the above are strains by NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 Formula commercial firm ADEKA system) etc..

In addition it is also possible to be suitable for using Japanese Patent Publication 58-49860 bulletin, Japanese Patent Publication 56-17654 bulletin, Recorded in Japanese Patent Publication 62-39417 bulletin or Japanese Patent Publication 62-39418 bulletin with skeletal oxirane Carbamate compounds class, their content are included into present specification.

When solidification compound of the invention includes the compound with epoxy group, the content of the compound with epoxy group All solids ingredient relative to solidification compound is preferably the range of 0.1~20 mass %, more preferably 0.5~10 matter Measure the range of %, the further preferably range of 1~5 mass %.

Solidification compound of the invention can only comprising a kind with epoxy group compound, also may include two kinds with On.Comprising two or more, preferably total amount reaches above range.

<<compound with oxetanyl>>

Solidification compound of the invention also may include the compound with oxetanyl.With oxetanes The compound of base can also have 1 oxetanyl, but preferably 2 or more in the molecule.

As the specific example of the compound with oxetanyl, can be used ARON OXETANE OXT-121, OXT-221, OX-SQ, PNOX (the above are Toagosei Co., Ltd's systems).

In addition, the compound comprising oxetanyl is preferably used in mixed way individually or with the compound comprising epoxy group.

When solidification compound of the invention includes the compound with oxetanyl, with oxetanyl The content of compound is preferably the range of 0.1~20 mass % relative to all solids ingredient of solidification compound, more preferably For the range of 0.5~10 mass %, the further preferably range of 1~5 mass %.

Solidification compound of the invention can also may include only comprising a kind of compound with oxetanyl It is two or more.Comprising two or more, preferably total amount reaches above range.

<<blocked isocyanate compounds>>

Solidification compound of the invention also may include blocked isocyanate compounds.

As blocked isocyanate compounds, as long as the compound with blocked isocyanate base does not limit especially then System, from the viewpoint of curability, compound of preferably 1 intramolecular with 2 or more blocked isocyanate bases.It blocks different The upper limit of the number of cyanic acid ester group does not have special provision, but preferably 6 or less.

In addition, as blocked isocyanate compounds, skeleton is not particularly limited, as long as different with 2 in 1 molecule The compound of cyanic acid ester group then can be any compound, can be aliphatic, alicyclic or aromatic polyisocyanate.Example Such as can be suitable for using 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, nine methylene diisocyanate of 1,9-, 1, 10- decamethylene diisocyanate, 1,4- cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, diphenylmethyl Alkane -4,4 '-diisocyanate, ortho-xylene diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, Di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexamethylene -1,3- dimethylene diisocyanate, hexamethylene -1,4- dimethylene two Isocyanates, 1,5- naphthalene diisocyanate support -4,4 '-diisocyanates to phenylene diisocyanate, 3,3 '-xylenes Ester, 4,4 '-diphenyl ether diisocyanates, tetrachloro phenylene diisocyanate, norbornene alkyl diisocyanate, hydrogenation 1,3- benzene two It methyl diisocyanate, hydrogenation 1,4- xylylene diisocyanate etc. isocyanate compounds and is derived from by these compounds The compound of the skeleton of prepolymer type.In them, particularly preferred first phenylene diisocyanate (TDI), two isocyanide of diphenyl methane Acid esters (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).

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

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

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

When solidification compound of the invention includes blocked isocyanate compounds, the content of blocked isocyanate compounds All solids ingredient relative to solidification compound is preferably the range of 0.1~20 mass %, more preferably 0.5~10 matter Measure the range of %, the further preferably range of 1~5 mass %.

Solidification compound of the invention can only include a kind of blocked isocyanate compounds, also may include two kinds with On.Comprising two or more, preferably total amount reaches above range.

<<multifunctional sulfhydryl compound>>

Solidification compound of the invention also may include multifunctional sulfhydryl compound.

As multifunctional sulfhydryl compound, as long as the compound with 2 or more sulfydryls is then not particularly limited, preferably Compound with 2~6 sulfydryls, more preferably with 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 At least two of compound and the hydrogen atom of aliphatic alkyl that the combination of race's alkyl and-O- ,-C (=O)-are constituted is taken by sulfydryl The compound in generation.

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

When solidification compound of the invention includes multifunctional sulfhydryl compound, the content of multifunctional sulfhydryl compound is excellent The range for being selected in 0.1~20 mass % of all solids ingredient of solidification compound includes, more preferably in 0.5~10 mass % Range include further preferably to include in the range of 1~5 mass %.

Solidification compound of the invention can only include a kind of multifunctional sulfhydryl compound, also may include two or more. Comprising two or more, preferably total amount reaches above range.

<<polythiaether compound>>

In addition, solidification compound of the invention also may include polythiaether compound.By containing polythiaether compound, Substrate adaptation and the excellent cured film of moisture-proof can be obtained.

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

In addition, polythiaether key can be any one of for straight-chain, branched or ring-type, but more sulphur of preferably straight-chain Ehter bond.

In addition, being preferably bonded with aliphatic alkyl, aromatic series respectively in the two sides of polythiaether key as polythiaether compound Alkyl, heterocycle or by the compound of the group of 1 valence obtained from their 2 combination of the above, more preferably two in polythiaether key Side is bonded with aliphatic alkyl, aromatic hydrocarbyl or respectively by the chemical combination of the group of 1 valence obtained from their 2 combination of the above Object.Above-mentioned aliphatic alkyl, aromatic hydrocarbyl or heterocycle also can have substituent group.As substituent group, it is not particularly limited, Can enumerate aliphatic alkyl, aromatic hydrocarbyl, heterocycle, halogen atom, carboxyl, amide groups, alkoxy, alkoxy carbonyl, Silicyl etc..Wherein, particularly preferably have trialkoxysilyl as substituent group.That is, as polythiaether compound, it is special It is not preferably bonded with the compound of the aliphatic alkyl with trialkoxysilyl respectively in the two sides of polythiaether key.

The specific example of polythiaether compound described below, but the present invention is not limited to specific examples below.In addition, In following formula, Ph indicates that phenyl, Me indicate that methyl, Et indicate ethyl.

[chemical formula 9]

In the present invention, polythiaether compound be can be used alone, and can also be used in combination two or more.

In the present invention, all solids ingredient of the content of polythiaether compound relative to solidification compound, preferably 0.01~20 mass %, more preferably 0.1~10 mass %, further preferably 0.5~5 mass %.It, can if above range Obtain substrate adaptation and the excellent cured film of moisture-proof.

In solidification compound of the invention, can also without departing from the spirit and scope of the invention comprising except it is above-mentioned with Other outer compounds (for example, containing alkoxy methyl compound etc.).

As alkoxy methyl compound is contained, can enumerate the paragraph 0192 of Japanese Unexamined Patent Publication 2011-221494 bulletin~ The compound recorded in 0194.

In the present invention, olefinic unsaturated compound, the compound with epoxy group, the chemical combination with oxetanyl The total content of object, blocked isocyanate compounds and multifunctional sulfhydryl compound preferably accounts for be led to included in solidification compound Overheat or light carry out the 90 mass % or more (more preferable 95 mass % or more) of the total amount of cured ingredient, olefinic unsaturation The total content for closing object and blocked isocyanate compounds more preferably accounts for included in solidification compound through heat or light progress The 90 mass % or more (further preferred 95 mass % or more) of the total amount of cured ingredient.

In addition, when including the compound with epoxy group, the compound with oxetanyl, blocked isocyanate Close object and multifunctional sulfhydryl compound it is at least one kind of when, in terms of they total, preferably account for included in solidification compound 0.1~20 mass % that the total amount of cured ingredient is carried out by heat or light, further preferably accounts for 1~10 mass %.Pass through It is set as such composition, can more effectively play effect of the invention.

<surfactant>

Solidification compound of the invention can also contain surfactant.

As surfactant, any one of anionic system, cationic system, nonionic system or both sexes can be used, it is excellent The surfactant of choosing is nonionic surfactants.The preferred nonionic surfactants of surfactant, more preferable fluorine It is surfactant.

As the surfactant that can be used in the present invention, such as the Megafac as commercially available product can be enumerated 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 Nitre Co. Ltd. system), EFTOP EF351, EFTOP EF352, EFTOP EF801, EFTOP EF802 (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Ftergent 250 (Neos Corporation system). In addition, in addition to the foregoing, KP (Shin-Etsu Chemial Co., Ltd's system), POLYFLOW (common prosperity society chemistry strain formula can be enumerated 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..

In addition, as surfactant, can also enumerate the paragraph 0119 of Japanese Unexamined Patent Publication 2014-238438 bulletin~ The compound recorded in 0123 is as preferred example.

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

Surfactant can only include a kind, also may include two or more.Comprising two or more, Preferred total amount reaches above range.

<antioxidant>

Solidification compound of the invention can also contain antioxidant.It, can be containing well known anti-as antioxidant Oxidant.By adding antioxidant, the coloring for preventing cured film is had the advantage that, or can reduce due to decomposition Caused film thickness is reduced, in addition, heat resistant transparent is excellent.

As such antioxidant, such as phosphorous antioxidant, amides, hydrazides, amine system of being obstructed can be enumerated and resisted Oxidant, sulfur antioxidant, phenolic antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, sulphur Thiosulfate, hydroxy amine derivatives etc..In them, from the viewpoint of being reduced the coloring of cured film, film thickness, particularly preferred phenol system Antioxidant, amine antioxidant of being obstructed, phosphorous antioxidant and/or sulfur antioxidant, most preferably phenolic antioxidant.It Can be used alone, can also be by two or more mixing.

As specific example, it can enumerate and be recorded in the paragraph 0026~0031 of Japanese Unexamined Patent Publication 2005-29515 bulletin Compound, Japanese Unexamined Patent Publication 2011-227106 bulletin paragraph 0106~0116 in the compound recorded, their content received Enter in present specification.

As preferred commercially available product, ADEKA STAB AO-60, ADEKA STAB AO-80, ADEKA STAB can be enumerated AO-412S (the above are Asahi Denka Co., Ltd.'s systems), IRGANOX 1035, IRGANOX 1098 (the above are BASF AG's systems).

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

<polymerization inhibitor>

Solidification compound of the invention can also contain polymerization inhibitor.So-called polymerization inhibitor is for passing through exposure or heat by gathering Close initiator generate polymerization initiation radical ingredient implement hydrogen supply with (or hydrogen is authorized), energy supply and (or energy is authorized), electricity Son for (or electronics is authorized) etc., play the substance of effect for inactivate polymerization initiation radical and forbidding polymerizeing initiation.For example, The compound etc. recorded in the paragraph 0154~0173 of Japanese Unexamined Patent Publication 2007-334322 bulletin can be used.

As preferred compound, phenthazine, phenoxazine, quinhydrones, 3,5- dibutyl -4- hydroxy-methylbenzene can be enumerated.

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

<binder polymer>

Adhesive can also be contained from viewpoints, the solidification compound of the invention such as resolution and the raising of epithelium characteristic Polymer.

It as binder polymer, is not particularly limited, well known polymer can be used, but it is preferable to use linear organic Polymer.As such threadlike organic polymers, well known polymer can be arbitrarily used.It is aobvious preferred to water is able to carry out Shadow or weak base water development select the threadlike organic polymers in water or week-base water for soluble or swellability.It is linear organic poly- It closes object and serves not only as peel-forming agent, it can also 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.For example, being able to carry out water development if using water dissolvable organic polymer.As such line Shape organic polymer, can enumerate side chain have carboxylic acid group free radical polyalcohol, such as Japanese Unexamined Patent Application 59-44615 Bulletin, Japanese Patent Publication 54-34327 bulletin, Japanese Patent Publication 58-12577 bulletin, Japanese Patent Publication 54-25957 public affairs Report, Japanese Unexamined Patent Application 54-92723 bulletin, Japanese Unexamined Patent Application 59-53836 bulletin, Japanese Unexamined Patent Application 59-71048 bulletin The polymer of middle record, i.e., by resin obtained from monomer homopolymerization or copolymerization with carboxyl, by the monomer homopolymerization with acid anhydrides Be copolymerized and make anhydride unit hydrolyze or half-esterification or semi-amidation obtained from resin, by epoxy resin with unsaturated monocarboxylic And it is anhydride modified obtained from epoxy acrylate etc..As the monomer with carboxyl, acrylic acid, metering system can be enumerated Acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4- carboxyl styrene etc. can enumerate Malaysia as the monomer with acid anhydrides Acid anhydrides etc..

In addition, there are also the acid cellulose derivatives equally in side chain with carboxylic acid group.Furthermore in the polymerization with hydroxyl Substance obtained from addition cyclic acid anhydride etc. is useful on object.

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

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

<other ingredients>

In solidification compound of the invention, as needed, in addition to the foregoing, plasticizer can be added, hot acid generates The others ingredient such as agent, acid proliferation generator.About these ingredients, Japanese Unexamined Patent Publication 2009-98616 bulletin or day can be used for example The substance and other well known substances recorded in this special open 2009-244801 bulletin.In addition it is also possible to will " macromolecule addition The additions such as various ultraviolet absorbing agents, the metal inactivator recorded in the new expansion (Nikkan Kogyo Shimbun, Co., Ltd.) of agent " Into solidification compound of the invention.

(solidfied material, cured film and their manufacturing method)

Solidfied material of the invention is solidfied material made of solidifying solidification compound of the invention, preferably will be of the invention Solidification compound in organic solvent at least part remove and solidify obtained from solidfied material.As above-mentioned solidification Object, preferably cured film.In addition, obtained from the manufacturing method of solidfied material of the invention preferably by solidfied material of the invention Solidfied material.

As long as the manufacturing method of solidfied material of the invention solidifies solidification compound of the invention to manufacture solidfied material Method, then be not particularly limited, the process for preferably comprising (1) below~(3).

(1) process being applied to solidification compound of the invention on substrate

(2) process of solvent is removed from the solidification compound being coated with

(3) process of heat cure is carried out

In addition, the manufacturing method of solidfied material of the invention more preferably includes the process of (1) below, (2), (2 ') and (3).

(1) process being applied to solidification compound of the invention on substrate

(2) process of organic solvent is removed from the solidification compound being coated with

The solidification compound for eliminating organic solvent is carried out cured process by light by (2 ')

(3) the cured process of hot further progress will be passed through by the cured solidfied material of light

In addition, the manufacturing method of the solidfied material of aforementioned present invention is preferably the manufacturing method of cured film.

In the process being coated of (1), preferably solidification compound of the invention is applied on substrate and is made Wrap solvent-laden wet film.Before solidification compound is applied on substrate, neutralizing treatment can be carried out or plasma is washed The washing for the substrate washed etc.And then substrate surface can be handled with hexamethyldisilazane etc. after substrate washing. By carrying out the processing, there are the tendencies of solidification compound improved with the adaptation of substrate.

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

As inorganic substrate, for example, can enumerate glass, quartz, silicon, silicon nitride and be vapor-deposited on such substrate molybdenum, The composite substrate of titanium, aluminium, copper etc..

As resin, can enumerate by polybutylene terephthalate (PBT), polyethylene terephthalate, poly- naphthalene diformazan Sour glycol ester, polybutylene naphthalate, polystyrene, polycarbonate, polysulfones, polyether sulfone, polyarylate, allyl two are sweet Alcohol carbonic ester, polyamide, polyimides, polyamidoimide, polyetherimide, polybenzoxazoles, polyphenylene sulfide, polycyclic alkene The fluororesin such as hydrocarbon, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, organosilicon tree Rouge, ionomer resin, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide-alkene are total The substrate that the synthetic resin such as polymers, cellulose, episulfide resin are constituted.The feelings that these substrates are directly used in the form of above-mentioned Condition is less, in general, according to the form of final product, such as form TFT (Thin-Film Transistor, thin film transistor (TFT)) member Multilayer laminate constructions as part.

Solidification compound of the invention is due to relative to the close of the metal film or metal oxide being film-made by sputtering It closes well, so preferably comprising the metal film being film-made by sputtering as substrate.As metal, preferably titanium, copper, aluminium, indium, Tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and their oxide or alloy, further preferably molybdenum, titanium, aluminium, copper and they Alloy.In addition, metal or metal oxide can be used alone, can also be used in combination a variety of.

Coating method on substrate is not particularly limited, can be used for example ink-jet method, slot coated method, spray-on process, The methods of rolling method, method of spin coating, cast coating method, slit rotary process, print process.

In the process of the removing solvent of (2), preferably from the above-mentioned film being coated with, by decompression (vacuum) and/or Heating etc. removes solvent and forms dry coating on substrate.The heating condition of solvent removal step be preferably 70~130 DEG C and 30~300 seconds or so.In addition, in above-mentioned solvent removal step, it is not necessary that by the organic solvent in solidification compound It completely removes, as long as at least part is removed.

And then in the present invention, after the process that (2) remove solvent and before the process of (3) progress heat cure, mentioned from film hardness From the perspective of height, the process for carrying out whole face exposure also may include.

In addition, after the process that (2) remove solvent and before the process of (3) progress heat cure, from the viewpoint of film hardness raising It sets out, preferably comprises (2 ') for the solidification compound for eliminating organic solvent and cured process is carried out by light, more preferably wrap Cured process is carried out by whole face exposure containing the solidification compound that will eliminate organic solvent.In addition, in the manner described above that When sample is solidified by light, solidification compound of the invention preferably comprises Photoepolymerizationinitiater initiater.

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

In addition, in order to form pattern, the process that pattern exposure, development can also be carried out after the solvent removal step of (2). The method of pattern exposure is it is preferable to use the method for mask or utilizes directly the methods of description of laser etc..In the state that oxygen blocks Lower these whole face exposures of progress or pattern exposure are preferred from the viewpoint of promoting solidification.As the means for blocking oxygen, It can exemplify and be exposed or be arranged oxygen barrier film under nitrogen atmosphere.

About pattern exposure and development, well known method, well known developer solution can be used.It such as can be suitable for using day The pattern exposure method recorded in this special open 2011-186398 bulletin, Japanese Unexamined Patent Publication 2013-83937 bulletin and development side Method.

In the process that (3) carry out heat cure, the polymerization such as olefinic unsaturated compound can be formed by heating solid Change film, the solidfied material after solidification can also further be solidified.When being polymerize by heating, curability combination of the invention Object preferably comprises thermal polymerization.

As heating temperature, preferably 180 DEG C hereinafter, more preferably 150 DEG C hereinafter, further preferably 130 DEG C or less. Lower limit value is preferably 80 DEG C or more, and more preferably 90 DEG C or more.The method of heating is not particularly limited, and well known side can be used Method.Such as hot plate, baking oven, infrared heater can be enumerated etc..

In addition, as heating time, preferably 1 minute~30 minutes or so in the case where hot plate, in addition to this in the case where It is preferred that 20 minutes~120 minutes or so.It can solidify in the range in the case where not damaged to substrate, device. From the viewpoint of the Adjusting Shape after heating, it can also be heated, be carried out at higher temperatures later at relatively low temperatures first Heat (the addition of intermediate roasting procedure.Such as carry out 90 DEG C, 30 minutes first and heat, 120 DEG C, 30 minutes are carried out later adds Heat).

Cured film of the invention is solidification obtained from being solidified the film formed as solidification compound of the invention Film, the film that preferably will be removed at least part of organic solvent from solidification compound of the invention and formed solidify and obtain The cured film arrived.

Cured film of the invention can be used as protective film or interlayer dielectric is suitable for using.In addition, cured film of the invention Cured film obtained from manufacturing method preferably by cured film of the invention.

Solidification compound through the invention can also obtain having sufficient hardness even if being solidified at low temperature Cured film.For example, the solidification that the pencil hardness under the available load 750g measured according to JIS K5600:1999 is 3H or more Film.The protective film that solidification compound of the invention is solidified to form is due to cured film physical properties excellent, so for organic EL Display device or liquid crystal display device, touch panel, touch panel display device purposes be useful.

Solidification compound of the invention is since curability and cured film characteristic are excellent, so as MEMS (Micro Electro Mechanical Systems, MEMS) equipment structure member, curability of the invention can be combined The a part of solidfied material obtained from object solidifies or corrosion-resisting pattern as partition walls or as mechanical driving member assembles and makes With.As such MEMS equipment, such as SAW (Surface Acoustic Wave, surface acoustic wave) filtering can be enumerated Device, BAW (Bulk Acoustic Wave, acoustic bulk wave) filter, gyro sensor, display micro- shutter, image sensing The components such as device, Electronic Paper, ink gun, biochip, sealant.More specific example is illustrated in Japanese Unexamined Patent Application Publication 2007-522531 In number bulletin, Japanese Unexamined Patent Publication 2008-250200 bulletin and Japanese Unexamined Patent Publication 2009-263544 bulletin etc..

Solidification compound of the invention is since flatness, the transparency are excellent, so can be used for such as Japanese Unexamined Patent Publication Bank layer (16) and planarization film (57), the Japanese Unexamined Patent Publication 2010-9793 public affairs recorded in Fig. 2 of 2011-107476 bulletin In Figure 10 of the partition walls (12) and planarization film (102), Japanese Unexamined Patent Publication 2010-27591 bulletin recorded in Fig. 4 (a) of report The middle note of Fig. 4 (a) of the bank layer (221) of record and the 3rd interlayer dielectric (216b), Japanese Unexamined Patent Publication 2009-128577 bulletin Remember in Fig. 3 of the 2nd interlayer dielectric (125) and the 3rd interlayer dielectric (126), Japanese Unexamined Patent Publication 2010-182638 bulletin that carry In the formation of the planarization film (12) and pixel separation insulating film (14) etc. of load.In addition it is also possible to be suitable for liquid crystal display dress The colour filter or color filter protecting layer of the spacer for the thickness of liquid crystal layer to be kept fixed, liquid crystal display device in setting, The imaging optical system of the piece providing color filters of fax, electronic copier, solid-state imager etc. or the lenticule of optical fiber connector.

(organic EL display device)

Organic EL display device of the invention is characterized in that thering is cured film of the invention.

As organic EL display device of the invention, formed in addition to having the solidification compound using aforementioned present invention Planarization film or interlayer dielectric other than be not particularly limited, the well known various organic EL for taking various structures can be enumerated Display device or liquid crystal display device.

For example, the specific example as TFT possessed by organic EL display device of the invention, can enumerate amorphous silicon- TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention is excellent due to electrical characteristics, it is possible to group Close in these TFT and it is preferable to use.

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

The TFT1 of bottom gate type is formed on glass substrate 6, is formed with covering the state of the TFT1 by Si₃N₄The insulation of composition Film 3.It is formed after being omitted here the contact hole of diagram, is formed on the insulating film 3 via the contact hole and TFT1 on the insulating film 3 The wiring 2 (being highly 1.0 μm) of connection.Wiring 2 is the organic EL element for will be formed between TFT1 or by subsequent process The wiring being connect with TFT1.

In turn, for the concave-convex planarization that will be generated because being routed 2 formation, the bumps generated because being routed 2 are filled out The state buried forms planarization film 4 on the insulating film 3.

The organic EL element of bottom emission type is formed on planarization film 4.That is, being made of on planarization film 4 ITO First electrode 5 connect and formed with wiring 2 via contact hole 7.In addition, first electrode 5 is equivalent to the anode of organic EL element.

The insulating film 8 for forming the shape of the periphery of covering first electrode 5 can prevent first by the way that the insulating film 8 is arranged Short circuit between electrode 5 and the second electrode for passing through process formation thereafter.

In turn, it although not illustrated in Fig. 1, via desired pattern mask, is successively deposited and that hole is arranged is defeated Layer, organic luminous layer, electron supplying layer are sent, then, the second electrode being made of Al is formed in the whole face above substrate, passes through It is bonded and is sealed using glass for sealing plate and ultraviolet hardening epoxy resin, can be obtained and connect in each organic EL element The organic EL display device of active array type made of being connected to for driving its TFT1.

(liquid crystal display device)

Liquid crystal display device of the invention is characterized in that thering is cured film of the invention.

As liquid crystal display device of the invention, formed in addition to having the solidification compound using aforementioned present invention It is not particularly limited other than protective film, planarization film or interlayer dielectric, the well known liquid crystal for taking various structures can be enumerated Display device.

In addition, TN can be enumerated as the liquid crystal drive mode that liquid crystal display device of the invention can be taken (Twisted Nematic, twisted-nematic) mode, VA (Vertical Alignment, vertically oriented) mode, IPS (In- Plane-Switching, in-plane switching) mode, FFS (Fringe Field Switching, fringing field switching) mode, OCB (Optically Compensated Bend, optical compensation curved) mode etc..

In panel composition, even the liquid crystal of COA (Color Filter on Array, colour filter array) mode Cured film of the invention also can be used in display device, such as can be used as the organic of Japanese Unexamined Patent Publication 2005-284291 bulletin Organic insulating film (212) use of insulating film (115), Japanese Unexamined Patent Publication 2005-346054 bulletin.In addition, as of the invention The liquid crystal orientation film that liquid crystal display device can be taken it is specific aligned, friction orientation method, optical alignment method can be enumerated Deng.In addition it is also possible to by Japanese Unexamined Patent Publication 2003-149647 bulletin, record in Japanese Unexamined Patent Publication 2011-257734 bulletin PSA (Polymer Sustained Alignment, polymer stabilizing orientation) technology carries out polymer orientation support.

In addition, solidification compound of the invention and cured film of the invention are not limited to such use, it can be each Kind with using on the way.For example, other than planarization film, interlayer dielectric protective film can also be suitable for, for liquid crystal The spacer for being kept fixed the thickness of liquid crystal layer in showing device, be set in solid-state imager it is micro- on colour filter Mirror etc..

Fig. 2 is the conceptual sectional view for indicating an example of liquid crystal display device 10 of active matrix mode.The color liquid crystal Display device 10 is liquid crystal display panel overleaf with backlight unit 12, and liquid crystal panel has and is being pasted with polarizing film Two pieces of glass substrates 14,15 between the element of whole corresponding TFT 16 of pixel that configures.On being formed in glass substrate Each element on, by the contact hole 18 formed in cured film 17, be routed the ito transparent electrode 19 of tangible pixel electrode.? On ito transparent electrode 19, it is provided with the layer of liquid crystal 20 and the RGB colour filter 22 configured with black matrix".

It as the light source of backlight, is not particularly limited, well known light source can be used.For example, white can be enumerated LED, blue, red or green etc. be multi-colored led, fluorescent lamp (cold-cathode tube), organic EL etc..

In addition, the liquid crystal display device or touch panel type of 3D (stereopsis) type can be made in liquid crystal display device Liquid crystal display device.And then flexible type can also be made, it can be used as the recorded in Japanese Unexamined Patent Publication 2011-145686 bulletin The interlayer dielectric (520) recorded in 2 interlayer dielectrics (48), Japanese Unexamined Patent Publication 2009-258758 bulletin uses.

(touch panel and touch panel display device)

Touch panel of the invention is the touch panel with cured film of the invention.

Touch panel display device of the invention is the touch panel display device with cured film of the invention, preferably Touch panel display device with touch panel of the invention.

As touch panel of the invention, resistive film mode, electrostatic capacity, ultrasonic wave mode, electromagnetism sense can be Answer mode well known to mode etc..Wherein, preferred electrostatic capacity.

As touch panel type, so-called embedded (in-cell) type can be enumerated (for example, Japanese Unexamined Patent Application Publication 2012-517051 The touch panel recorded in Fig. 5, Fig. 6, Fig. 7 and Fig. 8 of number bulletin), so-called (on-cell) type that is externally embedded to is (for example, Japanese Unexamined Patent Publication Remember in Fig. 1, Fig. 5 of the touch panel, Japanese Unexamined Patent Publication 2012-89102 bulletin recorded in Figure 19 of 2013-168125 bulletin The touch panel of load), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type is (for example, Japanese Unexamined Patent Publication Fig. 2, Fig. 3, the figure of the touch panel and Japanese Unexamined Patent Publication 2015-15042 bulletin recorded in Fig. 2 of 2013-54727 bulletin The touch panel recorded in 4 and Fig. 5), other constitute (for example, being recorded in Fig. 6 of Japanese Unexamined Patent Publication 2013-164871 bulletin Touch panel) various plug-in (out-cell) types (so-called GG, G1G2, GFF, GF2, GF1, G1F etc.).

In addition, Fig. 3 indicates the composition concept map with an example of the liquid crystal display device of touch panel.

For example, cured film of the invention is suitable for the protective film between each layer suitable for Fig. 3, in addition, being also suitable for being applicable in The interlayer dielectric separated between the detecting electrode by touch panel.In addition, the detecting electrode as touch panel, preferably Transparent electrode (ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) etc.) and metal electrode (silver, copper, molybdenum, Titanium, aluminium etc. and their laminated body and alloy etc.) or their laminated body.

In Fig. 3,110 indicate pixel substrate, and 140 indicate liquid crystal layer, and 120 indicate counter substrate, and 130 indicate sensor portion. Pixel substrate 110 from the downside of Fig. 3 successively have polarizing film 111, transparent substrate 112, common electrode 113, insulating layer 114, Pixel electrode 115, alignment films 116.Counter substrate 120 from the downside of Fig. 3 successively have alignment films 121, colour filter 122, thoroughly Bright substrate 123.Sensor portion 130 is respectively provided with phase-contrast film 124, adhesive layer 126, polarizing film 127.In addition, in Fig. 3,125 For sensor detecting electrode.Cured film of the invention can insulating layer (114) in pixel substrate part (also referred to as interlayer is exhausted Velum), various protective films (not shown), the various protective films (not shown) of pixel substrate part, counter substrate part it is various Protective film (not shown), Sensor section various protective films (not shown) etc. in use.

In adhesive layer 126, polarizing film 127, well known bonding layer composition can be used.

As polarizing film, the specific example of adhesive layer, the embodiment of Japanese Unexamined Patent Publication 2014-152319 bulletin can be enumerated 1, embodiment 7, the embodiment of the polarizing film with adhesive layer recorded in embodiment 13, Japanese Unexamined Patent Publication 2014-191005 bulletin 1, the embodiment of the polarizing film with adhesive layer, Japanese Unexamined Patent Publication 2013-100386 bulletin recorded in embodiment 3 and embodiment 6 1, the polarizing film with adhesive layer and Japanese Unexamined Patent Publication 2013- recorded in embodiment 3, embodiment 6, embodiment 11 and embodiment 14 The adhesive layer recorded in the embodiments 1 of No. 163783 bulletins, embodiment 2, embodiment 3 and embodiment 4.

In adhesive layer, electrostatic, preferably comprises antistatic agent in order to prevent.

As antistatic agent, well known antistatic agent can be used.Can be used for example metallic, metal oxide, Electric conductive polymer and quaternary ammonium salt, lithium salts isoiony compound.

As the specific example of antistatic agent, can enumerate the paragraph 0107 of Japanese Unexamined Patent Publication 2014-191005 bulletin~ It is recorded in the paragraph 0046~0054 of the antistatic agent, Japanese Unexamined Patent Publication 2013-100386 bulletin recorded in 0115 antistatic The antistatic agent recorded in the paragraph 0027~0047 of agent and Japanese Unexamined Patent Application Publication 2014-515046 bulletin.

In turn, even the liquid crystal display device of static drive mode, design can be also shown by being applicable in the present invention High pattern.As an example, as the polymer network type liquid crystal as being recorded in Japanese Unexamined Patent Publication 2001-125086 bulletin Insulating film can be applicable in the present invention.

In addition, Fig. 4 is another composition concept map with the liquid crystal display device of touch panel.

Comprising have the lower part display board 200 for being equivalent to thin film transistor display panel of thin film transistor (TFT) (TFT) 440, with Lower part display board 200 is opposed and have multiple colour filters 330 on the face opposed with lower part display board 200 is equivalent to colour filter The top display board 300 of display board and the liquid crystal layer 400 being formed between lower part display board 200 and top display board 300. Liquid crystal layer 400 includes liquid crystal molecule (not shown).

Lower part display board 200 includes the 1st insulating substrate 210, the thin film transistor (TFT) being configured on the 1st insulating substrate 210 (TFT), the pixel electricity for being formed in the insulating film 280 of the upper surface of thin film transistor (TFT) (TFT) and being configured on insulating film 280 Pole 290.Gate insulation film 240, the semiconductor layer that thin film transistor (TFT) (TFT) may include gate electrode 220, cover gate electrode 220 250, ohmic contact layer 260,262, source electrode 270 and drain electrode 272.

Contact hole 282 is formed in such a way that the drain electrode 272 of thin film transistor (TFT) (TFT) exposes on insulating film 280.

Top display board 300 includes to be configured in the one side of the 2nd insulating substrate 310 and with the light-blocking member of rectangular arrangement 320, the colour filter 330 being configured on the 2nd insulating substrate 310 and the alignment films being configured on light-blocking member 320 and colour filter 330 350 and be configured in alignment films 350 and with the pixel electrode of lower part display board 200 290 accordingly to liquid crystal layer 400 apply voltage Common electrode 370.

In liquid crystal display device shown in Fig. 4, sensing electrode is configured on the another side of the 2nd insulating substrate 310 410, insulating film 420, driving electrodes 430 and protective film 280.Like this, in the manufacture of liquid crystal display device shown in Fig. 4, When forming top display board 300, sensing electrode 410, the insulating film 420 of the constituent element as touch screen can be formed together And driving electrodes 430 etc..Cured film obtained from especially solidification compound of the invention is solidified can be suitable for absolutely In velum 420.

On protective film 280, can also be bonded with above-mentioned adhesive layer 126 and polarizing film 127 illustration with the inclined of adhesive layer Shake piece or adhesive layer.

Embodiment

Embodiment is exemplified below out to be more specifically illustrated the present invention.Material shown in embodiment below makes Dosage, ratio, process content, processing step etc. can be suitably changed without departing from purport of the invention.Therefore, originally The range of invention is not limited to specific example as shown below.In addition, unless otherwise specified, " part ", " % " are quality Benchmark.

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

By 50.4 parts of hexamethylene diisocyanate trimer (Asahi Kasei Corporation's system, TPA-100) in toluene solvant (diazabicylo endecatylene (the DBU)-caprylate, San- of U-CAT SA 102 as curing catalysts is added in middle mixing Apro Ltd. system) 0.15 part, heat within 1 hour at 60 DEG C under nitrogen atmosphere.Mixing is added dropwise thereto by dipentaerythritol five Solution obtained from 157.4 parts of acrylate (using after Aldrich society product is carried out column purification) is dissolved into toluene solvant, It carries out at 60 DEG C heating for 5 hours under nitrogen atmosphere.

After letting cool, reaction mixture purified with silica gel column chromatography, point take and to obtain (a-1) -1.It is obtained (a-1) -1 weight average molecular weight by gel permeation chromatography (GPC) measurement is 15,300.

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

[chemical formula 10]

By methacrylic acid 2- isocyanato ethyl (116.4 parts) and propylene glycol monomethyl ether (PGMEA, 135.8 part) mixed solution be heated to 70 DEG C under nitrogen flowing.The mixed solution side is stirred, 2 hours dropwise addition free radicals of Bian Yong Polymerization initiator V-65 (trade name, 2,2 '-azos bis- (2,4- methyl pentane nitriles), Wako Pure Chemical Industries, Ltd.'s system, 4 parts) And the mixed solution of PGMEA (135.8 parts).After completion of dropwise addition, carry out reacting for 4 hours at 70 DEG C.

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

The weight average molecular weight by gel permeation chromatography (GPC) measurement of obtained (a-1) -2 is 30,000.

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

[chemical formula 11]

In synthesis example 2, the additive amount of polymerization initiator V-65 is changed to 8 parts, the additive amount of PGMEA is set as It 232.7 parts, in addition to this, is operated in the same way with synthesis example 2, obtains ' -3 polymer (a-1).

The weight average molecular weight by gel permeation chromatography (GPC) measurement of obtained ' -3 (a-1) is 8,000.

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

[chemical formula 12]

By 50.4 parts of hexamethylene diisocyanate trimer (Asahi Kasei Corporation's system, TPA-100) and two Ji Wusi Five acrylate of alcohol (uses after Aldrich society product is carried out column purification.) 157.4 parts mixed in toluene solvant, addition is made For 0.2 part of the U-CAT SA 102 (San-Apro Ltd. system) of curing catalysts, carry out 6 hours at 60 DEG C under nitrogen atmosphere plus Heat.

After letting cool, reaction mixture purified with silica gel column chromatography, point take and to obtain (a-2) -1.

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

[chemical formula 13]

In addition to the hexamethylene diisocyanate trimer in synthesis example 4 is changed to hexamethylene diisocyanate (east Capital chemical conversion industry Co. Ltd. system) other than, synthesis is carried out similarly with synthesis example 4, purifying obtains (a-2) -2.

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

[chemical formula 14]

It (will in addition to the Dipentaerythritol Pentaacrylate in synthesis example 5 is changed to pentaerythritol triacrylate Aldrich society product uses after carrying out column purification) other than, synthesis is carried out similarly with synthesis example 5, purifying obtains (a-2) -3.

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

[chemical formula 15]

In addition to the Dipentaerythritol Pentaacrylate in synthesis example 4 is changed to acrylic acid 2- hydroxy methacrylate, (Tokyo is melted into Industrial Co., Ltd's system) other than, synthesis is carried out similarly with synthesis example 4, purifying obtains ' -4 (a-2).

<carbamate (methyl) acrylate>

(a-1) -1: urethane acrylate, the Mw:15,300, functional group number made in synthesis example 1: many, tool Have and constitutes repetitive unit shown in above-mentioned formula Aa-1.

(a-1) -2: urethane acrylate, the Mw:30,000, functional group number made in synthesis example 2: many, tool Have and constitutes repetitive unit shown in above-mentioned formula Aa-2.

(a-1) ' -3: urethane acrylate, the Mw:8,000, functional group number made in synthesis example 3: many, tool Have and constitutes repetitive unit shown in above-mentioned formula Aa-2.

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

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

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

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

<olefinic unsaturated compound in addition to carbamate (methyl) acrylate>

A-1: dipentaerythritol hexaacrylate

A-2: Dipentaerythritol Pentaacrylate

A-3: pentaerythritol tetraacrylate

In addition, A-1~A-3 is used after the substance of Aldrich is carried out column purification.

<ingredient B: radical polymerization initiator>

B-1: following compounds 1, oxime ester compound

[chemical formula 16]

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

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

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

[chemical formula 17]

<ingredient 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- acryloyloxypropyltrimethoxysilane, 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 (ruthenium trimethoxysilane, Shin-Etsu Chemial Co., Ltd's system)

<ingredient D: organic solvent>

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

D-2: Methylethyl diethylene glycol (DEG) (Japanese emulsifier Co. Ltd. system)

D-3:1,3- butanediol diacetate esters

D-4: tetrahydrofurfuryl alcohol

<ingredient E: inorganic particulate>

(Nissan Chemical Ind Ltd's system, silicon dioxide granule, average grain diameter are 10~15nm, admittedly to E-1:PMA-ST 30%) body constituent concentration is

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

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

<multifunctional sulfhydryl compound>

S-1:Karenz MT-PE-1 (pentaerythrite four (3- mercaptobutylate), Showa Denko K. K's system), function Group's number 4

S-2:Karenz MT-BD-1 (1,4- bis- (3- sulfydryl butyryl acyloxy) butane, Showa Denko K. K's system), official Number 2 can be rolled into a ball

<blocked isocyanate compounds>

(oxime of isophorone diisocyanate blocks body, solid component concentration 60%, three to S-3:TAKENATE B870N Well Chemical Co., Ltd. system)

(precursor structure has biuret structure to S-4:DURANATE 17B-60P, and closed-end structure is the envelope of oxime ester structure Isocyanate terminated compound, solid component concentration 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 structures, Kawasaki Kasei Chemicals Ltd.'s system)

[chemical formula 18]

(in formula, Bu indicates butyl.)

<antioxidant>

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

<polymerization inhibitor>

K-1:4- metoxyphenol

(Examples 1 to 26 and comparative example 1~6)

<modulation of solidification compound>

As in following table 1~table 4 record as, by each components matching, stirring and be made organic solvent solution and/or Dispersion liquid is filtered with the polytetrafluoroethylene (PTFE) filter that aperture is 0.3 μm, obtains solidification compound of the invention.About under The unit for stating each ingredient of 1~table of table 4, in addition to the ratio and ingredient A of the ingredient A in whole organic solid ingredients is relative to complete It is mass parts other than the ratio of portion's solid component.In addition, in addition to blocked isocyanate compounds, inorganic particulate and organic solvent In addition, the mass parts of solid component conversion are indicated.About blocked isocyanate compounds and inorganic particulate, indicate above-mentioned solid at Divide the mass parts of the solution of concentration.In addition, in table "-" indicate without containing the compound met.

<evaluation of pencil hardness>

Each solidification compound of above-mentioned modulation is spun on the glass substrate for being vapor-deposited with titanium, carries out 90 DEG C, 120 seconds Prebake conditions obtain the coated film that film thickness is 3.0 μm.Then 500mJ/cm is carried out by high-pressure sodium lamp²The illumination of (conversion of i ray) It penetrates, and then carries out 120 DEG C, 60 minutes with baking oven and toast, thus make cured film.

Relative to obtained cured film, pencil is carried out by the method (load 750g) according to JIS K5600:1999 Hardness test evaluates film-strength according to benchmark below.A, B and C is usage range.

A:6H or more

B:5H

C:3H or 4H

D:2H or less or film peel off

<evaluation of coating (the wetting scalability on the glass substrate with ITO)>

Each solidification compound is sputtered in the half of 550mm × 650mm ITO (film thickness is 0.2 μm) and a semi-nudity Expose and carry out slot coated in such a way that film thickness reaches 1.0 μm on the glass substrate of glass, observes the end of solution.ITO and The more consistent two ends of glass the better, if wetting extension occurs compared with another for a material side, for difference.It is described below Evaluation criteria.A is usage range.

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

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

Table 1

Table 2

Table 3

Table 4

As even if solidification compound of the invention solidifies at low temperature, also having as showing above-mentioned 1~table of table 4 There is high hardness, in addition, coating is excellent.

(embodiment 27)

<production of display device>

In display device shown in Fig. 4, solidification compound obtained in each Examples 1 to 26 is respectively used to touch The formation of detecting electrode protective film (insulating film, 420), makes display device respectively.Specifically, protective film (420) is to pass through Solidification compound obtained in each embodiment of ink-jet application carries out the prebake conditions of 90 DEG C, 120 seconds, is carried out by high-pressure sodium lamp 500mJ/cm²The light of (conversion of i ray) irradiates, and then formed with 120 DEG C of baking oven progress, baking in 60 minutes.Display device Other parts according in Japanese Unexamined Patent Publication 2013-168125 bulletin as Figure 19 record manufacturing method and make.It is made The display performance of any of the display device of work, touch detection performance are all excellent.

The explanation of symbol

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

Claims (14)

1. a kind of solidification compound, which is characterized in that contain:

As ingredient A olefinic unsaturated compound,

As ingredient B polymerization initiator,

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

As ingredient D organic solvent and

As the inorganic particulate of ingredient E,

Ingredient A includes carbamate (methyl) acrylate of 5 functions or more,

The content of carbamate (methyl) acrylate more than 5 function is relative to 100 mass parts of content of ingredient A 20~100 mass parts,

Carbamate (methyl) acrylate more than 5 function includes the amino first that weight average molecular weight is 10,000 or more Acid esters (methyl) acrylate and molecular weight are 5,000 carbamate (methyl) acrylate below.

2. solidification compound according to claim 1, wherein ingredient B includes oxime ester compound.

3. solidification compound according to claim 1 or 2, wherein ingredient A includes except amino more than 5 function Olefinic unsaturated compound other than formic acid esters (methyl) acrylate.

4. solidification compound according to claim 3, wherein except carbamate (methyl) more than 5 function Olefinic unsaturated compound other than acrylate is polyfunctional ethylenically unsaturated compound.

5. solidification compound according to claim 1 or 2, wherein the content of ingredient A is relative to solidification compound Whole organic solid ingredients are 70 mass % or more.

6. solidification compound according to claim 1 or 2, wherein carbamate (methyl) more than 5 function Acrylate includes that the two or more molecular weight is 5,000 carbamate (methyl) acrylate below.

7. solidification compound according to claim 1 or 2, wherein further containing selected from by the change with epoxy group In the group for closing object, the compound with oxetanyl, blocked isocyanate compounds and multifunctional sulfhydryl compound composition It is at least one kind of.

8. a kind of cured film is by cured film made of solidification compound of any of claims 1 or 2 solidification.

9. cured film according to claim 8 is protective film.

10. cured film according to claim 8, hard according to the pencil under the load 750g of JIS K5600:1999 measurement Degree is 3H or more.

11. a kind of organic EL display device, with cured film according to any one of claims 8.

12. a kind of liquid crystal display device, with cured film according to any one of claims 8.

13. a kind of touch panel, with cured film according to any one of claims 8.

14. a kind of touch panel display device, with cured film according to any one of claims 8.